CN105738998A - Polarizing film with coating layer, polarizing film with adhesive layer and image display device - Google Patents

Polarizing film with coating layer, polarizing film with adhesive layer and image display device Download PDF

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Publication number
CN105738998A
CN105738998A CN201510977156.XA CN201510977156A CN105738998A CN 105738998 A CN105738998 A CN 105738998A CN 201510977156 A CN201510977156 A CN 201510977156A CN 105738998 A CN105738998 A CN 105738998A
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coating
adhesive phase
coating layer
layer
polarizing coating
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CN105738998B (en
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藤田昌邦
外山雄祐
森本有
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Nitto Denko Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G02B1/116—Multilayers including electrically conducting layers
    • 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
    • G02B5/3058—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state comprising electrically conductive elements, e.g. wire grids, conductive particles

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  • Chemical & Material Sciences (AREA)
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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Liquid Crystal (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

The invention relates to a polarizing film with a coating layer, a polarizing film with an adhesive layer and an image display device. The invention aims to provide a polarizing film with a coating layer. According to the technical scheme of the polarizing film with the coating layer, even when the polarizing film is laminated on a transparent conductive layer via an adhesive layer, the deterioration of the transparent conductive layer is inhibited. Meanwhile, the surface resistance value of the transparent conductive layer is prevented from rising. Moreover, even when the adhesive layer is formed, the polarizing film is still excellent in adhesion property. The polarizing film with the coating layer successively comprises a transparent protective film, an iodine-based polarizer containing iodine and/or iodide ions, and a coating layer. The invention is characterized in that the iodine-based polarizer and/or the coating layer contains a phosphorus compound.

Description

Polarizing coating with coating layer, the polarizing coating with adhesive phase and image display device
Technical field
The present invention relates to the polarizing coating with coating layer successively with transparent protective film, iodine system polaroid and coating layer and there is the polarizing coating with adhesive phase of this polarizing coating with coating layer and adhesive phase.Moreover, it relates to have the image display devices such as the liquid crystal indicator (LCD) of the above-mentioned polarizing coating with adhesive phase, organic EL display.
Background technology
In recent years, the nesa coating such as tin indium oxide (ITO) thin film is widely used in a variety of applications where.The side contrary with the liquid crystal layer contact side of transparency carrier constituting liquid crystal cells of the such as known liquid crystal indicator employing liquid crystal cells that above-mentioned nesa coating is formed at transverse electric field effect (IPS) mode etc., as antistatic backing.Additionally, transparent resin film is formed with the transparent and electrically conductive film electrode base board for touch panel of above-mentioned nesa coating, for instance the input equipment liquid crystal indicator being used in mobile phone or portable music player etc. or image display device and the combination of this touch panel used extensively is popularized gradually.
The input equipment used as touch panel is combined with image display device, in the past being arranged on liquid crystal indicator by the transparent and electrically conductive film being formed with transparency conducting layer on the transparent base comprising glass plate or transparent resin film the Out-Cell type of (side more top than the observation side polarizing coating of liquid crystal indicator) is widely used, but in recent years, known have the On-Cell type being formed in the top glass substrate of liquid crystal cells by the electrode comprising nesa coating, by various compositions such as the In-Cell types of electrode assembling to the form within liquid crystal cells that comprises nesa coating.It addition, it is also known that by as touch sensing as the ITO layer of the antistatic backing of image display device and to be patterned and to realize touch panel function.
Fit in such ITO layer the optical components such as polarizing coating sometimes through adhesive phase, but when known binders has carboxyl, ITO layer can be corroded and make electric conductivity reduce, as the binding agent suppressing this electric conductivity to reduce, it is known that the binding agent (referring for example to patent documentation 1) containing phosphorous antioxidant.
Prior art literature
Patent documentation
Patent documentation 1: No. 5540383 description of patent
Summary of the invention
The problem that invention to solve
For employing the liquid crystal indicator of above-mentioned nesa coating, image display device etc., it is strongly required lighting, slimming in recent years, slimming, lighting are also required that for the polarizing coating used in this liquid crystal indicator etc..As the slimming of polarizing coating, lightening method, for instance known have the manufacture method etc. making the method for one side protection polarizing coating only arranging transparent protective film in the one side of polaroid or the slim polarizing coating making the thickness of polaroid self thinning.
Such as when using nesa coating as antistatic backing purposes, generally on the liquid crystal cells have this antistatic backing, laminated belt has the polarizing coating of adhesive phase, is made the antistatic backing and the polarizing coating laminating that comprise nesa coating by adhesive phase.Additionally, when use nesa coating is as the electrode applications of touch panel, composition according to touch panel, on above-mentioned electrode nesa coating, laminated belt has the polarizing coating of adhesive phase sometimes, is made the antistatic backing and the polarizing coating laminating that comprise nesa coating by adhesive phase.
When polarizing coating is iodine system polarizing coating, if making transparency conducting layer and this iodine system polarizing coating laminating as described above, carry out humidification long duration test (common long duration test), then the resistance value of transparency conducting layer can rise sometimes.The reason that known above-mentioned resistance value rises is in that, iodine contained in polaroid oozes out into adhesive phase, and this iodine arrives transparency conducting layer and corrodes transparency conducting layer.
Slim iodine system polaroid especially with regard to thickness less than 10 μm, known must improve the iodine concentration in polaroid to have the polarization characteristic same with conventional polaroid, when the polarizing coating comprising the higher polaroid of above-mentioned iodine concentration is fitted with transparency conducting layer, it is easy to produce the corrosion caused by iodine of transparency conducting layer.Additionally, it is known that when using the iodine system polarizing coating of one side protection, transparency conducting layer is fitted on iodine system polaroid either directly through adhesive phase, thus also easily produces the corrosion of transparency conducting layer.
It addition, the adhesive phase formed by the binding agent containing phosphorous antioxidant recorded in patent documentation 1 cannot substantially ensure that the adaptation to polarizing coating.
Therefore, it is an object of the invention to provide a kind of polarizing coating with coating layer, even if the described polarizing coating with coating layer is when by adhesive phase stacking over transparent conductive layer, it also is able to suppress the deterioration of transparency conducting layer, the sheet resistance value suppressing transparency conducting layer rises, even and if when defining adhesive phase, the adaptation of polarizing coating is also excellent.It addition, the present invention also aims to provide a kind of polarizing coating with adhesive phase, it is provided with adhesive phase on the above-mentioned polarizing coating with coating layer.It addition, the present invention also aims to provide a kind of image display device, its adhesive phase comprising the above-mentioned polarizing coating with adhesive phase and there is the liquid crystal panel of transparency conducting layer.
The method solving problem
The present inventor etc. conduct in-depth research, found that can solve above-mentioned problem by the following polarizing coating with coating layer, the polarizing coating etc. with adhesive phase, thus completing the present invention.
That is, the present invention relates to a kind of polarizing coating with coating layer, there is transparent protective film, iodine system polaroid containing iodine and/or iodide ion and coating layer successively, it is characterised in that
Above-mentioned iodine system polaroid and/or above-mentioned coating layer contain phosphorus series compound.
Above-mentioned phosphorus series compound preferably comprises the phosphoric acid based compound of more than a kind in the polymer of the compound shown in the compound shown in following formula (1) and described formula (1) and/or is selected from the phosphonic acids based compound of the compound shown in following formula (2) and more than a kind in salt thereof
[changing 1]
(in formula, R1And R2Represent hydrogen atom independently of one another, maybe can contain the hydrocarbon residue of the carbon number 1～18 of oxygen atom),
[changing 2]
(in formula, R is hydrogen atom, the hydrocarbon residue that maybe can contain the carbon number 1～18 of oxygen atom).
The thickness of above-mentioned iodine system polaroid is preferably less than 10 μm.
Above-mentioned iodine and/or the content of iodide ion in above-mentioned iodine system polaroid can be 3～12 weight %.
Transparent protective film can not be had between above-mentioned iodine system polaroid and above-mentioned coating layer.
Above-mentioned coating layer is preferably formed by the resin combination of at least one resin contained in polyurethane series resin, polyvinyl alcohol resin and acrylic resin.
Moreover, it relates to a kind of polarizing coating with adhesive phase, the described polarizing coating with adhesive phase is characterised by, has adhesive phase in the coating layer side of the above-mentioned polarizing coating with coating layer.
Above-mentioned adhesive phase preferably comprises ionic compound.
It addition, the polarizing coating with adhesive phase of the present invention can be fitted in the way of the transparency conducting layer with the transparent conductive member with transparency conducting layer contacts, the adhesive phase of the polarizing coating with adhesive phase uses.
Above-mentioned transparency conducting layer is preferably formed by tin indium oxide.It addition, above-mentioned tin indium oxide is preferably noncrystalline tin indium oxide.
Additionally, the present invention relates to a kind of image display device, it is characterized in that, the adhesive phase of the above-mentioned polarizing coating with adhesive phase is fitted with the liquid crystal panel with transparency conducting layer in the way of making the adhesive phase of the above-mentioned polarizing coating with adhesive phase contact with the transparency conducting layer of above-mentioned liquid crystal panel.
Invention effect
Even if the polarizing coating with coating layer of the present invention is when by adhesive phase stacking over transparent conductive layer, it is also possible to suppress the deterioration of transparency conducting layer, it is suppressed that the sheet resistance value of transparency conducting layer rises.This is presumably because, the effect of the phosphorus series compound by containing in iodine system polaroid and/or coating layer, it is possible to suppress the iodine contained in iodine system polaroid to shift as a result, the corrosion of transparency conducting layer can be prevented to layer at transparent layer.
It addition, when adhesive phase is fitted over transparent conductive layer by the polarizing coating with adhesive phase of the present invention even if described above, it is also possible to suppress the deterioration of transparency conducting layer.It addition, the polarizing coating with adhesive phase of the present invention via coating layer by polarizing coating and adhesive phase stacking, and be combined with phosphorus series compound in iodine system polaroid and/or coating layer, therefore, the excellent adhesion of adhesive phase and polarizing coating or coating layer.As a result, it is possible to prevent the stripping caused by generation of adhesive deposit when doing over again, durability, add the adhesive paste deficiency etc. in man-hour.It addition, the present invention can provide a kind of image display device, its adhesive phase comprising the above-mentioned polarizing coating with adhesive phase and there is the liquid crystal panel of transparency conducting layer.
Accompanying drawing explanation
Fig. 1 is an example of the summary section of the polarizing coating with coating layer of the present invention.
Fig. 2 is an example of the summary section of the polarizing coating with adhesive phase of the present invention.
Detailed description of the invention
1. with the polarizing coating of coating layer
The polarizing coating with coating layer of the present invention has transparent protective film, iodine system polaroid containing iodine and/or iodide ion and coating layer successively, it is characterised in that
Above-mentioned iodine system polaroid and/or above-mentioned coating layer contain phosphorus series compound.
Hereinafter, use the Fig. 1 as an embodiment of the invention, the composition with the polarizing coating of coating layer of the present invention is illustrated.But, the polarizing coating with coating layer of the present invention is not limited to the mode of Fig. 1.
The polarizing coating 1 with coating layer of the present invention has transparent protective film 3, iodine system polaroid 2 and coating layer 4 successively.Although not shown, but iodine system polaroid 2 and transparent protective film 3 carry out stacking usually by bond layer etc..It addition, coating layer 4 can be directly arranged at the face without transparent protective film 3 of iodine system polaroid 2.It addition, as described later, coating layer 4 can be 1 layer can also be more than 2 layers; it addition, can have transparent protective film between iodine system polaroid 2 and coating layer 4, but for the present invention; when iodine system polaroid 2 is made directly stacking with coating layer 4, the effect of the present invention is comparatively notable.Hereinafter, respective material is illustrated.
