CN104854490A - Polarizing film production method - Google Patents

Polarizing film production method Download PDF

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Publication number
CN104854490A
CN104854490A CN201380064757.0A CN201380064757A CN104854490A CN 104854490 A CN104854490 A CN 104854490A CN 201380064757 A CN201380064757 A CN 201380064757A CN 104854490 A CN104854490 A CN 104854490A
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China
Prior art keywords
polaroid
polarizing coating
methyl
protective film
transparent protective
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CN201380064757.0A
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Chinese (zh)
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CN104854490B (en
Inventor
姜太艳
齐藤武士
品川雅
冈本美纪
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • 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
    • B32B37/1284—Application of adhesive
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B32B2038/166—Removing moisture
    • 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
    • B32B2309/02—Temperature
    • 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
    • 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
    • B32B2309/14—Velocity, e.g. feed speeds
    • 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
    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)

Abstract

This polarizing film production method is characterized by having: (1) a step in which an activation process is conducted on a polarizer having a moisture content of not more than 11 wt% so as to provide a surface roughness (Ra) of 0.6 nm or higher; (2) a step in which the polarizer is conveyed while the surface of the activated polarizer is in contact with a guide roll; (3) a step in which an adhesive is applied to the polarizer and/or a transparent protective film; and (4) a step in which the polarizer and the transparent protective film are bonded together via the adhesive. This production method enables a polarizing film to be produced with good conveying properties.

Description

The manufacture method of polarizing coating
Technical field
The present invention relates to the manufacture method of polarizing coating.The polarizing coating obtained by this manufacture method can form the image display device such as liquid crystal indicator (LCD), organic EL display, CRT, PDP separately or with the form of its blooming be laminated.
Background technology
The market demand of liquid crystal indicator in the fields such as wrist-watch, mobile phone, PDA, notebook computer, PC display, DVD player, TV increases sharply.Liquid crystal indicator is the visualization device of the polarization state that makes to be caused by the conversion of liquid crystal, according to its displaying principle, uses polaroid.Especially in the purposes such as TV, require all the more high brightness, high-contrast, wide viewing angle, polarizing coating also starts requirement high-transmission rate, high-polarization, high color reproducibility etc.
As polaroid, due to high-transmission rate, high-polarization will be had, therefore general the most widely used be such as make iodine be adsorbed in polyvinyl alcohol (PVA) and the iodine system polaroid of structure after stretching.For such polaroid, there is physical strength extremely weak, can due to heat, moisture and shrinking thus the shortcoming that significantly declines of polarization function.Therefore, the polaroid obtained is used as polarizing coating after wanting horse back to be fitted by tackifier and the transparent protective film being coated with tackifier.
In addition, in order to improve the bonding strength of polaroid and transparent protective film further, propose: after implementing activation process to the face that will arrange adhesive layer of polaroid, polaroid and transparent protective film are fitted manufacture polarizing coating (patent documentation 1).Generally speaking, polaroid is manufactured by hydrophilic macromolecule films such as polyvinyl alcohol mesenteries, and therefore polaroid has moisture rate to a certain degree.Record in patent documentation 1, the moisture rate of polaroid is preferably less than 20 % by weight, and more preferably 0 ~ 17 % by weight, further preferably 1 ~ 16 % by weight.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-008660 publication
Summary of the invention
The problem that invention will solve
All the time, polaroid utilizes deflector roll to transport, but because the moisture rate of this polaroid is more than 11 % by weight, though therefore when with guide rollers contact and transport, also do not have problems in transport property.In recent years, trend towards manufacturing the polaroid that moisture rate is less than 11 % by weight.But; when the moisture rate of polaroid is below 11 % by weight; polaroid and transport polaroid deflector roll between holding force (Network リ ッ プ power) increase, transport property in produce bad, or afterwards with the laminating of transparent protective film in produce bad.Especially, when making the surface of polaroid and guide rollers contact limit transport on limit, easily produce bad in transport property.
The object of the present invention is to provide and a kind ofly can transport property manufacture the method for polarizing coating well, described polarizing coating is provided with transparent protective film at least one side of polaroid by adhesive layer.
Solve the method for problem
The present inventor has carried out research extensively and profoundly to solve above-mentioned problem, found that the manufacture method etc. of following polarizing coating, and has completed the present invention.
That is, the present invention relates to a kind of manufacture method of polarizing coating, it is characterized in that, be the manufacture method being at least simultaneously provided with the polarizing coating of transparent protective film by adhesive layer at polaroid, it comprises:
Operation (1), implement activation process by least one side of the polaroid to moisture rate being less than 11 % by weight, the surfaceness (Ra) making polaroid surface is thus more than 0.6nm,
Operation (2), for the polaroid implemented after described activation process, while make the surface of the polaroid after this activation process and guide rollers contact limit transport,
Operation (3), to the face for the formation of described adhesive layer of the polaroid transported by described deflector roll and/or the face adhesive coating for the formation of described adhesive layer of transparent protective film,
Operation (4), is fitted polaroid and transparent protective film by described tackifier.
The thickness that the manufacture method of above-mentioned polarizing coating compatibly can be applied to polaroid is the situation of less than 10 μm.
The manufacture method of above-mentioned polarizing coating can compatibly be applied to following polaroid, described polaroid is the continuous band-shaped polarizing coating comprising polyvinyl alcohol resin after making dichroic substance orientation, and comprise by utilization the 2 sections of stretching process stretched in aerial assisting tension and boric acid water stretch to duplexer and obtain, described duplexer is the duplexer of the polyvinyl alcohol resin layer comprise masking on thermoplastic resin base material after.
In the manufacture method of above-mentioned polarizing coating, as above-mentioned activation process, corona treatment or Cement Composite Treated by Plasma can be adopted.
In the manufacture method of above-mentioned polarizing coating, preferably: the activation process based on above-mentioned activation process is corona treatment, and the discharge capacity in corona treatment is 250 ~ 1000W/m 2/ min.
Invention effect
In the manufacture method of polarizing coating of the present invention, use moisture rate is the polaroid of the low moisture rate of less than 11 % by weight, and before utilizing tackifier to fit this polaroid and transparent protective film, while make surface and the guide rollers contact of polaroid, while transport.On the other hand, in the manufacture method of polarizing coating of the present invention, before the surface making polaroid and guide rollers contact, to want and activation process is implemented in the face of polaroid of guide rollers contact, the mode reaching more than 0.6nm with the surfaceness of polaroid (Ra) controls.Known like this, as long as the mode reaching more than 0.6nm with surfaceness (Ra) carries out the polaroid controlled, even if when making polaroid and the guide rollers contact of low moisture rate, also can transport well.As a result, the laminating of tackifier that utilizes of polaroid afterwards and transparent protective film becomes good, can produce polarizing coating efficiently.
Accompanying drawing explanation
Fig. 1 is the concept map of an example of the embodiment involved by manufacture method representing polarizing coating of the present invention.
Embodiment
Below the manufacture method of polarizing coating of the present invention is described.Polarizing coating of the present invention is provided with transparent protective film at least one side of polaroid by adhesive layer.Described polarizing coating of the present invention obtains to operation (4) by implementing operation (1) successively.With below with reference to Fig. 1, while be described to (4) operation (1).Exemplified with following situation in Fig. 1: for the polarizing coating F1 protected at the one side that the one side of polaroid P is provided with transparent protective film T1 by adhesive layer A1, implement operation (1) to (4), thus manufacture the polarizing coating F2 of two sides protection.
< operation (1) >
In operation (1), implement activation process by least one side of the polaroid to moisture rate being less than 11 % by weight, the surfaceness (Ra) making polaroid surface is more than 0.6nm.In Fig. 1, at treatment tube R1 place, activation process is carried out by activation process unit C in the surface of the polaroid P of the polarizing coating F1 of one side protection.
< polaroid >
Polaroid is not particularly limited, and can use various polaroid.As polaroid, such as, can list: make the hydrophilic macromolecule film absorption dichroic material such as iodine, dichroic dye such as polyvinyl alcohol mesentery, part formalizing polyvinyl alcohol mesentery, the partly-hydrolysed film of vinyl-vinyl acetate copolymer system and the polaroid carrying out uniaxial tension and obtain; The polyenoid system alignment films etc. such as the processed thing of polyvinyl alcohol (PVA), the desalination acid treatment thing of Polyvinylchloride.Wherein, the polaroid comprising the dichroic substance such as polyvinyl alcohol mesentery and iodine is preferred.The thickness of these polaroids is not particularly limited, and is generally about 1 ~ 80 μm.The thickness of polaroid preferably less than 30 μm, more preferably less than 20 μm, preferably less than 10 μm further.
To dye to polyvinyl alcohol mesentery with iodine and the polaroid carrying out uniaxial tension and obtain such as can dye by the aqueous solution that polyvinyl alcohol (PVA) is immersed in iodine, 3 ~ 7 times that are then stretched to raw footage make.As required, also can be immersed in and can contain in the aqueous solution of the potassium iodide of boric acid, zinc sulfate, zinc chloride etc.And then, before dyeing polyvinyl alcohol mesentery can also be immersed in water as required and wash.By washing polyvinyl alcohol mesentery, the spot on polyvinyl alcohol mesentery surface, anti blocking agent can be cleaned, in addition, also having and making polyvinyl alcohol mesentery swelling and the effect preventing dye speck etc. uneven.Stretching can be carried out after dyeing with iodine, also can stretch on Edge Coloring limit, in addition, can also dye with iodine after the stretch.Can in the aqueous solution of boric acid, potassium iodide etc., stretch in water-bath.
