CN104854490B - The manufacturing method of polarizing coating - Google Patents

The manufacturing method of polarizing coating Download PDF

Info

Publication number
CN104854490B
CN104854490B CN201380064757.0A CN201380064757A CN104854490B CN 104854490 B CN104854490 B CN 104854490B CN 201380064757 A CN201380064757 A CN 201380064757A CN 104854490 B CN104854490 B CN 104854490B
Authority
CN
China
Prior art keywords
polarizing
film
polarizing film
adhesive
polarizing coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201380064757.0A
Other languages
Chinese (zh)
Other versions
CN104854490A (en
Inventor
姜太艳
齐藤武士
品川雅
冈本美纪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN104854490A publication Critical patent/CN104854490A/en
Application granted granted Critical
Publication of CN104854490B publication Critical patent/CN104854490B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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

Abstract

A kind of manufacturing method of polarizing coating, it is characterised in that including：Process (1); by implementing to be activated at least one side that moisture rate is 11 weight % polarizing films below; thus make the surface roughness i.e. Ra 0.6nm or more on polarizing film surface; process (2); it is transported when the surface of the polarizing film after making to be activated is with guide rollers contact, process (3), to polarizing film and/or transparent protective film adhesive coating; polarizing film is bonded with transparent protective film by the adhesive by process (4).By the manufacturing method, can transport property manufacture polarizing coating well.

