CN104272149A - Method for manufacturing laminated film - Google Patents
Method for manufacturing laminated film Download PDFInfo
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- CN104272149A CN104272149A CN201380024250.2A CN201380024250A CN104272149A CN 104272149 A CN104272149 A CN 104272149A CN 201380024250 A CN201380024250 A CN 201380024250A CN 104272149 A CN104272149 A CN 104272149A
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- Prior art keywords
- tackifier
- film
- blooming
- hyaline membrane
- active energy
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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
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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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
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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
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/0046—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by constructional aspects of the apparatus
- B32B37/0053—Constructional details of laminating machines comprising rollers; Constructional features of the rollers
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1207—Heat-activated adhesive
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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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
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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
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
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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
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
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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
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
- B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
- B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
- B32B37/203—One or more of the layers being plastic
- B32B37/206—Laminating a continuous layer between two continuous plastic layers
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Abstract
A method provided with, in this order, an adhesive application step for applying an active-energy-ray curable adhesive to one or both surfaces of at least one film of a plurality of films, a bonding step for bonding together the plurality of films by inserting the films between a pair of bonding rolls rotating in a conveyance direction in a state in which adjacent films are laminated so that the adhesive is interposed therebetween, and an active-energy-ray irradiation step for curing the adhesive by irradiating active energy rays to the plurality of films that have been bonded together, the surface roughness of the surface to which the adhesive was not applied in the adhesive application step from among the plurality of films, which is the surface contacting the adhesive in the bonding step, being 200 nm or less.
Description
Technical field
The present invention relates to a kind of manufacture method for the stacked film in the various uses such as optics.
Background technology
Polarizing coating is used widely by the film obtained as making dichromatism pigment be adsorbed on polyvinyl alcohol resin film also orientation, there will be a known the iodine system polarizing coating using iodine as dichromatism pigment, dyestuff system polarizing coating etc. using dichromatism direct dyes as dichromatism pigment.These polarizing coatings make polarization plates at its one or both sides by hyaline membranes such as tackifier laminating tri acetyl cellulose membranes usually.
As the method for the one or both sides laminating transparent film at polarizing coating, there is following method, namely, in advance after the coat activated energy ray-curable resin in the surface of hyaline membrane, fit by polarizing coating and hyaline membrane are clamped with a pair doubling roller, then irradiate active energy beam and make it bonding solidification (such as with reference to Japanese Unexamined Patent Publication 2004-245925 publication (patent documentation 1), Japanese Unexamined Patent Publication 2009-134190 publication (patent documentation 2), Japanese Unexamined Patent Publication 2011-95560 publication (patent documentation 3) etc.).
In the manufacture of stacked film like this that multiple film is bonded to each other by the tackifier of active energy ray curable, be mixed into bubble between film and film sometimes.This is the impossible phenomenon when using the bonding agent etc. of water system in the past, is considered to the distinctive problem caused because using the tackifier of active energy ray curable.In recent years, the further slimming of stacked film is being pursued.Thus there is following problem, that is, when being intended to the thickness of tackifier of thinning active energy ray curable, just especially easily produce the problem be mixed into of bubble.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-245925 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-134190 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2011-95560 publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, in the manufacture of the stacked film that multiple film is bonded to each other by the tackifier of active energy ray curable, suppress bubble to being mixed between film and film.
For the method for dealing with problems
The invention provides a kind of manufacture method of stacked film, it is by the manufacture method of multiple film by the tackifier of active energy ray curable stacked film bonded to each other,
Described manufacture method possesses successively:
Tackifier painting process, to the tackifier of the coat activated energy ray-curable of one or both sides of at least 1 film in described multiple film;
Bonding process, under the mode of tackifier carries out stacked state described in sandwiched between with adjacent film, is clamped in described multiple film between a pair doubling roller rotating along carriage direction, carries out bonded to each other thus; And
Active energy beam irradiation process, makes described adhesive solidification to being irradiated active energy beam by described multiple films bonded to each other,
In described multiple film, in described tackifier painting process, be not coated with described tackifier and be below 200nm with the surfaceness in the face of described adhesive contact in described bonding process.
Preferred described multiple film comprises blooming and hyaline membrane, and described stacked film is polarization plates.
Preferred described multiple film comprises 1 blooming and 2 hyaline membranes,
In described tackifier painting process, tackifier described in the respective coated on one side of 2 described hyaline membranes,
In described bonding process, under carrying out stacked state in the mode making the described tackifier of 2 described hyaline membranes contact with the two sides of described blooming, described blooming and described hyaline membrane are clamped between described a pair doubling roller, carry out bonded to each other thus.
Preferred described multiple film comprises 1 blooming and 1 hyaline membrane,
In described tackifier painting process, tackifier described in the coated on one side of described hyaline membrane,
In described bonding process, under carrying out stacked state in the mode making the described tackifier of described hyaline membrane contact with the one side of described blooming, described blooming and described hyaline membrane are clamped between described a pair doubling roller, carry out bonded to each other thus.
The effect of invention
According to the present invention, in the manufacture of the stacked film that multiple film is bonded to each other by the tackifier of active energy ray curable, bubble can be suppressed to being mixed between film and film.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the formation representing device entirety used in the manufacture method of embodiment 1.
Fig. 2 is the schematic diagram of the formation representing device entirety used in the manufacture method of embodiment 2.
Fig. 3 is the schematic diagram of the formation representing device entirety used in the manufacture method of embodiment 2.
Embodiment
The present invention is by the manufacture method of multiple film by the tackifier of active energy ray curable stacked film bonded to each other,
Described manufacture method possesses successively:
Tackifier painting process, to the tackifier of the coat activated energy ray-curable of one or both sides of at least 1 film in described multiple film;
Bonding process, under described in sandwiched, the mode of tackifier carries out stacked state between with adjacent film, is clamped between a pair doubling roller rotating along carriage direction, thus by bonded to each other for described multiple film by described multiple film; And
Active energy beam irradiation process, makes described adhesive solidification to being irradiated active energy beam by described multiple films bonded to each other.
In the present invention, in described multiple film, in described tackifier painting process, be not coated with described tackifier and be below 200nm with the surfaceness in the face of described adhesive contact in described bonding process.
So-called surfaceness in the present invention, refers to 10 mean roughness (Rzjis in calendar year 2001 revised edition JIS B 0601; Wherein, datum length is set to 2.5mm, evaluation length is set to 12.5mm.), be sometimes elliptically denoted as Rz below.The unit of surfaceness (Rz) is nm.The measurement example of this surfaceness (Rz) is as used (strain) Tokyo precision system " HANDYSURF E35A " as determinator, shear force (カ ッ ト オ Off value) (datum length) is set as 2.5mm, mensuration distance is set as 12.5mm, obtains the mean value when placing of said determination device being measured on object film 10 subsurface roughness.When this surfaceness is greater than 200nm, in described bonding process, be easily mixed into bubble intermembranous.Surfaceness is preferably below 100nm, is more preferably below 80nm.The film with this surfaceness can be selected from commercially available product.In addition, also adjustment form surface roughness can be carried out by the surface-coating resins etc. to film.