The slim polaroid >> of <<
As polaroid, thickness can be used to be the slim polaroid of less than 10 μm.From the viewpoint of slimming, this thickness is preferably 1 ~ 7 μm.Uneven thickness is few, and observation property is excellent, and change in size is few, therefore excellent durability, and also achieves slimming as the thickness of polarizing coating, slim polaroid preferably so from the above considerations.
As slim polaroid, can enumerate typically: the slim polarizing coating recorded in the instructions of Japanese Laid-Open Patent Publication 51-069644 publication, Japanese Unexamined Patent Publication 2000-338329 publication, WO2010/100917 pamphlet, PCT/JP2010/001460 or Japanese Patent Application 2010-269002 instructions, Japanese Patent Application 2010-263692 instructions.These slim polarizing coatings can be obtained with the method for making of carrying out the operation dyeed by the operation comprised polyvinyl alcohol resin (hereinafter also referred to PVA resinoid) layer and stretching resin base material carry out stretching in the state of duplexer.If this method for making, even if then PVA resinoid layer is thinner, also can by by stretching resin base material support and when can not due to stretch produce fracture etc. bad stretch.
As above-mentioned slim polarizing coating, the state being included in duplexer is carried out the operation that stretches and is carried out in the method for making of the operation dyeed, polarization property is improved from the viewpoint of high magnification can be stretched to, preferably by WO2010/100917 pamphlet, the instructions of PCT/JP2010/001460, or Japanese Patent Application 2010-269002 instructions, the method for making of carrying out the operation stretched in boric acid aqueous solution that is included in that Japanese Patent Application 2010-263692 instructions is recorded obtains, particularly preferably by Japanese Patent Application 2010-269002 instructions, what Japanese Patent Application 2010-263692 instructions was recorded be included in stretch in boric acid aqueous solution before auxiliarily carry out the aerial operation stretched method for making obtain.
The slim high function polarizing coating that the instructions of above-mentioned PCT/JP2010/001460 is recorded is integrated film forming and forms on resin base material, by the PVA resinoid making dichroic substance carry out orientation and thickness is the slim high function polarizing coating of less than 7 μm, has monomer transmissivity and is more than 42.0% and degree of polarization is the optical characteristics of more than 99.95%.
Above-mentioned slim high function polarizing coating can manufacture by the following method: have at least 20 μm thickness resin base material on be coated with PVA resinoid and make it dry, generate PVA resinoid layer thus, the PVA resinoid layer of generation is impregnated in the dyeing liquor of dichroic substance, dichroic substance is made to be adsorbed in PVA resinoid layer, the PVA resinoid layer having adsorbed dichroic substance is stretched integratedly with resin base material in boric acid aqueous solution, makes total stretching ratio reach more than 5 times of former length.
In addition, comprising in manufacture makes dichroic substance carry out in the method for the laminate film of the slim high function polarizing coating of orientation, by comprising following operation, above-mentioned slim high function polarizing coating can be manufactured, described operation is: generate laminate film, and described laminate film comprises the resin base material of the thickness with at least 20 μm and contains the resinoid aqueous solution of PVA and the PVA resinoid layer making it dry and formed by coating on the one side of resin base material; The above-mentioned laminate film of PVA resinoid layer of the one side comprising resin base material and be formed in resin base material is impregnated in the dyeing liquor containing dichroic substance, in the PVA resinoid layer making dichroic substance be adsorbed onto thus to contain in laminate film; The above-mentioned laminate film comprising the PVA resinoid layer having adsorbed dichroic substance is stretched in boric acid aqueous solution, makes total stretching ratio reach more than 5 times of former length; The PVA resinoid layer and resin base material that have adsorbed dichroic substance are stretched integratedly, the one side being manufactured on resin base material is thus formed comprise and makes that dichroic substance has carried out the PVA resinoid layer of orientation, thickness is less than 7 μm and there is monomer transmissivity to be more than 42.0% and degree of polarization is the laminate film of the slim high function polarizing coating of the optical characteristics of more than 99.95%.
In the present invention, as the polaroid that thickness is less than 10 μm, following polaroid can be used, it is the continuous band-shaped polarizing coating comprising polyvinyl alcohol resin after making dichroic substance orientation, and comprise by utilization the 2 sections of stretching process stretched in aerial assisting tension and boric acid water stretch to duplexer and obtain, described duplexer is the duplexer of the polyvinyl alcohol resin layer comprise masking on thermoplastic resin base material after.As above-mentioned thermoplastic resin base material, preferred amorphism ester based thermoplastic resin base material or crystallinity ester based thermoplastic resin base material.
Above-mentioned Japanese Patent Application 2010-269002 instructions, the slim polarizing coating of Japanese Patent Application 2010-263692 instructions are the polarizing coating comprising PVA resinoid continuous band-shaped (ウ ェ Block) making dichroic substance carry out orientation, carry out stretching and be formed as the thickness of less than 10 μm in its 2 sections of stretching process formed by being stretched in by aerial assisting tension and boric acid water by the duplexer comprising the PVA resinoid layer being formed in amorphism ester analog thermoplastic resin base material.Described slim polarizing coating preferably has following optical characteristics, when monomer transmissivity being set to T, degree of polarization being set to P, meets P >-(10 0.929T-42.4-1) condition of × 100 (wherein, T < 42.3) and P>=99.9 (wherein, T>=42.3).
Specifically, above-mentioned slim polarizing coating can be manufactured by the manufacture method of the slim polarizing coating comprising following operation: carry out aerial drawing by high temperature to the PVA resinoid layer being formed in continuous band-shaped amorphism ester analog thermoplastic resin base material, generates the stretching intermediate product of the PVA resinoid layer after comprising orientation thus; Stretching intermediate product is carried out to the absorption of dichroic substance, generate thus and comprise the painted intermediate product making dichroic substance (potpourri of preferred iodine or iodine and organic dyestuff) carry out the PVA resinoid layer of orientation; Stretching in boric acid water with carrying out painted intermediate product, generating thus and comprising the polarizing coating that the thickness making dichroic substance carry out the PVA resinoid layer of orientation is less than 10 μm.
In this manufacture method, the total stretching ratio being formed in the PVA resinoid layer of amorphism ester analog thermoplastic resin base material stretched in aerial drawing by high temperature and boric acid water is preferably utilized to be more than 5 times.Liquid temperature for the boric acid aqueous solution stretched in boric acid water can be set as more than 60 DEG C.Before preferably painted intermediate product being stretched in boric acid aqueous solution, insoluble process is carried out to painted intermediate product, in this situation, flood above-mentioned painted intermediate product to carry out preferably by the boric acid aqueous solution being no more than 40 DEG C in liquid temperature.Above-mentioned amorphism ester analog thermoplastic resin base material preferably can be formed to comprise and makes phthalic acid copolymerization and the copolymerization polyethylene terephthalate obtained, make cyclohexanedimethanol copolymerization and the amorphism polyethylene terephthalate of the copolymerization polyethylene terephthalate obtained or other copolymerization polyethylene terephthalates and comprise the base material of transparent resin, and its thickness can be set as more than 7 times of the thickness of formed PVA resinoid layer.In addition, the stretching ratio of aerial drawing by high temperature is preferably less than 3.5 times, and the draft temperature of aerial drawing by high temperature is preferably more than the resinoid glass transition temperature of PVA, specifically, is preferably the scope of 95 DEG C ~ 150 DEG C.When carrying out aerial drawing by high temperature by free end uniaxial tension, the total stretching ratio being formed in the PVA resinoid layer of amorphism ester analog thermoplastic resin base material is preferably more than 5 times and less than 7.5 times.In addition, when carrying out aerial drawing by high temperature by stiff end uniaxial tension, the total stretching ratio being formed in the PVA resinoid layer of amorphism ester analog thermoplastic resin base material is preferably more than 5 times and less than 8.5 times.
More specifically, slim polarizing coating can be manufactured by method as described below.
Make 6 % by mole of phthalic acid copolymerization and make the continuous band-shaped base material of phthalic acid copolymerization polyethylene terephthalate (amorphism PET).The glass transition temperature of amorphism PET is 75 DEG C.The duplexer be made up of continuous band-shaped amorphism PET base material and polyvinyl alcohol (PVA) (PVA) layer makes in the following manner.By the way, the glass transition temperature of PVA is 80 DEG C.
Prepare 200 μm of thick amorphism PET base material and make the PVA powder of the degree of polymerization more than 1000, saponification degree more than 99% water-soluble and concentration that is that obtain be 4 ~ 5% PVA aqueous solution.Then, 200 μm of thick amorphism PET base material are coated with PVA aqueous solution, dry at the temperature of 50 ~ 60 DEG C, obtain being formed with the duplexer of 7 μm of thick PVA layers in amorphism PET base material.