Description

The manufacturing method of polarizing coating
Technical field
The present invention relates to the manufacturing methods of polarizing coating.The polarizing coating obtained by the manufacturing method can be individually or with its layer The form of optical film made of folded forms the images display dress such as liquid crystal display device (LCD), organic EL display device, CRT, PDP It sets.
Background technique
Liquid crystal display device is in wrist-watch, mobile phone, PDA, laptop, PC display, DVD player, electricity Depending on etc. market demand in fields increasing sharply.Liquid crystal display device is to make the polarization state as caused by the conversion of liquid crystal Visualization device uses polarizing film according to its displaying principle.Especially in TV and other uses, more require high brightness, height right Than degree, wide viewing angle, polarizing coating also starts to require high-transmission rate, high-polarization, high color reproducibility etc..
As polarizing film, due to high-transmission rate to be had, high-polarization, being generally most widely used that for example makes iodine The iodine system polarizing film of structure after being adsorbed in polyvinyl alcohol and being stretched.For such polarizing film, have mechanical strong Degree is extremely weak, can be shunk due to hot, moisture the shortcomings that being remarkably decreased to polarization function.Therefore, obtained polarizing film wants horse Upper pass through after adhesive is bonded with the transparent protective film coated with adhesive uses as polarizing coating.
In addition, being proposed to further increase the adhesive strength of polarizing film and transparent protective film：To setting for polarizing film The face for setting gluing oxidant layer is implemented after being activated, and polarizing film is bonded with transparent protective film to manufacture polarizing coating (patent document 1). In general, polarizing film is manufactured by hydrophilic macromolecule films such as polyvinyl alcohol mesenteries, therefore polarizing film has water to a certain degree Divide rate.It is recorded in patent document 1, the moisture rate of polarizing film is preferably 20 weight % hereinafter, more preferable 0~17 weight %, into one Walk preferably 1~16 weight %.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2009-008660 bulletin
Summary of the invention
Subject to be solved by the invention
All the time, polarizing film is transported using deflector roll, but since the moisture rate of the polarizing film is more than 11 weight %, because Even if this is with guide rollers contact and in the case where transported, also there is no problem in terms of transport property.In recent years, it is intended to make Making moisture rate is 11 weight % polarizing films below.But the moisture rate of polarizing film be 11 weight % or less when, polarizing film and fortune Send the chucking power (Network リ ッ プ power) between the deflector roll of polarizing film to increase, generated in terms of transport property it is bad, or later with It is generated in the fitting of transparent protective film bad.Particularly, when being transported at the surface and guide rollers contact for making polarizing film, hold It is easily generated in terms of transport property bad.
The purpose of the present invention is to provide it is a kind of can the transport property method that manufactures polarizing coating well, the polarizing coating exists At least one side of polarizing film is provided with transparent protective film by gluing oxidant layer.
The method to solve the problem
The present inventor has carried out research extensively and profoundly in order to solve the above problems, as a result, it has been found that the systems of following polarizing coatings Method etc. is made, and completes the present invention.
That is, the present invention relates to a kind of manufacturing methods of polarizing coating, which is characterized in that pass through for at least one side in polarizing film Gluing oxidant layer is provided with the manufacturing method of the polarizing coating of transparent protective film comprising：
Process (1), by implementing to be activated at least one side that moisture rate is 11 weight % polarizing films below, thus The surface roughness (Ra) for making polarizing film surface is 0.6nm or more,
Process (2), for implementing the polarizing film after the activation processing, while making the surface of the polarizing film after the activation processing It is transported with guide rollers contact side,
Process (3), to the face for being used to form the gluing oxidant layer of the polarizing film transported by the deflector roll and/or transparent guarantor The face adhesive coating for being used to form the gluing oxidant layer of cuticula,
Polarizing film is bonded with transparent protective film by the adhesive by process (4).
The manufacturing method of above-mentioned polarizing coating can be applied suitably to polarizing film with a thickness of 10 μm or less of situation.
The manufacturing method of above-mentioned polarizing coating can be applied suitably to following polarizing films, and the polarizing film is to make dichroism object The continuous band-shaped polarizing coating comprising polyvinyl alcohol resin after matter orientation, and by using including aerial assisting tension and boron The 2 sections of stretching process stretched in sour water, which stretch laminated body, to be obtained, and the laminated body is on thermoplastic resin substrate Laminated body comprising the polyvinyl alcohol resin layer after film.
In the manufacturing method of above-mentioned polarizing coating, as above-mentioned activation processing, it can use at sided corona treatment or plasma Reason.
In the manufacturing method of above-mentioned polarizing coating, preferably：Activation processing based on above-mentioned activation processing is sided corona treatment, corona Discharge capacity in processing is 250~1000W/m2/min。
Invention effect
It is the polarization of 11 weight % low moisture rate below using moisture rate in the manufacturing method of polarizing coating of the invention Piece, and before being bonded the polarizing film using adhesive with transparent protective film, while making surface and the guide rollers contact of polarizing film, side It is transported.On the other hand, in the manufacturing method of polarizing coating of the invention, before the surface and guide rollers contact for making polarizing film, To implement to be activated with the face of the polarizing film of guide rollers contact, 0.6nm or more is reached with the surface roughness (Ra) of polarizing film Mode controlled.As long as in this way it is found that being controlled in such a way that surface roughness (Ra) reaches 0.6nm or more inclined Shake piece, even if can also be transported well in the case where making the polarizing film and guide rollers contact of low moisture rate.As a result, it Polarizing film afterwards becomes good using being bonded for adhesive with transparent protective film, can efficiently produce polarizing coating.
Detailed description of the invention
Fig. 1 is the concept map for indicating an example of embodiment involved in the manufacturing method of polarizing coating of the invention.
Specific embodiment
The manufacturing method of polarizing coating of the invention is illustrated below.Polarizing coating of the invention in polarizing film at least one Face is provided with transparent protective film by gluing oxidant layer.The polarizing coating of the invention is by successively implementing process (1) to process (4) And it obtains.With below referring to Fig.1, while being illustrated to process (1) to (4).Following situation is instantiated in Fig. 1：For passing through Gluing oxidant layer A1 implements process (1) extremely in the polarizing coating F1 of the single side protection for being provided with transparent protective film T1 on one side of polarizing film P (4), to manufacture the polarizing coating F2 of two sides protection.
<Process (1)>
In process (1), by implementing to be activated at least one side that moisture rate is 11 weight % polarizing films below, make The surface roughness (Ra) on polarizing film surface is 0.6nm or more.In Fig. 1, at treatment tube R1, the polarizing coating F1's of single side protection The surface of polarizing film P is activated processing unit C and is activated.
<Polarizing film>
Polarizing film is not particularly limited, and various polarizing films can be used.As polarizing film, such as can enumerate：Make to gather The hydrophilies such as vinyl alcohol mesentery, part formalizing polyvinyl alcohol mesentery, the partly-hydrolysed film of vinyl-vinyl acetate copolymer system Polarizing film obtained from polymeric membrane adsorbs the dichroic materials such as iodine, dichroic dye and is uniaxially stretched；Polyvinyl alcohol The polyenoid system such as dehydration treatment, dehydrochlorinated products of polyvinyl chloride alignment films etc..It wherein, include polyvinyl alcohol mesentery and iodine etc. The polarizing film of dichroic substance is preferred.The thickness of these polarizing films is not particularly limited, and usually 1~80 μm or so.Partially Shake piece preferably 30 μm of thickness hereinafter, more preferable 20 μm hereinafter, further preferred 10 μm or less.
Polarizing film obtained from polyvinyl alcohol mesentery is dyed and is uniaxially stretched with iodine can for example pass through by Polyvinyl alcohol dipping is dyed in the aqueous solution of iodine, is stretched to 3~7 times of raw footage then to make.As needed, Can be immersed in can be in the aqueous solution of the potassium iodide containing boric acid, zinc sulfate, zinc chloride etc..It in turn, can also be as needed Polyvinyl alcohol mesentery dipping is washed in water before dyeing.By being washed to polyvinyl alcohol mesentery, Neng Gouqing Spot, the anti-blocking agent of polyvinyl alcohol mesentery surface are washed, in addition, also having makes polyethenol series membrane swelling and prevent dye speck Etc. non-uniform effect.Stretching can carry out after being dyed with iodine, can also be stretched with Edge Coloring side, furthermore it is also possible to It is dyed after the stretch with iodine.It can be stretched in aqueous solutions of boric acid, potassium iodide, etc., in water-bath.
<<Slim polarizing film>>
As polarizing film, can be used with a thickness of 10 μm of slim polarizing films below.For the viewpoint of slimming, the thickness Preferably 1~7 μm of degree.Uneven thickness is few, and observation property is excellent, and change in size is few, therefore excellent durability, and as inclined The thickness of vibrating diaphragm also achieves slimming, from the above considerations preferably such slim polarizing film.
As slim polarizing film, can typically enumerate：Japanese Unexamined Patent Application 51-069644 bulletin, Japanese Unexamined Patent Publication 2000-338329 bulletin, WO2010/100917 pamphlet, the specification of PCT/JP2010/001460 or Japanese Patent Application The slim polarizing coating recorded in 2010-269002 specification, Japanese Patent Application 2010-263692 specification.These are slim partially Vibrating diaphragm can be by including that polyvinyl alcohol resin (hereinafter also referred to PVA resinoid) layer and stretching resin base material are being laminated The preparation method of process that the state of body is stretched and the process dyed obtains.If it is the preparation method, even if then PVA class tree Rouge layer is relatively thin, can will not also produced fracture etc. in undesirable situation due to stretching and being supported by stretching with resin base material It is stretched.
As above-mentioned slim polarizing coating, the process stretched including the state in laminated body and the process dyed In preparation method, from high magnification can be stretched to from the viewpoint of improving polarization property, preferably pass through WO2010/100917 brochure Son, the specification of PCT/JP2010/001460 or Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010- What No. 263692 specifications were recorded includes that the preparation method of the process stretched in boric acid aqueous solution obtains, and particularly preferably passes through day What this Patent 2010-269002 specification, Japanese Patent Application 2010-263692 specification were recorded is included in boric acid aqueous solution The preparation method of the process auxiliarily stretched in the air before being stretched obtains.
The slim high function polarizing coating that the specification of above-mentioned PCT/JP2010/001460 is recorded is integrated film forming in resin It is constituted on substrate, by the PVA resinoid for being orientated dichroic substance and with a thickness of 7 μm of slim high function polarizations below Film has the optical characteristics that monomer transmissivity is 42.0% or more and degree of polarization is 99.95% or more.
Above-mentioned slim high function polarizing coating can manufacture by the following method：In the resin base of the thickness at least 20 μm It is coated with PVA resinoid on material and makes it dry, thus generates PVA resinoid layer, the PVA resinoid layer of generation is impregnated into two colors In the dyeing liquor of property substance, it is adsorbed on dichroic substance in PVA resinoid layer, the PVA class tree of dichroic substance will have been adsorbed Rouge layer is integrally stretched in boric acid aqueous solution with resin base material, so that total stretching ratio reaches 5 times or more of former length.
In addition, in the side of laminate film of the manufacture comprising the slim high function polarizing coating for being orientated dichroic substance In method, by the inclusion of following processes, above-mentioned slim high function polarizing coating can be manufactured, the process is：Generate laminate film, institute State the resin base material and contain by being coated on the single side of resin base material that laminate film includes the thickness at least 20 μm The aqueous solution of PVA resinoid and make it dry and the PVA resinoid layer that is formed；Comprising resin base material and resin base material will be formed in The above-mentioned laminate film of PVA resinoid layer of single side be impregnated into the dyeing liquor containing dichroic substance, thus make dichroism Substance is adsorbed onto the PVA resinoid layer contained in laminate film；It will be comprising the PVA resinoid layer that has adsorbed dichroic substance Above-mentioned laminate film is stretched in boric acid aqueous solution, so that total stretching ratio reaches 5 times or more of former length；Two will have been adsorbed The PVA resinoid layer of color substance is integrally stretched with resin base material, is thus manufactured and is formed on the single side of resin base material Have includes the PVA resinoid layer for being orientated dichroic substance, with a thickness of 7 μm or less and with monomer transmissivity 42.0% or more and degree of polarization be 99.95% or more optical characteristics slim high function polarizing coating laminate film.
In the present invention, as with a thickness of 10 μm of polarizing films below, following polarizing film can be used, be to make dichroism Substance orientation after the continuous band-shaped polarizing coating comprising polyvinyl alcohol resin, and by using include aerial assisting tension with The 2 sections of stretching process stretched in boric acid water, which stretch laminated body, to be obtained, and the laminated body is in thermoplastic resin substrate The upper laminated body comprising the polyvinyl alcohol resin layer after film.As above-mentioned thermoplastic resin substrate, preferably amorphism ester system Thermoplastic resin substrate or crystallinity ester based thermoplastic resin base material.
Above-mentioned Japanese Patent Application 2010-269002 specification, Japanese Patent Application 2010-263692 specification it is slim partially Vibrating diaphragm is the polarizing coating for continuous band-shaped (the ウ ェ Block) comprising PVA resinoid for being orientated dichroic substance, is passed through By the laminated body comprising the PVA resinoid layer for being formed in amorphism esters thermoplastic resin substrate by aerial assisting tension and boron It is stretched in sour water and is stretched in 2 sections of stretching process of composition and be formed as 10 μm of thickness below.The slim polarizing coating is excellent There is following optical characteristics to meet P >-(10 when monomer transmissivity to be set as T, degree of polarization is set as P for choosing0.929T-42.4-1) The condition of × 100 (wherein, T < 42.3) and P >=99.9 (wherein, T >=42.3).