The thickness of the described tackifier be preferably coated with in described tackifier painting process is less than 2 μm.When the thickness of be coated with tackifier is below 2 μm, easily especially in described bonding process, be mixed into bubble to intermembranous, the inhibition that the bubble therefore utilizing the present invention to play is mixed into will be obvious.And, when the thickness coating at least 1 tackifier in the tackifier on multiple film is below 2 μm, effect of the present invention can be played significantly.
As stacked film manufactured in the present invention, such as, polarization plates can be enumerated.When manufacturing stacked film, in multiple film, such as comprise blooming and hyaline membrane.
(blooming)
So-called blooming, be such as the pattern phase shift films (pattern retard film) of polarizing coating or phase retardation film, 3D TV, both can be 1 film, also can be the duplexer of multiple film.
In the present invention, the polarizing coating that uses is such as that polyvinyl alcohol resin film at uniaxial tension adsorbs dichromatism pigment and the film making it orientation and obtain when manufacturing polarization plates with the form of stacked film.Polyvinyl alcohol resin is by the resin saponification of polyvinyl acetate system being obtained.As polyvinyl acetate system resin, except the polyvinyl acetate of the homopolymer as vinyl acetate, can also enumerate vinyl acetate with can the multipolymer (such as vinyl-vinyl acetate copolymer) etc. of other monomer of copolymerization with it.As can with other monomer of vinyl acetate copolymerization, unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class can also be enumerated in addition, there is the acrylic amide etc. of ammonium.The saponification degree of polyvinyl alcohol resin is more than 85 % by mole, is preferably more than 90 % by mole, is more preferably 98 ~ 100 % by mole.The average degree of polymerization of polyvinyl alcohol resin is generally 1000 ~ 10000, is preferably 1500 ~ 5000.These polyvinyl alcohol resins also can be modified, the polyvinyl formal, polyvinyl acetal, polyvinyl butyral etc. that such as also can use by aldehydes modification.
The material this polyvinyl alcohol resin masking obtained is used by the former material film as polarizing coating.The method of polyvinyl alcohol resin masking is not particularly limited, known appropriate method masking can be utilized.The thickness of the former material film be made up of polyvinyl alcohol resin is not particularly limited, but such as about 10 ~ 150 μm.Usually with drum supply, thickness is in the scope of 20 ~ 100 μm, and be preferably in the scope of 30 ~ 80 μm, in addition, the width of industrial practicality is in the scope of 1500 ~ 6000mm.
As commercially available polyvinyl alcohol resin film, such as, can enumerate Vinylon (PVC ニ ロ Application) VF-PS#7500 (Kuraray system, former material thickness are 75 μm), OPL film M-7500 (Japan's synthesis system, former material thickness are 75 μm), Vinylon VF-PS#6000 (Kuraray system, former material thickness are 60 μm), Vinylon VF-PE#6000 (Kuraray system, former material thickness are 60 μm), Vinylon VF-PE#5000 (Kuraray system, former material thickness are 50 μm) etc.
Polarizing coating normally through polyvinyl alcohol resin film dichromatism pigment dyeing is adsorbed dichromatism pigment operation (dyeing treatment process), the operation (boric acid treatment process) of having adsorbed the polyvinyl alcohol resin film boric acid aqueous solution process of dichromatism pigment and the operation (washing treatment process) of carrying out washing after this utilizes the process of boric acid aqueous solution are manufactured.
In addition, when the manufacture of polarizing coating, usually by polyvinyl alcohol resin film uniaxial tension, and this uniaxial tension both can carry out before dyeing treatment process, also can carry out in dyeing treatment process, can also carry out after dyeing treatment process.When carrying out uniaxial tension after the treatment process that dyes, this uniaxial tension both can carry out before boric acid treatment process, also can carry out in boric acid treatment process.Certainly, also uniaxial tension can be carried out in these multiple stages.
Uniaxial tension both can stretch between the roller that peripheral speed is different single shaft, stretched with also can using hot-rolling single shaft.In addition, both can be the dry type stretching carrying out in an atmosphere stretching, also can be stretch in the wet type making it with solvent to carry out under swelling state stretching.Stretching ratio is generally about 3 ~ 8 times.
The dyeing of dichromatism pigment that utilizes of the polyvinyl alcohol resin film in dyeing treatment process such as can by carrying out polyvinyl alcohol resin film immersion in the aqueous solution containing dichromatism pigment.As dichromatism pigment, such as, iodine, dichroic dye etc. can be used.In dichroic dye, such as, comprise the dichromatism direct dyes that C.I.DIRECT RED 39 grade is made up of bis-azo compound, the dichromatism direct dyes be made up of compounds such as trisazo-, four azos.And polyvinyl alcohol resin film was preferably implemented to the dip treating in water before dyeing process.
When using iodine as dichromatism pigment, the method that usual employing is flooded polyvinyl alcohol resin film and dyeed in the aqueous solution containing iodine and potassium iodide.The content of the iodine in this aqueous solution is normally 0.01 ~ 1 weight portion in every 100 weight parts waters, and the content of potassium iodide is normally 0.5 ~ 20 weight portion in every 100 weight parts waters.When using iodine as dichromatism pigment, the temperature of aqueous solution used in dyeing is generally 20 ~ 40 DEG C, is generally 20 ~ 1800 seconds to the dip time (dyeing time) in this aqueous solution.
On the other hand, when using dichroic dye as dichromatism pigment, usually adopt to the method dyeed containing flooding polyvinyl alcohol resin film in the aqueous solution of dichroic dye.The content of the dichroic dye in this aqueous solution is normally 1 × 10 in 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.In this aqueous solution, also can contain the inorganic salts such as sodium sulphate as dyeing assistant.When using dichroic dye as dichromatism pigment, the temperature of aqueous dye solutions used in dyeing is generally 20 ~ 80 DEG C, in addition, is generally 10 ~ 1800 seconds to the dip time (dyeing time) in this aqueous solution.
Boric acid treatment process is by utilizing the polyvinyl alcohol resin film immersion of dichromatism pigment dyeing to carry out in containing boron aqueous acid.Amount containing the boric acid in boron aqueous acid is normally 2 ~ 15 weight portions in every 100 weight parts waters, is preferably 5 ~ 12 weight portions.When employing iodine as the dichromatism pigment in above-mentioned dyeing treatment process, the boron aqueous acid that contains used in this boric acid treatment process preferably contains potassium iodide.In this situation, the amount containing the potassium iodide in boron aqueous acid is normally 0.1 ~ 15 weight portion in every 100 weight parts waters, is preferably 5 ~ 12 weight portions.Be generally 60 ~ 1200 seconds to containing the dip time in boron aqueous acid, be preferably 150 ~ 600 seconds, be more preferably 200 ~ 400 seconds.Temperature containing boron aqueous acid is generally more than 40 DEG C, is preferably 50 ~ 85 DEG C, is more preferably 55 ~ 75 DEG C.
In ensuing washing treatment process, carry out washing process by being such as immersed in water by the polyvinyl alcohol resin film after above-mentioned boric acid process.The temperature of the water in washing process is generally 4 ~ 40 DEG C, and dip time is generally 1 ~ 120 second.After washing process, usually implement dry process, obtain polarizing coating.Dry processing example is as used air drier, far infra-red heater etc. suitably to carry out.The temperature of dry process is generally 30 ~ 100 DEG C, is preferably 50 ~ 80 DEG C.The time of dry process is generally 60 ~ 600 seconds, is preferably 120 ~ 600 seconds.