The duplexer comprising 7 μm of thick PVA layers is manufactured 3 μm of thick slim high function polarizing coatings through the following operation comprising the 2 sections of stretching process stretched in aerial assisting tension and boric acid water.By the aerial assisting tension operation of first stage, the duplexer and amorphism PET base material that comprise 7 μm of thick PVA layers are stretched integratedly, generate the stretching duplexer comprising 5 μm of thick PVA layers.Specifically, this stretching duplexer is stretching device by the duplexer comprising 7 μm of thick PVA layers being placed in the baking oven being configured in the draft temperature environment being set in 130 DEG C and to make stretching ratio be the duplexer that the mode of 1.8 times is carried out free end uniaxial tension and obtained.By this stretch processing, make the PVA layer contained in stretching duplexer be changed to PVA molecule and carried out the thick PVA layer of 5 μm of orientation.
Then, by dyeing process, be created on the painted duplexer that PVA molecule has carried out having adsorbed in the thick PVA layer of 5 μm of orientation iodine.Specifically, this painted duplexer be by by stretching duplexer liquid temperature 30 DEG C containing the dyeing liquor of iodine and potassium iodide in flood the arbitrary time and make the monomer transmissivity of the PVA layer forming the final high function polarizing coating generated be 40 ~ 44% thus make the PVA layer contained in stretching duplexer adsorb the duplexer of iodine.In this operation, dyeing liquor is using water as solvent, and iodine concentration is in the scope of 0.12 ~ 0.30 % by weight, and potassium iodide concentration is in the scope of 0.7 ~ 2.1 % by weight.Iodine is 1 to 7 with the concentration ratio of potassium iodide.By the way, when iodine is water-soluble, potassium iodide is needed.More specifically, by by stretching duplexer iodine concentration be 0.30 % by weight, potassium iodide concentration is flood 60 seconds in the dyeing liquor of 2.1 % by weight, is created on the painted duplexer that PVA molecule has carried out having adsorbed in the thick PVA layer of 5 μm of orientation iodine.
Then, by stretching process in the boric acid water of subordinate phase, further painted duplexer and amorphism PET base material are stretched integratedly, generate the optical film laminate of the PVA layer comprising 3 μm of thick high function polarizing coatings of formation.Specifically, this optical film laminate be by painted duplexer is placed in be configured in containing boric acid and potassium iodide and be set in the treating apparatus of the boric acid aqueous solution of liquid temperature scope 60 ~ 85 DEG C stretching device and to make stretching ratio be the duplexer that the mode of 3.3 times is carried out free end uniaxial tension and obtained.More specifically, the liquid temperature of boric acid aqueous solution is 65 DEG C.In addition, boric acid content is set as 4 weight portions relative to water 100 weight portion, potassium iodide content is set as 5 weight portions relative to water 100 weight portion.In this operation, first the painted duplexer that have adjusted iodine absorption number is flooded 5 ~ 10 seconds in boric acid aqueous solution.Then, directly being passed through between the stretching device be configured in treating apparatus and the different many groups roller of peripheral speed by this painted duplexer, was that the mode of 3.3 times carries out free end uniaxial tension with 30 ~ 90 seconds to make stretching ratio.By this stretch processing, the iodine making the PVA layer contained in painted duplexer be changed to absorption to have carried out the thick PVA layer of 3 μm of high order orientation with the form of many iodide ions complex compound along a direction.This PVA layer forms the high function polarizing coating of optical film laminate.
Although be not operation required in the manufacture of optical film laminate, but taken out from boric acid aqueous solution by optical film laminate preferably by matting, the boric acid potassium iodide aqueous solution that the surface to 3 μm that are formed in amorphism PET base material thick PVA layers is adhered to cleans.Then, the optical film laminate after cleaning is carried out drying by the drying process of the warm air utilizing 60 DEG C.In addition, matting is the operation for eliminating the bad orders such as boric acid precipitation.
Equally, although be not operation required in the manufacture of optical film laminate, but also can by laminating and/or transfer printing process coating binder on the surface being formed in amorphism PET base material 3 μm of thick PVA layers, and 80 μm of thick three cellulose acetate membranes of fitting, then, amorphism PET base material is peeled off, 3 μm of thick PVA layers is transferred on 80 μm of thick three cellulose acetate membranes.
[other operations]
In the manufacture method of above-mentioned slim polarizing coating, beyond above-mentioned operation, can also comprise other operations.As other operations, such as insoluble operation, cross-linking process step, drying (adjustment of moisture rate) operation etc. can be enumerated.Other operations can be carried out in arbitrary opportune moment.
Typically, above-mentioned insoluble operation can be undertaken by being impregnated in boric acid aqueous solution by PVA resinoid layer.By implementing insoluble process, water tolerance can be given to PVA resinoid layer.The relative concentration of this boric acid aqueous solution is preferably 1 weight portion ~ 4 weight portion in water 100 weight portion.The liquid temperature of insoluble bath (boric acid aqueous solution) is preferably 20 DEG C ~ 50 DEG C.Insoluble operation is preferably carried out before stretching process after duplexer makes, in dyeing process or water.
Typically, above-mentioned cross-linking process step is undertaken by being impregnated in boric acid aqueous solution by PVA resinoid layer.By implementing crosslinking Treatment, water tolerance can be given to PVA resinoid layer.The relative concentration of this boric acid aqueous solution is preferably 1 weight portion ~ 4 weight portion in water 100 weight portion.In addition, when carrying out cross-linking process step after above-mentioned dyeing process, preferably iodide are coordinated further.By coordinating iodide, the stripping of the iodine adsorbed in PVA resinoid layer can be suppressed.The use level of iodide is preferably 1 weight portion ~ 5 weight portion relative to water 100 weight portion.The concrete example of iodide is described above.The liquid temperature of crosslinked bath (boric acid aqueous solution) is preferably 20 DEG C ~ 50 DEG C.Cross-linking process step preferably carries out before stretching process in above-mentioned second boric acid water.Preferred embodiment, carry out stretching process in dyeing process, cross-linking process step and the second boric acid water successively.
The polaroid of the polaroid used in the method for making method of polarizing coating of the present invention to be moisture rate the be low moisture rate of less than 11 % by weight, owing to implementing operation (1) to polaroid, in operation (2), even if when the surface of polaroid and guide rollers contact transport, transport property is also good.The moisture rate of the polaroid within dry latter 6 hours can be less than 6 % by weight, can be less than 2 % by weight further.In addition, when moisture rate is too low, there is the problems such as polaroid breaks in transport, therefore preferably the moisture rate of polaroid is more than 1 % by weight.Especially, when above-mentioned slim polaroid, the present invention is effective when moisture rate is below 2 % by weight, is applicable further when 1 ~ 1.5 % by weight.
The moisture rate of polaroid of the present invention can by method suitable arbitrarily adjustment.Such as can enumerate: by the method controlled the condition adjustment of the drying process in the manufacturing process of polaroid.
The moisture rate of polaroid can be measured by following method.That is, being cut out by polaroid is the size of 100 × 100mm, measures the initial stage weight of this sample.Then, by this sample at 120 DEG C dry 2 hours, measure dry weight, utilize following formula to measure moisture rate.Moisture rate (% by weight)={ (initial stage weight-dry weight)/initial stage weight } × 100.The mensuration of weight carries out 3 times respectively, uses its mean value.
As activation process, corona treatment, Cement Composite Treated by Plasma, aura process, ozone treatment etc. can be illustrated.Corona treatment such as can be undertaken by the mode utilizing the corona treatment of springtime Motor Corporation to carry out discharging in atmospheric air.Cement Composite Treated by Plasma such as can be undertaken by the mode utilizing the plasma discharge machine of ponding chemical company to carry out discharging in atmospheric air or in the inactive gas such as nitrogen, argon atmosphere.For aura process, ozone treatment, also can utilize well-established law to carry out.Wherein, corona treatment or Cement Composite Treated by Plasma cost of equipment, processing charges in be suitable.
Above-mentioned activation process is implemented to make the mode that the surfaceness on the surface of polaroid (Ra) is more than 0.6nm.Above-mentioned surfaceness (Ra) is preferably more than 0.8nm, further preferred more than 1nm.Be more than 0.6nm by making above-mentioned surfaceness (Ra), even if when the moisture rate of polaroid is less than 11 % by weight and makes the surface of polaroid contact with deflector roll in operation (2), also polaroid can be transported well.In addition, when above-mentioned surfaceness (Ra) is excessive, heatproof water-based is deteriorated, and therefore above-mentioned surfaceness (Ra) is preferably below 10nm, more preferably below 5nm.
In the mensuration of above-mentioned surfaceness (Ra), with the parameter of arithmetic average roughness (mean value of concave-convex surface) presentation surface roughness.Surfaceness (Ra) uses Veeco (ビ ー コ) atomic force microscope (AFM) the Nanoscope IV of Inc., carries out measuring with Tapping pattern and the value that obtains.Cantilever (カ Application チ レ バ ー) such as uses metering probe (メ ト ロ ロ ジ ー プ ロ ー Block): Tap300 (RTESP type).Measurement range be 1 μm square.
As above-mentioned activation process, with the mode setting process condition being made polaroid reach above-mentioned surfaceness (Ra) by activation process.Such as, in corona treatment, discharge capacity is preferably 250 ~ 1000W/m 2/ min, more preferably 250 ~ 800W/m 2/ min, further preferred 250 ~ 600W/m 2/ min, further preferred 250 ~ 500W/m 2/ min.Activation process amount (discharge capacity: W/m 2/ min) calculating formula=output power (W)/linear velocity (m/min)/electrode long (m).Gap between electrode and sample (polaroid) is preferably 1mm ~ 2mm.The preferred aluminium roller of electricity Jie roller of activation process (corona treatment) or ceramic roller.The preferred Si roller of ground connection roller or metallic roll.