Specifically, above-mentioned slim polarizing coating can be made by the manufacturing method of the slim polarizing coating comprised the following steps It makes：Aerial drawing by high temperature is carried out to the PVA resinoid layer for being formed in continuous band-shaped amorphism esters thermoplastic resin substrate, by This generates the stretching intermediate product comprising the PVA resinoid layer after orientation；Suction to intermediate product progress dichroic substance is stretched It is attached, thus generate the PVA class tree comprising being orientated dichroic substance (the preferably mixture of iodine or iodine and organic dyestuff) The coloring intermediate product of rouge layer；Stretch in boric acid water with to coloring intermediate product, thus generate comprising making dichroic substance The PVA resinoid layer being orientated with a thickness of 10 μm of polarizing coatings below.
In the manufacturing method, amorphism esters thermoplastic is formed in preferably by what is stretched in aerial drawing by high temperature and boric acid water Property resin base material PVA resinoid layer total stretching ratio be 5 times or more.Liquid for the boric acid aqueous solution stretched in boric acid water Temperature can be set as 60 DEG C or more.It is preferred that before being stretched in boric acid aqueous solution to coloring intermediate product, it is intermediate to coloring Product carries out insoluble processing, in this case, it is preferred that above-mentioned by impregnating in boric acid aqueous solution of the liquid temperature no more than 40 DEG C Color intermediate product carries out.Above-mentioned amorphism esters thermoplastic resin substrate is preferably capable being formed comprising being total to phthalic acid Copolymerization polyethylene terephthalate obtained from poly- is copolymerized poly terephthalic acid obtained from being copolymerized cyclohexanedimethanol Glycol ester or other copolymerization polyethylene terephthalates amorphism polyethylene terephthalate and include transparent The substrate of resin, thickness can be set as 7 times or more that are formed by the thickness of PVA resinoid layer.In addition, aerial high temperature is drawn The stretching ratio stretched is preferably 3.5 times hereinafter, the draft temperature of aerial drawing by high temperature is preferably the glass transition of PVA resinoid More than temperature, specifically, it is preferable that being 95 DEG C~150 DEG C of range.Aerial high temperature drawing is carried out being uniaxially stretched by free end In the case where stretching, be formed in the PVA resinoid layer of amorphism esters thermoplastic resin substrate total stretching ratio be preferably 5 times with It is upper and 7.5 times or less.In addition, being formed in amorphism in the case where being uniaxially stretched the aerial drawing by high temperature of progress by fixing end Total stretching ratio of the PVA resinoid layer of esters thermoplastic resin substrate is preferably 5 times or more and 8.5 times or less.
More specifically, slim polarizing coating can be manufactured by method as described below.
Make 6 moles of % phthalic acid copolymerization and makes phthalic acid copolymerization polyethylene terephthalate (amorphous Property PET) continuous band-shaped substrate.The glass transition temperature of amorphism PET is 75 DEG C.By continuous band-shaped amorphism PET The laminated body that substrate and polyvinyl alcohol (PVA) layer are constituted makes in the following manner.It may be mentioned that the glass transition temperature of PVA Degree is 80 DEG C.
Prepare the amorphism PET base material of 200 μ m-thicks and makes the PVA powder of 1000 or more the degree of polymerization, 99% or more saponification degree It is dissolved in the PVA aqueous solution that concentration obtained from water is 4~5%.Then, PVA is coated in the amorphism PET base material of 200 μ m-thicks Aqueous solution obtains the stacking for the PVA layer that 7 μ m-thicks are formed in amorphism PET base material in 50~60 DEG C of at a temperature of drying Body.
The laminated body of PVA layer comprising 7 μ m-thicks is passed through into 2 sections of stretchings comprising stretching in aerial assisting tension and boric acid water Following processes of process manufacture the slim high function polarizing coatings of 3 μ m-thicks.It, will by the aerial assisting tension process of first stage The laminated body of PVA layer comprising 7 μ m-thicks is integrally stretched with amorphism PET base material, generates the stretching of the PVA layer comprising 5 μ m-thicks Laminated body.Specifically, the stretching laminated body be by by include 7 μ m-thicks PVA layer laminated body be placed in configure be set in Free end is carried out in stretching device in the baking oven of 130 DEG C of draft temperature environment and in a manner of making 1.8 times of stretching ratio Laminated body obtained from being uniaxially stretched.By the stretch processing, make to stretch the PVA layer variation contained in laminated body to be PVA molecule The PVA layer for 5 μ m-thicks being orientated.
Then, by dyeing process, generate adsorbed in the PVA layer for 5 μ m-thicks that PVA molecule is orientated iodine Chromatograph stack.Specifically, the coloring laminated body is by that will stretch laminated body at 30 DEG C of liquid temperature containing iodine and potassium iodide Impregnated in dyeing liquor the arbitrary time to constitute the monomer transmissivity of the PVA layer of high function polarizing coating ultimately generated for 40~ 44% to make the PVA layer contained in stretching laminated body adsorb the laminated body of iodine.In this process, dyeing liquor is using water as molten Agent, for iodine concentration in the range of 0.12~0.30 weight %, iodate potassium concn is in the range of 0.7~2.1 weight %.Iodine and iodine The concentration ratio for changing potassium is 1 to 7.It may be mentioned that needing potassium iodide when iodine is dissolved in water.More specifically, by that will stretch Laminated body impregnates 60 seconds in the dyeing liquor that iodine concentration is 0.30 weight %, iodate potassium concn is 2.1 weight %, generates in PVA The coloring laminated body of iodine has been adsorbed in the PVA layer for 5 μ m-thicks that molecule is orientated.
It then, further will coloring laminated body and amorphism PET base material by stretching process in the boric acid water of second stage It is integrally stretched, generates the optical film laminate of the PVA layer of the high function polarizing coating of composition comprising 3 μ m-thicks.Specifically, The optical film laminate is to contain boric acid and potassium iodide by that will colour laminated body and be placed in configure and be set in liquid temperature range 60 Freedom is carried out in stretching device in the processing unit of~85 DEG C of boric acid aqueous solution and in a manner of making 3.3 times of stretching ratio Laminated body obtained from end is uniaxially stretched.More specifically, the liquid temperature of boric acid aqueous solution is 65 DEG C.In addition, by boric acid content phase 4 parts by weight are set as 100 parts by weight of water, iodate potassium content is set as 5 parts by weight relative to 100 parts by weight of water.This work In sequence, the coloring laminated body for having adjusted iodine absorption number is impregnated 5~10 seconds in boric acid aqueous solution first.Then, by the coloring Laminated body directly passes through between the different multiple groups roller of stretching device, that is, peripheral speed in processing unit from configuration, with 30~90 seconds with Make 3.3 times of stretching ratio of mode carry out free end to be uniaxially stretched.By the stretch processing, makes to colour and contain in laminated body PVA layers of variation have carried out the PVA of 3 μ m-thicks of high order orientation for the iodine of absorption in one direction in the form of more iodide ion complex compounds Layer.The high function polarizing coating of the PVA layers of composition optical film laminate.
Although not being required process in the manufacture of optical film laminate, preferably optical film is laminated by cleaning process Body takes out from boric acid aqueous solution, to the boric acid adhered on the surface of the PVA layer for 3 μ m-thicks being formed in amorphism PET base material It is cleaned with potassium iodide aqueous solution.Then, the optical film laminate after cleaning is passed through into the back tender of the warm wind using 60 DEG C Sequence is dried.In addition, cleaning process is the process for eliminating the bad orders such as boric acid precipitation.
It equally, can also be by being bonded and/or transferring although not being required process in the manufacture of optical film laminate Process coating binder on the surface of the PVA layer for 3 μ m-thicks being formed in amorphism PET base material, and it is bonded 80 μ m-thicks Then three cellulose acetate membrane is removed amorphism PET base material, three acetic acid that the PVA layer of 3 μ m-thicks is transferred to 80 μ m-thicks are fine It ties up on plain film.
[other processes]
It can also include other processes other than above-mentioned operation in the manufacturing method of above-mentioned slim polarizing coating.As it His process, can enumerate such as insoluble process, cross-linking process step, drying (adjusting of moisture rate) process.Other processes can be with It is carried out in arbitrary opportune moment.
Typically, above-mentioned insoluble process can be carried out by the way that PVA resinoid layer to be impregnated into boric acid aqueous solution. By implementing insoluble processing, water resistance can be assigned to PVA resinoid layer.The concentration of the boric acid aqueous solution is relative to water 100 Parts by weight are preferably 1 parts by weight~4 parts by weight.The liquid temperature of insoluble bath (boric acid aqueous solution) is preferably 20 DEG C~50 DEG C.It is insoluble Chemical industry sequence carries out before stretching process preferably after laminated body production, in dyeing process or water.
Typically, above-mentioned cross-linking process step is carried out by the way that PVA resinoid layer to be impregnated into boric acid aqueous solution.Pass through reality Crosslinking Treatment is applied, water resistance can be assigned to PVA resinoid layer.The concentration of the boric acid aqueous solution is excellent relative to 100 parts by weight of water It is selected as 1 parts by weight~4 parts by weight.In addition, preferably further cooperating in the case where carrying out cross-linking process step after above-mentioned dyeing process Iodide.By cooperating iodide, it is able to suppress the dissolution of the iodine adsorbed in PVA resinoid layer.The use level of iodide is opposite In 100 parts by weight of water be preferably 1 parts by weight~5 parts by weight.The concrete example of iodide is as described above.Crosslinking bath (boric acid aqueous solution) Liquid temperature be preferably 20 DEG C~50 DEG C.Cross-linking process step preferably carries out before stretching process in above-mentioned second boric acid water.It is preferred real It applies in mode, successively stretching process in progress dyeing process, cross-linking process step and the second boric acid water.
Polarizing film used in the preparation method method of polarizing coating of the invention is that moisture rate is 11 weight % low moistures below The polarizing film of rate, due to being implemented process (1) to polarizing film, in process (2), even if surface and guide rollers contact in polarizing film In the case where being transported, transport property is also good.The moisture rate of polarizing film after drying within 6 hours can for 6 weight % with Under, it may further be 2 weight % or less.In addition, when moisture rate is too low, the problems such as rupture in transport there are polarizing film, Therefore preferably the moisture rate of polarizing film is 1 weight % or more.Particularly, in the case where above-mentioned slim polarizing film, the present invention exists It is effective that moisture rate, which is in 2 weight % situations below, is further suitable in the case where 1~1.5 weight %.
The moisture rate of polarizing film of the invention can be adjusted by any suitable method.Such as it can enumerate：By to inclined The method that the condition of drying process in the manufacturing process of vibration piece could be adjusted to control.
The moisture rate of polarizing film can be measured by the following method.That is, cutting out polarizing film for the big of 100 × 100mm It is small, measure the initial stage weight of the sample.Then, the sample is 2 hours dry at 120 DEG C, dry weight is measured, utilization is following Formula measures moisture rate.Moisture rate (weight %)={ (initial stage weight-dry weight)/initial stage weight } × 100.The measurement of weight point Carry out not be 3 times, use its average value.
As activation processing, sided corona treatment, corona treatment, aura processing, ozone treatment etc. may be exemplified.At corona Reason can for example be carried out in such a way that the corona treatment of springtime Motor Corporation is discharged in atmospheric air. Corona treatment for example can be by utilizing the plasma discharge machine of ponding chemical company in atmospheric air or nitrogen, argon Etc. the mode discharged in inactive gas atmospheres carry out.For aura processing, ozone treatment, well-established law also can use It carries out.Wherein, sided corona treatment or corona treatment are suitable in terms of cost of equipment, processing charges.
Above-mentioned activation processing is so that the surface roughness (Ra) on the surface of polarizing film is the mode of 0.6nm or more to implement. Above-mentioned surface roughness (Ra) is preferably 0.8nm or more, further preferred 1nm or more.By making above-mentioned surface roughness (Ra) For 0.6nm or more, even if the moisture rate in polarizing film is 11 weight % or less and makes the surface of polarizing film in process (2) In the case where being contacted with deflector roll, polarizing film can be also transported well.In addition, when above-mentioned surface roughness (Ra) is excessive, The aqueous variation of heatproof, therefore above-mentioned surface roughness (Ra) is preferably 10nm hereinafter, further preferably 5nm or less.
In the measurement of above-mentioned surface roughness (Ra), surface is indicated with arithmetic average roughness (average value of concave-convex surface) The parameter of roughness.Surface roughness (Ra) is using Veeco (ビ ー U) atomic force microscope (AFM) of corporation Nanoscope IV, value obtained from being measured with Tapping mode.Cantilever (カ Application チ レ バ ー) is for example visited using metering Needle (メ ト ロ ロ ジ ー プ ロ ー Block)：Tap300 (RTESP type).Measurement range is 1 μm of square.
As above-mentioned activation processing, set in a manner of making polarizing film reach above-mentioned surface roughness (Ra) by activation processing Determine treatment conditions.For example, discharge capacity is preferably 250~1000W/m in sided corona treatment2/ min, more preferable 250~800W/m2/ Min, further preferred 250~600W/m2/ min, further preferred 250~500W/m2/min.Activation processing amount (discharge capacity：W/ m2/ min) calculating formula=output power (W)/linear velocity (m/min)/electrode it is long (m).Between between electrode and sample (polarizing film) Gap is preferably 1mm~2mm.It is activated the preferred aluminium roller of electric Jie's roller or ceramic roller of (sided corona treatment).Be grounded the preferred Si roller of roller or Person's metallic roll.
In the manufacturing method of polarizing coating of the invention, at least one side of polarizing film is implemented to be activated in process (1), But in the case where making two sides and the guide rollers contact of polarizing film in process (2), preferably the two sides of polarizing film is implemented to be activated.
In addition, in the manufacturing method of polarizing coating of the invention, polarizing film in process (1) as activation processing object, As long as can be activated at least one side, as shown in Figure 1, for not as the polarizing film for being activated object Another side can be bonded transparent protective film by gluing oxidant layer.In addition, stating feelings of the slim polarizing film as polarizing film in use Under condition, in Fig. 1, it can replace one side in polarizing film P by gluing oxidant layer A1 and transparent protective film T1 be set, and use and resin The slim high function polarizing coating (polarizing film P) that substrate (amorphism ester based thermoplastic resin etc.) is integrally film-made.