Like this uniaxial tension, the dyeing utilizing dichromatism pigment, boric acid process and washing process are implemented to polyvinyl alcohol resin film, just can obtain polarizing coating.The thickness of this polarizing coating is generally in the scope of 5 ~ 50 μm.
(hyaline membrane)
In the present invention, when manufacturing polarization plates with the form of stacked film, at the one or both sides laminating hyaline membrane of above-mentioned blooming.When the two sides laminating hyaline membrane of blooming, each hyaline membrane both can be the film of identical type, also can be different types of film.
As the material forming hyaline membrane, such as, can enumerate the membrane material that cyclic olefine resin, acetate fiber prime system resin, polyethylene terephthalate or the polyester based resin of PEN, polybutylene terephthalate and so on, polycarbonate-based resin, acrylic resin, polypropylene etc. are used widely in this field all the time.
So-called cyclic olefine resin is such as norborene, the thermoplastic resin (also referred to as thermoplastic cyclic olefin system resin) with the unit of the monomer be made up of cyclic olefin (cycloolefin) of many rings norborneol alkene monomer and so on.Cyclic olefine resin both can be the ring-opening polymerization polymer of above-mentioned cycloolefin or employ the hydride of ring opening copolymer thing of cycloolefin of more than two kinds, also can be the addition polymer of cycloolefin and chain olefin, the aromatics with vinyl etc.In addition, the resin having imported polar group is also effective.
When using cycloolefin and chain olefin and/or there is the multipolymer of aromatics of vinyl, as chain olefin, ethene, propylene etc. can be enumerated, in addition as the aromatics with vinyl, styrene, α-methyl styrene, core alkyl-substituted styrene etc. can be enumerated.In this kind of multipolymer, the unit of the monomer be made up of cycloolefin also can be less than 50 % by mole (being preferably 15 ~ 50 % by mole).Particularly, when using cycloolefin and chain olefin and having the terpolymer of aromatics of vinyl, the unit of the monomer be made up of cycloolefin can be set to less amount as described above.In this terpolymer, the unit of the monomer be made up of chain olefin is generally 5 ~ 80 % by mole, and the unit of the monomer be made up of the aromatics with vinyl is generally 5 ~ 80 % by mole.
Cyclic olefine resin can use appropriate commercially available product suitably, such as Topas (Ticona Inc.), Arton (JSR (strain) system), ZEONOR (Japanese Zeon (strain) system), ZEONEX (Japanese Zeon (strain) system), Apel (ア ペ Le) (Mitsui Chemicals (strain) system), OXIS (great Cang industrial group system) etc.When this kind of cyclic olefine resin masking is formed film, solvent cast (キ ャ ス ト) the known method such as method, extrusion by melting suitably can be used.In addition, Escena (エ ス シ ー Na) (ponding chemical industry (strain) system), SCA40 (ponding chemical industry (strain) system), ZEONOR film ((strain) OPTES (オ プ テ ス) system) etc. such as also can be used by the commercially available product of the resinous film of cyclic olefine of masking in advance.
Cyclic olefine resin molding also can by uniaxial tension or biaxial stretch-formed film.By stretching, just arbitrary phase difference value can be given to cyclic olefine resin molding.Stretch and normally carry out continuously while film reel is rolled out, in heating furnace, stretch to the direct of travel (length direction of film) of reel or the direction vertical with this direct of travel (Width of film) or this both direction.The temperature of heating furnace adopts the scope to glass temperature+100 DEG C near the glass temperature of cyclic olefine resin usually.The multiplying power stretched is generally 1.1 ~ 6 times, is preferably 1.1 ~ 3.5 times.
When cyclic olefine resin molding is in reel state, easily producing the trend of adhesion with regard to having bonding between film, therefore usually after laminating diaphragm, making reel.In addition, cyclic olefine resin molding generally speaking surfactivity is poor, therefore preferably carries out the surface treatments such as Cement Composite Treated by Plasma, corona treatment, Ultraviolet radiation process, flame (flame) process, saponification process to the surface bonding with blooming.Wherein, be suitably for can implement with comparalive ease Cement Composite Treated by Plasma, particularly atmospheric plasma treatment, corona treatment.
So-called acetate fiber prime system resin is cellulosic partially or completely carboxylate, such as, can enumerate the film be made up of cellulosic acetic acid esters, propionic ester, butyric ester, their mixed ester etc.More specifically, tri acetyl cellulose membrane, diacetyl cellulose film, cellulose acetate propionate film, cellulose acetate butyrate film etc. can be enumerated.As this kind of cellulose esters resin film, appropriate commercially available product can be used suitably, such as, Fujitac (Off ジ タ ッ Network) TD80 (Fuji Photo Film (Ltd.)), Fujitac TD80UF (Fuji Photo Film (Ltd.)), Fujitac TD80UZ (Fuji Photo Film (Ltd.)), KC8UX2M (Konica Minolta Opt (strain) system), KC8UY (Konica Minolta Opt (strain) system), Fujitac TD60UL (Fuji Photo Film (Ltd.)), KC4UYW (Konica Minolta Opt (strain) system), KC6UAW (Konica Minolta Opt (strain) system) etc.
In addition, as hyaline membrane, the cellulose acetate resin film imparting phase difference characteristics also can be used suitably.Be endowed the commercially available product of the cellulose acetate resin film of phase difference characteristics as this, WV BZ 438 (Fuji Photo Film (Ltd.)), KC4FR-1 (Konica Minolta Opt (strain) system), KC4CR-1 (Konica Minolta Opt (strain) system), KC4AR-1 (Konica Minolta Opt (strain) system) etc. can have been enumerated.Cellulose acetate also can be called acetylcellulose, also may be referred to cellulose ethanoate.
These cellulose acetate resin films easily absorb water, and the moisture rate of polarization plates impacts the lax of end of polarization plates sometimes.The equilibrium moisture rate that moisture rate when manufacturing polarization plates is more preserved in warehouse close to the Conservation environment of polarization plates, the production line of such as dust free room or reel is better, although also will determine according to the formation of stacked film, but be such as preferably about 2.0 ~ 3.5%, be more preferably 2.5% ~ 3.0%.The numerical value of the moisture rate of this polarization plates is the value utilizing dry weight method to measure, and is to use the weight change of calibration cell at the temperature of 105 DEG C before and after the drying process of 120 minutes.
The thickness of hyaline membrane used in polarization plates of the present invention gets over Bao Yuehao, if but too thin, intensity reduce, become the material of poor in processability.If on the other hand blocked up, can produce the transparency reduce, stacked after the problems such as required curing time is elongated.Thus, the appropriate thickness of hyaline membrane is such as 5 ~ 200 μm, is preferably 10 ~ 150 μm, is more preferably 10 ~ 100 μm.
In order to improve the cementability of tackifier and blooming and/or hyaline membrane, also the surface treatment such as corona treatment, flame treatment, Cement Composite Treated by Plasma, UV treatment, silane coupling agent coating process, saponification process can be implemented to blooming and/or hyaline membrane.