In the manufacture method of polarizing coating of the present invention, in operation (1), activation process is implemented at least one side of polaroid, but when making two sides and the guide rollers contact of polaroid in operation (2), preferably activation process is implemented to the two sides of polaroid.
In addition; in the manufacture method of polarizing coating of the present invention; as the polaroid of activation process object in operation (1); as long as can at least simultaneously carrying out activation process; as shown in Figure 1; for the another side of polaroid not becoming activation process object, can be fitted transparent protective film by adhesive layer.In addition; when using above-mentioned slim polaroid as polaroid; in Fig. 1; can replace arranging transparent protective film T1 in the one side of polaroid P by adhesive layer A1, and use the slim high function polarizing coating (polaroid P) with resin base material (amorphism ester based thermoplastic resin etc.) masking integratedly.
< operation (2) >
In operation (2), for the polaroid implemented after described activation process, while make the surface of the polaroid after this activation process and guide rollers contact limit transport.In operation (2), transport with making the surface of polaroid and guide rollers contact, but with the surface of the polaroid of guide rollers contact owing to having carried out activation process in the mode of the surfaceness (Ra) reaching regulation in operation (1), therefore transport property is good.In Fig. 1, for polaroid P surface by after activation process one side protection polarizing coating F1 for, while make the activation process face of this polaroid P contact with deflector roll G1, G2, while be transported.
< operation (3) >
Then, by operation (3), to the face that will form described adhesive layer of the polaroid transported by described deflector roll and/or the face adhesive coating that will form described adhesive layer of transparent protective film.In Fig. 1, at application roll R2 place, the surface of the polaroid P after the activation process of the polarizing coating F1 of one side protection is by coating element D adhesive coating A2.
As long as the tackifier used in the laminating of above-mentioned polaroid and transparent protective film is optically transparent; then be not particularly limited; can use the various forms of water system, solvent system, hot melt system, radical-curable, but water system tackifier or radical-curable tackifier are suitable.In addition, in the polarizing coating F that the one side of Fig. 1 is protected, transparent protective film T1 also can be used same tackifier with the adhesive layer A1 that polaroid P fits.
As water system tackifier, be not particularly limited, such as, can illustrate: vinyl polymerization system, gelatin system, ethene base system latex system, polyurethane series, isocyanate-based, Polyester, epoxy etc.In such water system tackifier, crosslinking chemical, other catalyzer such as adjuvant, acid can also be coordinated as required.As above-mentioned water system tackifier, preferably use the tackifier etc. containing polyvinyl, as polyvinyl, preferably polyethylene alcohol system resin.In addition, the water-soluble cross-linkers such as boric acid, borax, glutaraldehyde, melamine, ethane diacid can be contained in polyvinyl alcohol resin.Especially, when using the polymer film of polyethenol series as polaroid, using the tackifier containing polyvinyl alcohol resin, is preferred from the viewpoint of cementability.In addition, from the view point of raising permanance, the tackifier containing the polyvinyl alcohol resin with acetoacetyl is more preferably used.
Above-mentioned polyvinyl alcohol resin is not particularly limited, but from the view point of cementability, preferred average degree of polymerization is about 100 ~ 3000, and mean saponification degree is about 85 ~ 100 % by mole.In addition, as the concentration of tackifier aqueous solution, the thickness according to target adhesive layer is suitably determined, so there is no special restriction, but is preferably 0.1 ~ 15 % by weight, is more preferably 0.5 ~ 10 % by weight.If this solution concentration is too high, then excess stickiness raises, and is therefore easy to the concavo-convex inequality producing striated, if solution concentration is too low, then coating is deteriorated, and easily produces inequality.
Polyvinyl alcohol resin can be enumerated: the polyvinyl alcohol (PVA) obtained by saponifying polyvinyl acetate; Its derivant; And with to have with the multipolymer of the monomer of the copolymerizable of vinyl acetate saponified; By the modified polyvinylalcohol of Polyvinyl acetal, urethane, etherificate, grafting, Phosphation etc.As above-mentioned monomer, can enumerate: unsaturated carboxylic acid and the ester classes thereof such as maleic acid (acid anhydride), fumaric acid, crotonic acid, itaconic acid, (methyl) acrylic acid; The alpha-olefin such as ethene, propylene; (methyl) allyl sulphonic acid (sodium (ソ ー ダ)), sodium sulfonate (monoalkyl maleate), sodium disulfonate alkyl maleate, N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid alkali salt, NVP, NVP derivant etc.These polyvinyl alcohol resins can be used alone, and also can be used together two or more.
Polyvinyl alcohol resin containing acetoacetyl can utilize known method to make polyvinyl alcohol resin and diketen react to obtain.Such as can enumerate: polyvinyl alcohol resin is dispersed in acetic acid equal solvent in advance, adds the method for diketen wherein; In advance polyvinyl alcohol resin is dissolved in dimethyl formamide Huo diox equal solvent, adds the method etc. of diketen wherein.Can enumerate in addition, make the method that polyvinyl alcohol (PVA) directly contacts with diketen gas or aqueous diketen.
As long as the acetoacetyl modified degree of the polyvinyl alcohol resin containing acetoacetyl is more than 0.1 % by mole, be then not particularly limited.If be less than 0.1 % by mole, then the water tolerance of adhesive layer is insufficient, inappropriate.Acetoacetyl modified degree is preferably about 0.1 ~ 40 % by mole, preferably 1 ~ 20 % by mole further, particularly preferably 2 ~ 7 % by mole.When acetoacetyl modified degree is more than 40 % by mole, reduce with the reflecting point of crosslinking chemical, the raising effect of water tolerance is little.Acetoacetyl modified degree like this can measure by using nuclear magnetic resonance device (NMR:Nuclear Magnetic Resonance).
As crosslinking chemical, can be not particularly limited to use the crosslinking chemical used in general tackifier, such as when using the tackifier of above-mentioned polyvinyl alcohol resin, preferably can use and at least there are 2 with polyvinyl alcohol resin, there is reactive functional group.Such as can enumerate, ethylenediamine, triethylenediamine, hexamethylene diamine etc. have alkylidene and 2 amino alkylene diamine classes; Toluene diisocyanate, HTDI, trimethylolpropane toluene diisocyanate adduct, triphenylmethane triisocyanate, di-2-ethylhexylphosphine oxide (4-phenylmethane triisocyanate, isophorone diisocyanate and the isocyanates such as their ketoxime block thing or phenol block thing; The epoxies such as ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl base ether, glycerine two or triglycidyl group ether, 1,6-hexane diol diglycidyl ether, trimethylolpropane tris glycidyl ether, diglycidylaniline, diglycidyl amine; Single aldehydes such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde; Glyoxal, the twain-aldehyde compound such as MDA, amber dialdehyde, glutaraldehyde, maleic dialdehyde, o-phthalaldehyde(OPA); The amino-formaldehyde resins such as the condensation product of methylolurea, methylol melamine, alkylated methylol groups urea, alkylated methylol groups melamine, acetylguanamine, benzoguanamine and formaldehyde; And the salt of the divalent metal such as sodium, potassium, magnesium, calcium, aluminium, iron, nickel or trivalent metal and oxide thereof.Wherein, amino-formaldehyde resins, the methylol compound particularly with methylol are applicable.
About the use level of crosslinking chemical, about generally using 0.1 ~ 35 weight portion relative to resin 100 weight portion, preferred use 10 ~ 25 weight portion, when paying attention to the permanance of tackifier, replace shortening and form time (up time (Ke Shi Time Inter) of adhesive layer from being prepared into of tackifier), coordinate more than 30 weight portions and crosslinking chemical below 46 weight portions, more preferably more than 32 weight portions and below 40 weight portions is also effective.
In addition, the tackifier of electric wire curing type, ultraviolet hardening isoreactivity energy ray-curable can also be exemplified.The active energy ray curable that particularly preferably can be cured with the short time, further preferably can with the low-yield ultraviolet hardening tackifier be cured.
As ultraviolet hardening tackifier, be roughly divided into free radical polymerization curing type adhesive and cationic polymerization type tackifier.In addition, free radical polymerization curing type adhesive can use as thermohardening type tackifier.
As the curability composition of free radical polymerization curing type adhesive, the compound with (methyl) acryloyl group, the compound with vinyl can be enumerated.These curability compositions can use simple function or two senses with upper any one.In addition, these curability compositions can be used singly or in combination of two or more.As these curability compositions, the compound such as, with (methyl) acryloyl group is applicable.
As the compound with (methyl) acryloyl group, can enumerate such as particularly, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2-methyl-2-nitro propyl ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) t-amyl, (methyl) acrylic acid 3-pentyl ester, (methyl) acrylic acid 2, 2-dimethyl butyl ester, the just own ester of (methyl) acrylic acid, (methyl) acrylic acid cetyl, (methyl) n-octyl, (methyl) 2-EHA, (methyl) acrylic acid 4-methyl-2-propyl pentyl ester, (methyl) acrylic acid (carbon number 1-20) alkyl esters such as (methyl) acrylic acid n-octadecane base ester.