<Process (2)>
In process (2), for implementing the polarizing film after the activation processing, while making the table of the polarizing film after the activation processing It is transported with guide rollers contact side in face.In process (2), transport the surface of polarizing film with guide rollers contact, but and deflector roll The surface of the polarizing film of contact in process (1) in a manner of reaching defined surface roughness (Ra) due to having been carried out at activation Reason, therefore transport property is good.In Fig. 1, for the single side protection that is activated that treated of the surface of polarizing film P polarizing coating F1 and Speech, while contacting the activation processing face of polarizing film P with deflector roll G1, G2, while being transported.
<Process (3)>
Then, by process (3), to the face that will form the gluing oxidant layer of the polarizing film transported by the deflector roll And/or the face adhesive coating that will form the gluing oxidant layer of transparent protective film.In Fig. 1, at application roll R2, single side is protected The surface of polarizing film P after the activation processing of the polarizing coating F1 of shield is by coating element D adhesive coating A2.
As long as adhesive used in being bonded of above-mentioned polarizing film and transparent protective film be optically it is transparent, do not have Water system, solvent system, the various forms for heating system, radical-curable, but water system adhesive or free radical can be used in especially limitation Curing type adhesive is suitable.In addition, transparent protective film T1 is bonded with polarizing film P in the polarizing coating F that the single side of Fig. 1 is protected Gluing oxidant layer A1 same adhesive also can be used.
It as water system adhesive, is not particularly limited, such as may be exemplified：Polyvinyl system, gelatin system, vinyl It is latex system, polyurethane series, isocyanates system, Polyester, epoxy etc..In such water system adhesive, may be used also as needed To cooperate the catalyst such as crosslinking agent, other additives, acid.As above-mentioned water system adhesive, it is preferable to use containing vinyl polymerization The adhesive etc. of object, as polyvinyl, preferably polyvinyl alcohol resin.In addition, can contain in polyvinyl alcohol resin There are the water-soluble cross-linkers such as boric acid, borax, glutaraldehyde, melamine, ethanedioic acid.Particularly, in the polymer using polyethenol series It is preferred from the viewpoint of cementability using the adhesive containing polyvinyl alcohol resin in the case that film is as polarizing film 's.In addition, more preferably using from the viewpoint of improving durability containing the polyvinyl alcohol resin with acetoacetyl Adhesive.
Above-mentioned polyvinyl alcohol resin is not particularly limited, but from the viewpoint of cementability, and preferred average degree of polymerization is 100~3000 or so, mean saponification degree is 85~100 moles of % or so.In addition, the concentration as adhesive aqueous solution, according to The thickness of target gluing oxidant layer is suitably determined, therefore is not particularly limited, but preferably 0.1~15 weight %, more preferably For 0.5~10 weight %.If the solution concentration is excessively high, excess stickiness is increased, therefore the bumps for being easy to generate striated are uneven, If solution concentration is too low, coating is deteriorated, and is easy to produce unevenness.
Polyvinyl alcohol resin can be enumerated：By polyvinyl alcohol obtained from saponifying polyvinyl acetate；Its derivative；And It is saponified with the copolymer of the monomer of the copolymerizable of vinyl acetate with having；By Polyvinyl acetal, carbamate Modified polyvinylalcohol made of change, etherificate, grafting, Phosphation etc..As above-mentioned monomer, can enumerate：Maleic acid (acid anhydride), richness Unsaturated carboxylic acids and its esters such as horse acid, crotonic acid, itaconic acid, (methyl) acrylic acid；The alpha-olefins such as ethylene, propylene；(methyl) Allyl sulphonic acid (sodium (ソ ー ダ)), sodium sulfonate (monoalkyl maleate), sodium disulfonate alkyl maleate, N- methylol third Acrylamide, acrylamide alkyl sulfonic acid alkali salt, n-vinyl pyrrolidone, n-vinyl pyrrolidone derivative etc..These are poly- Vinyl alcohol resin can be used alone, and also can be used together two or more.
Polyvinyl alcohol resin containing acetoacetyl, which can use well known method, makes polyvinyl alcohol resin and double Ketenes reacts to obtain.Such as it can enumerate：Polyvinyl alcohol resin is dispersed in acetic acid equal solvent in advance, addition is double wherein The method of ketenes；Polyvinyl alcohol resin is dissolved in dimethylformamide Huo dioxane equal solvent in advance, addition is double wherein The method etc. of ketenes.In addition it can enumerate, the method for contacting polyvinyl alcohol directly with diketene gas or liquid diketene.
As long as the acetoacetyl modified degree of the polyvinyl alcohol resin containing acetoacetyl is 0.1 mole of % or more, Then it is not particularly limited.If less than 0.1 mole %, the water resistance of gluing oxidant layer is insufficient, inappropriate.It is acetoacetyl modified Degree is preferably 0.1~40 mole of % or so, further preferred 1~20 mole of %, particularly preferred 2~7 moles of %.Acetoacetyl When modification degree is more than 40 moles of %, reduced with the reflecting point of crosslinking agent, the improvement effect of water resistance is small.Such acetoacetyl Modification degree can be by using nuclear magnetic resonance device (NMR：Nuclear Magnetic Resonance) it measures.
It as crosslinking agent, can be not particularly limited using crosslinking agent used in general adhesive, such as use It is preferable to use at least have 2 and polyvinyl alcohol resin in the case where the adhesive of above-mentioned polyvinyl alcohol resin With reactive functional group.Such as can enumerate, ethylenediamine, triethylenediamine, hexamethylene diamine etc. have alkylidene and 2 ammonia The alkylene diamine class of base；Toluene di-isocyanate(TDI), hydrogenated toluene diisocyanate, trimethylolpropane toluene diisocyanate add Close object, triphenylmethane triisocyanate, di-2-ethylhexylphosphine oxide (4- phenylmethane triisocyanate, isophorone diisocyanate and The isocyanates such as their ketoxime block object or phenol block object；Ethylene glycol diglycidyl base ether, polyethylene glycol diglycidyl are sweet Oleyl ether, glycerol two or triglycidyl group ether, 1,6- hexane diol diglycidyl ether, trimethylolpropane tris shrink are sweet The epoxies such as oleyl ether, diglycidylaniline, diglycidyl amine；The list aldehydes such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde；Second The twain-aldehyde compounds such as dialdehyde, malonaldehyde, amber dialdehyde, glutaraldehyde, maleic dialdehyde, o-phthalaldehyde；Methylolurea, methylol melamine, The amino-formaldehydes tree such as condensation product of alkylated methylol groups urea, alkylated methylol groups melamine, acetylguanamine, benzoguanamine and formaldehyde Rouge；And the salt and its oxide of the divalent metals such as sodium, potassium, magnesium, calcium, aluminium, iron, nickel or trivalent metal.Wherein, amino-formaldehyde Resin, particularly methylol compound with methylol are suitable.
About the use level of crosslinking agent, generally relative to 100 parts by weight of resin using 0.1~35 parts by weight or so, preferably Using 10~25 parts by weight, in the case where paying attention to the durability of adhesive, glue is formed instead of shortening from being prepared into for adhesive The time (up time (Ke Shi Time Inter) of adhesive layer), cooperate 30 parts by weight or more and 46 parts by weight or less, more preferable 32 weight It measures part or more and 40 parts by weight crosslinking agent below is also effective.
Alternatively, it is also possible to exemplify the gluing of electric wire curing type, ultraviolet hardening isoreactivity energy ray-curable Agent.Particularly preferably cured active energy ray curable can be carried out with the short time, further preferably can with low energy into The cured ultraviolet curing adhesive of row.
As ultraviolet curing adhesive, it is roughly divided into free radical polymerization curing type adhesive and cationic polymerization type glue Stick.In addition, free radical polymerization curing type adhesive can be used as the use of thermohardening type adhesive.
As the curability composition of free radical polymerization curing type adhesive, the chemical combination with (methyl) acryloyl group can be enumerated Object, the compound with vinyl.These curability compositions can be used simple function or two functions it is of the above any one.Separately Outside, these curability compositions can be used singly or in combination of two or more.As these curability compositions, example Such as, the compound with (methyl) acryloyl group is suitable.
As the compound with (methyl) acryloyl group, can specifically enumerate for example, (methyl) methyl acrylate, (first Base) 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) acrylic acid uncle Butyl ester, (methyl) acrylic acid n-pentyl ester, (methyl) t-amyl, (methyl) acrylic acid 3- pentyl ester, (methyl) acrylic acid 2, 2- dimethyl butyl ester, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid cetyl, (methyl) n-octyl, (methyl) (the first such as 2-EHA, (methyl) acrylic acid 4- methyl-2-propyl pentyl ester, (methyl) acrylic acid n-octadecane base ester Base) acrylic acid (carbon number 1-20) alkyl esters.
In addition, can enumerate as the compound with (methyl) acryloyl group for example, (methyl) acrylate ester (example Such as, (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester etc.), (methyl) acrylic acid aralkyl ester is (for example, (methyl) third Olefin(e) acid benzyl ester etc.), polycycle (methyl) acrylate is (for example, (methyl) acrylic acid 2- isobornyl thiocyanoacetate, (methyl) acrylic acid 2- drop Bornyl methyl esters, (methyl) acrylic acid 5- norbornene -2- base-methyl esters, (methyl) acrylic acid 3- methyl -2- norborny methyl esters Deng), hydroxyl (methyl) esters of acrylic acid (for example, (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) methacrylic acid 2,3- dihydroxypropyl methyl-butyl acrylate etc.), (methyl) esters of acrylic acid containing alkoxy or phenoxy group ((methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- methoxymethoxy Ethyl ester, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic ethyl carbitol, (methyl) phenoxyethyl acrylate Deng), (methyl) esters of acrylic acid (for example, (methyl) glycidyl acrylate etc.) containing epoxy group is halogen-containing (methyl) Esters of acrylic acid is (for example, (methyl) acrylic acid 2,2,2- trifluoro ethyl ester, (methyl) acrylic acid 2,2,2- trifluoroethyl ethyl ester, (first Base) acrylic acid tetrafluoro propyl ester, (methyl) acrylic acid hexafluoro propyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid 17 Fluorine last of the ten Heavenly stems ester etc.), (methyl) acrylic acid alkylaminoalkyl ester (for example, (methyl) acrylate etc.) etc..
In addition, can be enumerated, hydroxyethyl acryloyl as the compound other than the above with (methyl) acryloyl group Amine, N hydroxymethyl acrylamide, N- methoxy acrylamide (SP value 22.9), N- ethoxymethyl acrylamide, (first Base) amide-containings such as acrylamide monomer etc..In addition, nitrogen containing monomers such as acryloyl morpholine etc. can be enumerated.
In addition, the curability composition as above-mentioned free radical polymerization curing type adhesive, may be exemplified with multiple (first Base) polymeric double bonds such as acryloyl group, vinyl compound, which can also be used as crosslinking component and is mixed into gluing In agent ingredient.As the curability composition for becoming the crosslinking component, can enumerate for example, tripropylene glycol diacrylate, 1,9- Nonanediol diacrylate, Tricyclodecane Dimethanol diacrylate, cyclic trimethylolpropane dimethoxym ethane acrylate, bis- Evil Alkane omega-diol diacrylate, EO modified two glycerol tetraacrylates, 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 Company system), CD-536 (Sartomer Corporation) etc..In addition, can enumerate as needed, various epoxy (methyl) acrylate, carbamate (methyl) acrylic acid Ester, polyester (methyl) acrylate, various (methyl) acrylate monomers etc..
Free radical polymerization curing type adhesive contains above-mentioned curability composition, but in addition to the aforementioned ingredients, also according to cured Type adds radical polymerization initiator.In the case where using above-mentioned adhesive with electron beam curing type, above-mentioned adhesive In do not need containing radical polymerization initiator especially, but with ultraviolet hardening, thermohardening type use, Use radical polymerization initiator.The usage amount of radical polymerization initiator, relative to 100 parts by weight of curability composition, usually For 0.1~10 parts by weight or so, preferably 0.5~3 parts by weight.Alternatively, it is also possible to as needed in free radical polymerization curing type glue The photosensitizer for improving curing rate, sensitivity using electron ray of the representatives such as carbonyls is added in stick.It is photosensitive The usage amount of agent, relative to 100 parts by weight of curability composition, usually 0.001~10 parts by weight or so, preferably 0.01~3 Parts by weight.
As the curability composition of cation polymerization curing type adhesive, can enumerate with epoxy group, oxetanyl Compound.Compound with epoxy group does not limit especially then as long as intramolecular has the substance of at least two epoxy group System, can be used commonly known various curability epoxides.As preferred epoxide, example can be enumerated：Point The sub interior compound (hereinafter referred to as " aromatic system epoxide ") at least two epoxy group and at least one aromatic rings, Intramolecular has at least two epoxy group and wherein at least 1 forms between adjacent 2 carbon atom for constituting ester ring Compound (hereinafter referred to as " cycloaliphatic epoxy ") etc..
<Epoxide>
As aromatic system epoxide, as long as not interfering effect of the invention, it is not particularly limited, as example It can enumerate：The diglycidyl of the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F and brominated bisphenol A The bisphenol-type epoxy resins such as ether；The phenol aldehyde type epoxy resins such as phenol novolak type epoxy and cresol novolak type epoxy resin；With And biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, terephthalic acid (TPA) two contracting Water glyceryl ester, phthalic acid 2-glycidyl base ester, the epoxides of styrene-butadiene copolymer, styrene-isoamyl Epoxides, terminal carboxylic's polybutadiene enester and addition reaction of bisphenol A type epoxy resin of diene copolymers etc..
Here, epoxy resin refers to, there is average 2 or more epoxy groups in molecule and carried out by reaction cured Compound or polymer.According to customary in the art, in this specification, as long as intramolecular has 2 property cured above The substance of epoxy group, even then monomer is also sometimes referred to as epoxy resin.
As cycloaliphatic epoxy, as long as not interfering effect of the invention, it is not particularly limited, as an example, It can enumerate：Dicyclopentadiene, limonene dioxide, 4 vinyl cyclohexene dioxide, 3,4- epoxycyclohexyl Methyl, 3,4- epoxycyclohexane carboxylate and bis- (3,4- epoxycyclohexyl-methyl) adipate esters etc. have at least one epoxide ring The compound etc. of hexyl.
Other than above-mentioned, 1,6- hexane diol diglycidyl ether, trimethylolpropane tris glycidyl ether, Ji Wusi The fatty families epoxide such as alcohol four glycidyl group ether and polytetramethylene glycol diglycidyl ether；Hydrogenated bisphenol A The aromatic rings such as diglycidyl ether be hydrogenated after epoxide；It is contracted two ends of the polybutadiene of two terminal hydroxyls The double bond of compound, the inside epoxides of polybutadiene, styrene-butadiene copolymer after water glyceryl etherificate is by one Compound (for example, " the エ Port Off レ Application De " of Daicel chemical industry (strain) system) and Ethylene/Butylene copolymerization after dividing epoxidation The isoprene unit of the block copolymer of object and polyisoprene is by the compound after a part of epoxidation (for example, KRATON " L-207 " of corporation) etc. polymer systems epoxide etc. can also become the epoxide of (A) ingredient.