In addition, also separately or with combining two or more the surface treatments such as non-glare treated, antireflection process, hard conating process, electrostatic prevention process, antifouling process can be implemented to hyaline membrane.In addition, hyaline membrane and/or hyaline membrane sealer also can contain the plastifier such as the ultraviolet light absorber such as benzophenone based compound, benzotriazole based compound or phenyl phosphate ester based compound, phthalate compound.
In addition, hyaline membrane can be made to have the function as phase retardation film, the function as brightness enhancement film, function as reflectance coating, the function as Transflective film, the function as diffusion barrier, function as the optics such as function of optical compensation films.In this situation, such as can by making it that there is this kind of function at optical functional films such as the stacked phase retardation film in the surface of hyaline membrane, brightness enhancement film, reflectance coating, Transflective film, diffusion barrier, optical compensation films, in addition, this kind of function can also be given to hyaline membrane self.In addition, also can as have brightness enhancement film function diffusion barrier etc., make hyaline membrane have multiple function.
Such as, the process to recording in the stretch processing recorded in above-mentioned hyaline membrane date of execution this patent No. 2841377 publication, patent No. 3094113 publication etc. or date of execution this patent No. 3168850 publication can be passed through, and give the function as phase retardation film.For the phase difference characteristics of phase retardation film, the scope etc. that such as front phase difference value is 5 ~ 100nm, thickness direction phase difference value is 40 ~ 300nm can suitably be selected.In addition, can by above-mentioned hyaline membrane, the method recorded in Japanese Unexamined Patent Publication 2002-169025 publication or Japanese Unexamined Patent Publication 2003-29030 publication is utilized to form micropore, or select by overlapping the cholesteric liquid crystal layer of more than 2 layers that the centre wavelength of reflection is different, and give the function as brightness enhancement film.
If utilize evaporation, sputtering etc. to form metallic film on above-mentioned hyaline membrane, then can give the function as reflectance coating or Transflective film.Containing fine-grained resin solution, the function as diffusion barrier can be given by coating on above-mentioned hyaline membrane.In addition, by being coated with the liquid crystal compounds such as collar plate shape liquid crystal compounds and making it orientation on above-mentioned hyaline membrane, the function as optical compensation films can be given.In addition, also can make in hyaline membrane containing the compound showing phase differential.In addition, also can use suitable tackifier, various optical functional film is directly fitted on blooming.As the commercially available product of optical functional film, such as, can enumerate the visual angle such as brightness enhancement film, WV film (Fuji Photo Film (Ltd.)) improvement film, Arton film (JSR (strain) system), ZEONOR film ((strain) OPTES system), Escena (ponding chemical industry (strain) system), the poor films of VA-TAC (Konica Minolta Opt (strain) system), Sumika Light (ス ミ カ ラ イ ト) (Sumitomo Chemical (strain) system) equiphase etc. such as DBEF (3M Inc., can buy from Sumitomo 3M (strain) in Japan).
(active energy ray curable tackifier)
As the tackifier of active energy ray curable used in the present invention, consider from weatherability or the viewpoint such as refractive index, cationically polymerizable, such as, can enumerate the tackifier be made up of the epoxy system resin composition containing the epoxy resin solidified because of the irradiation of active energy beam.But, be not limited thereto, the tackifier (organic solvent system tackifier, hot melt system tackifier, solventless adhesive etc.) of the various active energy ray curables all the time used in the manufacture of polarization plates can be adopted.
So-called epoxy resin, refers to the compound of the epoxy radicals in molecule with more than 2.Consider from the viewpoint such as weatherability, refractive index, cationically polymerizable, contained epoxy resin is preferably the epoxy resin (such as with reference to patent documentation 1) not containing aromatic rings in molecule in as the curable epoxy resin composition of tackifier.As this kind of epoxy resin, hydrogenated epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin etc. can be exemplified.
Hydrogenated epoxy resin can utilize following method to obtain, namely, make the polyol as the raw material of aromatic epoxy resin optionally core hydrogenation occur in the presence of a catalyst, under elevated pressure, glycidyl ether is carried out to the core hydrogenated polyol of gained.As aromatic epoxy resin, such as, 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 novolac type such as phenol linear phenolic epoxy resin, cresol novalac epoxy resin and hydroxy benzaldehyde phenol linear phenolic epoxy resin; The epoxy resin etc. of the multifunctional types such as the glycidol ether of tetrahydroxy benzene methylmethane, the glycidol ether of tetrahydroxybenzophenone and epoxidation polyvinylphenol.In hydrogenated epoxy resin, the glycidol ether of the bisphenol-A of preferred hydrogenation.
So-called alicyclic epoxy resin, refers to the epoxy resin of the epoxy radicals of closing with ester ring type ring key in molecule with more than 1.So-called " epoxy radicals of closing with ester ring type ring key ", refers to the oxygen atom-O-of the bridge joint in the structure shown in following formula.In following formula, m is the integer of 2 ~ 5.
[changing 1]
By (the CH of above-mentioned formula
2)
min one or more hydrogen atoms remove after the group of form and the compound of other chemical constitution bonding can become alicyclic epoxy resin.(CH
2)
min one or more hydrogen atom also suitably can be replaced by the straight-chain such as methyl, ethyl alkyl.In the middle of alicyclic epoxy resin, have the oxabicyclohexane ring compound of m=3 (in the above-mentioned formula), the oxabicyclo heptane ring compound of m=4 (in the above-mentioned formula) epoxy resin owing to showing excellent cementability, therefore preferably use.Below exemplify the alicyclic epoxy resin preferably used particularly, but be not limited to these compounds.
A 7-oxa-bicyclo[4.1.0 formic acid epoxycyclohexanecarboxylate class that () represents with following formula (I):
[changing 2]
(in formula, R
1and R
2represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another).
The 7-oxa-bicyclo[4.1.0 formate ester of b alkane diol that () represents with following formula (II):
[changing 3]
(in formula, R
3and R
4represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another, n represents the integer of 2 ~ 20).
The epoxycyclohexyl-methyl ester class of c dicarboxylic acid that () represents with following formula (III):
[changing 4]
(in formula, R
5and R
6represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another, p represents the integer of 2 ~ 20).
The epoxycyclohexyl-methyl ethers of d polyglycol that () represents with following formula (IV):
[changing 5]
(in formula, R
7and R
8represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another, q represents the integer of 2 ~ 10).
The epoxycyclohexyl-methyl ethers of e alkane diol that () represents with following formula (V):
[changing 6]
(in formula, R
9and R
10represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another, r represents the integer of 2 ~ 20).
F diepoxy three spiro-compounds that () represents with following formula (VI):
[changing 7]
(in formula, R
11and R
12represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another).
G diepoxy list spiro-compounds that () represents with following formula (VII):
[changing 8]
(in formula, R
13and R
14represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another).
H vinyl cyclohexene diepoxide class that () represents with following formula (VIII):
[changing 9]
(in formula, R
15represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5).
I epoxycyclopentyl ethers that () represents with following formula (IX):
[changing 10]
(in formula, R
16and R
17represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5 independently of one another).
J diepoxy tristane class that () represents with following formula (X):
[changing 11]
(in formula, R
18represent the straight-chain alkyl of hydrogen atom or carbon number 1 ~ 5).