In addition, as the compound with (methyl) acryloyl group, can enumerate such as, (methyl) acrylate ester (such as, (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester etc.), (methyl) acrylic acid aralkyl ester (such as, (methyl) benzyl acrylate etc.), polycycle (methyl) acrylate (such as, (methyl) acrylic acid 2-isobornyl thiocyanoacetate, (methyl) acrylic acid 2-norborny methyl esters, (methyl) acrylic acid 5-norborene-2-base-methyl esters, (methyl) acrylic acid 3-methyl-2-norborny methyl esters etc.), hydroxyl (methyl) esters of acrylic acid (such as, (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) methacrylic acid 2, 3-dihydroxypropyl methyl-butyl acrylate etc.), containing (methyl) esters of acrylic acid ((methyl) acrylic acid 2-methoxy acrylate of alkoxy or phenoxy group, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-methoxymethoxy ethyl ester, (methyl) acrylic acid 3-methoxybutyl, (methyl) acrylic acid ethyl carbitol ester, (methyl) acrylate etc.), containing epoxy radicals (methyl) esters of acrylic acid (such as, (methyl) glycidyl acrylate etc.), halogen-containing (methyl) esters of acrylic acid (such as, (methyl) acrylic acid 2, 2, 2-trifluoro ethyl ester, (methyl) acrylic acid 2, 2, 2-trifluoroethyl ethyl ester, (methyl) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro propyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid 17 fluorine ester in the last of the ten Heavenly stems etc.), (methyl) acrylic acid alkyl aminoalkyl ester (such as, (methyl) acrylate etc.) etc.
In addition; as the compound with (methyl) acryloyl group other than the above; can enumerate, the monomer etc. of the amide-containings such as hydroxyethyl acrylamide, N hydroxymethyl acrylamide, N-methoxy acrylamide (SP value 22.9), N-ethoxymethyl acrylamide, (methyl) acrylamide.In addition, the nitrogen containing monomers etc. such as acryloyl morpholine can be enumerated.
In addition; as the curability composition of above-mentioned free radical polymerization curing type adhesive; can illustrate the compound with double bond such as polymerism such as multiple (methyl) acryloyl group, vinyl etc., this compound also can be mixed in adhesive component as crosslinking component.As the curability composition becoming described crosslinking component, can enumerate such as, tripropylene glycol diacrylate, 1, 9-nonanediol diacrylate, Tricyclodecane Dimethanol diacrylate, cyclic trimethylolpropane dimethoxym ethane acrylate, diox omega-diol diacrylate, EO modification two glycerine tetraacrylate, Aronix M-220 (East Asia Synesis Company system), Light acrylate 1, 9ND-A (chemical company of common prosperity society system), Light acrylate DGE-4A (chemical company of common prosperity society system), Light acrylate DCP-A (chemical company of common prosperity society system), SR-531 (Sartomer Inc.), CD-536 (Sartomer Inc.) etc.In addition, can enumerate as required, various epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyester (methyl) acrylate, various (methyl) acrylic ester monomer etc.
Free radical polymerization curing type adhesive contains above-mentioned curability composition, but in addition to the aforementioned ingredients, also adds radical polymerization initiator according to the type of solidification.When using above-mentioned tackifier with electron ray curing type, do not need containing radical polymerization initiator especially in above-mentioned tackifier, but when using with ultraviolet hardening, thermohardening type, radical polymerization initiator be used.The use amount of radical polymerization initiator, relative to curability composition 100 weight portion, about being generally 0.1 ~ 10 weight portion, preferably 0.5 ~ 3 weight portion.In addition, that also can add the representatives such as carbonyls as required in free radical polymerization curing type adhesive utilizes the photosensitizer that electron ray makes curing rate, sensitivity improves.The use amount of photosensitizer, relative to curability composition 100 weight portion, about being generally 0.001 ~ 10 weight portion, preferably 0.01 ~ 3 weight portion.
As the curability composition of cation polymerization curing type tackifier, the compound with epoxy radicals, oxetanyl can be enumerated.There is the compound of epoxy radicals, as long as have the material of at least 2 epoxy radicals in molecule, be then not particularly limited, generally known various curability epoxy compounds can be used.As preferred epoxy compound, its example can be enumerated: the compound in molecule with at least 2 epoxy radicals and at least 1 aromatic rings is (following, be called " fragrant family epoxy compound "), there are at least 2 epoxy radicals in molecule and wherein at least 1 forming the compound (hereinafter referred to as " cycloaliphatic epoxy ") etc. formed between 2 adjacent carbon atoms of ester ring type ring.
< epoxy compound >
As fragrant family epoxy compound, as long as do not hinder effect of the present invention, be not particularly limited, exemplarily 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 brominated bisphenol A; The phenol aldehyde type epoxy resins such as phenol novolak type epoxy and cresol novolak type epoxy resin; And the addition reaction etc. of biphenyl type epoxy resin, p-dihydroxy-benzene diglycidyl ether, resorcinol diglycidyl ether, terephthalic acid (TPA) diglycidyl ester, phthalic acid diglycidyl ester, the epoxide of Styrene-Butadiene, the epoxide of styrene-isoprene copolymer, terminal carboxylic's polybutadiene ester and bisphenol A type epoxy resin.
At this, epoxy resin refers to, have in molecule average more than 2 epoxy radicals and by reacting the compound that is cured or polymkeric substance.According to the convention in this area, in this instructions, as long as have the material of the epoxy radicals of more than 2 curability in molecule, even then monomer is also sometimes referred to as epoxy resin.
As cycloaliphatic epoxy, as long as do not hinder effect of the present invention, be not particularly limited, exemplarily, can enumerate: dicyclopentadiene, limonene dioxide, 4 vinyl cyclohexene dioxide, 3,4-epoxycyclohexyl-methyl, 3,4-epoxycyclohexane carboxylate and two (3,4-epoxycyclohexyl-methyl) adipate etc. have the compound etc. of at least 1 epoxycyclohexyl.
Beyond above-mentioned, the fatty family epoxy compounds such as 1,6-hexane diol diglycidyl ether, trimethylolpropane tris glycidyl ether, pentaerythrite four glycidyl group ether and polytetramethylene glycol diglycidyl ether, epoxy compound after the aromatic rings such as the diglycidyl ether of hydrogenated bisphenol A are hydrogenated, two ends of the polybutadiene of two terminal hydroxyls are by the compound after glycidyl etherified, the inner loop oxide of polybutadiene, the double bond of Styrene-Butadiene by the compound after a part of epoxidation (such as, " エ Port Off レ Application De " that Daicel chemical industry (strain) is made), with the isoprene unit of the segmented copolymer of ethylene-butene copolymer and polyisoprene by the compound after a part of epoxidation (such as, " L-207 " of KRATON Inc.) etc. polymer system epoxy compound etc. also can become the epoxy compound of (A) composition.
Wherein, fragrant family epoxy compound is owing to making the excellences such as the permanance after polarization plates, and excellent in adhesion particularly with polaroid and diaphragm, therefore preferably.In addition, as this fragrant family epoxy compound, can preferably enumerate as preference: the glycidyl ether of aromatics or the glycidyl esters etc. of aromatics.The concrete example of the glycidyl ether of aromatics can be enumerated: the bisphenol-type epoxy resins such as the diglycidyl ether of the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F and brominated bisphenol A; The phenol aldehyde type epoxy resins such as phenol novolak type epoxy and cresol novolak type epoxy resin; Biphenyl type epoxy resin; P-dihydroxy-benzene diglycidyl ether; Resorcinol diglycidyl ether etc.In addition, the concrete example of the glycidyl esters of aromatics can preferably be enumerated: terephthalic acid (TPA) diglycidyl ester, phthalic acid diglycidyl ester etc.
Wherein, the glycidyl ether of aromatics due to adaptation when polaroid is bonding with diaphragm, make the permanance after polarization plates more preferably, therefore particularly preferably.As compound particularly preferred in the glycidyl ether of aromatics, can enumerate: the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F and phenol novolak type epoxy.
Epoxy compound can be used alone a kind, also can be mixed with two or more.Such as, the fragrant family epoxy compound that can be mixed with two or more, or mix cycloaliphatic epoxy based on fragrant family epoxy compound.
< oxetane compound >
As long as have the material of at least 1 oxetanyl in oxetane compound molecule, be then not particularly limited, the various compounds with oxetanyl can be used.As oxetane compound (B), can enumerate as preference: there is in molecule the compound (hereinafter referred to as " multifunctional oxetanes ") in the compound (hereinafter referred to as " simple function oxetanes ") of 1 oxetanyl and molecule with the oxetanyl of more than 2.
As simple function oxetanes, can enumerate as preference: 3-ethyl-3-(2-Ethylhexoxymethyl) oxetanes etc. are containing the simple function oxetanes of alkoxyalkyl, 3-ethyl-3-phenoxymethyloxetane etc. contain the simple function oxetanes of aromatic series base, the hydroxyl simple function oxetanes etc. such as 3-ethyl-3-hydroxymethyl oxetane.