(1) iodine system polaroid
As iodine system polaroid 2, as long as being the polaroid containing iodine and/or iodide ion, then can use any polaroid, for instance can enumerate: make iodine be adsorbed on the hydrophilic macromolecule films such as polyvinyl alcohol (PVA) mesentery, part formalizing PVA mesentery, the partly-hydrolysed film of vinyl-vinyl acetate copolymer system and carry out the polaroid etc. of uniaxial tension.Among these, it is preferred to comprise the polaroid of PVA mesentery and iodine.The thickness of these polaroids is not particularly limited, and is generally about less than 80 μm.
With iodine PVA mesentery dyeed and carry out the polaroid of uniaxial tension and such as can make in the following way: dyeing by PVA being impregnated in the aqueous solution of iodine, being stretched to 3～7 times of raw footage.Also can impregnated in as required in the aqueous solution of potassium iodide etc. that boric acid maybe can comprise zinc sulfate, zinc chloride etc..And then also before dyeing PVA mesentery can be impregnated in water as required and wash.By PVA mesentery is washed, the dirt on PVA mesentery surface, antiblocking agent can be cleaned, additionally, by making PVA mesentery swelling, also have the effect of the unequal inequality that prevents from dyeing.Stretching can carry out after utilizing iodine to dye, it is possible to an Edge Coloring stretches, additionally, it is possible to utilize iodine to dye after the stretch.Also can stretch in the aqueous solution of boric acid, potassium iodide etc., water-bath.
It addition, in the present invention, it is possible to the slim iodine system polaroid using thickness to be less than 10 μm aptly.For the viewpoint of slimming, the thickness of described iodine system polaroid is preferably 1～7 μm.Such slim iodine system polaroid is less due to uneven thickness, and observation property is excellent, further, since change in size is less and excellent in te pins of durability, and then also realize slimming as the thickness of polarizing coating and preferably.
As slim polaroid, typically, slim polarizing coating described in Japanese Laid-Open Patent Publication 51-069644 publication, Japanese Unexamined Patent Publication 2000-338329 publication, No. 2010/100917 pamphlet of International Publication, No. 2010/100917 pamphlet of International Publication or No. 4751481 description of Japan Patent or Japanese Unexamined Patent Publication 2012-073563 publication can be enumerated.These slim polarizing coatings can obtain by including the manufacture method of the operation of operation and dyeing PVA resin and stretching resin base material stretched when duplexer.According to this manufacture method, even if PVA resin is relatively thin, it is possible to by be stretched with resin base material supporting when and have no way of stretch caused fracture etc. bad stretch.
nullAs above-mentioned slim polarizing coating，In the manufacture method including carrying out the operation of operation and the dyeing stretched when duplexer，Polarization property is promoted from the viewpoint of being stretchable to high magnification，Preferably by No. 2010/100917 pamphlet of such as International Publication、The manufacture method of the operation including carrying out stretching in boric acid aqueous solution described in No. 2010/100917 pamphlet of International Publication or No. 4751481 description of Japan Patent or Japanese Unexamined Patent Publication 2012-073563 publication and the polarizing coating that obtains，Be particularly preferably by No. 4751481 description of Japan Patent or Japanese Unexamined Patent Publication 2012-073563 publication described include stretching in boric acid aqueous solution before secondarily carry out the manufacture method of operation of aerial stretching and the polarizing coating that obtains.
By the coating layer etc. that stacking on the iodine system polaroid 2 utilizing preceding method to obtain contains phosphorus series compound described later, thus phosphorus series compound is transferred to iodine system polaroid 2 from this coating layer etc. sometimes, thus containing phosphorus series compound in iodine system polaroid 2.When containing phosphorus series compound in iodine system polaroid 2 in this wise, it is also possible to the corrosion of suppression transparency conducting layer, therefore preferably.As the phosphorus series compound that can contain in above-mentioned iodine system polaroid 2, the material equal with phosphorus series compound described later can be enumerated.
When iodine system polaroid 2 is containing phosphorus series compound, as its content, iodine system polaroid 2 is preferably below 3 weight %, more preferably 0.01～1 weight %, more preferably 0.02～0.6 weight %.
It addition, (below, be also sometimes referred to as content of iodine about the iodine of the iodine system polaroid 2 used in the present invention and/or the content of iodide ion.), polaroid can be 3～12 weight %, it is possible to be 4～7.5 weight %.For the polarizing coating 1 with coating layer of the present invention, even if the content of iodine in iodine system polaroid 2 is many as above-mentioned scope, it is also possible to inhibition layer is laminated on the sheet resistance of the transparency conducting layer of the polarizing coating 1 of the present invention and rises.This is presumably because, the effect of the phosphorus series compound by containing in iodine system polaroid 2 and/or coating layer described later 4, it is possible to suppress the iodine contained in iodine system polaroid to be transferred to layer at transparent layer as a result, the corrosion of transparency conducting layer can be prevented.
(2) transparent protective film
As the material forming transparent protective film 3, it is preferred to the material that the transparency, mechanical strength, heat stability, moisture barrier, isotropism etc. are excellent.Such as can enumerate: styrenic, the Merlon based polymers etc. such as the acrylic acid series polymeric compounds such as cellulose-based polymer, polymethyl methacrylate such as the Polyester polymer such as polyethylene terephthalate or PEN, diacetyl cellulose or triacetyl cellulose, polystyrene or acrylonitritrile-styrene resin (AS resin).Additionally, example as the polymer forming above-mentioned transparent protective film 3, also can enumerate: polyethylene, polypropylene, there is ring system or the polyolefin of norborene structure, the polyolefin polymer such as ethylene-propylene copolymer, vinyl chloride-based polymer, the amide based polymer such as nylon or aromatic polyamide, imide series polymer, sulfone based polymer, polyether sulfone based polymer, polyether-ether-ketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol system polymer, vinylidene chloride based polymer, butyral based polymer, aromatic ester based polymer, polyformaldehyde based polymer, the blend etc. of epoxy polymer or above-mentioned polymer.Transparent protective film 3 also can be formed with the form of the thermohardening types such as acrylic acid series, carbamate system, propenoic methyl carbamate system, epoxy, silicone-based, the cured layer of ultraviolet curing resin.
The thickness of above-mentioned transparent protective film 3 can suitably determine, generally from viewpoints such as the workability such as intensity or operability, thin film, is about 1～500 μm; preferably 1～300 μm; more preferably 5～200 μm, it is preferred that 5～150 μm, it is particularly preferred to 20～100 μm.
Above-mentioned transparent protective film 3 can only be configured at the one side (one side protection polarizing coating) of above-mentioned iodine system polaroid 2, it is also possible to is configured at two-sided (the two-sided protection polarizing coating) of above-mentioned iodine system polaroid 2.During use one side protection polarizing coating (that is, when not having transparent protective film between iodine system polaroid 2 and coating layer 4), the effect of the present invention is comparatively notable.Even if it addition, be two-sided protection polarizing coating, during thickness thin (being such as less than 25 μm) at the transparent protective film (not shown) of the side that contacts with above-mentioned coating layer 4, the effect of the present invention is also comparatively notable.
Above-mentioned iodine system polaroid 2 and transparent protective film 3 are generally closely sealed via water system bonding agent etc..As water system bonding agent, isocyanate-based bonding agent, polyethenol series bonding agent, gelatin system bonding agent, ethylene system, latex system, aqueous polyurethane, water system polyester etc. can be illustrated.Than that described above, as the bonding agent of iodine system polaroid 2 with transparent protective film 3, it is possible to enumerate ultraviolet hardening bonding agent, electronic beam solidified bonding agent etc..Electronic beam solidified polarizing coating bonding agent demonstrates suitable cementability for above-mentioned various transparent protective films 3.It addition, in the bonding agent used in the present invention, metallic compound filler can be contained.
Face for the not bonding iodine system polaroid 2 of above-mentioned transparent protective film 3, it is possible to the functional layers such as hard conating, anti-reflection layer, tissue adhesion layer, diffusion layer or antiglare layer are set.Additionally, above-mentioned functions layer can be arranged at transparent protective film 3 itself, it is also possible to be configured as the film different from transparent protective film 3.
(3) coating layer
When only arranging transparent protective film 3 at the one side of iodine system polaroid 2; coating layer 4 is arranged at another one side (face of non-laminating transparent protecting film 3) of iodine system polaroid 2; when the two sides of iodine system polaroid 2 arranges transparent protective film 3; coating layer 4 can be arranged at a transparent protective film; at the thickness of 2 transparent protective films not likewise it is preferred that be arranged at thin transparent protective film side.
The thickness of coating layer 4 is not particularly limited, from the view point of thin layer and optics reliability, it is preferred to less than 10 μm, more preferably less than 5 μm, more preferably less than 3 μm.It addition, coating layer 4 can be 1 layer, it is also possible to be more than 2 layers, but when being more than 2 layers, it is preferable that multiple coating layer entirety meet above-mentioned thickness.When coating layer 4 is more than 2 layers, containing phosphorus series compound at least 1 layer.
Coating layer 4 can be formed by various materials, for instance can be formed by coating layer formation resin combination is coated iodine system polaroid 2.As the resin material contained in above-mentioned coating layer formation resin combination, for instance can enumerate: various polymer classes or the colloidal sol of metal-oxide, silicon dioxide gels etc. such as polyester based resin, polyethers system resin, polycarbonate-based resin, polyurethane series resin, silicone-based resin, polyamide series resin, polyimides system resin, PVA system resin, acrylic resins.These resins can coordinate cross-linking agent aptly.These resin materials can be used alone a kind, or combination uses two or more, but wherein from the view point of with the adaptation of iodine system polaroid, optics reliability, it is preferable that more than a kind in polyurethane series resin, PVA system resin, acrylic resin, more preferably PVA system resin.It addition, the form of above-mentioned resin can be any one in water system, solvent system.
In addition, adhesive phase contain acid composition time (such as, monomeric unit as (methyl) acrylic acid series polymeric compounds, during containing carboxyl group-containing monomers such as acrylic acid), from the view point of guarantee adaptation, the coating layer of adhesive phase side preferably comprises to possess has the compound of reactive functional group (such as, azoles quinoline base etc.) with above-mentioned acid composition.Such as, when coating layer is more than 2 layers, the coating layer near adhesive phase side preferably comprises the polymer containing azoles quinoline base.
(the coating layer formation resin combination containing PVA system resin)
As above-mentioned PVA system resin, for instance PVA can be enumerated.PVA can by obtaining saponifying polyvinyl acetate.It addition, as PVA system resin, vinyl acetate can be enumerated and there is with it copolymer saponified of monomer of copolymerizable.When the above-mentioned monomer with copolymerizable is ethylene, vinyl-vinyl alcohol copolymer can be obtained.It addition, as the above-mentioned monomer with copolymerizable, can enumerate: unsaturated carboxylic acid and esters thereof such as maleic acid (anhydride), fumaric acid .beta.-methylacrylic acid, itaconic acid, (methyl) acrylic acid；The alpha-olefin such as ethylene, propylene；(methyl) allyl sulphonic acid (sodium), sodium sulfonate (monoalkyl maleate), sodium disulfonate alkyl maleate, N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid alkali salt, NVP, NVP derivant etc..These PVA system resins can be used alone or two or more kinds may be used.Wherein, it is preferable that the PVA that saponifying polyvinyl acetate is obtained.
It addition, as above-mentioned PVA system resin, it is possible to use above-mentioned PVA or the side chain at its copolymer have the modified PVA system resin of hydrophilic functional group.As above-mentioned hydrophilic functional group, for instance acetoacetyl, carbonyl etc. can be enumerated.Furthermore it is also possible to use the modified PVA after PVA system resin acetalation, urethane, etherificate, grafting, Phosphation etc..
The coating layer 4 used in the present invention can be formed by containing above-mentioned PVA system resin formed with resin combination as main component and the coating layer containing phosphorus series compound described later, and above-mentioned resin combination can contain curable composition (cross-linking agent) etc..The ratio of the PVA system resin in coating layer 4 or resin combination (solid constituent) is preferably more than 80 weight %, more preferably more than 90 weight %, it is preferred that more than 95 weight %.
(the coating layer formation resin combination containing acrylic resin)
It is resin as aforesaid propylene acid, it is preferable that the curing type containing following curable composition forms material.As curable composition, it is possible to be roughly divided into electronic beam solidified, ultraviolet hardening, luminous ray curing type isoreactivity energy ray-curable and thermohardening type.It addition, ultraviolet hardening, luminous ray curing type can be divided into radical polymerization curing type and cation polymerization curing type.In the present invention, being 10nm by wave-length coverage is expressed as ultraviolet less than the active energy beam of 380nm, and the active energy beam of wave-length coverage 380nm～800nm is expressed as luminous ray.The curable composition of above-mentioned radical polymerization curing type, it is possible to the curable composition as thermohardening type uses.
(radical polymerization curing type forms material)
As above-mentioned curable composition, for instance free-radical polymerised compound can be enumerated.Free-radical polymerised compound can enumerate the compound of the free-radical polymerised functional group with (methyl) carbon-to-carbon double bond such as acryloyl group, vinyl.These curable compositions can use any one in the multifunctional free-radical polymerised compound of more than monofunctional free radical's polymerizable compound or two senses.It addition, these free-radical polymerised compounds can be used alone a kind, or combination uses two or more.As these free-radical polymerised compounds, for instance be suitably for the compound with (methyl) acryloyl group.Additionally, in the present invention, (methyl) acryloyl group refers to acryloyl group and/or methylacryloyl, below (methyl) there is same containing.
(form of radical polymerization curing type formation material)
Radical polymerization curing type forms material can as the formation materials'use of active energy ray curable or thermohardening type.When active energy beam uses electron beam etc., this active energy ray curable forms material without containing Photoepolymerizationinitiater initiater, but when active energy beam uses ultraviolet or luminous ray, it is preferable that containing Photoepolymerizationinitiater initiater.On the other hand, when using above-mentioned curable composition as Thermocurable composition, this formation material preferably comprises thermal polymerization.
Based on the formation of the coating layer forming material of above-mentioned curing type, form material by coating curing type on the face of iodine system polaroid (or transparent protective film), be then carried out solidification and carry out.It addition, iodine system polaroid (or transparent protective film) is before applying above-mentioned curing type formation material, it is possible to carry out surface modification treatment.As concrete process, the process etc. processed based on sided corona treatment, Cement Composite Treated by Plasma, saponification can be enumerated.
Curing type forms the application pattern of material can form the viscosity of material, the suitable selection of target thickness according to this curing type.Example as application pattern, for instance can enumerate: reversion coating machine, gravure coater (Direct-type, counter-rotative type, graph brush-type), scraper reversible type coating machine, roll coater, die coating machine, bar coater, bar coater etc..Additionally, coating can suitably use the modes such as dip coating manner.
The solidification forming material can carry out in the following manner.
(active energy ray curable)
Material is formed about active energy ray curable; after iodine system polaroid (or transparent protective film) is applied active energy ray curable formation material; irradiate active energy beam (electron beam, ultraviolet, luminous ray etc.); active energy ray curable is formed material solidify, form coating layer.The direction of illumination of active energy beam (electron beam, ultraviolet, luminous ray etc.) can be irradiated from arbitrarily suitable direction.It is irradiated preferably from coating layer side.
(thermohardening type)
On the other hand, form material about thermohardening type, by being heated after polaroid is fitted with transparent protective film, thus utilize thermal polymerization to cause polymerization, form solidification nitride layer.Heating-up temperature sets according to thermal polymerization, but is about 60～200 DEG C, it is preferable that 80～150 DEG C.
(the coating layer formation resin combination containing polyurethane series resin)
As the polyurethane series resin used in the present invention, for the resin that can obtain by making polyhydric alcohol react with polyisocyanate, specifically as the polyurethane series resin being preferably used, for instance the Denatron growing rapids chemical conversion company can be enumerated serial etc..
When utilizing water system material to form coating layer, use water-dispersed polymer.As water-dispersed polymer, can enumerate: the material that uses emulsifying agent to be obtained by various to polyurethane, polyester etc. resin emulsions, in above-mentioned resin, import the anion base of water dispersible, cation radical or nonionic base and the material etc. that carries out self emulsifying and obtain.
(phosphorus series compound)
In the present invention, any one or both in above-mentioned iodine system polaroid and above-mentioned coating layer contain phosphorus series compound.As phosphorus series compound, for instance can enumerate phosphoric acid based compound, phosphonic acids based compound, phosphorous antioxidant, in the present invention, it is possible to they be used alone, or combination uses more than two kinds.Wherein, it is preferable that phosphoric acid based compound or phosphonic acids based compound.
As phosphoric acid based compound, for instance the phosphoric acid based compound in the polymer of the compound shown in the compound shown in following formula (1) and described formula (1) can be enumerated,
[changing 3]
(in formula, R1And R2Represent hydrogen atom independently of one another, maybe can contain the hydrocarbon residue of the carbon number 1～18 of oxygen atom.).
As above-mentioned phosphoric acid based compound, as described later, phosphoric acid, phosphate ester or their salt, dimer, trimer etc. can be enumerated.Hereinafter, in detail they are illustrated.
In formula (1), R1And R2It is each independently hydrogen atom, maybe can contain the hydrocarbon residue of the carbon number 1～18 of oxygen atom.As the hydrocarbon residue of the carbon number 1～18 that can contain oxygen atom, the alkyl of carbon number 1～18, the thiazolinyl of carbon number 1～18, the aryl of carbon number 6～18 ,-(CH can be enumerated2CH2O)nR3(R3For the aryl of the alkyl of carbon number 1～18, the thiazolinyl of carbon number 1～18 or carbon number 6～18, n is the integer of 0～15.) etc..It addition, alkyl, thiazolinyl can be straight-chain, it is also possible to for branched.Wherein, be the hydrocarbon residue of 1～18 as above-mentioned carbon number, it is preferable that the alkyl of the straight or branched of carbon number 1～10, carbon number 6～18 aryl, the more preferably alkyl of the straight or branched of carbon number 2～6.
In the present invention, it is also possible to compatibly use the R of formula (1)1And R2In the phosphoric acid (H that any one is hydrogen atom3PO4).Alternatively, it is also possible to compatibly use the salt (slaine, the ammonium salt etc. such as sodium, potassium and magnesium) of above-mentioned phosphoric acid.
It addition, in the present invention, the compound shown in formula (1) is preferably acid phosphoric acid ester.At this, acid phosphoric acid ester is the R of formula (1)1And R2It is the situation (diester body) of the hydrocarbon residue of the carbon number 1～18 that can contain oxygen atom；Or R1、R2In the situation (monoesters body) of the hydrocarbon residue that any one is hydrogen atom and another one is the carbon number 1～18 that can contain oxygen atom, for instance the following phosphate ester based compound shown in formula (1 ') can be enumerated,
[changing 4]
(in formula, R1As described above, R3For the aryl of the alkyl of carbon number 1～18, the thiazolinyl of carbon number 1～18 or carbon number 6～18, n is the integer of 0～15.).
The R of formula (1 ')1R with formula (1)1Equally, the hydrocarbon residue of the carbon number 1～18 of oxygen atom maybe can be contained for hydrogen atom.As the hydrocarbon residue of the carbon number 1～18 that can contain oxygen atom, group similar to the above can be enumerated.R as formula (1 ')1, it is preferred to the aryl of hydrogen atom, the alkyl of straight or branched of carbon number 1～18 or carbon number 6～18, more preferably the alkyl of the straight or branched of hydrogen atom or carbon number 1～10, the more preferably alkyl of the straight or branched of hydrogen atom or carbon number 2～6.As R3, the aryl of the alkyl of carbon number 1～18, the thiazolinyl of carbon number 1～18 or carbon number 6～18 can be enumerated, it is preferred to the alkyl of carbon number 1～18, carbon number 6～18 aryl, the more preferably alkyl of carbon number 1～10, it is preferred that the alkyl of carbon number 2～6.It addition, n is the integer of 0～15, it is preferred to the integer of 0～10.It addition, in the present invention, from the view point of prevent deterioration, it is preferable that do not contain poly(ethylene oxide) structure (CH2CH2O) (that is, in formula (1 '), n=0).
As the phosphate ester based compound shown in formula (1 '), from the view point of the adsorption effect to adherend, it is preferable that R1For hydrogen atom, R3For the phosphate monoester of alkyl of the straight or branched of carbon number 1～18, more preferably R1For hydrogen atom, R3For the phosphate monoester of alkyl of the straight or branched of carbon number 1～10, it is preferred that R1For hydrogen atom, R3The phosphate monoester of alkyl for the straight or branched of carbon number 2～6.
It addition, in the present invention, the compound shown in formula (1 ') can mix two or more and use, further, it is possible to use the mixture of the compound shown in formula (1 ') and above-mentioned phosphoric acid.It addition, generally the many mixture as monoesters Yu diester of phosphate ester based compound shown in formula (1 ') obtain, it is preferable that use after adding above-mentioned phosphoric acid further in the above-mentioned monoesters mixture with diester.
In the present invention, it is also possible to compatibly use the salt (slaine, the ammonium salt etc. such as sodium, potassium and magnesium) of the compound shown in formula (1 ').
As the commercially available product of the phosphate ester based compound shown in above-mentioned formula (1 '), can enumerate: " PhosphanolSM-172 " (R of formula (1 ') that east nation's chemical industry (strain) is made1=R3=C8H17, n=0, mono bis mixture (monoesters body: diester body=5: 5 (weight ratios), acid number: 219mgKOH/g), " PhosphanolGF-185 " (R of formula (1 ')1=R3=C13H27, n=0, mono bis mixture, acid number: 158mgKOH/g), " PhosphanolBH-650 " (R of formula (1 ')1=R3=C4H9, n=1, mono bis mixture, acid number: 388mgKOH/g), " PhosphanolRS-410 " (R of formula (1 ')1=R3=C13H27, n=4, mono bis mixture (monoesters body: diester body=5: 5 (weight ratios), acid number: 105mgKOH/g), " PhosphanolRS-610 " (R of formula (1 ')1=C13H27, R3=C13H27, n=6, mono bis mixture, acid number: 82mgKOH/g), " PhosphanolRS-710 " (R of formula (1 ')1=C13H27, R3=C13H27, n=10, mono bis mixture (monoesters body: diester body=5: 5 (weight ratios)), acid number: 62mgKOH/g), " PhosphanolML-220 " (R of formula (1 ')1=R3=C12H25, n=2, mono bis mixture), " PhosphanolML-200 " (R of formula (1 ')1=R3=C12H25, n=0, mono bis mixture), " PhosphanolED-200 " (R of formula (1 ')1=R3=C8H17, n=1, mono bis mixture), " PhosphanolRL-210 " (R of (1 ')1=R3=C18H37, n=2, mono bis mixture), " PhosphanolGF-339 (R of formula (1 ')1=R3=C6H13～C10H21Mixing, n=0, mono bis mixture), " PhosphanolGF-199 " (R of formula (1 ')1=R3=C12H25, n=0, mono bis mixture), " PhosphanolRL-310 " (R of formula (1 ')1=R3=C18H37, n=3, mono bis mixture), " PhosphanolLP-700 " (R of formula (1 ')1=R3=C6H5, n=6, mono bis mixture), " AP-1 " (R of formula (1 ') that big eight chemical industry (strain) are made1=R3=CH3, n=0, mono bis mixture, acid number: more than 650mgKOH/g), " AP-4 " (R of formula (1 ')1=R3=C4H9, n=0, mono bis mixture, acid number: 452mgKOH/g), " DP-4 " (R of formula (1 ')1=R3=C4H9, n=0, diester body, acid number: 292mgKOH/g), " MP-4 " (R of formula (1 ')1=H, R3=C4H9, n=0, mono bis mixture (monoesters body: diester body=8: 2 (weight ratios)), acid number: 670mgKOH/g), " AP-8 " (R of formula (1 ')1=R3=C8H17, n=0, mono bis mixture, acid number: 306mgKOH/g), " AP-10 " (R of formula (1 ')1=R3=C10H21, n=0, mono bis mixture, acid number: 263mgKOH/g), " MP-10 " (R of formula (1 ')1=H, R3=C10H21, n=0, monoesters body, acid number: 400mgKOH/g), " JP-508 " (R of formula (1 ') that north of the city chemistry (strain) is made1=R3=C8H17, n=0, mono bis mixture, acid number: 288mgKOH/g), " JP-513 " (R of formula (1 ')1=R3=C13H27, n=0, mono bis mixture), " JP-524R " (R of formula (1 ')1=R3=C24H49, n=0, mono bis mixture), " DBP " (R of formula (1 ')1=R3=C4H9, n=0, mono bis mixture (monoesters body: diester body=1: 9 (weight ratios)), acid number: 266mgKOH/g), " LB-58 " (R of formula (1 ')1=R3=C8H17, n=0, diester body, acid number: 173mgKOH/g), " NikkolDDP-2 " (R of formula (1 ') that daylight chemistry (strain) is made1=R3=C12H25～C15H31Mixture, n=2) etc. and their salt.Additionally, above-mentioned " mono bis mixture " refers to monoesters (R1=H) and diester (R1=hydrocarbon residue of carbon number 1～18 of oxygen atom can be contained) mixture, for instance during for PhosphanolSM-172, be expressed as the monoesters (R of formula (1 ')1=H, R3=C8H17, n=0) and the diester (R of formula (1 ')1=R3=C8H17, n=0) mixture.
As the phosphoric acid based compound used in the present invention, can will be used alone selected from the compound (or the compound shown in formula (1 ')) shown in formula (1) or the compound a kind in their salt, polymer, they use after can also be mixed two or more, it is preferably selected from the mixture of more than two kinds in phosphoric acid, phosphate monoester and di-phosphate ester, more preferably comprise the mixture of phosphate monoester and phosphoric acid.At this, phosphate monoester refers to the R of formula (1)1And R2In the hydrocarbon residue that any one is hydrogen atom and another one is the carbon number 1～18 that can contain oxygen atom compound (when formula (1 '), R1Compound for hydrogen atom), di-phosphate ester refers to the R of formula (1)1And R2For can contain oxygen atom carbon number 1～18 hydrocarbon residue compound (when formula (1 '), R1For the compound of the hydrocarbon residue of the carbon number 1～18 of oxygen atom can be contained).
It addition, the acid number of the phosphate cpd used in the present invention is preferably below 900mgKOH/g, more preferably 50～800mgKOH/g, it is preferred to 10～700mgKOH/g.It addition, from the view point of produce on process, the acid number of above-mentioned phosphate cpd is preferably below 400mgKOH/g, more preferably 50～400mgKOH/g, more preferably 50～350mgKOH/g, it is particularly preferred to be 100～300mgKOH/g.In the compositions forming coating layer 4 containing cross-linking agent, phosphate cpd according to the kind (such as isocyanate-based cross-linking agent) of this cross-linking agent sometimes catalysts as cross-linking reaction play a role, now, sometimes shorten the working life as the compositions forming coating layer 4, be sometimes deteriorated in treatability.By making the acid number of phosphate cpd reach above-mentioned scope, it is possible to suppress as the effect answering catalyst, therefore from the view point of form the working life of the compositions of coating layer 4, be preferred.It addition, from the view point of effect can be played effectively, be added being preferred with addition described later by the phosphate cpd with the acid number of above-mentioned scope.
It addition, as the polymer of the compound shown in above-mentioned formula (1), the dimer of compound shown in above-mentioned formula (1), trimer etc. can be enumerated.
It addition, as phosphorus series compound, phosphonic acids based compound can be enumerated.As phosphonic acids based compound, for instance can enumerate selected from the compound shown in following formula (2) and the phosphonic acids based compound in salt thereof,
[changing 5]
(in formula, R is hydrogen atom, the hydrocarbon residue that maybe can contain the carbon number 1～18 of oxygen atom.).
In formula (2), R is hydrogen atom, the hydrocarbon residue that maybe can contain the carbon number 1～18 of oxygen atom.As the hydrocarbon residue of the carbon number 1～18 that can contain oxygen atom, the aryl etc. of the alkyl of carbon number 1～18, the thiazolinyl of carbon number 1～18, carbon number 6～18 can be enumerated.It addition, alkyl, thiazolinyl can be straight-chain, it is also possible to for branched.
Can be the phosphonic acids that R the is hydrogen atom (HP (=O) (OH) of formula (2)2).It addition, be suitable for use of the salt (slaine, the ammonium salt etc. such as sodium, potassium and magnesium) of above-mentioned phosphonic acids.
As the phosphonic acids based compound shown in above-mentioned formula (2), specifically can enumerate: phosphonic acids, methylphosphonic acid, ethylphosphonic acid, n-pro-pyl phosphonic acids, isopropyl phosphonic acids, normal-butyl phosphonic acids, tert-butylphosphonic acid, sec-butyl phosphonic acids, isobutyl group phosphonic acids, n-pentyl phosphonic acids, n-hexyl phosphonic acids, isohesyl phosphonic acids, n-heptyl phosphonic acids, n-octyl phosphonic acids, iso-octyl phosphonic acids, t-octyl phosphonic acids, n-nonyl phosphonic acids, positive decylphosphonic acid, isodecyl phosphonic acids, dodecyl phosphonic acids, Fancol ID base phosphonic acids, n-tetradecane base phosphonic acids, n-hexadecyl phosphonic acids, n-octadecane base phosphonic acids, AI3-28404 base phosphonic acids, cyclobutyl phosphonic acids, cyclopenta phosphonic acids, cyclohexyl phosphonic acids, norborny phosphonic acids, phenyl-phosphonic acid, naphthyl phosphonic acids, biphenyl phosphonic acids, methoxyphenyl phosphonic acids, ethoxyl phenenyl phosphonic acids and their salt.In the present invention, they can be used alone, or combination uses more than two kinds.
It addition, as phosphorus series compound, phosphorous antioxidant can be enumerated.nullConcrete example as phosphorous antioxidant，Can enumerate: tricresyl phosphite octyl group ester、Trilauryl、Three (tridecyl) phosphite ester、Three isodecyl phosphite、Phenyl diisooctyl phosphite ester、Phenyl diiso decyl phosphite ester、Phenyl two (tridecane) phosphite ester、Diphenyl iso-octyl phosphite ester、Diphenyl isodecyl phosphite、Diphenyl tridecane phosphite ester、Triphenyl phosphite、Three (nonyl phenyl) phosphite ester、Three (2，4-di-t-butyl phenyl) phosphite ester、Three (butoxyethyl group) phosphite ester、Four (tridecyls)-4，4 ' double; two (the 3 methy 6 tert butyl phenol)-diphosphites of-Ding fork、4，4 '-isopropylidene-biphenol alkyl phosphite is (wherein，Alkyl is carbon number about 12～15)、4，Double; two (2-TBP)/bis-(nonyl phenyl) phosphite ester of 4 '-isopropylidene、Three (xenyl) phosphite ester、Four (tridecyls)-1，1，3-tri-(2-methyl-5-tert-butyl-hydroxy phenyl) butane diphosphites、Three (3，5-di-t-butyl-4-hydroxy phenyl) phosphite ester、Hydrogenation-4，4 '-isopropylidenediphenol gathers phosphite ester、Double; two (octyl phenyls)/bis-s [4，4 '-Ding forks double; two (3 methy 6 tert butyl phenol)]/1，6-hexanediol diphosphites、Six (tridecyls)-1，1，3-tri-(2-methyl-4-hydroxyl-5-tert-butyl phenol) diphosphites、Three [4，4 '-isopropylidene double; two (2-TBP)] phosphite ester、Three (1，3-distearyl acyloxy isopropyl) phosphite ester、9，10-dihydro-9-phospho hetero phenanthrene-10-oxide、Four (2，4-di-t-butyl phenyl)-4，4 '-biphenylen、Distearyl pentaerythrityl diphosphite、Two (nonyl phenyl) pentaerythritol diphosphites、Phenyl/4，4 '-isopropylidenediphenol/pentaerythritol diphosphites、Double; two (2，4-di-t-butyl phenyl) pentaerythritol diphosphites、Double; two (2，6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites and phenyl bisphenol-A-pentaerythritol diphosphites etc..
The addition of above-mentioned phosphorus series compound, relative to resinous principle 100 weight portion contained in coating layer formation resin combination, it is preferred to 0.01～10 weight portion, more preferably 0.01～5 weight portion, more preferably 0.1～5 weight portion.By making the addition of phosphorus series compound in above-mentioned scope, it is possible to suppress the sheet resistance value of transparency conducting layer to rise, therefore preferably.It addition, in the present invention, as set forth above, it is possible to and use phosphorus series compound of more than two kinds, now can be added in the way of making total amount reach above-mentioned scope.
It addition, the formation material of coating layer can contain antistatic agent.As long as antistatic agent is the material that can give electric conductivity, then it is not particularly limited, for instance ionic surfactant, electric conductive polymer, metal-oxide, carbon black and carbon nanomaterial etc. can be enumerated, among these, preferred electric conductive polymer, more preferably aqueous-dispersible conductive polymer.
As water-soluble conducting polymer, polyaniline sulfonic acid (manufacturing through the weight average molecular weight 150000 of polystyrene conversion, the beautiful sun of Rhizoma Sparganii (strain)) etc. can be enumerated, as aqueous-dispersible conductive polymer, polythiophene system electric conductive polymer (manufacture of long rapids chemical conversion company, Denatron series) etc. can be enumerated.
The use level of above-mentioned antistatic agent is such as below 70 weight portions relative to the forming above-mentioned polymer class 100 weight portion used in material of coating layer, it is preferred to below 50 weight portions.For the aspect of anti-static effect, it is preferred to be set to more than 10 weight portions, and then be set to more than 20 weight portions.
It addition, the deterioration etc. of the adhesive phase produced during in order to suppress with coating layer, iodine system polaroid, the formation material of coating layer can coordinate various additive, in order to give function to coating layer, it is possible to coordinate various additive.For example, it is possible to add antioxidant (beyond phosphorus system), deterioration preventing agent, UV absorbent, fluorescent whitening agent etc..
Forming method as above-mentioned coating layer, it does not have be particularly limited to, can be undertaken by generally well-known method.It addition, when forming coating layer, it is possible to above-mentioned polarizing coating 1 is granted activation.Activation processing can adopt various method, for instance can adopt sided corona treatment, low pressure UV process, plasma treatment etc..
In the present invention, by making the polarizing coating with coating layer with the coating layer 4 formed by the resin combination containing above-mentioned phosphoric acid based compound, thus, even if by this with coating layer polarizing coating by adhesive phase stacking over transparent conductive layer, it is also possible to suppress transparency conducting layer sheet resistance rise.
2. with the polarizing coating of adhesive phase
The polarizing coating with adhesive phase of the present invention is characterised by, has adhesive phase in the coating layer side of the above-mentioned polarizing coating with coating layer.
Hereinafter, use the Fig. 2 as an embodiment of the invention that the composition with the polarizing coating of adhesive phase of the present invention is illustrated.Wherein, the polarizing coating with adhesive phase of the present invention is not limited to the mode of Fig. 2.
About the polarizing coating 6 with adhesive phase of the present invention, as in figure 2 it is shown, there is adhesive phase 5 in coating layer 4 side of the above-mentioned polarizing coating 1 with coating layer.Partition (not shown) can be set at the adhesive phase 5 with the polarizing coating 6 of adhesive phase of the present invention, before for practicality, protect adhesive phase 5.Furthermore it is possible to arrange surface protection film (not shown) in transparent protective film 3 side of the polarizing coating 6 with adhesive phase.Hereinafter, respective material is illustrated.
Can using suitable binding agent in the formation of adhesive phase 5, its kind is not particularly limited.As binding agent, such as can enumerate: elastomeric adhesive, acrylic adhesive, silicone-based adhesive, carbamate system binding agent, vinyl alkyl ethers system binding agent, polyethenol series binding agent, polyvinyl pyrrolidone system binding agent, Polyacrylamide binding agent, cellulose-based binding agent etc., wherein, from the view point of optical transparence is excellent, demonstrate suitable adaptation, compendency and the adhesion characteristic of cementability, weatherability or thermostability etc. excellent, it is preferred to use acrylic adhesive.
It is binding agent as aforesaid propylene acid, can enumerate containing (methyl) acrylic acid series polymeric compounds binding agent.As above-mentioned (methyl) acrylic acid series polymeric compounds, it is not particularly limited, the polymer such as preferably polymerizing monomer components containing (methyl) alkyl acrylate obtained, it is preferred to the polymer that the polymerizing monomer components containing (methyl) alkyl acrylate and hydroxyl monomer is obtained.Additionally, (methyl) alkyl acrylate refers to alkyl acrylate and/or alkyl methacrylate, with (methyl) of the present invention, there is same implication.
As the alkyl of (methyl) alkyl acrylate, the various alkyl of straight-chain or branched can be used.nullConcrete example as above-mentioned (methyl) alkyl acrylate，Such as can illustrate: (methyl) propyl acrylate、(methyl) n-butyl acrylate、(methyl) Isobutyl 2-propenoate、(methyl) sec-butyl acrylate、(methyl) tert-butyl acrylate、(methyl) acrylic acid n-pentyl ester、(methyl) acrylic acid isoamyl (イ ソ ペ Application チ Le) ester、(methyl) acrylic acid isoamyl (イ ソ ア ミ Le) ester、The just own ester of (methyl) acrylic acid、(methyl) heptylacrylate、(methyl) 2-EHA、(methyl) Isooctyl acrylate monomer、(methyl) acrylic acid ester in the positive ninth of the ten Heavenly Stems、(methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems、(methyl) acrylic acid ester in the positive last of the ten Heavenly stems、(methyl) isodecyl acrylate、(methyl) acrylic acid dodecyl ester、The different myristin of (methyl) acrylic acid、(methyl) acrylic acid n-tridecane base ester、(methyl) acrylic acid myristyl ester、(methyl) stearyl acrylate ester、(methyl) octadecyl acrylate、Or (methyl) dodecylacrylate etc..These can be used alone or in combination.Among these, it is preferably (methyl) alkyl acrylate of the alkyl with carbon number 4～18, more preferably there is (methyl) acrylate of the alkyl of carbon number 4～10, more preferably (methyl) n-butyl acrylate, (methyl) 2-EHA, it is particularly preferred to for (methyl) n-butyl acrylate.
It addition, as the monomer of hydroxyl, can use without particular limitation and there is (methyl) acryloyl group or vinyl etc. there is the polymerizable functional group of unsaturated double-bond and there is the monomer of hydroxyl.Monomer as hydroxyl, such as can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid 12-hydroxylauric ester, (methyl) acrylic acid (4-Hydroxymethyl-cyclo-hexyl) methyl ester etc., these can be used alone a kind or by two or more mixing use.Among these, it is preferable that acrylic acid 4-hydroxybutyl.It addition, when using isocyanate-based cross-linking agent as aftermentioned cross-linking agent, by using acrylic acid 4-hydroxybutyl as the monomer of hydroxyl, the crosslinking points of NCO with isocyanate-based cross-linking agent can be guaranteed expeditiously, thus preferably.
In the monomer component of (methyl) acrylic acid series polymeric compounds used in forming the present invention, the monomer etc. of (methyl) alkyl acrylate of the above-mentioned alkyl with carbon number 4～18, optional above-mentioned hydroxyl can be contained, except these monomers, it is possible to use carboxylic monomer, monomer containing aryl, other comonomers are as monomer component.
As carboxyl group-containing monomer, can use without particular limitation and there is (methyl) acryloyl group or vinyl etc. there is the polymerizable functional group of unsaturated double-bond and there is the monomer of carboxyl.As carboxyl group-containing monomer, such as can enumerating acrylic acid, methacrylic acid, (methyl) carboxyethyl acrylates, (methyl) acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid .beta.-methylacrylic acid etc., these can be used alone or in combination.
As containing aryl monomer, can use without particular limitation and there is (methyl) acryloyl group or vinyl etc. there is the polymerizable functional group of unsaturated double-bond and there is the monomer of aryl.As containing aryl monomer, for instance (methyl) aryl acrylate such as (methyl) phenyl acrylate, (methyl) benzyl acrylate can be enumerated.
As other comonomers; as long as having the monomer that (methyl) acryloyl group or vinyl etc. has the polymerizable functional group of unsaturated double-bond; then it is not particularly limited, can enumerate: (methyl) acrylate ring type hydrocarbon esters such as such as (methyl) cyclohexyl acrylate, (methyl) acrylic acid norbornene ester, (methyl) isobornyl acrylate；The such as vinyl esters such as vinyl acetate, propionate；The styrenic monomers such as such as styrene；The such as monomer containing epoxy radicals such as (methyl) glycidyl acrylate, (methyl) acrylic acid methylglycidyl esters；The such as monomer containing alkoxyl such as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate；The such as monomer of the cyano-containing such as acrylonitrile, methacrylonitrile；The functional monomers such as such as Carbimide. 2-methacryloyloxyethyl；The olefinic monomers such as such as ethylene, propylene, isoprene, butadiene, isobutene.；The vinyl Ether system monomers such as such as vinyl Ether；The monomer etc. of the halogen atom-containings such as such as vinyl chloride.
It addition, as co-polymerized monomer, can enumerate: the maleimide system monomer such as such as N-N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, N-phenylmaleimide；The clothing health imide series monomers such as such as N-methyl clothing health acid imide, N-ethyl clothing health acid imide, N-butyl clothing health acid imide, N-octyl group clothing health acid imide, N-2-ethylhexyl clothing health acid imide, N-cyclohexyl clothing health acid imide, N-lauryl clothing health acid imide；The butanimide system monomers such as such as N-(methyl) acryloyl-oxy methylene butanimide, N-(methyl) acryloyl group-6-oxygen base hexa-methylene butanimide, N-(methyl) acryloyl group-8-oxygen base eight methylene butanimide；Such as styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) sulfopropyl acrylate, (methyl) propane sulfonic acid etc. are containing sulfonic monomer.
It addition, as co-polymerized monomer, amide-containing monomer can be enumerated.Amide-containing monomer is containing amide groups and the compound containing polymerism unsaturated double-bond such as (methyl) acryloyl group, vinyl etc. in its structure.As amide-containing monomer concrete example, can enumerate: (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, NIPA, N-methyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-hexyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methylol-N-propane (methyl) acrylamide, amino methyl (methyl) acrylamide, amino-ethyl (methyl) acrylamide, mercapto methyl (methyl) acrylamide, the acrylamide monomers such as mercaptoethyl (methyl) acrylamide；The N-acryloyl group heterocyclic monomers such as N-(methyl) acryloyl morpholine, N-(methyl) acryloylpiperidine, N-(methyl) acryloyl group nafoxidine；The lactams system monomer etc. containing N-vinyl such as NVP, N-vinyl-Epsilon-caprolactam.Amide-containing monomer is preferred from the viewpoint of what meet durability, in amide-containing monomer, is preferred especially with the lactams system monomer of N-vinyl from the viewpoint of meeting the durability of transparency conducting layer.
Additionally, as co-polymerized monomer, can enumerate: the glycol system acrylate monomers such as such as (methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid polypropylene glycol ester, (methyl) methoxyethyl glycol ester, (methyl) methoxyethyl polypropylene glycol ester；Additionally, the acrylic ester monomer etc. that such as (methyl) tetrahydrofurfuryl acrylate, fluorine (methyl) acrylate etc. are containing heterocycle or halogen atom.
It addition, as co-polymerized monomer, multi-functional monomer can be used.As multi-functional monomer, the compound etc. of (methyl) unsaturated double-bond such as acryloyl group, vinyl with more than 2 can be enumerated.Such as can enumerate: ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, TEG two (methyl) acrylate etc. (single or poly-) ethylene glycol bisthioglycolate (methyl) acrylate；(single or poly-) aklylene glycol two (methyl) acrylate such as propylene glycol two (methyl) acrylate etc. (single or poly-) propylene glycol two (methyl) acrylate；In addition, also can enumerate the carboxylate of (methyl) acrylic acid such as neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, dipentaerythritol six (methyl) acrylate and polyhydric alcohol；The polyfunctional vinyl compounds such as divinylbenzene；(methyl) allyl acrylate, (methyl) vinyl acrylate etc. have the compound etc. of reactive unsaturated double-bond.Additionally; as multi-functional monomer, it is possible to use polyester (methyl) acrylate of (methyl) unsaturated double-bond such as acryloyl group, vinyl as the functional group identical with monomer component of addition more than 2, epoxy (methyl) acrylate, carbamate (methyl) acrylate etc. on the skeletons such as polyester, epoxide, carbamate.
The manufacture of such (methyl) acrylic acid series polymeric compounds can suitably select the known manufacture methods such as polymerisation in solution, polymerisation in bulk, emulsion polymerization, various radical polymerizations, is not particularly limited.It addition, (methyl) acrylic acid series polymeric compounds obtained can be any one in random copolymer, block copolymer, graft copolymer etc..