In the middle of the above-mentioned alicyclic epoxy resin exemplified, alicyclic epoxy resin below can commercially be buied, or its analog, obtaining than being easier to, for these reasons, more preferably using.
(A) 7-oxabicyclo [4.1.0] heptane-3-formic acid and (7-oxa--two ring [4.1.0]-3-in heptan base) methyl alcohol carboxylate [in formula (I), R
1=R
2the compound of=H],
(B) 4-methyl-7-oxabicyclo [4.1.0] heptane-3-formic acid and (4-methyl-7-oxa--two ring [4.1.0]-3-in heptan base) methyl alcohol carboxylate [in formula (I), R
1=4-CH
3, R
2=4-CH
3compound],
(C) 7-oxabicyclo [4.1.0] heptane-3-formic acid and 1,2-ethylene glycol carboxylate [in formula (II), R
3=R
4the compound of=H, n=2],
(D) (7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol and hexane diacid carboxylate [in formula (III), R
5=R
6the compound of=H, p=4],
(E) (4-methyl-7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol and hexane diacid carboxylate [in formula (III), R
5=4-CH
3, R
6=4-CH
3, p=4 compound],
(F) (7-oxabicyclo [4.1.0]-3-in heptan base) methyl alcohol and 1,2-ethylene glycol etherate [in formula (V), R
9=R
10the compound of=H, r=2].
In addition, as aliphatic epoxy resin, the polyglycidyl ether of aliphatic polyol or its alkylene oxide addition product can be enumerated.More specifically, the diglycidyl ether of BDO can be enumerated; 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; The alkylene oxide (oxirane or epoxypropane) one kind or two or more by addition on the aliphatic polyols such as ethylene glycol, propylene glycol and glycerine and the polyglycidyl ether etc. of the polyether glycol obtained.
The epoxy resin forming the tackifier formed by epoxy system resin composition both can only be used alone a kind, and also two or more kinds may be used.The epoxide equivalent of epoxy resin used in said composition is generally 30 ~ 3000g/ equivalent, is preferably in the scope of 50 ~ 1500g/ equivalent.If epoxide equivalent is below 30g/ equivalent, then the flexibility of the composite polarizing plate after solidification is likely made to reduce or bonding strength reduction.On the other hand, if be greater than 3000g/ equivalent, then likely reduce with the compatibility of contained other composition in tackifier.
In this tackifier, consider from reactive viewpoint, as the curing reaction of epoxy resin, preferably use cationic polymerization.Thus, in the curable epoxy resin composition of the tackifier as active energy ray curable, preferably coordinate cationic polymerization initiators.Cationic polymerization initiators produces kation kind or lewis acid because of the irradiation of luminous ray, ultraviolet, X ray, electron beam isoreactivity energy-ray, causes the polyreaction of epoxy radicals.Below, the irradiation because of active energy beam is produced kation kind or lewis acid, the cationic polymerization initiators of polyreaction of initiation epoxy radicals is called " light cationic polymerization initiators ".
Make the solidification that can realize by the method that light cationic polymerization initiators utilizes the irradiation of active energy beam to carry out the solidification of tackifier under normal temperature, consider the thermotolerance of blooming or reduced by the necessity of the distortion caused of expanding, can, by intermembranous bonding well, consider favourable from this point.In addition, because light cationic polymerization initiators is the effect utilizing light to play catalyzer, even if be therefore mixed into epoxy resin, its storage stability, operability are also excellent.
As light cationic polymerization initiators, such as, aromatic diazonium salt can be enumerated; The salt such as aromatic iodonium salts or aromatic series sulfonium salt; Iron-arene complex etc.
As aromatic diazonium salt, such as, can enumerate benzene diazonium hexafluoro antimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoro borate etc.In addition, as aromatic iodonium salts, such as, can enumerate diphenyl iodine four (pentafluorophenyl group) borate, diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoro antimonate, two (4-nonyl phenyl) iodine hexafluorophosphate etc.
As aromatic series sulfonium salt, such as 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-(to tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium-diphenylsulfide hexafluoro antimonate, 4-(to tert-butyl-phenyl carbonyl)-4 '-two (p-methylphenyl) sulfonium-diphenylsulfide four (pentafluorophenyl group) borate etc.
In addition; as iron-arene complex, such as, can enumerate dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, cumene-cyclopentadienyl group iron (II) hexafluorophosphate, dimethylbenzene-cyclopentadienyl group iron (II)-three (trifluoromethyl sulfonyl) methide (メ タ Na イ De) etc.
The commercially available product of these light cationic polymerization initiators can easily be buied, such as, can enumerate " Kayarad PCI-220 " and " Kayarad PCI-620 " (above is Japanese chemical drug (strain) system) according to trade name respectively, " UVI-6990 " (Union Carbide Inc.), " Adeka Optomer SP-150 " and " Adeka Optomer SP-170 " (being (strain) ADEKA system above), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S " and " CIP-2064S " (being Japanese Cao Da (strain) system above), " 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 " and " DTS-103 " (being Midori Kagaku (body ど り chemistry) (strain) system above), " PI-2074 " (Rhodia Inc.) etc.
Light cationic polymerization initiators both can only be used alone a kind, also can be mixed with two or more.Wherein, aromatic series sulfonium salt, owing to also having Ultraviolet Light in the wavelength region may of more than 300nm, therefore can provide curability excellence, have good physical strength and the solidfied material of bonding strength, so preferably use.
For the use level of light cationic polymerization initiators, be generally 0.5 ~ 20 weight portion relative to epoxy resin 100 weight portion, be preferably more than 1 weight portion, be preferably below 15 weight portions in addition.If the use level of light cationic polymerization initiators below 0.5 weight portion, is then solidified insufficient relative to epoxy resin 100 weight portion, physical strength and bonding strength have the trend of reduction.In addition, if the use level of light cationic polymerization initiators is greater than 20 weight portions relative to epoxy resin 100 weight portion, then the hydroscopicity of solidfied material can be uprised because the ionic substance in solidfied material increases, endurance quality likely reduces.
When making with light cationic polymerization initiators, curable epoxy resin composition can as required also containing photosensitizer.By using photosensitizer, the reactivity of cationic polymerization will improve, and can improve physical strength and the bonding strength of solidfied material.As photosensitizer, such as, can enumerate carbonyls, organosulfur compound, persulfide, redox based compound, azo and diazo-compounds, halogen compound, photo-reduction pigment etc.
If enumerate the example more specifically of photosensitizer, then such as there are benzoin methylether, benzoin iso-propylether and α, the benzoin derivatives such as alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone; The benzophenone derivates such as benzophenone, 2,4-dichloro benzophenones, o-benzoyl yl benzoic acid methyl esters, 4,4 '-bis-(dimethylamino) benzophenone and 4,4 '-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 based compound, halogen compound etc.Photosensitizer both can only be used alone a kind, and also two or more kinds may be used.Preferably in curable epoxy resin composition 100 weight portion, containing photosensitizer in the scope of 0.1 ~ 20 weight portion.
Epoxy resin contained in tackifier is cured because of light cationic polymerization, but the both sides of light cationic polymerization and hot cationic polymerization also can be utilized to be cured.In the latter case, preferably light cationic polymerization initiators and hot cationic polymerization initiators are used.
As hot cationic polymerization initiators, benzylsulfonium, thiophene salt, thiophane salt (チ オ ラ ニ ウ system), hexadecyldimethyl benzyl ammonium, pyridiniujm, hydrazonium salt, carboxylate, sulphonic acid ester, amine acid imide etc. can be enumerated.These hot cationic polymerization initiators easily can be buied as commercially available product, such as, all can enumerate " Adeka Opton CP77 " and " Adeka Opton CP66 " (above is Asahi Denka Co., Ltd.'s system), " CI-2639 " and " CI-2624 " (above is Tso Tat Co., Ltd., Japan's system), " Sun-aid SI-60L ", " Sun-aid SI-80L " and " Sun-aid SI-100L " (being three new chemical industry Co., Ltd. systems above) etc. according to trade name.
The tackifier of active energy ray curable still can promote the compound of cationic polymerization containing oxetanes class or polyalcohols etc.
Oxetanes class is the compound in molecule with quaternary cyclic ethers, such as can enumerate 3-ethyl-3-hydroxymethyl oxetane, 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-Ethylhexoxymethyl) oxetanes, phenol novolac oxetanes etc.These oxetanes classes easily can be buied as commercially available product, such as, all can enumerate " ARONE OXETANE (ア ロ Application オ キ セ タ Application) OXT-101 ", " ARONE OXETANE OXT-121 ", " ARONE OXETANE OXT-211 ", " ARONE OXETANE OXT-221 " and " ARONE OXETANE OXT-212 " (being East Asia synthesis (strain) system above) etc. according to trade name.Usually with 5 ~ 95 % by weight, preferably contain these oxetanes classes with the ratio of 30 ~ 70 % by weight in curable epoxy resin composition.
As polyalcohols, preferably there is not the acidic-group beyond phenolic hydroxyl group, such as, can enumerate the polyol compound of the functional group do not had beyond hydroxyl, polyester polyol compound, polycaprolactone polyol compound, the polyol compound with phenolic hydroxyl group, polycarbonate polyol etc.The molecular weight of these polyalcohols is generally more than 48, is preferably more than 62, is more preferably more than 100, is preferably less than 1000 in addition.In curable epoxy resin composition, usually with less than 50 % by weight, preferably contain these polyalcohols with the ratio of less than 30 % by weight.
In the tackifier of active energy ray curable, also can coordinate the adjuvant such as ion capturing agent, antioxidant, chain-transferring agent, thickening agent, thermoplastic resin, filling agent, flow modifier, leveling agent, plastifier, defoamer.The mineral compounds such as pulverous bismuth system, antimony system, magnesium system, aluminium system, calcium system, titanium system and their mixed stocker can be enumerated as ion capturing agent, hindered phenol system antioxidant etc. can be enumerated as antioxidant.
The tackifier of active energy ray curable can use as the solventless adhesive in fact not containing solvent composition, but owing to having best range of viscosities in each coating method respectively, therefore also can contain solvent to adjust viscosity.As solvent, preferably use the optical property of blooming can not be made to reduce solvent that composition epoxy resin etc. is dissolved well, such as can enumerate with toluene be representative hydro carbons, take ethyl acetate as the organic solvent such as ester class of representative.The viscosity of the tackifier of active energy ray curable used in the present invention is such as the scope of about 5 ~ 1000mPas, is preferably 10 ~ 200mPas, is more preferably 20 ~ 100mPas.
Below, accompanying drawing is used to be described in detail to the embodiment manufacturing stacked film.
(embodiment 1)
In present embodiment, stacked film is by 1 blooming and 2 hyaline membrane manufactures.In addition, in described tackifier painting process, tackifier described in the respective coated on one side of 2 described hyaline membranes, in described bonding process, under carrying out stacked state in the mode making the described tackifier of 2 described hyaline membranes contact with the two sides of described blooming, described blooming and described hyaline membrane are clamped between described a pair doubling roller, carry out bonded to each other thus.
Below, with reference to while accompanying drawing, the manufacture method of present embodiment is being described.Fig. 1 is the schematic diagram of the formation representing device entirety used in the manufacture method of present embodiment.
In the manufacturing installation of the stacked film shown in Fig. 1, be provided with at hyaline membrane 2 successively along carriage direction, the tackifier apparatus for coating 11 of the coated on one side tackifier of 3, 12, for by hyaline membrane 2, 3 fit with blooming 1 and obtain the doubling roller (niproll) 51 of duplexer 4, 52, for making hyaline membrane 2 in duplexer 4, 3 rollers 13 closely sealed with blooming 1, be arranged on the first active energy beam irradiation unit 14 of the position facing with the outer peripheral face of this roller 13, 15, be arranged on the second later active energy beam irradiation unit 16 ~ 18 in carriage direction downstream by comparison, and transport with niproll 19.
First, the one side of the hyaline membrane 2,3 extracted out continuously in the state from tubular wound into a roll, utilizes the tackifier < tackifier painting process > of the coat activated energy ray-curable of tackifier apparatus for coating 11,12.
After this, the two sides of the blooming 1 extracted out continuously in the state from tubular wound into a roll, by the stacked hyaline membrane 2,3 being coated with tackifier of tackifier, holding them under the state between a pair doubling roller 51,52 rotated along carriage direction, the direction of the doubling roller of at least one party to the doubling roller of the opposing party is pushed, thus blooming 1 and hyaline membrane 2,3 are fitted, form duplexer 4 < bonding process >.
Then, carry out in the process of transporting while making this duplexer 4 and the outer peripheral face of roller 13 closely sealed, irradiate active energy beam from the first active energy beam irradiation unit 14,15 to the outer peripheral face of roller 13, make tackifier polymerizing curable < active energy beam irradiation process >.
And the second later active energy beam irradiation unit 16 ~ 18 being configured in carriage direction downstream is the devices for making tackifier fully polymerizing curable, can add as required, omit.Finally, duplexer 4, by transport niproll 19, is wound on take up roll 20 by as stacked film.Below, each operation is described in detail.
< tackifier painting process >
Coating process to the tackifier on hyaline membrane 2,3 is not particularly limited, but scraper, wire drawing rod, mould such as can be utilized to be coated with the various coating methods such as machine, comma coating machine, gravure coater.Wherein, if consider the degree of freedom of film coated, roll line, corresponding etc. with fabric width, then as the preferred gravure roll of tackifier apparatus for coating 11,12.
When using gravure roll to carry out the coating of tackifier as tackifier apparatus for coating 11,12, the thickness (coating thickness) of the tackifier be coated with is preferably about 0.1 ~ 10 μm, is more preferably 0.2 μm ~ 4 μm.The draw ratio as the velocity ratio of the speed of gravure roll and the linear velocity of hyaline membrane is utilized to adjust the coating thickness of tackifier.Generally speaking, by draw ratio (speed/linear velocity of gravure roll) is adjusted to 0.5 ~ 10, just the coating thickness of tackifier can be adjusted to about 0.1 ~ 10 μm.More specifically, by the linear velocity of hyaline membrane 2,3 is set to 10 ~ 100m/ minute, gravure roll is rotated along the direction contrary with the carriage direction of hyaline membrane 2,3, the speed of gravure roll is set to 5 ~ 1000m/ minute, just the coating thickness of tackifier can be adjusted to about 0.1 ~ 10 μm.