As multifunctional oxetanes, can enumerate such as, 3-ethyl-3-((3-Ethyloxetane-3-base) methoxy) oxetanes, Isosorbide-5-Nitrae-bis-((3-Ethyloxetane-3-base) methoxy) benzene, Isosorbide-5-Nitrae-bis-((3-Ethyloxetane-3-base) methoxyl) benzene, two ((3-Ethyloxetane-3-base) methoxyl) benzene of 1,3-, two ((3-Ethyloxetane-3-base) methoxyl) benzene of 1,2-, 4,4 '-bis-((3-Ethyloxetane-3-base) methoxyl) biphenyl, 2,2 '-bis-((3-Ethyloxetane-3-base) methoxyl) biphenyl, 3,3 ', 5,5 '-tetramethyl-4,4 '-bis-((3-Ethyloxetane-3-base) methoxyl) biphenyl, two ((3-Ethyloxetane-3-base) methoxyl) naphthalene of 2,7-, two (4-{ (3-Ethyloxetane-3-base) methoxyl } phenyl) methane, two (2-{ (3-Ethyloxetane-3-base) methoxyl } phenyl) methane, 2,2-pair (4-{ (3-Ethyloxetane-3-base) methoxyl } phenyl propane, the etherification modified thing of the 3-chloromethyl-3-Ethyloxetane of novolac type phenolics, 3 (4), 8 (9)-bis-((3-Ethyloxetane-3-base) methoxy)-three ring [5.2.1.0 2,6] decane, 2, two ((3-Ethyloxetane-3-base) methoxy) norcamphane of 3-, 1, 1, 1-tri-((3-Ethyloxetane-3-base) methoxy) propane, 1-butoxy-2, two ((3-Ethyloxetane-3-base) methoxy) butane of 2-, 1, two ({ 2-(3-Ethyloxetane-3-base) methoxyl } ethylsulfanyl) ethane of 2-, two ({ 4-(3-Ethyloxetane-3-base) methylsulfany } phenyl) thioether, 1, two ((3-Ethyloxetane-3-base) methoxyl)-2 of 6-, 2, 3, 3, 4, 4, 5, 5-octafluoro hexane, the hydrolytic condensate of 3-((3-Ethyloxetane-3-base) methoxyl) propyl-triethoxysilicane, the condensation product etc. of four ((3-Ethyloxetane-3-base) methyl) esters of silicon acis.
About oxetane compound, from the view point of screening characteristics, make polarization plates time and the adaptation of diaphragm, be aqueous compound under the room temperature of preferred molecular weight less than 500.In addition, from the view point of the excellent durability of polarization plates, as long as simple function oxetanes, then more preferably there is the material of aromatic rings or multifunctional oxetanes in molecule.As the example of so particularly preferred oxetane compound, can enumerate: 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-((3-Ethyloxetane-3-base) methoxy) oxetanes and Isosorbide-5-Nitrae-bis-((3-Ethyloxetane-3-base) methoxy) benzene etc.
Oxetane compound, except can be used alone a kind, can also be mixed with two or more.
The ratio > of < epoxy compound and oxetane compound
The usage ratio of epoxy compound and oxetane compound, with mass ratio range, is 90/10 ~ 10/90.When this ratio is too not enough, the effect in short time solidification cannot be given full play of.From being low viscosity thus screening characteristics is excellent, show sufficient adaptation and flexual viewpoint after hardening before curing, both suitable part by weight are about 70/30 ~ 20/80, and part by weight suitable is further about 60/40 ~ 25/75.
< light cationic polymerization initiators >
In cation polymerization curing type tackifier, as curability composition, containing epoxy compound described above and oxetane compound, they are the material solidified by cationic polymerization, therefore coordinate light cationic polymerization initiators.This light cationic polymerization initiators produces kation kind or lewis acid by irradiation visible ray, ultraviolet, X ray, electron ray isoreactivity energy-ray, causes the polyreaction of epoxy radicals, oxetanyl.
By coordinating light cationic polymerization initiators, the solidification under normal temperature can be carried out, considering the thermotolerance of polaroid, expansion or the necessity of strain caused by shrinking reduces, can be bonding well by diaphragm.In addition, light cationic polymerization initiators plays catalytic effect under the irradiation of active energy beam, even if be therefore mixed in epoxy compound and oxetane compound, storage stability, workability are also excellent.Produce kation kind, lewis acidic compound as the irradiation by active energy beam, can enumerate such as, salt, the iron-arene complexes etc. such as aromatic diazonium salt, aromatic iodonium salts, aromatic series sulfonium salt.
As aromatic diazonium salt, can enumerate such as, benzene diazonium hexafluoro antimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoro borate etc.
As aromatic iodonium salts, can enumerate such as, 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, can enumerate such as, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, diphenyl (4-(thiophenyl) phenyl) sulfonium hexafluorophosphate, diphenyl (4-(thiophenyl) phenyl) sulfonium hexafluoro antimonate, the two hexafluorophosphate of 4,4 '-bis-(diphenylsulfidyl) diphenylsulfide, the two hexafluoro antimonate of 4,4 '-bis-(two (beta-hydroxy ethoxy) phenylsulfartyl) diphenylsulfide, the two hexafluorophosphate of 4,4 '-bis-(two (beta-hydroxy ethoxy) phenylsulfartyl) diphenylsulfide, 7-(two (to methyl benzoyl) sulfenyl)-ITX hexafluoro antimonate, 7-(two (to methyl benzoyl) sulfenyl)-ITX four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-diphenylsulfidyl-diphenylsulfide hexafluorophosphate, 4-(to tert-butyl-phenyl carbonyl)-4 '-diphenylsulfidyl-diphenylsulfide hexafluoro antimonate, 4-(to tert-butyl-phenyl carbonyl)-4 '-two (to methyl benzoyl) sulfenyl-diphenylsulfide four (pentafluorophenyl group) borate etc.
As iron-arene complex, can enumerate such as, dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, cumene-cyclopentadienyl group iron (II) hexafluorophosphate, dimethylbenzene-cyclopentadienyl group iron (II)-three (trimethyl fluoride sulfonyl) methanides etc.
These light cationic polymerization initiators can individually use a kind, also can be mixed with two or more.Wherein, even if particularly aromatic series sulfonium salt also has Ultraviolet Light in the wavelength coverage of more than 300nm, therefore, it is possible to provide curability excellent, there is good physical strength, the solidfied material of bonding strength, therefore preferably use.
Light cationic polymerization initiators easily can obtain commercially available product, and such as, trade name can be enumerated respectively: " Kayarad PCI-220 ", " Kayarad PCI-620 " (more than, Japanese chemical drug (strain) is made), " UVI-6992 " (Dow Chemical's system), " Adeka Optomer SP-150 ", " Adeka OptomerSP-170 " (more than, (strain) ADEKA system), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (more than, Japanese Cao Da (strain) makes), " 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 " (more than, (strain) system is learned in greening), " PI-2074 " (Rhodia Inc.), " Irgacure 250 ", " Irgacure PAG103 ", " Irgacure PAG108 ", " Irgacure PAG121 ", " Irgacure PAG203 " (more than, Qi Ba Inc.), " CPI-100P ", " CPI-101A ", " CPI-200K ", " CPI-210S " (more than, San-Apro (strain) makes) etc., especially, preferably containing " UVI-6992 " of diphenyl (4-(thiophenyl) phenyl) sulfonium as the Dow Chemical of cation constituent, " CPI-100P " that San-Apro (strain) makes, " CPI-101A ", " CPI-200K ", " CPI-210S ".
About the mixing ratio of light cationic polymerization initiators, overall for benchmark with cation polymerization curing type tackifier, be set to the scope of 0.5 ~ 20 % by weight.Its ratio lower than 0.5 % by weight time, the solidification of tackifier is insufficient, physical strength, bonding strength decline, on the other hand, when its ratio is more than 20 % by weight, solidfied material ionic species increases, therefore the hydroscopicity that there is solidfied material increases, the possibility that endurance quality declines, therefore not preferred.
In addition, metallic compound filler can be contained in above-mentioned tackifier.By metallic compound filler, the mobility of adhesive layer can be controlled, make thickness stabilization, thus can to obtain having in good outward appearance, face evenly and there is not the polarization plates of cementability deviation.
In addition, as tackifier, under solvent-free or low solvent state can be used in, carry out the dry lamination method of fitting.As this dry lamination method, use known dry lamination to stick with glue agent and applying method, the method can be used on basis of the present invention.Thus, there is the concavo-convex unequal effect reducing striated further.
Stick with glue agent as above-mentioned dry lamination, bi-component curing type adhesive, two part solvent type tackifier, single-component solvent-free type tackifier etc. can be enumerated.As bi-component curing type adhesive, the resin of acrylic acid series etc. can be used, as two part solvent type tackifier, the resin of Polyester, aromatic polyester system, aliphatic polyester, polyester/polyurethane system, polyethers/polyurethane series etc. can be used, as single-component solvent-free type tackifier (moisture-curable), the resin of polyethers/polyurethane series etc. can be used.
Above-mentioned tackifier suitably can contain adjuvant as required.Example as adjuvant can be enumerated, silane coupling agent, the coupling agents such as titanium coupling agent, adhesion promoters representated by ethylene oxide, make the adjuvant that the wellability of transparent protective film is improved, acryloyl-oxy based compound, hydrocarbon system is (natural, synthetic resin) etc. representative make physical strength, the adjuvant that processability etc. improve, ultraviolet light absorber, antiaging agent, dyestuff, processing aid, ion capturing agent, antioxidant, tackifier, filling agent (except metallic compound filler), plastifier, levelling agent, frothing inhibitor, electrostatic prevention cuts, heat-resisting stabilizing agent, the stabilizing agents etc. such as stabilizer against hydrolysis.