Wherein, aromatic system epoxide due to durability after polarization plates are made etc. it is excellent, and especially with it is inclined It shakes the excellent in adhesion of piece and protective film, therefore preferably.In addition, as the aromatic system epoxide, it can as preference It is preferred that enumerating：Glycidyl ether or the glycidyl esters of aromatic compound of aromatic compound etc..Aromatic compound The concrete example of the glycidyl ether of object can be enumerated：The diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F and The bisphenol-type epoxy resins such as the diglycidyl ether of brominated bisphenol A；Phenol novolak type epoxy and cresol novolak type epoxy The phenol aldehyde type epoxy resins such as resin；Biphenyl type epoxy resin；Hydroquinone diglycidyl ether；Resorcinol 2-glycidyl Base ether etc..In addition, the concrete example of the glycidyl esters of aromatic compound is preferably enumerated：Terephthalic acid (TPA) 2-glycidyl Base ester, phthalic acid 2-glycidyl base ester etc..
Wherein, the glycidyl ether of aromatic compound is due to adaptation, the system by polarizing film with protective film when Nian Jie At the durability after polarization plates it is further preferred that therefore particularly preferably.As especially excellent in the glycidyl ether of aromatic compound The compound of choosing can be enumerated：The diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F and phenol novolac type ring Oxygen resin.
Epoxide can be used alone, and can also be mixed with two or more.For example, 2 kinds can be used in mixed way Above aromatic system epoxide, or based on aromatic system epoxide and mix alicyclic epoxy conjunction Object.
<Oxetane compound>
As long as oxetane compound intramolecular has the substance of at least one oxetanyl, then without special Limitation, can be used the various compounds with oxetanyl.As oxetane compound (B), as preference It can enumerate：Intramolecular has the compound (hereinafter referred to as " simple function oxetanes ") and intramolecular of 1 oxetanyl Compound (hereinafter referred to as " multifunctional oxetanes ") with 2 or more oxetanyls.
As simple function oxetanes, can be enumerated as preference：3- ethyl -3- (2- Ethylhexoxymethyl) oxa- The simple function oxetanes containing alkoxyalkyl such as cyclobutane, 3- ethyl -3- phenoxymethyloxetane etc. is containing fragrance The simple function oxetanes of race's base, hydroxyls simple function oxetanes such as 3- ethyl -3- hydroxymethyl oxetane etc..
As multifunctional oxetanes, can enumerate for example, 3- ethyl -3- ((3- Ethyloxetane -3- base) methoxy Ylmethyl) oxetanes, Isosorbide-5-Nitrae-bis- ((3- Ethyloxetane -3- base) methoxy) benzene, bis- ((the 3- ethyls of Isosorbide-5-Nitrae - Oxetanes -3- base) methoxyl group) benzene, 1,3- bis- ((3- Ethyloxetane -3- base) methoxyl group) benzene, the bis- ((3- of 1,2- Ethyloxetane -3- base) methoxyl group) benzene, 4,4 '-bis- ((3- Ethyloxetane -3- base) methoxyl group) biphenyl, 2, 2 '-bis- ((3- Ethyloxetane -3- base) methoxyl group) biphenyl, 3,3 ', 5,5 '-tetramethyl -4,4 '-bis- ((3- ethyl oxa-s Cyclobutane -3- base) methoxyl group) biphenyl, 2,7- bis- ((3- Ethyloxetane -3- base) methoxyl group) naphthalenes, bis- (4- { (3- ethyls Oxetanes -3- base) methoxyl group } phenyl) methane, bis- (2- { (3- Ethyloxetane -3- base) methoxyl group } phenyl) first Bis- (the 3- chlorine of 4- { (3- Ethyloxetane -3- base) methoxyl group } phenyl propane, novolac type phenolic resin of alkane, 2,2- Etherification modified object, 3 (4), 8 (9)-bis- ((3- Ethyloxetane -3- base) methoxyl group of methyl -3- Ethyloxetane Methyl)-tricyclic [5.2.1.02,6] decane, 2,3- bis- ((3- Ethyloxetane -3- base) methoxy) norcamphanes, 1, 1,1- tri- ((3- Ethyloxetane -3- base) methoxy) propane, bis- ((the 3- ethyl oxa- ring fourths of 1- butoxy -2,2- Alkane -3- base) methoxy) butane, bis- ({ 2- (3- Ethyloxetane -3- base) methoxyl group } ethylsulfanyl) second of 1,2- Alkane, bis- ({ 4- (3- Ethyloxetane -3- base) methylsulfany } phenyl) thioethers, bis- ((the 3- Ethyloxetanes-of 1,6- 3- yl) methoxyl group) -2,2,3,3,4,4,5,5- octafluoro hexanes, 3- ((3- Ethyloxetane -3- base) methoxyl group) propyl three The hydrolytic condensate of Ethoxysilane, condensation product of four ((3- Ethyloxetane -3- base) methyl) esters of silicon acis etc..
About oxetane compound, from the viewpoint of when screening characteristics, polarization plates are made and the adaptation of protective film, Preferred molecular weight 500 below is at room temperature the compound of liquid.In addition, from the viewpoint of the excellent durability of polarization plates, As long as simple function oxetanes, then more preferable intramolecular has the substance or multifunctional oxetanes of aromatic rings.As The example of such particularly preferred oxetane compound, can enumerate：3- ethyl -3- phenoxymethyloxetane, 3- ethyl -3- ((3- Ethyloxetane -3- base) methoxy) oxetanes and bis- ((the 3- ethyl oxa- rings of Isosorbide-5-Nitrae - Butane -3- base) methoxy) benzene etc..
Oxetane compound can also be mixed with two or more in addition to it can be used alone.
<The ratio of epoxide and oxetane compound>
The use ratio of epoxide and oxetane compound is 90/10~10/90 with weight ratio meter.This ratio When example is excessively insufficient, it is unable to give full play out in short time cured effect.From before curing for low viscosity to which screening characteristics is excellent It is different, show sufficient adaptation and pliability after hardening from the perspective of, the suitable weight ratio of the two be 70/30~ 20/80 or so, further suitable weight ratio is 60/40~25/75 or so.
<Light cationic polymerization initiator>
In cation polymerization curing type adhesive, as curability composition, contain epoxide described above and oxygen Oxetane compounds, they are by the cured substance of cationic polymerization, therefore cooperation light cationic polymerization initiator. The light cationic polymerization initiator is generated by irradiation visible light, ultraviolet light, X-ray, electron ray isoreactivity energy-ray Cation kind or lewis acid cause epoxy group, the polymerization reaction of oxetanyl.
By cooperating light cationic polymerization initiator, the solidification being able to carry out under room temperature considers the heat resistance, swollen of polarizing film Necessity that is swollen or shrinking caused strain is reduced, and can be bonded well protective film.In addition, light cationic polymerization initiator Catalytic effect is played under the irradiation of active energy beam, therefore even if is mixed into epoxide and oxetanes chemical combination In object, storage stability, workability are also excellent.Cation kind, Louis are generated as the irradiation by active energy beam The compound of acid can be enumerated for example, the salt such as aromatic diazonium salt, aromatic iodonium salts, aromatic series sulfonium salt, iron-aromatic hydrocarbons complexing Object etc..
As aromatic diazonium salt, can enumerate for example, benzene diazonium hexafluoro antimonate, benzene diazonium hexafluoro phosphate, benzene diazonium Hexafluoro borate etc..
As aromatic iodonium salts, can enumerate for example, diphenyl iodine four (pentafluorophenyl group) borate, diphenyl iodine six Fluorophosphate, diphenyl iodine hexafluoro antimonate, two (4- nonyl phenyl) iodine hexafluorophosphates etc..
As aromatic series sulfonium salt, can enumerate for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphen Base sulfonium four (pentafluorophenyl group) borate, diphenyl (4- (thiophenyl) phenyl) sulfonium hexafluorophosphate, diphenyl (4- (thiophenyl) benzene Base) sulfonium hexafluoro antimonate, 4,4 '-bis- (diphenylsulfidyl) diphenylsulfides double hexafluorophosphates, 4,4 '-bis- (two (beta-hydroxy second Oxygroup) phenylsulfartyl) diphenylsulfide double hexafluoro antimonates, 4,4 '-bis- (two (beta-hydroxy ethyoxyl) phenylsulfartyls) diphenyl The double hexafluorophosphates of thioether, 7- (two (to methyl benzoyl) sulfenyls) -2-isopropylthioxanthone hexafluoro antimonate, (two is (right by 7- Methyl benzoyl) sulfenyl) -2-isopropylthioxanthone 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 Deng.
As iron-arene complex, can enumerate for example, dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, isopropyl Benzene-cyclopentadienyl group iron (II) hexafluorophosphate, dimethylbenzene-cyclopentadienyl group iron (II)-three (trimethyl fluoride sulfonyl) methanation Object etc..
These light cationic polymerization initiators can use individually a kind, can also be mixed with two or more.Wherein, Especially aromatic series sulfonium salt has Ultraviolet Light the wave-length coverage in 300nm or more, therefore is capable of providing solid The excellent solidfied material with good mechanical strength, adhesive strength of the property changed, therefore it is preferable to use.
Light cationic polymerization initiator can be readily available commercially available product, for example, trade name can be enumerated respectively："Kayarad PCI-220 ", " Kayarad PCI-620 " (more than, Japanese chemical drug (strain) system), " UVI-6992 " (Dow Chemical's system), " Adeka Optomer SP-150 ", " Adeka Optomer SP-170 " (more than, (strain) ADEKA system), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (more than, Japanese Cao reach (strain) System), " DPI-101 ", " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", “BBI-102”、“BBI-103”、“BBI-105”、“TPS-101”、“TPS-102”、“TPS-103”、“TPS-105”、“MDS- 103 ", " MDS-105 ", " DTS-102 ", " DTS-103 " (more than, greening learn (strain) system), " PI-2074 " (Rhodia company System), " Irgacure 250 ", " Irgacure PAG103 ", " Irgacure PAG108 ", " Irgacure PAG121 ", " Irgacure PAG203 " (more than, Ciba's system), " CPI-100P ", " CPI-101A ", " CPI-200K ", " CPI- 210S " (more than, San-Apro (strain) system) etc., in particular it is preferred to contain diphenyl (4- (thiophenyl) phenyl) sulfonium as it is positive from " UVI-6992 " of the Dow Chemical of subconstiuent, San-Apro (strain) system " CPI-100P ", " CPI-101A ", “CPI-200K”、“CPI-210S”。
About the mixing ratio of light cationic polymerization initiator, on the basis of cation polymerization curing type adhesive entirety, It is set as the range of 0.5~20 weight %.When its ratio is lower than 0.5 weight %, the solidification of adhesive is insufficient, and mechanical strength is glued Intensity decline is connect, on the other hand, when ratio is more than 20 weight %, solidfied material ionic species increase, therefore there is solidification A possibility that hygroscopicity of object increases, and endurance quality declines, therefore not preferably.
In addition, metallic compound filler can be contained in above-mentioned adhesive.By metallic compound filler, glue can control The mobility of adhesive layer, stabilizes film thickness, so as to obtain having good appearance, in face uniformly and there is no cementabilities The polarization plates of deviation.
In addition, the dry lamination method being bonded under solvent-free or low solvent state can be used as adhesive.Make It can be in base of the invention using known dry lamination adhesive and applying method for the dry lamination method This method is used on plinth.Have the effect of that the bumps for further decreasing striated are unequal as a result,.
As above-mentioned dry lamination adhesive, can enumerate bi-component curing type adhesive, two part solvent type adhesive, Single-component solvent-free type adhesive etc..As bi-component curing type adhesive, the resin of acrylic acid series etc. can be used, as double groups Divide solvent-based adhesive, Polyester, aromatic polyester system, aliphatic polyester, polyester/polyurethane system, polyethers/poly- ammonia can be used The tree of polyethers/polyurethane series etc. can be used as single-component solvent-free type adhesive (moisture-curable) in the resin of ester system etc. Rouge.
Above-mentioned adhesive can suitably contain additive as needed.Example as additive can be enumerated, silane coupled The coupling agents such as agent, titanium coupling agent, adhesion promoters representated by ethylene oxide make to add to what the wellability of transparent protective film improved Add agent, the representatives such as acryloyl-oxy based compound, hydrocarbon system (natural, synthetic resin) make adding for the raisings such as mechanical strength, processability Add agent, ultraviolet absorbing agent, age resister, dyestuff, processing aid, ion capturing agent, antioxidant, tackifier, filler (removes Other than metallic compound filler), plasticizer, levelling agent, frothing inhibitor, antistatic cuts, heat-resisting stabilizing agent, stabilizer against hydrolysis Equal stabilizers etc..
The application pattern of adhesive can suitably be selected according to the viscosity of adhesive, target thickness.As application pattern Example can be enumerated for example, inverting coating machine, gravure coater (directly, compensation, offset printing), reversed bar coater, roll coater, die coating Machine, scraping strip coating machine, rod coater.In addition, the modes such as impregnation method can be suitably used in coating.
In addition, above-mentioned adhesive is coated in when using water system adhesive, preferably with finally formed adhesive The thickness of layer reaches the mode of 30~300nm to carry out.The thickness of above-mentioned gluing oxidant layer is more preferably 60~250nm.Separately On the one hand, using curing type adhesive, 0.1~200 μm of side is preferably reached with the thickness of above-mentioned adhesive layer Formula carries out.More preferably 0.5~50 μm, further preferred 0.5~10 μm.
<Process (4)>
In process (4), above-mentioned polarizing film is bonded with transparent protective film by above-mentioned adhesive.Polarizing film with it is transparency protected The fitting of film can be carried out by using roll squeezer etc..In Fig. 1, by crimping roller R3, R4, single side is protected using adhesive A2 The polarizing film P of the polarizing coating F1 of shield is bonded with transparent protective film T2, obtains the polarizing coating F2 of two sides protection.
<Transparent protective film>
As the material for constituting above-mentioned transparent protective film, preferably clear, mechanical strength, thermal stability, moisture block property, The excellent material such as isotropism.Such as can enumerate, the Polyesters such as polyethylene terephthalate, polyethylene naphthalate are poly- Close object, the cellulose-based polymer such as diacetyl cellulose, triacetyl cellulose, the acrylic polymerics such as polymethyl methacrylate Object, the styrenics such as polystyrene, acrylonitritrile-styrene resin (AS resin), polycarbonate based polymer etc..Separately Outside, polyethylene, polypropylene, the polyolefin with ring system or norbornene structure, the polymerization of the polyolefins such as ethylene-propylene copolymer Object, vinyl chloride-based polymer, the amides based polymer such as nylon, aromatic polyamide, imide series polymer, sulfone based polymer, Polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol based polymer, inclined dichloro Ethylene-based polymer, vinyl butyral based polymer, aromatic ester based polymer, polyoxymethylene based polymer, epoxy polymerization Blend of object or above-mentioned polymer etc., which also can be used as, to be formed the example of the polymer of above-mentioned transparent protective film and enumerates.Transparent guarantor 1 kind of any of the above additive appropriate can be contained in cuticula.As additive, can enumerate for example, ultraviolet absorbing agent, antioxygen Agent, lubricant, plasticizer, release agent, coloring agent, fire retardant, nucleating agent, antistatic agent, pigment, colorant etc..Thoroughly In bright protective film the content of above-mentioned thermoplastic resin be preferably 50~100 mass %, more preferable 50~99 mass %, further it is excellent Select 60~98 mass %, particularly preferred 70~97 mass %.The content of above-mentioned thermoplastic resin is 50 matter in transparent protective film It measures in % situation below, thermoplastic resin is possible to be unable to fully show high transparency etc. inherently.
The thickness of above-mentioned transparent protective film can be appropriately determined, but generally from the workability such as intensity, operability, thin layer etc. Viewpoint is set out, and is 1~500 μm or so.Particularly preferred 1~300 μm, more preferable 5~200 μm.