Tackifier after the production, is coated with under the environment of set point of temperature ± 5 DEG C (such as when set point of temperature is 30 DEG C, being 30 DEG C ± 5 DEG C) usually in the scope being adjusted to 15 ~ 40 DEG C, preferably ± 3 DEG C, more preferably ± 1 DEG C.
< bonding process >
In this operation, on the two sides of the blooming 1 extracted out continuously from the state reeled with drum, by the stacked hyaline membrane 2,3 utilizing above-mentioned operation to be coated with tackifier of tackifier.This duplexer being clamped under the state between a pair doubling roller 51,52 rotated along carriage direction, such as, the direction of doubling roller 51 to doubling roller 52 being pushed, thus blooming 1 and hyaline membrane 2,3 being fitted, form duplexer 4.
And, in Fig. 1, give hyaline membrane 2,3 one side equably coating binder and hyaline membrane 2,3 be coated with tackifier face superposition blooming 1 after utilize doubling roller 51,52 to carry out the method for fitting, but also can, at the two sides of blooming 1 coating binder equably, after the face being coated with tackifier of blooming 1 superposes hyaline membrane 2,3, utilize doubling roller 51,52 to fit.
Pushing is utilized to be not particularly limited duplexer applied pressure, but when using metal roller and rubber roller, the instantaneous pressure of Fujiphoto Double-piece type pressure-sensitive paper (プ レ ス ケ ー ス) is preferably 0.2 ~ 3.0MPa, is more preferably 0.5 ~ 2.3MPa.The external force of the pushing of this doubling roller is normally put on to the bearing components at the two ends of doubling roller.
A pair doubling roller also can have difference in the peripheral speed of the doubling roller of the doubling roller of a side and the opposing party.Such as, the peripheral speed of the doubling roller (the first doubling roller) of the side, face of fitting with liquid crystal panel being arranged on duplexer 4 is preferably fast than the peripheral speed of the doubling roller (the second doubling roller) of opposite side.Thus, when the stacked film of gained is polarization plates, just can give the face of fitting with liquid crystal panel making polarization plates is protruded, the face of its opposite side is recessed curling (just curling).When the polarization plates of gained is imparted make that the face of fitting with liquid crystal panel is recessed into, curling (inverse curling) that the face of its opposite side is protruded, when polarization plates is fitted on liquid crystal cell, easily produces and suck the not good situations such as bubble at central portion.And, in this situation, preferably use metal roller as the first doubling roller, use rubber roller as the second doubling roller.
In addition, when the peripheral speed of the second doubling roller is set to 1, the ratio of the peripheral speed of the first doubling roller is more preferably made to be 1.0050 ~ 1.0200.This is because, when the peripheral speed of the first doubling roller is faster than this scope, just curling amount of curl will be excessive, easily produce when polarization plates is fitted on liquid crystal cell and suck the not good situations such as bubble in end, this is external when being positioned under too harsh environment, likely promotes just curling further and the end of polarization plates is peeled off from liquid crystal cell.
The outer peripheral face of roller 13 is constituted convex surface by carrying out minute surface finishing in advance, transports, utilize active energy beam irradiation unit 14,15 to make tackifier polymerizing curable in this process while making duplexer 4 and the surface of roller 13 closely sealed to it.Making tackifier polymerizing curable, make duplexer 4 closely sealed fully in, the diameter of roller 13 is not particularly limited.To tackifier be preferably the duplexer 4 of its uncured state with the accumulated light during making by roller 13 for 10mJ/cm
2above mode irradiates active energy beam.Both roller 13 can have been made according to the mobile and driven of the production line of duplexer 4 or rotary actuation, or also can make it fixing and make duplexer 4 slip over its surface.In addition, when utilizing the polymerizing curable of irradiation of active energy beam, roller 13 also can be made to play a role as the chill roll for the heat produced in duplexer 4 being distributed.In this situation, preferably the surface temperature of chill roll is set as 20 ~ 30 DEG C.
(embodiment 2)
In present embodiment, stacked film is by 1 blooming and 1 hyaline membrane manufacture.In addition, in described tackifier painting process, tackifier described in the coated on one side of described hyaline membrane, in described bonding process, under carrying out stacked state in the mode making the described tackifier of described hyaline membrane contact with the one side of described blooming, described blooming and described hyaline membrane are clamped between described a pair doubling roller, carry out bonded to each other thus.
Below, with reference to while accompanying drawing, the manufacture method of present embodiment is being described.Fig. 2 is the schematic diagram of the formation representing device entirety used in the manufacture method of present embodiment.
In the manufacturing installation of the stacked film shown in Fig. 2, the tackifier apparatus for coating 11 for the coated on one side tackifier at hyaline membrane 2 is provided with successively along carriage direction, the doubling roller (niproll) 51 of duplexer 4 is obtained for hyaline membrane 2 and blooming 1 being fitted, 52, for the roller 13 making hyaline membrane 2 and blooming 1 closely sealed in duplexer 4, be arranged on the first active energy beam irradiation unit 14 of the position facing with the outer peripheral face of this roller 13, 15, be arranged on the second later active energy beam irradiation unit 16 ~ 18 in carriage direction downstream by comparison, and transport with niproll 19.
First, the one side of the hyaline membrane 2 extracted out continuously in the state from tubular wound into a roll, utilizes the tackifier < tackifier painting process > of the coat activated energy ray-curable of tackifier apparatus for coating 11.
After this, the one side of the blooming 1 extracted out continuously in the state from tubular wound into a roll, by the stacked hyaline membrane 2 being coated with tackifier of tackifier, holding them under the state between a pair doubling roller 51,52 rotated along carriage direction, the direction of the doubling roller of at least one party to the doubling roller of the opposing party is pushed, thus blooming 1 and hyaline membrane 2 are fitted, form duplexer 4 < bonding process >.
Then, carry out in the process of transporting while making this duplexer 4 and the outer peripheral face of roller 13 closely sealed, irradiate active energy beam from the first active energy beam irradiation unit 14,15 to the outer peripheral face of roller 13, make tackifier polymerizing curable < active energy beam irradiation process >.And the second later active energy beam irradiation unit 16 ~ 18 being configured in carriage direction downstream is the devices for making tackifier fully polymerizing curable, can add as required, omit.For the details of each operation, identical with embodiment 1, therefore omit.
Embodiment
Below will enumerate embodiment, the present invention is described in more detail, but the present invention is not limited to these embodiments.
< embodiment 1 >
In the present embodiment, use the device as shown in Figure 2 illustrated in above-mentioned embodiment 2, produce the stacked film of 2 film laminatings.
The cyclic olefine resin molding " ZEONOR " (Japanese Zeon (strain) system) of thick 60 μm and the tri acetyl cellulose membrane " KC8UX2MW " (Konica Minolta Inc.) of thick 80 μm are prepared.(strain) Tokyo precision system " HANDYSURF (Ha Application デ ィ サ ー Off) E35A " is utilized to determine the surfaceness (Rz) of cyclic olefine resin molding, consequently 30nm.And, this value be by measure distance be set as 12.5mm, the placing of said determination device is measured on object film 10 subsurface roughness time mean value.