In polymerisation in solution, as polymer solvent, for instance use ethyl acetate, toluene etc..As concrete polymerisation in solution example, reaction be add under the inert gas flows such as nitrogen polymerization initiator and generally in about 50～70 DEG C, carry out under the reaction condition of 5～30 hours.
The polymerization initiator that uses in radical polymerization, chain-transferring agent, emulsifying agent etc. are not particularly limited, and can suitably select to use.Additionally, the weight average molecular weight of (methyl) acrylic acid series polymeric compounds can be controlled by according to make consumption, the reaction condition of polymerization initiator, chain-transferring agent, adjust according to these kind and suitable make consumption.
In the acrylic adhesive composition used in the present invention, in order to promote adaptation when high temperature and humidity, various silane coupler can be added.As silane coupler, the material with functional group suitable arbitrarily can be used.As functional group, for instance vinyl, epoxy radicals, amino, sulfydryl, (methyl) acryloxy, acetoacetyl, NCO, styryl, polythiaether etc. can be enumerated.Specifically, for instance can enumerate: the silane coupler containing vinyl such as VTES, vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyltributoxysilane；The silane coupler containing epoxy radicals such as γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl diethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane；Gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-amino propyl methyl dimethoxysilane, γ-triethoxysilyl-N-(1, the 3-dimethyl butyrate fork base) silane coupler containing amino such as propylamine, N-phenyl-gamma-amino propyl trimethoxy silicane；The silane coupler containing sulfydryl such as γ-mercaptopropyi methyl dimethoxysilane；To the silane coupler containing styryl such as styryl trimethoxy silane；γ-silane coupler containing (methyl) acryloyl group such as acryloxypropyl trimethoxy silane, γ-methacryloxypropyl；The silane coupler containing NCO such as 3-isocyanates propyl-triethoxysilicane；The silane coupler etc. containing polysulfide ether such as double; two (triethoxysilylpropyltetrasulfide) four thioether.
It addition, pass through the acrylic adhesive composition used in the present invention adds cross-linking agent, the cohesiveness relevant to the durability of binding agent can be given, so preferably.
As cross-linking agent, multi-functional compound can be used, organic system cross-linking agent or multi-functional metallo-chelate can be enumerated.As organic system cross-linking agent, can enumerate: epoxy cross-linking agent, isocyanate-based cross-linking agent, carbon imidodicarbonic diamide system cross-linking agent, imines system cross-linking agent, azoles quinoline system cross-linking agent, aziridine system cross-linking agent, peroxidating system cross-linking agent etc..Multi-functional metallo-chelate is the material of polyvalent metal atom and organic compound covalent bonding or coordination bonding.As polyvalent metal atom, Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc. can be enumerated.As the atom in the organic compound of covalent bonding or coordination bonding, oxygen atom etc. can be enumerated, as organic compound, Arrcostab, alcoholic compound, carboxylic acid compound, ether compound, ketonic compound etc. can be enumerated.These cross-linking agent can be used alone a kind or combine two or more use.Among these, it is preferred to peroxidating system cross-linking agent, isocyanate-based cross-linking agent, more preferably combine these and use.
Isocyanate-based cross-linking agent refers to the compound in 1 molecule with more than 2 NCOs (including the isocyanates regenerative functional group of the temporary protection NCO by end-capping reagent or poly materialization etc.).
As isocyanate-based cross-linking agent, can enumerate: the aliphatic isocyanates such as alicyclic isocyanate, hexamethylene diisocyanate etc. such as the aromatic isocyanate such as toluene di-isocyanate(TDI), XDI, isophorone diisocyanate.
As peroxidating system cross-linking agent, use various peroxide.As peroxide, can enumerate: peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxide-butyl carbonate, new peroxide tert-butyl caprate, talkyl peropivalate, the peroxidating pivalic acid tert-butyl ester, dilauroyl peroxide, the positive decoyl of peroxidating two, peroxidating isopropylformic acid. 1,1,3,3-tetramethyl butyl ester, peroxidating 2 ethyl hexanoic acid 1,1,3,3-tetramethyl butyl esters, peroxidating two (4-toluyl), dibenzoyl peroxide, peroxidating tert-butyl isobutyrate etc..Among these, it is particularly preferred to ground uses peroxy dicarbonate two (4-tert-butylcyclohexyl) ester of cross-linking reaction efficiency excellence, dilauroyl peroxide, dibenzoyl peroxide.
It addition, pass through the acrylic adhesive composition used in the present invention adds ionic compound, thus from the view point of not only give electrostatic-proof function but also suppress the sheet resistance of transparency conducting layer to rise, it is preferred.
As ionic compound, it is preferable to use alkali metal salt and/or organic cation-anion salt.Alkali metal salt can use alkali-metal organic salt and inorganic salt.Additionally, so-called heretofore described " organic cation-anion salt " refers to that for the compound that organic salt and its cation portion are made up of Organic substance, anion portion can be Organic substance, it is possible to for inorganic matter." organic cation-anion salt " is also referred to as ionic liquid, ionic solid.
It addition, as ionic compound, except above-mentioned alkali metal salt, organic cation-anion salt, it is possible to enumerate: the inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, iron chloride, ammonium sulfate.These ionic compounds can be used alone or and with multiple.
Additionally, in the acrylic adhesive composition used in the present invention, also can suitably use viscosity modifier as required in without departing from the scope of the object of the invention, peel off regulator, viscosifier, plasticizer, softening agent, comprise the filler of glass fibre, bead, metal powder, other inorganic powders etc., the various additives such as pigment, coloring agent (pigment, dyestuff etc.), pH adjuster (acid or alkali), antioxidant, UV absorbent.These additives also can coordinate in the form of an emulsion.
It addition, the acrylic adhesive composition used in the present invention can contain in this specification the phosphorus series compound recorded, but from the view point of with the adaptation of polarizing coating or coating layer, it is preferable that do not contain.
The forming method of above-mentioned adhesive phase 5 is not particularly limited, can be that coating aforesaid propylene acid is adhesive composition on various base materials, the exsiccators such as oven heat are utilized to be dried, solvent etc. is made to be vaporized and form adhesive phase, the method that this adhesive phase is needed on the coating layer side of the above-mentioned polarizing coating 1 with coating layer, it is possible to above-mentioned with on the coating layer of the polarizing coating 1 of coating layer directly coating aforesaid propylene acid be adhesive composition and form adhesive phase 5.
As above-mentioned base material, it is not particularly limited, for instance the various base materials such as mold release film, transparent resin film base material can be enumerated.
As the coating process to above-mentioned base material or polarizing coating, various method can be used.Specifically, for instance can enumerate: the coating of jetting type coating machine, print roll coating, contact print roll coating, intaglio plate, reversely coating, roll-type are brushed, spraying, leaching print roll coating, bar type coating, scraper for coating, airblade coating, curtain, die lip are coated with, utilize the method such as extrusion coating methods of mould coating machine etc..
Drying condition (temperature, time) is not particularly limited, and suitably can set according to the composition of acrylic adhesive composition, concentration etc., for instance be about 80～170 DEG C, it is preferred to 90～200 DEG C, be 1～60 minute, it is preferred to 2～30 minutes.
The thickness (after drying) of adhesive phase 5 is such as preferably 5～100 μm, more preferably 10～60 μm, more preferably 12～40 μm.If the thickness of adhesive phase 5 is lower than 10 μm, then the adaptation to bonded body is had to be deteriorated, the tendency that durability under high temperature, high temperature and humidity is insufficient.On the other hand, when the thickness of adhesive phase 5 is more than 100 μm, there is the coating of acrylic adhesive composition when forming adhesive phase 5, dry time dry fully and remain bubble, or produce uneven thickness or the tendency that apparent problem becomes apparent upon in the face of adhesive phase.
Constituent material as above-mentioned mold release film, such as can enumerate the suitable sheets etc. such as the porous materials such as the resin moldings such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, paper, cloth, non-woven fabrics, net, foamed sheet, metal forming and these layered product, from the view point of surface smoothness is excellent, it is preferable to use resin molding.
As this resin molding, for instance can enumerate: polyethylene film, polypropylene screen, polybutene film, polybutadiene film, polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, vinyl-vinyl acetate copolymer film etc..
The thickness of above-mentioned mold release film is generally 5～200 μm, it is preferred to about 5～100 μm.For above-mentioned mold release film, also can carry out utilizing the antistatic of the demoulding of silicone-based, fluorine system, chain alkyl system or the releasing agent of fatty acid amide system, SiO 2 powder etc. and antifouling process or application type, mixed milling type, evaporation type etc. to process as required.Suitably carry out the lift-off processing such as silicone-treated, chain alkyl process, fluorine process especially by the surface of above-mentioned mold release film, can further improve the fissility from above-mentioned adhesive phase.
As above-mentioned transparent resin film base material, it is not particularly limited, the various resin moldings with the transparency can be used.This resin molding can be formed by 1 tunic.Such as its material, can enumerate: the polyester based resin such as polyethylene terephthalate, PEN, acetas system resin, polyether sulfone system resin, polycarbonate-based resin, polyamide series resin, polyimides system resin, polyolefin-based resins, (methyl) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate system resin, polyphenylene sulfide system resin etc..Among these, it is particularly preferred to polyester based resin, polyimides system resin and polyether sulfone system resin.
The thickness of above-mentioned film base material is preferably 15～200 μm.
Adhesive phase is above-mentioned described above with the forming method on the coating layer of the polarizing coating 1 of coating layer.
It addition, when the adhesive phase with the polarizing coating of adhesive phase of the present invention exposes, it is possible with mold release film (partition) before for practicality and protects adhesive phase.As mold release film, mold release film as above can be enumerated.When using mold release film as base material when making above-mentioned adhesive phase, by the adhesive phase in mold release film and the polarizing coating laminating of iodine system, thus this mold release film can be used as the mold release film of the adhesive phase of the polarizing coating with adhesive phase, can carry out the simplification in operation.
The above-mentioned polarizing coating with adhesive phase of the present invention can use after fitting in the way of the adhesive phase making the polarizing coating with adhesive phase contacts with the transparency conducting layer of the component with transparency conducting layer.
As the component with transparency conducting layer, it is not particularly limited, known component can be used, the component on the transparent bases such as hyaline membrane with transparency conducting layer can be enumerated or there is the component of transparency conducting layer and liquid crystal cells.
As transparent base, as long as having transparent base material, for instance the base material (such as lamellar or base material etc. membranaceous, tabular) etc. including resin molding or glass etc. can be enumerated, it is particularly preferred to for resin molding.The thickness of transparent base is not particularly limited, it is preferred to about 10～200 μm, more preferably about 15～150 μm.
As the material of above-mentioned resin molding, it is not particularly limited, the various plastic materials with the transparency can be enumerated.Such as its material, can enumerate: the polyester based resin such as polyethylene terephthalate, PEN, acetas system resin, polyether sulfone system resin, polycarbonate-based resin, polyamide series resin, polyimides system resin, polyolefin-based resins, (methyl) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate system resin, polyphenylene sulfide system resin etc..Among these, it is particularly preferred to polyester based resin, polyimides system resin and polyether sulfone system resin.
Additionally, for above-mentioned transparent base, it is possible to surface is implemented in advance the etch processes such as sputtering, corona discharge, flame, ultraviolet radiation, electron beam irradiation, chemical conversion, oxidation or primary coat and processes and promote the transparency conducting layer that the is arranged on adaptation for above-mentioned transparent base.It addition, before arranging transparency conducting layer, be possible with solvent clean, ultrasonic waves for cleaning etc. as required and carry out dedusting, clean.
As the constituent material of above-mentioned transparency conducting layer, being not particularly limited, the metal-oxide of at least one metal in the group that free indium, stannum, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten form is selected in use.In this metal-oxide, as required also can possibly together with the metallic atom shown in above-mentioned group.Such as can be preferably used the Indium sesquioxide. (ITO) containing stannum oxide, the stannum oxide etc. containing antimony, can particularly preferably use ITO.As ITO, it is preferable that containing Indium sesquioxide. 80～99 weight % and stannum oxide 1～20 weight %.
It addition, as above-mentioned ITO, crystallinity ITO, amorphism (amorphous) ITO can be enumerated.Crystallinity ITO by applying high temperature when sputtering or and then can heat amorphism ITO and obtain.Above-mentioned deterioration caused by iodine can produce significantly on amorphism ITO, so the polarizing coating with adhesive phase of the present invention is effective especially for amorphism ITO.
The thickness of above-mentioned transparency conducting layer is not particularly limited, it is preferable that be set to more than 7nm, is more preferably set to more than 10nm, more preferably it is set to 12～60nm, more preferably it is set to 15～45nm, is more preferably set to 18～45nm, it is particularly preferred to for being set to 20～30nm.If the thickness of transparency conducting layer is lower than 7nm, then there is the deterioration easily producing the transparency conducting layer caused by iodine, the tendency that the change of the resistance value of transparency conducting layer increases.On the other hand, when more than 60nm, having the productivity of transparency conducting layer to reduce, cost also rises, and then the tendency that optical characteristics also reduces.
As the forming method of above-mentioned transparency conducting layer, it is not particularly limited, known method can be adopted.Specifically, for instance can illustrate vacuum vapour deposition, method in sputtering method, ion plating.It addition, adopt suitable method also dependent on required thickness.
As the thickness of the base material with above-mentioned transparency conducting layer, 15～200 μm can be enumerated.And then, for the viewpoint of filming, it is preferred to 15～150 μm, more preferably 15～50 μm.When using the base material with above-mentioned transparency conducting layer in resistive film mode, for instance the thickness of 100～200 μm can be enumerated.It addition, when using with capacitance-type, for instance it is preferably the thickness of 15～100 μm, particularly with further filming requirement in recent years, more preferably the thickness of 15～50 μm, the more preferably thickness of 20～50 μm.
It addition, between transparency conducting layer and transparent base, priming coat can be set as required, oligomer prevents layer etc..
Additionally, as the component with transparency conducting layer and liquid crystal cells, the side not contacted with liquid crystal layer at this substrate of the liquid crystal cells of the composition comprising substrate (such as glass substrate etc.)/liquid crystal layer/substrate used in the image display devices such as various liquid crystal indicators can be enumerated there is the component of transparency conducting layer.It addition, when filter substrate is set on liquid crystal cell, it is possible on this color filter, there is transparency conducting layer.The method forming transparency conducting layer on the substrate of liquid crystal cells is same as described above.
3. image display device
Even if the polarizing coating with adhesive phase of the present invention is as it has been described above, when this is with stacking transparency conducting layer on the adhesive phase of the polarizing coating of adhesive phase, also can suppress the corrosion of transparency conducting layer, and the sheet resistance of transparency conducting layer can be suppressed to rise.Therefore, if the image display device of composition that contacts with transparency conducting layer of the adhesive phase for having a polarizing coating with adhesive phase, so that it may the polarizing coating with adhesive phase of the use present invention aptly.Such as the polarizing coating with adhesive phase of the present invention can be fitted with the liquid crystal panel with transparency conducting layer in the way of the adhesive phase of the above-mentioned polarizing coating with adhesive phase contacts with the transparency conducting layer of above-mentioned liquid crystal panel and make image display device.
And then specifically, can enumerate and use transparency conducting layer as the image display device of antistatic backing purposes or to use transparency conducting layer as the image display device of the electrode applications of touch panel.As using the transparency conducting layer image display device as antistatic backing purposes, specifically, for instance can enumerate: comprise constituting and image display device that above-mentioned antistatic backing, drive electrode are formed of polarizing coating/adhesive phase/antistatic backing/glass substrate/liquid crystal layer/drive electrode/glass substrate/adhesive phase/polarizing coating by transparency conducting layer.As the polarizing coating with adhesive phase of the upside (observation side) of this image display device, the polarizing coating with adhesive phase of the present invention can be used.Additionally, as using the transparency conducting layer image display device as the electrode applications of touch panel, such as can enumerate: for the composition (In-Cell type touch panel) of sensor layer/glass substrate/adhesive phase/polarizing coating of sensor layer/glass substrate/liquid crystal layer/double as drive electrode of polarizing coating/adhesive phase/double as antistatic backing, or the composition (On-Cell type touch panel) of the sensor layer/sensor layer/glass substrate/liquid crystal layer/drive electrode/glass substrate/adhesive phase/polarizing coating of polarizing coating/adhesive phase/double as antistatic backing and double as the sensor layer of antistatic backing, sensor layer, the image display device that drive electrode is formed by transparency conducting layer.As the polarizing coating with adhesive phase of the upside (observation side) of this image display device, the polarizing coating with adhesive phase of the present invention can be used.
Embodiment
Hereinafter, the present invention is described in detail to use embodiment, but as long as less than its purport, then the present invention is not limited to below example.
<content of iodine in polaroid>
Content of iodine (content of iodine and/or iodide ion) in polaroid is measured according to following operation.
1) multiple polaroids comprising ormal weight potassium iodide are measured fluorescent X-ray intensity, derive the relational expression of content of iodine and fluorescent X-ray intensity.
2) fluorescent X-ray of the unknown iodine system polaroid of content of iodine is measured, by this numerical value and use above-mentioned relation formula to calculate iodine number.
<mensuration of the weight average molecular weight (Mw) of acrylic acid series polymeric compounds>
The weight average molecular weight of the acrylic acid series polymeric compounds made is measured by GPC (gel permeation chromatography).
Device: Dong Cao company system, HLC-8220GPC
Post:
Sample column: Dong Cao company system, TSKguardcolumnSuperHZ-H
(1)+TSKgelSuperHZM-H (2)
Reference column: Dong Cao company system, TSKgelSuperH-RC (1)
Flow: 0.6mL/min
Injection rate: 10 μ L
Column temperature: 40 DEG C
Eluent: THF
Inject sample solution concentration: 0.2 weight %
Detector: differential refractometer
Additionally, weight average molecular weight is calculated by polystyrene conversion.
Manufacture example 1 (making of one side protection polarizing coating)
Masking in amorphism PET base material is made to have the duplexer of PVA layer of 9 μ m-thick to generate tensile layer stack by the aerial assisting tension at draft temperature 130 DEG C.Then, tensile layer stack is impregnated 60 seconds in the dyeing liquor containing iodine 0.1 weight portion, potassium iodide 0.7 weight portion relative to water 100 weight portion and generate dyed layer stack.And then, utilizing to stretch in the boric acid water at draft temperature 65 DEG C becomes, by total stretching ratio, the optical film laminate making dyed layer stack and amorphism PET base material one stretch in the way of in the of 5.94 times and to generate the PVA layer comprising 4 μ m-thick.Stretched by above-mentioned 2 steps, the optical film laminate of the PVA layer comprising thickness 4 μm constituting high function polarization layer can be generated, described high function polarization layer makes the PVA numberator height ground orientation of the PVA layer of institute's masking in amorphism PET base material, makes the iodine that adsorbs by dyeing with the form of poly-iodide ion complex highly orientation in one direction.And then; surface coating PVA system bonding agent at the polarization layer of this optical film laminate; and fit after the acrylic resin film (transparent protective film) of 40 μ m-thick of saponification process, the stripping of amorphism PET base material is made the one side protection polarizing coating only in the one side employing slim iodine system polaroid with transparent protective film.Hereinafter, one side protection polarizing coating (1) it is referred to as.The content of iodine of one side protection polarizing coating (1) is 5.1 weight %.
Manufacture example 2 (coating layer forms the preparation with resin combination (A1))
The PVA resin of the degree of polymerization 2500,99.0 moles of % of saponification degree is dissolved in pure water, prepare the aqueous solution of solid component concentration 4 weight %, then relative to solid constituent 100 weight portion of the above-mentioned polyvinyl alcohol resin in this aqueous solution, add mono phosphoric acid ester butyl ester (trade name: the MP-4 of 2 weight portions as phosphorus series compound, big eight chemical industry (strain) are made), obtain coating layer formation resin combination (A1).
Manufacture example 3 (coating layer forms the preparation with resin combination (A2))
The PVA resin of the degree of polymerization 2500,99.0 moles of % of saponification degree is dissolved in pure water, prepares the aqueous solution of solid component concentration 4 weight %, it can be used as coating layer formation resin combination (A2).
Manufacture example 4 (coating layer forms the preparation with resin combination (A3))
By N-hydroxyethyl acrylamide (trade name: HEAA, (strain) emerging people's system) 12.5 parts, acryloyl morpholine (trade name: ACMO (registered trade mark), (strain) emerging people's system) 25 parts, dihydroxymethyl tristane diacrylate (trade name: lightacrylateDCP-A, common prosperity society chemistry (strain) system) 62.5 parts, optical free radical polymerization initiator (2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, trade name: IRGACURE907, BASF AG's system) 2 parts, photosensitizer (diethyl thioxanthone, trade name: KAYACUREDETX-S, Japan's chemical medicine (strain) system) 2 parts of mixing, stir 1 hour at 50 DEG C, obtain mixture.Additionally, solid constituent 100 weight portion relative to said mixture, add the mono phosphoric acid ester butyl ester (trade name: MP-4, big eight chemical industry (strain) are made) of 2 weight portions as phosphorus series compound, obtain coating layer formation resin combination (A3).
Manufacture example 5 (coating layer forms the preparation with resin combination (A4))
Except without, except phosphorus series compound, according to the method same with manufacturing example 4, obtaining coating layer formation resin combination (A4).
Manufacture example 6 (coating layer forms the preparation with resin combination (A5))
The PVA resin of the degree of polymerization 2500,99.0 moles of % of saponification degree is dissolved in pure water, prepare the aqueous solution of solid component concentration 4 weight %, then relative to solid constituent 100 weight portion of the above-mentioned polyvinyl alcohol resin in this aqueous solution, add the phenyl-phosphonic acid (with light pure pharmaceutical worker industry (strain) reagent processed) of 5 weight portions as phosphorus series compound, obtain coating layer formation resin combination (A5).
Manufacture example 7 (coating layer forms the preparation with resin combination (B1))
Carbamate based polymer 30～90 weight % will be contained with solid component meter, solution (trade name: DenatronP-580W with polythiophene based polymer (conductive material) 10～50 weight %, long rapids chemical conversion (strain) system), solution (trade name: EpocrosWS-700 with acrylic acid series polymeric compounds 10～70 weight % comprised with solid component meter containing azoles quinoline base, Japan's catalyst (strain) system) add in (mixing) solution of water 100 weight %, it is prepared in the way of solid component concentration (base concentration) reaches 0.4 weight %, obtain coating layer formation resin combination (B1).