In addition, in the case where transparent protective film is arranged in the two sides of polarizing film, it can be in its front and back sides use comprising identical Polymer material protective film, the transparent protective film comprising different polymer material etc. also can be used.For example, such as Fig. 1 It is shown, in the case where manufacturing two sides protection polarizing coating F2 to process (4) to single side protection polarizing coating F1 implementation process (1), Single side protects the transparent protective film T1 of polarizing coating F1 preferably from cellulose-based polymer (triacetyl cellulose etc.), with norborneol The polyolefin of alkene structure, polyester based polymer, suitably selects in polyolefin polymer (polypropylene etc.) acrylic acid series polymeric compounds It uses.At this point, for transparent protective film T2, it is also preferred that from cellulose-based polymer (triacetyl cellulose etc.), there is drop It is the polyolefin of bornylene structure, acrylic acid series polymeric compounds, polyester based polymer, appropriate in polyolefin polymer (polypropylene etc.) Selection uses.
After above-mentioned bonding process, gluing oxidant layer is formed.The formation of gluing oxidant layer is carried out according to the type of adhesive. In addition, gluing oxidant layer can be pre-formed in process (3) in the case where water system adhesive, be pasted in process (4) It closes.
In the case where adhesive is water system adhesive, solvent system adhesive, after above-mentioned bonding process, implement drying Process forms gluing oxidant layer.Using water system adhesive, in 20~80 DEG C of drying temperature or so, preferably 40~80 DEG C and process is dried under conditions of 1~10 minute or so, preferably 1~5 minute.
In the case where adhesive is radical-curable adhesive, after above-mentioned bonding process, implement curing process To form gluing oxidant layer.Radical-curable adhesive be electron beam curing type in the case where, by electron beam irradiation come Implement curing process, in the case where ultraviolet hardening, curing process is implemented by ultraviolet processing, in the feelings of thermohardening type Under condition, implement curing process by being heat-treated.These curing process can be according to cured type, the type of adhesive, glue The thickness of adhesive layer suitably sets each condition.
In addition, there is above-mentioned operation (1) to process (4) in the manufacturing method of polarizing coating of the invention, but also may include Other processes other than above-mentioned operation.
For example, when being bonded, can be arranged between transparent protective film and gluing oxidant layer in polarizing film with transparent protective film Adhesive layer.Adhesive layer can use for example with polyester backbone, polyether skeleton, polycarbonate backbone, polyurethane skeleton, have The various resins of machine silicon class, polyamide backbone, polyimide backbone, polyvinyl alcohol skeleton etc. are formed.These fluoropolymer resins can To be used singly or in combination of two or more kinds.In addition, other additives can be added in the formation of adhesive layer. Specifically, stabilizers such as tackifier, ultraviolet absorbing agent, antioxidant, heat-resisting stabilizing agent etc. can also be used.
Adhesive layer is usually set in advance on transparent protective film, by the adhesive layer side of the transparent protective film and polarizing film It is bonded using gluing oxidant layer.The formation of adhesive layer is by utilizing well-known technique to be coated with the shape of adhesive layer on transparent protective film It is carried out at material and being dried.The forming material of adhesive layer usually considers thickness, the fairness of coating etc. after drying And it is adjusted in the form of the solution for being diluted to debita spissitudo.Thickness after the drying of adhesive layer is preferably 0.01~5 μm, Further preferably 0.02~2 μm, further preferably 0.05~1 μm.It should be noted that adhesive layer can be set it is more Layer, but in this case, it is also preferred that the overall thickness of adhesive layer is above range.
In the case where manufacturing polarizing coating of the invention using tinuous production, when linear velocity depends on the solidification of adhesive Between, but preferably 1~500m/ minutes, more preferably 5~300m/ minutes, further preferably 10~100m/ minutes.Linear velocity When too small, undercapacity, or it is excessive to the damage of transparent protective film, it can not make and be resistant to the inclined of durability test etc. Vibrating diaphragm.When linear velocity is excessive, the solidification of adhesive is become inadequate, and is unable to get target cementability sometimes.
The one or both sides in polarizing film can be obtained as described above with the polarizing coating of transparent protective film, in above-mentioned transparent guarantor The function such as hard conating, anti-reflection layer, antiblocking layers, diffusion layer or antiglare layer can be set in not being bonded on the surface of polarizing film for cuticula Ergosphere.It should be noted that the functional layers such as above-mentioned hard conating, anti-reflection layer, antiblocking layers, diffusion layer, antiglare layer are in addition to can be with It is arranged with transparent protective film sheet, can also be in addition provided separately with transparent protective film.
Polarizing coating of the invention can use in the form of with the optical film of other optics layer stackups in actual use.It closes In the optical layer, be not particularly limited, can be used 1 layer or 2 layers or more for example sometimes in reflecting plate, half transmitting plate, phase Optical layer used in the formation of the liquid crystal display devices such as poor plate (including 1/2,1/4 equiwavelength's plate), vision compensation film etc..Especially It is preferred that being further laminated with the reflective polarizing film or half transmitting of reflecting plate or Transflective plate on polarizing coating of the invention It is type polarizing coating, the elliptical polarization film that phase plate is further laminated on polarizing coating or circular polarization film, further in polarizing coating It is laminated with the wide viewing angle polarizing coating of vision compensation film or is further laminated with the polarizing coating of brightness enhancement film on polarizing coating.
The optical film that above-mentioned optical layer is laminated on polarizing coating can also be by the manufacture in liquid crystal display device etc. The mode that is successively individually laminated in journey is formed, but stacking in advance and stability of the optical film with quality, assembling is made Operation etc. it is excellent and liquid crystal display device can be improved etc. manufacturing process the advantages of.It is appropriate that adhesive layer etc. can be used in stacking Adhesion means.Above-mentioned polarizing coating, other optical films bonding when, their optic axis can be according to target phase difference characteristic Deng and form arrangement angles appropriate.
In polarizing coating above-mentioned, it is laminated on the optical film of at least 1 layer polarizing coating also to can be set and is used for and liquid crystal cells Deng the adhesive layer of other components bonding.The adhesive for forming adhesive layer is not particularly limited, and suitably use can be selected with for example The polymer of acrylic acid series polymeric compounds, silicone-based polymers, polyester, polyurethane, polyamide, polyethers, fluorine-containing or rubber etc. Adhesive as basic polymer.Especially it is possible to that it is preferable to use the optical transparences as acrylic adhesive is excellent, Show the adhesion characteristic of appropriate wetability, coherency and cementability and adhesive that weatherability and heat resistance etc. are excellent.
Adhesive layer can also be used as the overlapping layer of the different layer such as composition or type and the list of polarizing coating, optical film be arranged in Face or two sides.In addition, in the case of being arranged at two sides, can also on polarizing coating, the surface of optical film, the back side formation group At, the different adhesive layer such as type, thickness.The thickness of adhesive layer can be according to using purpose, bonding force etc. suitably to determine, usually It is 1~500 μm, preferably 1~200 μm, particularly preferably 1~100 μm.
For the exposed surface of adhesive layer, during until for practical, the temporarily adhesion such as its pollution in order to prevent Partition and protected.Thereby, it is possible to contact under common processing status with adhesive layer.As partition, above-mentioned thickness item is removed Other than part, can be used for example by plastic foil, sheet rubber, paper, cloth, non-woven fabrics, mesh, foamed sheet, metal foil and they The sheet-like article appropriate such as layered product etc. it is appropriate with organic silicon, chain alkyl class, fluorine-containing type, molybdenum sulfide etc. as needed Remover has carried out the partition etc. of coating process.
Polarizing coating or optical film of the invention can be used preferably in formation of the various devices such as liquid crystal display device etc.. The formation of liquid crystal display device can be carried out according to previous mode.That is, liquid crystal display device is generally by by liquid crystal cells and partially Driving circuit etc. is arranged after being suitably assembled to be formed in the component parts such as vibrating diaphragm or optical film and lighting system as needed, In the present invention, other than using polarizing coating or optical film of the invention, be not particularly limited, can according to existing way into Row.For liquid crystal cells, the arbitrary type such as TN type, STN type, π type can be used.
The unilateral side or two sides that liquid crystal cells can be formed in are configured with the liquid crystal display device of polarizing coating or optical film, use The liquid crystal display devices appropriate such as the display device of backlight, reflecting plate as lighting system.In this case, of the invention inclined Vibrating diaphragm or optical film can be set in the unilateral side or two sides of liquid crystal cells.When polarizing coating or optical film is arranged in two sides, they can It can also be different with identical.In addition, when forming liquid crystal display device, one or two layers or more can be configured in position The component appropriate such as diffuser plate, antiglare layer, antireflection film, protection board, prism array, lens array, light diffusing sheet, backlight.
Embodiment
The present invention is specifically described by the following examples, but the present invention is not limited to the examples.In addition, each example In part and % be weight basis.
Production protection polarizing coating.
<Piece protects the production of polarizing coating (1)>
In order to make slim polarizing coating, firstly, by the laminated body for the PVA layer for being formed with 9 μ m-thicks in amorphism PET base material It is generated by the aerial assisting tension that draft temperature is 130 DEG C and stretches laminated body, then, laminated body will stretched and generated by dyeing Laminated body is coloured, will further colour in the boric acid water that laminated body is 65 degree by draft temperature and stretch so that total stretching ratio It is integrally stretched for 5.94 times of modes and amorphism PET base material and dries 4 minutes and generated comprising 4 μ m-thicks at 50 DEG C PVA layers of optical film laminate.2 sections for can making in this way stretch and the PVA layer that is formed in amorphism PET base material PVA molecule carries out high order orientation, carries out height in one direction in the form of more iodide ion complex compounds the iodine that dyeing is adsorbed Secondary orientation and generate and constitute high function polarizing coating, the optical film laminate comprising 4 μm of thickness of PVA layers.Then, in the optical film The surface of the polarizing coating of laminated body applies polyethenol series adhesive, while the triacetyl for being bonded 40 μ m-thicks after saponification process is fine Plain film (transparent protective film) is tieed up, amorphism PET base material is then removed.Gains are known as slim protection polarizing coating (1).Piece is protected The moisture rate for protecting the polarizing coating (polarizing film) in polarizing coating (1) is 1.8%.
<Piece protects the production of polarizing coating (2)>
In speed than between different rollers, by 80 μm of thickness of polyvinyl alcohol film in 30 DEG C, the iodine solution of 0.3% concentration 1 minute side of Edge Coloring is stretched to 3 times.Then, 60 DEG C, the boric acid comprising 4% concentration, 10% concentration potassium iodide aqueous solution It is middle while impregnate 0.5 minute while be stretched to total stretching ratio be 6 times.Then, the water of the potassium iodide at 30 DEG C, comprising 1.5% concentration Impregnated 10 seconds in solution and after cleaning, it is 4 minutes dry at 50 DEG C, obtain 20 μm of thickness of polarizing film.Utilize polyethenol series glue Stick, 40 μm of thickness of the tri acetyl cellulose membrane (transparent protective film) after the two sides of the polarizing film is bonded saponification process, system At polarizing coating.Hereinafter, gains are known as piece protection polarizing coating (2).Piece protects the polarizing coating (polarizing film) in polarizing coating (2) Moisture rate is 11%.
<Transparent protective film>
After implementing sided corona treatment using the norbornene mesentery (Zeonor film, Nippon Zeon Co., Ltd.'s system) to 60 μm of thickness Film.
(preparation of active energy ray curable adhesive)
Following each ingredients are mixed with the ratio of 50 parts of HEAA, 50 parts of ACMO, 8193 parts of IRGACURE, 50 DEG C stirring 1 hour, obtain active energy ray curable adhesive.
HEAA (hydroxyethyl acrylamide), emerging people's corporation
ACMO (acryloyl morpholine), emerging people's corporation
IRGACURE 819 (bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, Japanese Ciba's system
Embodiment 1
(process 1)
So that the transparent protective film side of piece protection polarizing coating (1) is the mode for the treatment of tube side, in the way of Fig. 1, transport Piece protects polarizing coating (1).About activation processing, using corona irradiating machine (springtime Motor Corporation's system, CT-0212), with discharge capacity 250W/m2The condition of/min carries out sided corona treatment to the one side of polarizing film.The surface on the surface of the polarizing film after activation processing is thick Rugosity (Ra) is 0.62nm.
(process 2)
Then, for piece protection polarizing coating (1) that is activated that treated of the surface of polarizing film, so that polarizing film side is deflector roll The mode of side transports piece protection polarizing coating (1) in the way of Fig. 1.
(process 3)
Then, using micro- gravure coater, in the unilateral above-mentioned adhesive of coating of the polarization of sheet above protection polarizing coating (1) (active energy ray curable adhesive).
(process 4)
Then, after applying above-mentioned adhesive, by above-mentioned adhesive, above-mentioned transparent protective film is bonded using roller machine.From patch The transparent protective film side of conjunction irradiates ultraviolet light, obtains the polarizing coating for having transparent protective film on two sides.It is with line speed The condition of 20m/min is bonded.
Embodiment 2~3, comparative example 1~4
According to the type of piece protection polarizing coating in change embodiment 1 shown in table 1, to the Corona discharge Treatment amount of polarizing film, Make polarizing coating similarly to Example 1 in addition to this.In addition, the moisture rate of piece protection polarizing coating is controlled by drying temperature System.
[evaluation]
Following evaluations are carried out to polarizing coating obtained in embodiment and comparative example.The results are shown in Table 1.
<Transport property>
According to the transport in following benchmark evaluation processes (2).
○：It is all good, do not generated in transport fracture, scar etc..
×：Excessively high with the chucking power of roller, it is bad to generate the fractureing of film, scar, lamination,
Table 1
Symbol description
P polarizing film
T1, T2 transparent protective film
A1, A2 adhesive
F1 single side protects polarizing coating
Protect polarizing coating in the two sides F2