The application pattern of tackifier suitably can be selected according to the viscosity of tackifier, target thickness.As the example of application pattern, can enumerate such as, reversion coating machine, gravure coater (directly, compensation, offset printing), oppositely bar coater, roll coater, mould are coated with machine, scraping strip coating machine, rod coater.In addition, suitably the modes such as impregnation method can be used in coating.
In addition, above-mentioned tackifier be coated in situations such as using water system tackifier under, the mode preferably reaching 30 ~ 300nm with the thickness of the adhesive layer finally formed is carried out.The thickness more preferably 60 ~ 250nm of above-mentioned adhesive layer.On the other hand, when using curing type adhesive, the mode preferably reaching 0.1 ~ 200 μm with the thickness of above-mentioned adhesive layer is carried out.Be more preferably 0.5 ~ 50 μm, preferably 0.5 ~ 10 μm further.
< operation (4) >
In operation (4), above-mentioned polaroid and transparent protective film are fitted by above-mentioned tackifier.The laminating of polaroid and transparent protective film can be undertaken by using roll squeezer etc.In Fig. 1, by crimping roller R3, R4, polaroid P and the transparent protective film T2 of the polarizing coating F1 utilizing tackifier A2 to be protected by one side fit, and obtain the polarizing coating F2 of two sides protection.
< transparent protective film >
As the material forming above-mentioned transparent protective film, the material that preferably clear, physical strength, thermal stability, moisture blocking-up property, isotropy etc. are excellent.Such as can enumerate, the Polyester such as polyethylene terephthalate, Polyethylene Naphthalate polymkeric substance, the cellulose-based polymkeric substance such as diacetyl cellulose, triacetyl cellulose, the acrylic acid series polymeric compounds such as polymethylmethacrylate, the styrenics such as polystyrene, acrylonitritrile-styrene resin (AS resin), polycarbonate based polymer etc.In addition, tygon, polypropylene, there is the polyolefin of ring system or norborene structure, the polyolefin polymkeric substance such as ethylene-propylene copolymer, vinyl chloride-based polymer, nylon, the acid amides based polymers such as aromatic polyamide, imide series polymkeric substance, sulfone based polymer, polyethersulfone based polymer, polyetheretherketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol based polymer, vinylidene chloride based polymer, vinyl butyral based polymer, aromatic ester based polymer, polyoxymethylene based polymer, epoxy polymkeric substance, or the example that the blend etc. of above-mentioned polymkeric substance also can be used as the polymkeric substance forming above-mentioned transparent protective film is enumerated.Can containing more than a kind suitable arbitrarily adjuvant in transparent protective film.As adjuvant, can enumerate such as, ultraviolet light absorber, antioxidant, lubricant, plastifier, release agent, painted preventing agent, fire retardant, nucleator, antistatic agent, pigment, colorant etc.In transparent protective film, the content of above-mentioned thermoplastic resin is preferably 50 ~ 100 quality %, more preferably 50 ~ 99 quality %, further preferably 60 ~ 98 quality %, particularly preferably 70 ~ 97 quality %.When in transparent protective film, the content of above-mentioned thermoplastic resin is below 50 quality %, thermoplastic resin likely fully cannot show high transparent etc. inherently.
The thickness of above-mentioned transparent protective film can suitably be determined, but general from viewpoints such as the workability such as intensity, operability, thin layers, is about 1 ~ 500 μm.Particularly preferably 1 ~ 300 μm, more preferably 5 ~ 200 μm.
In addition, when the two sides of polaroid arranges transparent protective film, can use at its pros and cons the diaphragm comprising identical polymeric material, also can use the transparent protective film comprising different polymeric material etc.Such as; as shown in Figure 1; when implementing operation (1) to operation (4) to one side protection polarizing coating F1 and manufacturing two sides protection polarizing coating F2, the transparent protective film T1 preferably suitable choice for use from cellulose-based polymkeric substance (triacetyl cellulose etc.), the polyolefin with norborene structure, acrylic acid series polymeric compounds, Polyester polymkeric substance, polyolefin polymkeric substance (polypropylene etc.) of one side protection polarizing coating F1.Now; for transparent protective film T2, also preferred from cellulose-based polymkeric substance (triacetyl cellulose etc.), the polyolefin with norborene structure, acrylic acid series polymeric compounds, Polyester polymkeric substance, polyolefin polymkeric substance (polypropylene etc.) suitable choice for use.
After above-mentioned bonding process, form adhesive layer.The formation of adhesive layer is carried out according to the kind of tackifier.In addition, when water system tackifier, adhesive layer can be pre-formed in operation (3), fit in operation (4).
When tackifier is water system tackifier, solvent system tackifier, after above-mentioned bonding process, implement drying process and form adhesive layer.When using water system tackifier, carry out drying process baking temperature about 20 ~ 80 DEG C, preferably 40 ~ 80 DEG C under the condition of about 1 ~ 10 minute, preferably 1 ~ 5 minute.
When tackifier is radical-curable tackifier, after above-mentioned bonding process, implement curing process and form adhesive layer.When radical-curable tackifier is electron ray curing type, implement solidification process by electron beam irradiation, when ultraviolet hardening, implement solidification process by ultraviolet process, when thermohardening type, implement solidification process by thermal treatment.These solidification process can suitably set each condition according to the kind of solidification, the kind of tackifier, the thickness of adhesive layer.
In addition, there is above-mentioned operation (1) to operation (4) in the manufacture method of polarizing coating of the present invention, but also can comprise other operations beyond above-mentioned operation.
Such as, when the laminating of polaroid and transparent protective film, can easy adhesive linkage be set between transparent protective film and adhesive layer.Easy adhesive linkage can utilize such as have polyester backbone, polyether skeleton, polycarbonate backbone, polyurethane skeleton, silicone based, polyamide backbone, polyimide backbone, polyvinyl alcohol (PVA) skeleton etc. various resins formed.These fluoropolymer resins can be used alone one or combinationally use two or more.In addition, other adjuvants can be added in the formation of easy adhesive linkage.Specifically, the stabilizing agents etc. such as tackifier, ultraviolet light absorber, antioxidant, heat-resisting stabilizing agent can also be used.
Easy adhesive linkage is set in advance on transparent protective film usually, utilizes adhesive layer to fit the easy adhesive linkage side of this transparent protective film and polaroid.The formation of easy adhesive linkage is undertaken by the formation material being dried utilizing known technology be coated with easy adhesive linkage on transparent protective film.The formation material of easy adhesive linkage usually consider dried thickness, coating fairness etc. and regulate with the form of the solution being diluted to debita spissitudo.The dried thickness of easy adhesive linkage is preferably 0.01 ~ 5 μm, more preferably 0.02 ~ 2 μm, more preferably 0.05 ~ 1 μm.It should be noted that, easy adhesive linkage can arrange multilayer, but in this case, also preferably easily the gross thickness of adhesive linkage is above-mentioned scope.
When utilizing tinuous production to manufacture polarizing coating of the present invention, linear velocity depends on the set time of tackifier, but is preferably 1 ~ 500m/ minute, is more preferably 5 ~ 300m/ minute, more preferably 10 ~ 100m/ minute.When linear velocity is too small, undercapacity, or excessive to the damage of transparent protective film, the polarizing coating that can tolerate endurancing etc. cannot be made.When linear velocity is excessive, the solidification of tackifier becomes insufficient, sometimes cannot obtain target cementability.
The polarizing coating at the one or both sides of polaroid with transparent protective film can be obtained as mentioned above, the surface of the not bonding polaroid of above-mentioned transparent protective film can arrange the functional layers such as hard conating, anti-reflection layer, antiblocking layers, diffusion layer or antiglare layer.It should be noted that, the functional layers such as above-mentioned hard conating, anti-reflection layer, antiblocking layers, diffusion layer, antiglare layer except can be arranged on transparent protective film originally with it, also can in addition and transparent protective film arrange dividually.
Polarizing coating of the present invention can use with the form of the blooming stacked with other optical layers when reality uses.About this optical layers, be not particularly limited, the optical layers such as sometimes used in the formation of the liquid crystal indicators such as reflecting plate, half transmitting plate, polarizer (comprising 1/2,1/4 equiwavelength's plate), vision compensate film etc. of more than 1 layer or 2 layers can be used.Particularly preferably in polarizing coating of the present invention being laminated with further the reflective polarizing film of reflecting plate or Transflective plate or Semitransmissive polarizing coating, the elliptic polarization film that polarizing coating is laminated with polarizer further or circular polarization film, being laminated with the wide viewing angle polarizing coating of vision compensate film further at polarizing coating or being laminated with the polarizing coating of brightness enhancement film further on polarizing coating.
The blooming that polarizing coating is laminated with above-mentioned optical layers also can by carrying out stacked mode to be formed separately successively in the manufacture process of liquid crystal indicator etc., but stacked in advance and make blooming to have the stability, assembly operation etc. of quality excellent and can improve the advantage of the manufacturing process of liquid crystal indicator etc.The stacked adhesion means that bonding coat etc. can be used suitable.During above-mentioned polarizing coating, other bloomings bonding, their optic axis can form suitable arrangement angles according to target phase difference characteristic etc.
Aforesaid polarizing coating, be laminated with at least 1 layer of polarizing coating blooming on also can arrange for the bonding coat bonding with other components such as liquid crystal cells.Form the bonding agent of bonding coat to be not particularly limited, can the bonding agent of suitable choice for use polymkeric substance based on the polymkeric substance of such as acrylic acid series polymeric compounds, silicone-based polymers, polyester, polyurethane, polyamide, polyethers, fluorine-containing or rubber-like etc.Particularly, can preferably use optical transparence as acrylic adhesive so excellent, demonstrate the wetting state of appropriateness, the adhesion characteristic of coherency and cementability and the excellent bonding agent such as weatherability and thermotolerance.
Bonding coat also can be arranged on the one or two sides of polarizing coating, blooming as the overlapping layer of composition or the different layer such as kind.In addition, when being arranged at two sides, also can form the different bonding coat such as composition, kind, thickness on the surface of polarizing coating, blooming, the back side.The thickness of bonding coat suitably can determine according to application target, bonding force etc., is generally 1 ~ 500 μm, is preferably 1 ~ 200 μm, is particularly preferably 1 ~ 100 μm.
For the exposed surface of bonding coat, until during for practicality, the temporarily adhesion partition and protecting such as to pollute to prevent it.Thereby, it is possible to contact with bonding coat under common treatment state.As partition, except above-mentioned thickness condition, can use and such as sheet-like article suitable to plastic foil, sheet rubber, paper, cloth, nonwoven fabrics, net, foamed sheet, metal forming and their layered product etc. etc. carried out with suitable removers such as silicone based, chain alkyl class, fluorine-containing type, molybdenum sulfides the partition etc. being coated with process as required.
Polarizing coating of the present invention or blooming can preferably use in the formation etc. of the various devices such as liquid crystal indicator.The formation of liquid crystal indicator can be carried out according to mode in the past.Namely, liquid crystal indicator is generally formed by arranging driving circuit etc. after liquid crystal cells and polarizing coating or the component parts such as blooming and illuminator as required suitably being assembled, in the present invention, except using polarizing coating of the present invention or blooming, be not particularly limited, can carry out according to existing mode.For liquid crystal cells, arbitrary type such as such as TN type, STN type, π type etc. can be used.
Can be formed in the one-sided of liquid crystal cells or both sides be configured with polarizing coating or blooming liquid crystal indicator, use backlight, reflecting plate as the suitable liquid crystal indicator such as the display device of illuminator.In this case, polarizing coating of the present invention or blooming can be arranged on the one-sided of liquid crystal cells or both sides.When arranging polarizing coating or blooming in both sides, they can be the same or different.In addition, when forming liquid crystal indicator, one deck or the suitable parts of two-layer above diffuser plate, antiglare layer, antireflection film, fender, prism array, lens arra, light diffusing sheet, backlight etc. can be configured in position.
Embodiment
Specifically describe the present invention by the following examples, but the present invention is not limited to the examples.In addition, the part in each example and % are weight basis.
Make protection polarizing coating.
The making > of < sheet protection polarizing coating (1)
In order to make slim polarizing coating, first, the duplexer that amorphism PET base material is formed 9 μm of thick PVA layers is generated stretching duplexer by the aerial assisting tension that draft temperature is 130 DEG C, then, stretching duplexer is generated painted duplexer by dyeing, is to stretch in the boric acid water of 65 degree and to make total stretching ratio be that mode and the amorphism PET base material of 5.94 times stretches integratedly and drying generates the optical film laminate comprising 4 μm of thick PVA layers for 4 minutes at 50 DEG C further by draft temperature by painted duplexer.Can make to be stretched by such 2 sections and the PVA molecule being formed in the PVA layer in amorphism PET base material carries out high order orientation, the iodine adsorbed by dyeing carry out high order orientation with the form of many iodide ions complex compound along a direction and generate formed high function polarizing coating, the optical film laminate of the PVA layer that comprises thickness 4 μm.Then, at the surface application polyethenol series tackifier of the polarizing coating of this optical film laminate, 40 μm after the saponification process of simultaneously fitting thick tri acetyl cellulose membranes (transparent protective film), then peel off amorphism PET base material.Gains are called slim protection polarizing coating (1).The moisture rate of the polarizing coating (polaroid) in sheet protection polarizing coating (1) is 1.8%.
The making > of < sheet protection polarizing coating (2)
Between speed is than different rollers, by the polyvinyl alcohol film of thickness 80 μm 30 DEG C, Edge Coloring 1 minute limit is stretched to 3 times in the iodine solution of 0.3% concentration.Then, 60 DEG C, limit is flooded 0.5 minute limit to be stretched to total stretching ratio is 6 times in the aqueous solution that comprises the boric acid of 4% concentration, the potassium iodide of 10% concentration.Then, 30 DEG C, comprise 1.5% concentration potassium iodide aqueous solution in dipping 10 seconds and cleaning after, 50 DEG C of dryings 4 minutes, obtain the polaroid of thickness 20 μm.Utilize polyethenol series tackifier, the tri acetyl cellulose membrane (transparent protective film) of the thickness 40 μm after the laminating saponification process of the two sides of this polaroid, makes polarizing coating.Below, gains are called sheet protection polarizing coating (2).The moisture rate of the polarizing coating (polaroid) in sheet protection polarizing coating (2) is 11%.
< transparent protective film >
Film after using the norborene mesentery to thickness 60 μm (Zeonor film, Nippon Zeon Co., Ltd.'s system) to implement corona treatment.
(preparation of active energy ray curable tackifier)
Following each composition is mixed with the ratio of HEAA 50 parts, ACMO 50 parts, IRGACURE 8193 parts, stirs 1 hour at 50 DEG C, obtain active energy ray curable tackifier.
HEAA (hydroxyethyl acrylamide), Xing Ren Inc.
ACMO (acryloyl morpholine), Xing Ren Inc.
IRGACURE 819 (two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, Japanese Qi Ba Inc.
Embodiment 1
(operation 1)
To make sheet protect the transparent protective film side of polarizing coating (1) to be the mode for the treatment of tube side, according to the mode of Fig. 1, transport sheet protection polarizing coating (1).About activation process, use corona irradiating machine (springtime Motor Corporation's system, CT ?0212), with discharge capacity 250W/m 2the condition of/min carries out corona treatment to the one side of polaroid.The surfaceness (Ra) on the surface of the polaroid after activation process is 0.62nm.
(operation 2)
Then, polarizing coating (1) is protected by the sheet after activation process in the surface for polaroid, to make polaroid side for the mode of deflector roll side, according to the mode of Fig. 1, transports sheet protection polarizing coating (1).
(operation 3)
Then, use micro-gravure coater, at the above-mentioned tackifier of the unilateral coating of polarization (active energy ray curable tackifier) of sheet above protection polarizing coating (1).
(operation 4)
Then, after applying above-mentioned tackifier, by above-mentioned tackifier, utilize roller machine to fit above-mentioned transparent protective film.From the transparent protective film side irradiation ultraviolet radiation of laminating, obtain the polarizing coating on two sides with transparent protective film.Be that the condition of 20m/min is fitted with line speed.
Embodiment 2 ~ 3, comparative example 1 ~ 4
According to changing the sheet protection kind of polarizing coating, the Corona discharge Treatment amount to polaroid in embodiment 1 table 1 Suo Shi, make polarizing coating similarly to Example 1 in addition.In addition, the moisture rate of sheet protection polarizing coating is controlled by baking temperature.
[evaluation]
Following evaluation is carried out to the polarizing coating obtained in embodiment and comparative example.Result is as shown in table 1.
< transport property >
According to the transport in following benchmark evaluation operation (2).
Zero: all good, do not produce in transport fracture, scar etc.
×: too high with the holding force of roller, produce the fractureing of film, scar, lamination are bad,
Table 1
Symbol description
P polaroid
T1, T2 transparent protective film
A1, A2 tackifier
F1 one side protection polarizing coating
F2 two sides protection polarizing coating

Claims (5)

1. a manufacture method for polarizing coating, is characterized in that, be the manufacture method being at least simultaneously provided with the polarizing coating of transparent protective film by adhesive layer at polaroid, it comprises:
Operation (1), implements activation process by least one side of the polaroid to moisture rate being less than 11 % by weight, makes the surfaceness on polaroid surface and Ra be more than 0.6nm thus,
Operation (2), for the polaroid implemented after described activation process, while make the surface of the polaroid after this activation process and guide rollers contact limit transport,
Operation (3), to the face that will form described adhesive layer of the polaroid transported by described deflector roll and/or the face adhesive coating that will form described adhesive layer of transparent protective film,
Operation (4), is fitted polaroid and transparent protective film by described tackifier.
2. the manufacture method of polarizing coating as claimed in claim 1, is characterized in that,
The thickness of described polaroid is less than 10 μm.
3. the manufacture method of polarizing coating as claimed in claim 1 or 2, is characterized in that,
Described polaroid is the continuous band-shaped polarizing coating comprising polyvinyl alcohol resin after making dichroic substance orientation, and comprises the 2 sections of stretching process stretched in aerial assisting tension and boric acid water and stretch to duplexer by utilizing and obtain,
Described duplexer is the duplexer of the polyvinyl alcohol resin layer comprise masking on thermoplastic resin base material after.
4. the manufacture method of the polarizing coating according to any one of claims 1 to 3, is characterized in that,
Described activation process is corona treatment or Cement Composite Treated by Plasma.
5. the manufacture method of the polarizing coating according to any one of Claims 1 to 4, is characterized in that,
Described activation process is corona treatment,
Discharge capacity in corona treatment is 250 ~ 1000W/m 2/ min.
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