In the one side of tri acetyl cellulose membrane, tackifier apparatus for coating is used to be coated with the composition epoxy resin " KR-70T " (ADEKA Inc., viscosity: 44mPas) of the tackifier as ultraviolet hardening.Now, the linear velocity of the film laminated body in tackifier apparatus for coating is set to 25m/ minute, gravure roll is rotated along the direction contrary with the carriage direction of stacking material, is the mode coating binder (and the thickness of the tackifier after solidification is 2.0 μm) of 2.0 μm to make thickness.
Then, a pair niproll (doubling roller) reinstating diameter 250mm with the duplexer one of the mode stacked ring ethylene series resin molding with the adhesive contact be coated on tri acetyl cellulose membrane is clamped, with the pressure bias of 1.0MPa, thus above-mentioned cyclic olefine resin molding and above-mentioned tri acetyl cellulose membrane are fitted.
The duplexer of the above-mentioned 2 kinds of films of laminating is transferred with the linear velocity of 25m/ minute while the tension force applying 600N/m along its length, irradiates total accumulated light (semi-invariant of the photo-irradiation intensity in the wavelength region may of wavelength 280 ~ 320nm) to duplexer and be about 250mJ/cm
2the ultraviolet (UVB) of (utilizing analyzer: the measured value that FusionUV Inc. UV Power PuckII obtains), obtains stacked film.
For the stacked film of gained, between film, utilize visualization less than bubble.
< embodiment 2 >
In the present embodiment, use device as shown in Figure 3, produce the stacked film of 2 film laminatings.Device shown in Fig. 3 is the device eliminating chill roll 13 grade in the device shown in Fig. 2 illustrated in above-mentioned embodiment 2, detailed.And the reference marks in Fig. 3 uses with the meaning identical with Fig. 2.
The tri acetyl cellulose membrane " KC4CR-1 " (Konica Minolta Inc.) of thick 40 μm and the composite membrane duplexer of thick 135 μm are prepared.Tokyo precision system " HANDYSURFE35A " is utilized to determine the surfaceness (Rz) of KC4CR-1, consequently 50nm.And, this value be by measure distance be set as 12.5mm, the placing of said determination device is measured on object film 10 subsurface roughness time mean value.
In the one side of composite membrane duplexer, tackifier apparatus for coating is used to be coated with the composition epoxy resin " KR-70T " (ADEKA Inc., viscosity: 44mPas) of the tackifier as ultraviolet hardening.Now, the linear velocity of the film laminated body in tackifier apparatus for coating is set to 25m/ minute, gravure roll is rotated along the direction contrary with the carriage direction of stacking material, is the mode coating binder (and the thickness of the tackifier after solidification is 1.0 μm) of 1.0 μm to make thickness.
The duplexer of the above-mentioned 2 kinds of films of laminating is transferred with the linear velocity of 25m/ minute while the tension force applying 600N/m along its length, irradiates total accumulated light (semi-invariant of the photo-irradiation intensity in the wavelength region may of wavelength 280 ~ 320nm) to duplexer and be about 250mJ/cm
2the ultraviolet (UVB) of (utilizing analyzer: the measured value that FusionUV Inc. UV Power PuckII obtains), obtains stacked film.
For the stacked film of gained, between film, utilize visualization less than bubble.
< comparative example 1 >
Employ except the polyvinyl alcohol mesentery (Vinylon VF-PS#7500, the former material thickness of Kuraray are 75 μm) that surfaceness (Rz) is 280nm except substituted cycloalkene mesentery, produce stacked film identically with embodiment 1.For the stacked film of gained, utilize between film and be visually observed bubble.
According to above result, in the film forming stacked film, in tackifier painting process, there is no coating binder and be in the embodiment 1 of below 200nm with the surfaceness in the face of adhesive contact in bonding process, bubble is not mixed into intermembranous, employ in the comparative example 1 of the film of extraneous surfaceness of the present invention, be mixed into bubble intermembranous.
And, in embodiment 1, the film being 30nm as surfaceness employs cycloolefin mesentery, the film being 280nm as surfaceness in comparative example employs polyvinyl alcohol mesentery, and this is employ the different film of material in order to the different film of option table surface roughness from commercially available film.That is, can think, though when to belong to the film of identical material and film that just surfaceness is different compare, also can observe the difference of identical effect.Thus, in the present invention, each film forming stacked film is not limited to the material recorded in above-described embodiment, and the film be made up of various material can be used to manufacture stacked film.
The explanation of symbol
1 blooming,
2,3 hyaline membranes,
4 duplexers,
51,52 doubling rollers,
11,12 tackifier apparatus for coating,
13 rollers,
14,15,16,17,18 active energy beam irradiation units,
19 transport niprolls,
20 take up rolls.
Claims (5)
1. a manufacture method for stacked film, it is by the manufacture method of multiple film by the tackifier of active energy ray curable stacked film bonded to each other,
Described manufacture method possesses successively:
Tackifier painting process, to the tackifier of the coat activated energy ray-curable of one or both sides of at least 1 film in described multiple film;
Bonding process, under the mode of tackifier carries out stacked state described in sandwiched between with adjacent film, is clamped in described multiple film between a pair doubling roller rotating along carriage direction, carries out bonded to each other thus; And
Active energy beam irradiation process, makes described adhesive solidification to being irradiated active energy beam by described multiple films bonded to each other,
In described multiple film, in described tackifier painting process, be not coated with described tackifier and be below 200nm with the surfaceness in the face of described adhesive contact in described bonding process.
2. method according to claim 1, wherein,
The thickness of the described tackifier be coated with in described tackifier painting process is less than 2 μm.
3. method according to claim 1 and 2, wherein,
Described multiple film comprises blooming and hyaline membrane, and described stacked film is polarization plates.
4. method according to claim 3, wherein,
Described multiple film comprises 1 blooming and 2 hyaline membranes,
In described tackifier painting process, tackifier described in the respective coated on one side of 2 described hyaline membranes,
In described bonding process, under carrying out stacked state in the mode making the described tackifier of 2 described hyaline membranes contact with the two sides of described blooming, described blooming and described hyaline membrane are clamped between described a pair doubling roller, carry out bonded to each other thus.
5. method according to claim 3, wherein,
Described multiple film comprises 1 blooming and 1 hyaline membrane,
In described tackifier painting process, tackifier described in the coated on one side of described hyaline membrane,
In described bonding process, under carrying out stacked state in the mode making the described tackifier of described hyaline membrane contact with the one side of described blooming, described blooming and described hyaline membrane are clamped between described a pair doubling roller, carry out bonded to each other thus.
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KR (1) | KR101908172B1 (en) |
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TWI613084B (en) | 2018-02-01 |
WO2013191095A1 (en) | 2013-12-27 |
KR101908172B1 (en) | 2018-10-15 |
KR20150031409A (en) | 2015-03-24 |
JPWO2013191095A1 (en) | 2016-05-26 |
TW201410473A (en) | 2014-03-16 |
CN104272149B (en) | 2017-03-01 |
JP6404715B2 (en) | 2018-10-17 |
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