Claims (5)

1. a kind of manufacturing method of polarizing coating, which is characterized in that be provided with for at least one side in polarizing film by gluing oxidant layer The manufacturing method of the polarizing coating of transparent protective film comprising：
Thus process (1) is made partially by implementing to be activated at least one side that moisture rate is 11 weight % polarizing films below Shake piece surface surface roughness, that is, Ra be 0.6nm or more and 5nm hereinafter,
Process (2), for implementing the polarizing film after the activation processing, while making the surface of the polarizing film after the activation processing and leading Roller contact edge is transported,
Process (3), to the face that will form the gluing oxidant layer of the polarizing film transported by the deflector roll and/or transparent protective film The face adhesive coating that will form the gluing oxidant layer,
Polarizing film is bonded with transparent protective film by the adhesive by process (4).
2. the manufacturing method of polarizing coating as described in claim 1, which is characterized in that
The polarizing film with a thickness of 10 μm or less.
3. the manufacturing method of polarizing coating as claimed in claim 1 or 2, which is characterized in that
The polarizing film is the continuous band-shaped polarizing coating comprising polyvinyl alcohol resin after being orientated dichroic substance, and is led to It crosses to stretch laminated body using 2 sections of stretching process including stretching in aerial assisting tension and boric acid water and be obtained,
The laminated body is the laminated body comprising the polyvinyl alcohol resin layer after film on thermoplastic resin substrate.
4. the manufacturing method of polarizing coating as claimed in claim 1 or 2, which is characterized in that
Described be activated is sided corona treatment or corona treatment.
5. the manufacturing method of polarizing coating as claimed in claim 1 or 2, which is characterized in that
Described be activated is sided corona treatment,
Discharge capacity in sided corona treatment is 250W/m2/ min~1000W/m2/min。
CN201380064757.0A 2012-12-13 2013-11-20 The manufacturing method of polarizing coating Active CN104854490B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012-272606 2012-12-13
JP2012272606A JP6066707B2 (en) 2012-12-13 2012-12-13 Manufacturing method of polarizing film
PCT/JP2013/081289 WO2014091894A1 (en) 2012-12-13 2013-11-20 Polarizing film production method