Manufacture example 8 (coating layer forms the preparation with resin combination (B2))
Replace manufacturing the DenatronP-580W of example 7 and use carbamate based polymer solution (trade name: the DenatronB-510C that do not comprise polythiophene based polymer, long rapids chemical conversion (strain) system), obtain coating layer formation resin combination (B2) according to the method same with manufacturing example 7 in addition.
Manufacture example 9 (making of acrylic adhesive layer (C1))
Possessing condensing tube, nitrogen ingress pipe, temperature take into account in the reaction vessel of agitating device, butyl acrylate 99 parts, acrylic acid 4-hydroxybutyl 1 part and add up to (solid constituent) 100 parts to be 0.3 part relative to described monomer 2 are added together with ethyl acetate, 2 '-azodiisobutyronitrile, react after 4 hours under stream of nitrogen gas and at 60 DEG C, in this reactant liquor, add ethyl acetate and obtain the polymer solution (solid component concentration 30 weight %) of acrylic acid series polymeric compounds (a1) containing weight average molecular weight 1,650,000.Solid constituent 100 parts relative to aforesaid propylene acid based polymer solution, coordinate dibenzoyl peroxide (trade name: the NYPERBMT as 0.3 part of cross-linking agent, Nippon Yushi (Co., Ltd.)), trimethylolpropane dimethyl diisocyanate (trade name: the TakenateD110N of 0.1 part, three well force field chemistry (strain) systems), silane coupler (trade name: the A-100 containing acetoacetyl of 0.2 part, combine and grind chemistry (strain) system), with as mono phosphoric acid ester butyl ester (trade name: the MP-4 of 0.1 part of phosphorus series compound, big eight chemical industry (strain) are made), obtain acrylic adhesive solution.By the surface that aforesaid propylene acid is the release sheet (partition) formed by polyethylene terephthalate film (thickness: 38 μm) after binder solution (C1) coats lift-off processing, making dried thickness is 25 μm, dry formation adhesive phase (C1).
Manufacture example 10 (making of acrylic adhesive layer (C2))
When the preparation of binder solution without phosphorus series compound, it is identically formed acrylic adhesive layer (C2) with manufacture example 9 in addition.
Manufacture example 11 (making of acrylic adhesive layer (C3))
Add double; two (trifyl) acid imide of the 1-methyl isophthalic acid-ethyl pyrrolidine as conductive material (bank field chemistry (strain) system) 0.5 part when the preparation of binder solution further, be identically formed acrylic adhesive layer (C3) with manufacture example 9 in addition.
Manufacture example 12 (making of acrylic adhesive layer (C4))
When the preparation of binder solution without phosphorus series compound, it is identically formed acrylic adhesive layer (C4) with manufacture example 11 in addition.
Manufacture example 13 (making of acrylic adhesive layer (C5))
Possessing condensing tube, nitrogen ingress pipe, temperature take into account in the reaction vessel of agitating device, add together with ethyl acetate butyl acrylate 95 parts, acrylic acid 4-hydroxybutyl 1 part, 4 parts of acrylic acid and relative to described monomer add up to (solid constituent) 100 parts be 1 part as the 2 of initiator, 2 '-azodiisobutyronitrile, reacts 7 hours under stream of nitrogen gas and at 60 DEG C.Then, in this reactant liquor, add ethyl acetate and obtain the solution (solid component concentration 30 weight %) of acrylic acid series polymeric compounds (a2) containing weight average molecular weight 1,550,000.
The solution containing acrylic acid series polymeric compounds (a1) is replaced in manufacturing example 9, and use the above-mentioned solution containing acrylic acid series polymeric compounds (a2), coordinate cross-linking agent, silane coupler, phosphorus series compound to obtain acrylic adhesive solution in the same manner as manufacturing example 9 in addition.It addition, using aforesaid propylene acid is that binder solution is identically formed adhesive phase (C5) with manufacturing example 9.
Manufacture example 14 (making of acrylic adhesive layer (C6))
When the preparation of binder solution without phosphorus series compound, it is identically formed acrylic adhesive layer (C6) with manufacture example 13 in addition.
Manufacture example 15 (making of acrylic adhesive layer (C7))
Add double; two (trifyl) acid imide of the 1-methyl isophthalic acid-ethyl pyrrolidine as conductive material (bank field chemistry (strain) system) 0.5 part when the preparation of binder solution further, be identically formed acrylic adhesive layer (C7) with manufacture example 9 in addition.
Manufacture example 16 (making of acrylic adhesive layer (C8))
When the preparation of binder solution without phosphorus series compound, it is identically formed acrylic adhesive layer (C8) with manufacture example 15 in addition.
Embodiment 1
Use bar coating machine; face (polarization being not provided with transparent protective film the is unilateral) coating of the polaroid of one side protection polarizing coating (1) obtained in manufacturing example 1 is adjusted to coating layer formation resin combination (A1) of 25 DEG C; making dried thickness is 1 μm; then in 60 DEG C of hot air dryings 1 minute; form coating layer 1, make the one side with 1 layer of coating layer and protect polarizing coating.
Then; use bar coating machine; the one side with 1 layer of coating layer obtained in above-mentioned protects on the coating layer 1 of polarizing coating coating to be further adjusted to the coating layer compositions (B1) of 25 DEG C; making dried thickness is 1 μm; then in 60 DEG C of hot air dryings 1 minute; form coating layer 2, make the polarizing coating with 2 layers of coating layer.
Then, on the coating layer 2 of the polarizing coating with 2 layers of coating layer obtained in above-mentioned, laminating forms the adhesive phase (C2) in the lift-off processing face of above-mentioned release sheet (partition), makes the polarizing coating with adhesive phase.
Embodiment 2～11, comparative example 1～12
In embodiment 1 coating layer formation resin combination, adhesive phase are such as changed shown in table 1,2, form the polarizing coating with adhesive phase in addition similarly to Example 1.
Below the polarizing coating with adhesive phase obtained in above-described embodiment and comparative example is evaluated.Result is such as shown in table 1,2.
<resistance change rate>
The conductive film (trade name: Elecrysta (P400L), day east electrician (strain) manufacture) being formed with ITO layer on surface is cut into 15mm × 15mm, the polarizing coating with adhesive phase obtained in embodiment and comparative example is cut into 8mm × 8mm, after fitting in the central part on this conductive film after peeling off partition film, 50 DEG C, implement 15 minutes autoclaves under 5atm and process, using the sample that obtains as corrosion resistance measurement sample.Following determinator is used to measure the resistance value of the test sample obtained, it is set to " initial resistivity value ".
Then, by test sample in temperature 60 C, humidity 95% environment under put into after 500 hours, measure resistance value, be set to " resistance value after damp and hot ".Additionally, above-mentioned resistance value uses the HL5500PC that AccentOpticalTechnologies company manufactures to be measured.Resistance change rate (%) from " initial resistivity value " that record in the above described manner and " resistance value after damp and hot " and when calculating respective humid tropical condition according to following formula.
Resistance change rate is less than 150%, and the ascensional range of damp and hot caused resistance value is little, and corrosion resistance is good.
<closing force>
The polarizing coating with adhesive phase obtained in embodiment and comparative example is cut into the size of 25mm × 150mm, fits in the way of making its binding agent aspect contact with the evaporation face of the evaporation film having indium-stannum oxide at the polyethylene terephthalate film surface of 50 μ m-thick evaporation.Then, the end hands of above-mentioned polyethylene terephthalate film is peeled off, confirm that adhesive phase is attached to polyethylene terephthalate film rear flank, use the cupping machine AG-1 of (strain) Shimadzu Seisakusho Ltd., measure the stress (N/25mm) when (25 DEG C) are peeled off with the speed of 300mm/ minute along 180 ° of directions.
When closing force is more than 15N/25mm, it is absent from generation of adhesive deposit when doing over again, adds the adhesive paste deficiency in man-hour, well.
[table 1]
[table 2]
Abbreviation in table is as follows respectively.
(A1)～(A4): coating layer is formed with resin combination (A1)～(A4)
(B1), (B2): anchor layer compositions (B1), (B2)
(C1)～(C8): adhesive phase (C1)～(C8)
It addition, be recited as " with or without " project in, "○" represents " containing ", and "-" represents " not containing ".
Symbol description
1 with the polarizing coating of coating layer
2 iodine system polaroids
3 transparent protective films
4 coating layers
5 adhesive phases
6 with the polarizing coating of adhesive phase

Claims (12)

1., with a polarizing coating for coating layer, there is transparent protective film, iodine system polaroid containing iodine and/or iodide ion and coating layer successively, it is characterised in that
Described iodine system polaroid and/or described coating layer contain phosphorus series compound.
2. the polarizing coating with coating layer as claimed in claim 1, it is characterised in that
Described phosphorus series compound contains the phosphoric acid based compound of more than a kind in the polymer of the compound shown in the compound shown in following formula (1) and described formula (1) and/or selected from the phosphonic acids based compound of the compound shown in following formula (2) and more than a kind in salt thereof
In formula, R1And R2Represent hydrogen atom independently of one another, maybe can contain the hydrocarbon residue of the carbon number 1～18 of oxygen atom,
In formula, R is hydrogen atom, the hydrocarbon residue that maybe can contain the carbon number 1～18 of oxygen atom.
3. the polarizing coating with coating layer as claimed in claim 1 or 2, it is characterised in that
The thickness of described iodine system polaroid is less than 10 μm.
4. the polarizing coating with coating layer as according to any one of claims 1 to 3, it is characterised in that
Described iodine and/or the content of iodide ion in described iodine system polaroid are 3～12 weight %.
5. the polarizing coating with coating layer as according to any one of Claims 1 to 4, it is characterised in that
Between described iodine system polaroid and described coating layer, not there is transparent protective film.
6. the polarizing coating with coating layer as according to any one of Claims 1 to 5, it is characterised in that
Described coating layer is formed by the resin combination of at least one resin contained in polyurethane series resin, polyvinyl alcohol resin and acrylic resin.
7. the polarizing coating with adhesive phase, it is characterised in that
The coating layer side of the polarizing coating with coating layer according to any one of claim 1～6 has adhesive phase.
8. the polarizing coating with adhesive phase as claimed in claim 7, it is characterised in that
Described adhesive phase contains ionic compound.
9. as claimed in claim 7 or 8 with the polarizing coating of adhesive phase, it is characterised in that
The adhesive phase with the polarizing coating of adhesive phase described in claim 7 or 8 of fitting in the way of the transparency conducting layer with the transparent conductive member with transparency conducting layer contacts uses.
10. the polarizing coating with adhesive phase as claimed in claim 9, it is characterised in that
Described transparency conducting layer is formed by tin indium oxide.
11. the polarizing coating with adhesive phase as claimed in claim 10, it is characterised in that
Described tin indium oxide is noncrystalline tin indium oxide.
12. an image display device, it is characterised in that
The adhesive phase of the polarizing coating with adhesive phase according to any one of claim 7～11 is fitted in the way of making the described adhesive phase with the polarizing coating of adhesive phase contact with the transparency conducting layer of described liquid crystal panel with the liquid crystal panel with transparency conducting layer.
CN201510977156.XA 2014-12-24 2015-12-23 Polarizing film with coating layer, polarizing film with adhesive layer, and image display device Active CN105738998B (en)

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KR20160078257A (en) 2016-07-04
CN105738998B (en) 2020-06-16
JP6684043B2 (en) 2020-04-22

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