Publications (2)

Publication Number Publication Date
CN104854490A CN104854490A (en) 2015-08-19
CN104854490B true CN104854490B (en) 2018-11-30

Family

ID=50934189

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380064757.0A Active CN104854490B (en) 2012-12-13 2013-11-20 The manufacturing method of polarizing coating

Country Status (5)

Country Link
JP (1) JP6066707B2 (en)
KR (1) KR101985994B1 (en)
CN (1) CN104854490B (en)
TW (1) TWI598644B (en)
WO (1) WO2014091894A1 (en)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016052538A1 (en) * 2014-09-30 2016-04-07 日東電工株式会社 Method for producing polarizing film
CN107076908B (en) * 2014-09-30 2020-09-29 日东电工株式会社 Single-side protective polarizing film, polarizing film with adhesive layer, image display device, and continuous production method therefor
JP6931518B2 (en) * 2015-09-28 2021-09-08 日東電工株式会社 Single-sided protective polarizing film, polarizing film with adhesive layer, image display device and its continuous manufacturing method
JP6077620B2 (en) 2014-09-30 2017-02-08 日東電工株式会社 Single protective polarizing film, polarizing film with pressure-sensitive adhesive layer, image display device, and continuous production method thereof
JP6018276B2 (en) * 2015-02-13 2016-11-02 日東電工株式会社 Polarizing film, polarizing film with pressure-sensitive adhesive layer, and image display device
WO2016052549A1 (en) * 2014-09-30 2016-04-07 日東電工株式会社 One-side-protected polarizing film, adhesive-layer-equipped polarizing film, image display device, and method for continuously producing same
WO2016052540A1 (en) * 2014-09-30 2016-04-07 日東電工株式会社 Polarizing film, adhesive-layer-equipped polarizing film, and image display device
JP6077619B2 (en) 2014-09-30 2017-02-08 日東電工株式会社 Single protective polarizing film, polarizing film with pressure-sensitive adhesive layer, image display device, and continuous production method thereof
KR101883795B1 (en) * 2014-09-30 2018-08-01 닛토덴코 가부시키가이샤 Method for producing polarizing film
CN106796318B (en) * 2014-09-30 2018-09-28 日东电工株式会社 Polarizing coating, polarizing coating and image display device with adhesive phase
JP6078132B1 (en) * 2015-08-27 2017-02-08 日東電工株式会社 Manufacturing method of polarizing film
CN107407761B (en) * 2015-03-03 2021-01-05 住友化学株式会社 Method for producing polarizing film with protective film
TWI618953B (en) * 2015-05-20 2018-03-21 住華科技股份有限公司 Corona method
JP2017003906A (en) 2015-06-15 2017-01-05 日東電工株式会社 Polarization film with adhesive layer on both sides, and image formation apparatus
KR20170052991A (en) * 2015-11-05 2017-05-15 스미또모 가가꾸 가부시키가이샤 Polarizer and method of preparing the same
JP6359003B2 (en) * 2015-12-18 2018-07-18 住友化学株式会社 Polarizing film manufacturing apparatus and manufacturing method, and polarizing film
JP2017173793A (en) * 2016-03-22 2017-09-28 住友化学株式会社 Polarizer, polarization film, and method for producing polarizer
JP6737609B2 (en) * 2016-03-22 2020-08-12 日東電工株式会社 Method for producing one-sided protective polarizing film with adhesive layer
KR102455461B1 (en) * 2016-06-14 2022-10-19 닛토덴코 가부시키가이샤 Polarizing film with double-sided adhesive layer and image display device
JP6306675B1 (en) * 2016-11-28 2018-04-04 住友化学株式会社 Method for producing polarizing laminated film with protective film and method for producing polarizing plate
JP2017076141A (en) * 2016-12-20 2017-04-20 日東電工株式会社 Method for manufacturing polarizing film
JP6566993B2 (en) * 2017-06-02 2019-08-28 日東電工株式会社 Polarizing film and image display device
WO2018230429A1 (en) * 2017-06-13 2018-12-20 日東電工株式会社 Laminate, method for producing laminate, polarizing plate and method for producing polarizing plate
CN107652923A (en) * 2017-11-16 2018-02-02 山西亮龙涂料有限公司 One kind is without aldehyde building adhesive and preparation method thereof
JP7149975B2 (en) * 2020-02-13 2022-10-07 日東電工株式会社 Polarizing film with double-sided adhesive layer and image display device
JP7090197B2 (en) * 2020-08-07 2022-06-23 住友化学株式会社 Method for manufacturing polarizing film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004020672A (en) * 2002-06-13 2004-01-22 Nitto Denko Corp Polarizing plate and its manufacturing method
CN101056918A (en) * 2004-11-02 2007-10-17 日本合成化学工业株式会社 Polyvinyl alcohol film and method for producing the same
JP2009008860A (en) * 2007-06-27 2009-01-15 Nitto Denko Corp Method for manufacturing polarizing plate, polarizing plate, optical film and image display device
WO2011145552A1 (en) * 2010-05-18 2011-11-24 日東電工株式会社 Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive optical film, and image display device

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07124969A (en) * 1993-11-05 1995-05-16 Fujimori Kogyo Kk Manufacture of antiglare optical sheet
JP4390247B2 (en) * 2003-04-25 2009-12-24 富士フイルム株式会社 Solution casting method
CN1307252C (en) * 2003-12-29 2007-03-28 日本合成化学工业株式会社 Process for preparing polyvinyl alcohol thin film and polarization thin film used thereby
JP4483329B2 (en) * 2004-02-16 2010-06-16 住友化学株式会社 Manufacturing method of polarizing film
JP2009237047A (en) * 2008-03-26 2009-10-15 Fujifilm Corp Polarizing plate and liquid crystal display
JP2011519750A (en) * 2008-04-03 2011-07-14 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング Continuous lamination of polymethyl methacrylate (PMMA) films in the manufacture of Fresnel lenses
JP5149916B2 (en) * 2010-01-20 2013-02-20 住友化学株式会社 Optical matte film
JP5130413B2 (en) * 2010-03-08 2013-01-30 積水化学工業株式会社 Surface treatment equipment
KR101255106B1 (en) * 2011-01-27 2013-04-19 에이피시스템 주식회사 System for treating web
JP2012173544A (en) * 2011-02-22 2012-09-10 Nitto Denko Corp Method for manufacturing polarizer
JP5451672B2 (en) * 2011-03-25 2014-03-26 富士フイルム株式会社 Method for producing light reflective film
CN202448440U (en) * 2012-01-17 2012-09-26 浙江港龙新材料有限公司 Film-coating type laminator
JP2013254153A (en) * 2012-06-08 2013-12-19 Nitto Denko Corp Activation treatment method and manufacturing method of optical film, optical film, and image display device
CN102806172A (en) * 2012-07-16 2012-12-05 苏州奥美材料科技有限公司 Device and method for producing online surface anti-scratching polycarbonate film
JP5584259B2 (en) * 2012-08-03 2014-09-03 住友化学株式会社 Double-sided laminated film, double-sided polarizing laminated film, double-sided laminated film and single-sided laminated film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004020672A (en) * 2002-06-13 2004-01-22 Nitto Denko Corp Polarizing plate and its manufacturing method
CN101056918A (en) * 2004-11-02 2007-10-17 日本合成化学工业株式会社 Polyvinyl alcohol film and method for producing the same
JP2009008860A (en) * 2007-06-27 2009-01-15 Nitto Denko Corp Method for manufacturing polarizing plate, polarizing plate, optical film and image display device
WO2011145552A1 (en) * 2010-05-18 2011-11-24 日東電工株式会社 Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, pressure-sensitive adhesive optical film, and image display device

Also Published As

Publication number Publication date
CN104854490A (en) 2015-08-19
KR101985994B1 (en) 2019-06-04
JP2014119501A (en) 2014-06-30
JP6066707B2 (en) 2017-01-25
TWI598644B (en) 2017-09-11
WO2014091894A1 (en) 2014-06-19
TW201428359A (en) 2014-07-16
KR20150096382A (en) 2015-08-24

Similar Documents

Publication Publication Date Title
CN104854490B (en) The manufacturing method of polarizing coating
CN104745104B (en) Photocurable adhesive agent composition, polarizer and its manufacturing method, optical component and liquid crystal display device
JP6164609B2 (en) Photocurable adhesive composition, polarizing plate and method for producing the same, optical member and liquid crystal display device
CN102533135B (en) Photocurable adhesive composition, polaroid and manufacture method thereof, optics and liquid crystal indicator
CN103497691B (en) Photo-cured adhesive composition, polarizing plate and producing method for the same, optical member and liquid crystal display device
JP6223349B2 (en) Photocurable adhesive composition, polarizing plate and method for producing the same, optical member and liquid crystal display device
CN102344763B (en) Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device
JP5855947B2 (en) Photocurable adhesive, polarizing plate and laminated optical member using the same
TWI592457B (en) Active energy ray-curable adhesive composition, polarizing adhesive film, method of manufacturing the same, optical film and image display device (1)
JP5267919B2 (en) Polarizing plate, optical member, and liquid crystal display device
WO2009099049A1 (en) Polarizing plate, optical member, and liquid crystal display device
CN105807357A (en) Manufacturing method of polarizing plate
TWI593771B (en) Active energy ray-curable adhesive composition, polarizing adhesive film, method of manufacturing the same, optical film and image display device (2)
CN108351459A (en) Polarization plates and IPS mode LCDs
JP2013160775A (en) Polarizer and optical member
CN109591431A (en) Manufacturing method, optical film and the image display device of optical film
CN104076427B (en) Manufacturing method, polarization plates, optical film and the image display device of polarization plates
KR20200012883A (en) Polarizing plate with pressure-sensitive adhesive layer
JP5596207B2 (en) Photocurable adhesive composition, polarizing plate and method for producing the same, optical member and liquid crystal display device
CN104285168B (en) Polarization plates
TWI710613B (en) Adhesive, bonded object and bonded object manufacturing method
KR101813756B1 (en) Adhesive for polarizing plate, and display device using the same
CN105301676A (en) Polarizing sheet and liquid crystal display device
TW201936384A (en) Polarizing film, method for manufacturing same, optical film, and image display device

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant