CN100410694C - Polarizing plate and its mfg method - Google Patents
Polarizing plate and its mfg method Download PDFInfo
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- CN100410694C CN100410694C CNB2004100571146A CN200410057114A CN100410694C CN 100410694 C CN100410694 C CN 100410694C CN B2004100571146 A CNB2004100571146 A CN B2004100571146A CN 200410057114 A CN200410057114 A CN 200410057114A CN 100410694 C CN100410694 C CN 100410694C
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- Prior art keywords
- film
- polarizer
- polarizing film
- light polarizing
- resin
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
Abstract
To improve adhesion strength between films by using an appropriate adhesive, in a process of laminating a protective film, made of a cycloolefin resin, on a polyvinylalcohol polarizing film to obtain a polarizing plate. The polarizing plate comprises layers of a polarizing film, made of a polyvinylalcohol resin and a cycloolefin resin film laminated on at least via one surface of the polarizing film with an adhesive layer. The adhesive layer comprises a polyester ionomer urethane resin and a compound having a glycidyloxy group. The method for manufacturing the polarizing plate is carried out, by laminating a cycloolefin resin film on a polarizing film made of a polyvinylalcohol resin, with an aqueous adhesive containing a polyester ionomer urethane resin and a compound having a glycidyloxy group.
Description
Technical field
The present invention relates to a kind of bonding cycloolefin based resin film forms on the light polarizing film that polyvinyl alcohol resin forms Polarizer and manufacture method thereof.
Background technology
Polarizer is normally on by surface of the light polarizing film that forms of polyvinyl alcohol resin that is adsorbed with bitintability pigment and orientation or two surfaces; transparent resin film by adhesive layer is stacked, for example Triafol T is that the cellulose acetate class diaphragm of representative constitutes.Adopt cementing agent and this Polarizer is fitted on the liquid crystal cell, make the component parts of liquid crystal display cells by other required optical thin film.
Along with the purposes of liquid crystal indicator enlarges, in order to use under various environment, it is higher environment resistant to require its component parts to have.For example, in the liquid crystal indicator of mobile purposes that with the portable phone is representative, expect that it also can use under damp and hot condition.And wherein used Polarizer is also required to have high moisture-proof heat durability.But in the Polarizer of existing structure, if expose the long period under damp and hot especially environment, the problem of generation comprises that its polarizing properties descends easily, and peel off easily at the interface of light polarizing film and cellulose acetate class film.
At these problems, proposed the scheme of thermoplasticity cycloolefin resinoid as the diaphragm use of Polarizer.For example (patent documentation 1) put down in writing at least one surface of polyvinyl alcohol thin slice by the stacked thermoplasticity saturated norbornene of acrylic adhesive resin sheet in Japanese patent laid-open 5-212828 communique, and made the scheme of Polarizer by hot pressing.(patent documentation 2) discloses the scheme that the diaphragm that is formed by thermoplasticity saturated norbornene resinoid by lamination is made Polarizer at least one surface of polyvinyl alcohol light polarizing film in Japanese patent laid-open 6-51117 communique; used for this reason cementing agent has exemplified by mixing dry lamination that polyurethanes resin solution and polyisocyanate class solution forms with cementing agent, styrene butadiene ribber class cementing agent, epoxies biliquid curing type cementing agent etc.In addition; open (patent documentation 3) in the 2000-321430 communique the Jap.P. spy and disclose the adhesive layer that forms by the potpourri by polyvinyl alcohol cementing agent and dual liquid type cementing agent at least one surface in the polyvinyl alcohol light polarizing film, the diaphragm that lamination is made by the cyclic olefin resinoid is made the scheme of Polarizer.In addition, open the diaphragm that (patent documentation 4) discloses polyvinyl alcohol light polarizing film and the formation of thermoplasticity saturated norbornene resinoid in the 2000-321432 communique the Jap.P. spy and bond, make the scheme of Polarizer by the polyurethanes cementing agent.
But himself thickness of the cementing agent of acrylic compounds etc. (being also referred to as the pressure-sensitive cementing agent) is the 10-50 micron, must have thickness to a certain degree.Therefore in addition, dry lamination contains organic solvent with cementing agent, styrene butadiene ribber class cementing agent, epoxies biliquid curing type cementing agent etc., aspect environment and to operator's healthy aspect existing problems.And, if when this cementing agent that comprises organic solvent is used for existing not with an organic solvent Polarizer manufacturing equipment, antiknock device need be set newly, produce the trouble of scrap build.In addition, under the situation of such as the cementing agent that adopts general known polyvinyl alcohol or carbamates, acrylic compounds, vinyl acetate class etc. with polyvinyl alcohol light polarizing film and cycloolefin resin film bonding, by the combination of two kinds of films, be difficult to obtain enough cohesiveness.
On the other hand, in the prior art mainly with Triafol T etc. as diaphragm, the bonding mode between itself and the polyvinyl alcohol light polarizing film has been proposed various schemes.For example in Japanese patent laid-open 8-101307 communique (patent documentation 5), put down in writing the stacked Polarizer that forms of cementing agent that polyvinyl alcohol light polarizing film and support (diaphragm) are formed by the pure and mild aliphatics polyvalent isocyanate of polyester polyols.
Jap.P. patent documentation 1 spy opens flat 5-212828 communique
Jap.P. patent documentation 2 spies open flat 6-51117 communique
Jap.P. patent documentation 3 spies open the 2000-321430 communique
Jap.P. patent documentation 4 spies open the 2000-321432 communique
Jap.P. patent documentation 5 spies open flat 8-101307 communique
This shows that above-mentioned existing Polarizer and manufacture method thereof obviously still have inconvenience and defective, and demand urgently further being improved in structure, manufacture method and use.In order to solve the problem that Polarizer and manufacture method thereof exist, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and common product does not have appropriate structure to address the above problem, and this obviously is the problem that the anxious desire of relevant dealer solves.
Because the defective that above-mentioned existing Polarizer and manufacture method thereof exist, the inventor is based on being engaged in this type of product design manufacturing abundant for many years practical experience and professional knowledge, and the utilization of scientific principle is gone up in cooperation, actively studied innovation, in the hope of founding a kind of new Polarizer and manufacture method thereof, can improve general existing Polarizer and manufacture method thereof, make it have more practicality.Through constantly research, design, and after studying sample and improvement repeatedly, create the present invention who has practical value finally.
Summary of the invention
The objective of the invention is to; overcome the defective that existing Polarizer exists; and provide a kind of new Polarizer; technical matters to be solved is to make its stacked diaphragm that is formed by the cycloolefin resinoid on the polyvinyl alcohol light polarizing film; during with the preparation Polarizer; by adopting suitable cementing agent to improve cohesive force between the two, thereby be suitable for practicality more.
Another object of the present invention is to, overcome the defective that existing polarizing plate making method exists, and provide a kind of polarizing plate making method, technical matters to be solved is to make it adopt the aqueous binders that does not contain organic solvent in fact, polyvinyl alcohol light polarizing film and cycloolefin based resin film are firmly bonded together, make Polarizer thus, thereby be suitable for practicality more.
Present inventors etc. have carried out wholwe-hearted research at these purposes; when found that on the polyvinyl alcohol light polarizing film the stacked diaphragm that forms by the cycloolefin resinoid; cooperate the potpourri that forms as cementing agent by adopting by special component; can obtain the Polarizer of cohesiveness excellence between polyvinyl alcohol light polarizing film and the diaphragm, obtain the present invention thus.
Promptly, the invention provides a kind of Polarizer, it is the Polarizer that forms by adhesive layer stacked ring olefine kind resin film at least one surface of the light polarizing film that polyvinyl alcohol resin forms, and this adhesive layer is formed by polyesters ionomer type carbamate resins and the compound that contains glycidoxypropyl.
At this, the cycloolefin based resin film is configurable on a surface of light polarizing film, perhaps is configured on two films of light polarizing film.On a surface of light polarizing film during stacked cycloolefin resinoid, can the stacked diaphragm of making by the resin beyond the cycloolefin resinoid, for example cellulose acetate class film on another surface.
In addition, the present invention also provides a kind of manufacture method of Polarizer, it by comprising polyesters ionomer type carbamate resins and the aqueous binders stacked ring olefine kind resin film that contains glycidoxypropyl, forms Polarizer by on the light polarizing film that forms at polyvinyl alcohol resin thus.At this, aqueous binders can not contain the form of organic solvent in fact to be used.
Via as can be known above-mentioned, the invention relates to a kind of Polarizer and manufacture method thereof, be that the stacked diaphragm of being made by the cycloolefin resinoid improves cohesiveness between the two by using suitable cementing agent when making Polarizer on the polyvinyl alcohol light polarizing film.This Polarizer, be the Polarizer that forms by adhesive layer stacked ring olefine kind resin film at least one surface of the light polarizing film that polyvinyl alcohol resin forms, this adhesive layer is formed by polyesters ionomer type carbamate resins and the compound that contains glycidoxypropyl.In addition, the manufacture method of this Polarizer, be by on the light polarizing film that forms at polyvinyl alcohol resin, come stacked ring olefine kind resin film with the aqueous binders that contains glycidoxypropyl, make Polarizer thus by comprising polyesters ionomer type carbamate resins.
By technique scheme, Polarizer of the present invention and manufacture method thereof have following advantage at least:
Compare with the situation that adopts cementing agent of the prior art,, can make the Polarizer of cohesiveness excellence between the diaphragm that polyvinyl alcohol light polarizing film and cycloolefin resinoid are made according to the present invention.In addition; when making this Polarizer,, be favourable therefore to environment and safety and sanitation aspect owing to need not with an organic solvent; and can adopt with prior art in make Polarizer by transparent protective film/light polarizing film equipment make the samely, need not bigger equipment investment.
In sum, the Polarizer that the present invention is special is the stacked diaphragm that is formed by the cycloolefin resinoid on the polyvinyl alcohol light polarizing film, with preparation during Polarizer, improves cohesive force between the two by adopting suitable cementing agent.In addition, the polarizing plate making method that the present invention is special is to adopt the aqueous binders that does not contain organic solvent in fact, and polyvinyl alcohol light polarizing film and cycloolefin based resin film are firmly bonded together, and makes Polarizer thus.It has above-mentioned many advantages and practical value, and in like product and manufacture method, do not see have similar structural design and method to publish or use and really genus innovation, no matter it all has bigger improvement on product structure, manufacture method or function, have large improvement technically, and produced handy and practical effect, and more existing Polarizer and manufacture method thereof have the multinomial effect of enhancement, thereby be suitable for practicality more, and have the extensive value of industry, really be a new and innovative, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of instructions, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by a plurality of preferred embodiments, be described in detail as follows.
Embodiment
Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with preferred embodiment, to Polarizer and its embodiment of manufacture method, structure, manufacture method, step, feature and the effect thereof that foundation the present invention proposes, describe in detail as after.
Polarizer is by making by the stacked transparent protective film of adhesive layer on one or two surface of the light polarizing film of making at polyvinyl alcohol resin.The light polarizing film of being made by polyvinyl alcohol resin particularly is to adsorb the bitintability pigment and be orientated to form in the polyvinyl alcohol resin film of uniaxial extension.In the present invention, as stacked diaphragm at least one surface of above-mentioned light polarizing film, adopt the cycloolefin based resin film, and, adopt polyesters ionomer type carbamate resins and the potpourri that contains glycidoxypropyl as cementing agent.
The polyvinyl alcohol resin that constitutes Polarizer can obtain by the polyvinyl acetate resinoid is alkalized.As the polyvinyl acetate resinoid, except polyvinyl acetate, can also enumerate vinyl acetate and other polymerisable monomer formation interpolymer etc. as vinyl acetate list polymers.As with other monomer of vinyl acetate copolymerization, can enumerate for example unsaturated carboxylic acid class, olefines, the ethene ethers, the unsaturated sulfonic acid class has the acrylic amide of ammonium etc.The basicity of polyvinyl alcohol resin is generally 85-100 mole %, preferably at 98 moles more than the %.This polyvinyl alcohol resin can further be modified, and for example can use by aldehydes modified polyethylene alcohol resinoid and polyvinyl acetal etc.In addition, the degree of polymerization of polyvinyl alcohol resin is generally 1000-10000, is preferably 1500-5000.
By the film that this polyvinyl alcohol resin is made, the former anti-film that can be used as light polarizing film uses.The film-forming method of polyvinyl alcohol resin is not particularly limited, and can adopt known method system film.Thickness to the former anti-film of polyvinyl alcohol is not particularly limited, and for example can be 10 microns-150 microns.
Light polarizing film is made through following steps usually: the step of this polyvinyl alcohol resin film being carried out uniaxial extension, with the bitintability pigment polyvinyl alcohol resin film is dyeed, to adsorb the step of this bitintability pigment, the step that the polyvinyl alcohol resin film that has adsorbed the bitintability pigment is handled with boric acid aqueous solution, and by after this boric acid aqueous solution processing, the step of washing.
The uniaxial extension step can be implemented before dyeing, also can implement with staining procedure, also can implement after dyeing.Implementing after the dyeing under the situation of uniaxial extension, this uniaxial extension can be implemented before boric acid is handled, and also can implement in the boric acid processing procedure.Certainly, also can implement uniaxial extension in above-mentioned a plurality of stages.When uniaxial extension, can adopt two different rollers of circular velocity to carry out uniaxial extension, also can adopt hot-rolling to carry out uniaxial extension.In addition, can adopt in atmosphere the dry type of implementing to extend etc. to extend mode, also can adopt wet type to extend, the mode of extending under the state that promptly in solvent, expands.Extension ratio is generally 3-8 doubly.
When adopting the bitintability pigment that the polyvinyl alcohol resin film is dyeed, for example can in the aqueous solution that includes the bitintability pigment, implement polyvinyl alcohol resin is thin film dipped.As the bitintability pigment, specifically can adopt iodine and bitintability dyestuff.Wherein preferably before dyeing is handled, the polyvinyl alcohol resin film is carried out dip treating in water.
Adopting under the situation of iodine as the bitintability pigment, adopt the thin film dipped method that in the aqueous solution that comprises iodine and potassium iodide, dyes of polyvinyl alcohol resin usually.In this aqueous solution, the content of iodine is generally per 100 weight parts waters and contains the 0.01-1 weight portion.The content of potassium iodide is generally per 100 weight parts waters and contains the 0.5-20 weight portion.The temperature of used aqueous solution is generally 20-40 ℃ during dyeing.In addition, the dip time in this aqueous solution (dyeing time) is generally 20-1800 second.
On the other hand, adopting under the situation of bitintability dyestuff as the bitintability pigment, adopt the thin film dipped method that in the aqueous solution that comprises water-soluble bitintability dyestuff, dyes of polyvinyl alcohol resin usually.In this aqueous solution, the content of bitintability dyestuff is generally per 100 weight parts waters and contains 1 * 10-4-10 weight portion, preferably comprises 1 * 10-3-1 weight portion, in addition, and also can be for example below 1 * 10-2 weight portion.This aqueous solution can comprise the inorganic salts as sodium sulphate of dyeing assistant etc.The temperature of used aqueous dye solutions is generally 20-80 ℃ during dyeing.In addition, the dip time in this aqueous solution (dyeing time) is generally 10-1800 second.
Carry out the boric acid processing after adopting the bitintability pigment dyeing, this step is to implement in comprising the aqueous solution of boric acid by the polyvinyl alcohol resin that will be colored is thin film dipped.In comprising the aqueous solution of boric acid, the amount of boric acid is generally per 100 weight parts waters and contains the 2-15 weight portion, preferably contains the 5-12 weight portion.Under the situation that iodine is used as the bitintability pigment, this borated aqueous solution preferably contains potassium iodide.In borated aqueous solution, the amount of potassium iodide is generally per 100 weight parts waters and contains the 0.1-15 weight portion, preferably contains the 5-12 weight portion.Dip time in borated aqueous solution is generally 60-1200 second, is preferably 150-600 second, more preferably 200-400 second.The temperature of borated aqueous solution is preferably 50-85 ℃ usually more than 50 ℃, more preferably 60-80 ℃.
Polyvinyl alcohol resin film after boric acid is handled is washed processing usually.Washing is for example handled and can be implemented in water borated polyvinyl alcohol resin is thin film dipped.Water temperature when washing is handled is generally 5-40 ℃, and dip time is generally 1-120 second.Carry out dried after the washing, obtain light polarizing film.Dried adopts air drier or far infra-red heater to implement usually.The temperature of dried is generally 30-100 ℃, is preferably 50-80 ℃.The time of dried is generally 60-600 second, is preferably 120-600 second.
Handle the acquisition light polarizing film by the polyvinyl alcohol resin film being implemented uniaxial extension, bitintability pigment dyeing and boric acid thus.The thickness of this light polarizing film is the 5-40 micron.In the present invention, at least one surface of this light polarizing film,, make Polarizer by adhesive layer stacked ring olefine kind resin film.
Described cycloolefin resinoid is for example for having the thermoplastic resin of the similar norborene and the monomeric unit of cyclic olefin (cycloolefin) formation of many ring norborneol vinyl monomers.This cycloolefin resinoid is except the ring-opening polymerization polymer that can be above-mentioned cycloolefin or adopt the hydrogenation products of the ring opening copolymer thing that cycloolefin obtains more than 2 kinds, also can or have the additional multipolymer of the aromatics of vinyl for cycloolefin and chain alkene.In addition, the polymkeric substance that has imported polar group also is effective.
Under the situation of multipolymer that is cycloolefin and chain alkene or aromatics with vinyl, example as chain alkene, can enumerate ethene and propylene etc., in addition, as the example of aromatics, can enumerate the styrene of styrene, α-Jia Jibenyixi, the replacement of nuclear alkyl etc. with vinyl.In this interpolymer, the monomeric unit that is formed by cycloolefin for example can be 15-50 mole % at 50 moles below the %.In particular for cycloolefin and chain alkene and have under the situation of terpolymer of aromatics of vinyl, comparable this scope of monomeric unit that is formed by cycloolefin is little.In this terpolymer, the monomeric unit that is formed by chain alkene is generally 5-80 mole %, and the monomeric unit that is formed by the aromatics with vinyl is generally 5-80 mole %.
As commercially available thermoplasticity cyclic olefin resinoid, " Topas " that the Ticona society sale of De イ Star is for example arranged, " ア-ト Application " that ジ エ イ エ ス ア-Le Co., Ltd. sells, " the ゼ オ ノ ア (ZEONOR) " and " ゼ オ ネ Star Network ス (ZEONEX) " that Japan ゼ オ Application Co., Ltd. sells, " the ア ペ Le " that Mitsui Chemicals, Inc sells etc.By to these cycloolefin resinoid system films to form film, when the system film, can adopt the known method of solvent cast method, extrusion by melting etc.Also sell the cycloolefin based resin film make film on the market, " エ ス シ-Na " and " SCA40 " that Sekisui Chemical Co., Ltd sells for example arranged and from " the ゼ オ ノ ア film " of the sale of オ プ テ ス Co., Ltd. etc.
The thickness of diaphragm is preferably thinner, if but thickness is too thin, strength degradation then, the processability variation, on the other hand when this thickness too thick, will produce transparency reduction, perhaps the problem of the bigger grade of the weight of Polarizer.Therefore, the diaphragm particularly suitable thickness of cycloolefin based resin film is the 5-200 micron for example, is preferably the 10-150 micron, more preferably the 20-100 micron.
The diaphragm that is formed by this cycloolefin resinoid can be fitted on the surface of light polarizing film, also can be fitted on two surfaces.Under the situation of the diaphragm that applying on two surfaces of light polarizing film is made by the cycloolefin resinoid, 2 diaphragms can be identical type or are different kinds.Under the situation of the diaphragm that applying on the surface of light polarizing film is made by the cycloolefin resinoid, with the diaphragm that can fit on this surface facing surfaces and make by the resin beyond the cycloolefin resinoid.As the example of the due care film of making by the resin beyond the cycloolefin resinoid, can enumerate in the prior art widely used cellulose acetate based resin film in polarization board protective film.The cellulose acetate based resin film for example can be cellulose triacetate film or cellulose diacetate film etc.Cellulose triacetate film includes " Off ジ Star Network TD80 ", " the Off ジ Star Network TD80UF " and " Off ジ Star Network TD80UZ " that Fuji description film Co., Ltd. sells, from " KC8UX2M " and " KC8UY " of the sale of コ ニ カ Co., Ltd. etc.The thickness of cellulose acetate class diaphragm is the 20-200 micron.In addition; as other example of the diaphragm of making by the resin beyond the cycloolefin resinoid, also can enumerate the film of the film made as the polyester resin of polyethylene terephthalate, poly-naphthalene glycol ester, polybutylene terephthalate, optical transparence excellences such as film that polycarbonate resin is made.
In said protection film, for can implement also with the surface of the surface opposite that is pasted with light polarizing film that non-glare treated, hard conating are handled, the surface treatment of anti-charged processing, antireflection processing etc.In addition, also can form the coating that forms by liquid crystal compounds and high-molecular weight compounds etc. thereof.Under the situation of the diaphragm of making by the cycloolefin resinoid when fitting on two surfaces in light polarizing film; can apply these surface treatments and coating to a surface of film; and the diaphragm of on a surface of light polarizing film, fitting and making by the cycloolefin resinoid; and fitted under the situation of the diaphragm made by the resin beyond the cycloolefin resinoid in another surface, also can apply these surface treatments and coating to any one surface of film.
In the present invention, as previously discussed, by at least one surface of the light polarizing film made at polyvinyl alcohol resin by the stacked aforesaid cycloolefin based resin film of adhesive layer, make Polarizer thus.Also can be on a surface of light polarizing film stacked cycloolefin based resin film, the stacked diaphragm of making by the resin beyond the cycloolefin resinoid on another surface.At this used cementing agent, used cementing agent when particularly boning with the cycloolefin based resin film can be polyesters ionomer type carbamate resins and contains the potpourri of the compound of glycidoxypropyl.Under the situation of the stacked diaphragm of making by the resin beyond the cycloolefin resinoid on the surface of light polarizing film; its cementing agent also needn't be defined as the cementing agent that limits at this; but calm easy working aspect sees that it is favourable that identical cementing agent is used on general two surfaces.
Polyesters ionomer type carbamate resins described herein refers to the carbamate resins with polyester backbone, and wherein importing has a spot of ionic composition (hydrophilic component).This ionomer type carbamate resins can not use emulsifying agent, and directly emulsification in water forms emulsion, therefore is suitable for as aqueous binders.Polyesters ionomer type carbamate resins is known itself just, has for example put down in writing to make phenolic resin be dispersed in the example of the macromolecule dispersing agent in the aqueous medium in Japanese patent laid-open 7-97504 communique.This polyesters ionomer type carbamate resins for example can be by following method manufacturing.
(1) by making the compound (A), polyesters polyvalent alcohol (B) and the polyisocyanate (C) that contain the water wettability base react the urethane resin that contains the water wettability base emulsification in water that obtains, obtains the method for ionomer resin.
(2) be dispersed in the water by the water wettability base that made importing that the compound (A) that contains the water wettability base, polyesters polyvalent alcohol (B) and polyisocyanate (C) reaction obtain, the urethane polymer that contains the isocyanate group end group, and itself and polyamine are reacted, obtain the method for copolymer resin etc.
As the above-mentioned compound (A) that contains the water wettability base, can exemplify out as 2-hydroxyethanesulfonic acid, sulfosuccinic acid, sulfanilic acid, 2,4-diaminotoluene sulfonic acid etc. contain sulfonic compound, as 2,2-dihydromethyl propionic acid, dihydroxymaleic acid, 3,4-and the carboxylic compound of amino benzoic acid etc. have the polyoxyethylene glycol of 1 reactive hydrogen or polyoxyethylene-polyoxypropylene interpolymer glycol etc. at least in the polymkeric substance.
Above-mentioned polyester polyol (B) can also obtain polyester, the perhaps polyester copolymerization of these materials by the open loop exchange reaction for the cyclic ester compound as 6-caprolactone except the polyester that is obtained by dehydration condensation by diol component and sour composition.In the glycol component that in polyester polyol, adopts, comprise ethylene glycol, propylene glycol, 1, ammediol, 1, the 4-butylene glycol, 1, the 5-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 1, the 6-hexanediol, neopentyl glycol, diglycol, triethylene glycol, tetraethylene glycol, polyglycol (molecular weight 300-6000), dipropylene glycol, tripropylene glycol, 2,2-diethyl-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 2-amyl group-2-propyl group-1, ammediol, 2-butyl-2-hexyl-1, ammediol, 2-ethyl-1, the 3-hexanediol, the dihydroxy ethoxybenzene, 1, the 4-cyclohexane diol, 1,4 cyclohexane dimethanol, bisphenol-A, the hydrogenation bisphenol-A, the alkylene oxide addition product of quinhydrones and these materials etc.In addition, in sour composition, comprise succinic acid, hexane diacid, azelaic acid, decanedioic acid, dodecanedicarboxylic acid, anhydrous maleic acid, fumaric acid, 1,3-cyclopentane dicarboxylic acid, 1, the 4-cyclohexane dicarboxylic acid, terephthalic acid (TPA), m-phthalic acid, phthalic acid, 1,4-naphthalene diacid, 2,5-naphthalene diacid, 2,6-naphthalene diacid, naphthoic acid, connect benzene dicarboxylic acid, 1,2-two (phenoxy group) ethane-p, the acid anhydrides of p '-dicarboxylic acid and these dicarboxylic acid or ester formation property derivant, to Para Hydroxy Benzoic Acid, the ester of the hydroxycarboxylic acid of p-(2-amyl group ethoxy) benzoic acid and these materials formation property derivant etc.
Wherein polyesters ionomer type carbamate resins is except above-mentioned polyester polyol, in the scope of not damaging effect of the present invention, can also and with other heavy polymer composition or the low-molecular-weight compound bearing active hydrogen that contains.As the polyvalent alcohol of high molecular, can exemplify out polyester polyol, polycarbonate polyol, polyacetal polyvalent alcohol, polyacrylate polyol, polyesteramide polyvalent alcohol, polythiaether polyvalent alcohol etc.In addition,, can exemplify out the polyol of 6-hexane diol, glycerine, trimethylolpropane, as diamine compound of ethylenediamine, piperidines etc. as ethylene glycol, neopentyl glycol, 1 as the low-molecular-weight compound bearing active hydrogen that contains.Be preferred form also wherein with the low-molecular-weight compound bearing active hydrogen that contains.
The compound of described polyisocyanate (C) for having 2 isocyanate group at least in the molecule, specifically can exemplify out 2,4-toluenediisocyanate, phenylene vulcabond, 4,4 '-methyl diphenylene diisocyanate, 1,6-cyclohexane diisocyanate, isophorone diisocyanate etc.
These reactions that contain between compound (A), polyester polyol (B) and the polyisocyanate (C) of water wettability base can be implemented under solvent-free condition, but also can implement in organic solvent.The resin of gained by with as the non-volatile alkali of NaOH or potassium hydroxide etc., neutralize as the amine or the ammonium of triethylamine or dimethylethanolamine, and, can obtain the aqueous liquid dispersion of polyesters ionomer type carbamate resins to wherein adding water.
Polyesters ionomer type carbamate resins is to adopt organic solvent etc. and comprising under the situation about obtaining under the state of organic solvent in when reaction, is removed by distilling this organic solvent etc.Because this carbamate resins is the ionomer type, therefore in water, can be atomic little particle, and can form stable colloid, form the aqueous binders that does not contain organic solvent.
The weight-average molecular weight of polyesters ionomer type carbamate resins is preferably more than 5000, and weight-average molecular weight is more preferably more than 10000 and below 300000.When this weight-average molecular weight 5000 when following, can not obtain enough tack coat intensity, in addition, when this weight average molecule greater than 300000 the time, viscosity is too high when being made into aqueous dispersions, is difficult to operation.
In the present invention, under the state that this polyesters ionomer type carbamate resins is dispersed in the water, make aqueous binders.The viscosity of this aqueous binders solution is when 2000mPa.sec is following, because processing ease therefore preferably, and more preferably below the 1000mPa.sec, is preferably below the 500mPa.sec especially.Viscosity is low more, the easy more coating operation of carrying out cementing agent, and in addition, the outward appearance of the Polarizer of gained is also good.From viscosity and cohesive strength viewpoint, the concentration of the solid constituent of polyesters ionomer type carbamate resins is preferably in the scope of 10-70 weight %, in the scope particularly preferably in 20-50 weight % in this aqueous binders solution.
In the aqueous dispersions of polyesters ionomer type carbamate resins, can further add polyglycol and polyoxyethylene etc. or surfactant etc.In addition, can also add poly hydroxy ethyl acrylate, Poly(Hydroxyethyl Methacrylate), the water soluble resin of polyacrylic acid, polyvinyl alcohol resin etc.
As the spendable suitable commercially available polyesters ionomer type carbamate resins of the present invention, can exemplify out " Ha イ De ラ Application AP-20 " that Dainippon Ink. ﹠ Chemicals Inc sells, " Ha イ De ラ Application APX-101H " etc.
In the present invention, except aforesaid polyesters ionomer type carbamate resins, also use compound with glycidoxypropyl.By and have the compound of glycidoxypropyl with this, can improve the cohesiveness between light polarizing film and the cycloolefin based resin film.Glycidoxypropyl described herein is the group shown in the following formula, and the call of pure chemistry should be 2, the 3-glycidoxy.
Above-mentioned glycidoxypropyl is preferably the group with ether linking especially.Compound with glycidoxypropyl, be preferably the compound that has at least two above glycidyls in a part, can exemplify out polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, the polytetramethylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, two glycerin diglycidyl ethers, ethylene glycol diglycidylether, propylene glycol diglycidylether, 1, the 4-butanediol diglycidyl ether, 1,6-hexane diol diglycidyl ether, bisphenol A diglycidyl ether, the Bisphenol F diglycidyl ether, resorcinolformaldehyde resin, T 55, trihydroxymethylpropanyltri diglycidyl ether, the pentaerythrite polyglycidyl ether, sorbitol polyglycidylether, the sorbitan polyglycidyl ether, polyglycereol polyglycidyl ether etc.The molecular weight of compound that contains glycidoxypropyl in weight-average molecular weight preferably below 5000.In the commercially available product of compound, can exemplify out " CR-5L " that sell from Dainippon Ink. ﹠ Chemicals Inc etc. with glycidoxypropyl.
Polyesters ionomer type carbamate resins is preferably selected in such scope aptly with the mixing ratio with compound of glycidoxypropyl, promptly, with respect to 100 weight portion polyesters ionomer type carbamate resins, compound with glycidoxypropyl is the 5-100 weight portion, the compound that further preferably has glycidoxypropyl is the 5-60 weight portion, is preferably the 5-30 weight portion especially.When the ratio of the compound with glycidoxypropyl is too low, can not obtain sufficient cohesive strength, in addition, when this ratio was excessive, the viscosity of cementing agent was too high, was difficult to operate.
In above-described the present invention, its key character is for using the aqueous binders that comprises polyesters ionomer type carbamate resins and have the compound of glycidoxypropyl.This aqueous binders need not in fact with an organic solvent, can not bring adverse effect to environment and operator's health, and owing to also with the compound with glycidoxypropyl, can obtain higher cohesive force.
Adopt cementing agent with the method for light polarizing film with the diaphragm bonding of making by the cycloolefin resinoid; perhaps under the situation of the stacked diaphragm of making by the resin beyond the cycloolefin resinoid on the surface of light polarizing film; with the two method that bonds; can adopt known method usually; for example can enumerate and be coated with by levelling method, rod that method, intaglio plate are coated with method, mould is coated with method, dip coating, spraying process etc. and is coated with cementing agent, the method that the two is stacked on the adhesive surface of light polarizing film and/or diaphragm.Described levelling method is light polarizing film or the diaphragm that moves on the direction of direction, approximate horizontal in approximate vertical or the vergence direction between the two as applied thing, flows down the method that cementing agent spreads coating simultaneously in its surface.Behind the coating cementing agent, clamp light polarizing film and diaphragm by nip rolls etc., fit thus.
In addition, for improving cohesiveness, can on the bonding surface of light polarizing film and/or diaphragm, implement suitable surface treatment, for example plasma treatment, corona treatment, ultraviolet treatment with irradiation, calcination (flame) processing, basification etc.As basification, can enumerate the method that is immersed in as in the alkaline aqueous solution of NaOH or potassium hydroxide.
After light polarizing film and diaphragm is stacked, carry out dried.Dried can be implemented by for example spraying hot blast, and the temperature of this moment is preferably selected in 60-100 ℃ scope aptly from 40-100 ℃.Be 20-1200 second drying time.After the drying, preferred further in room temperature or the temperature higher a little than room temperature, time of maintenance 12-600 hour under 20-50 ℃ temperature for example.The thickness of dry back tack coat is generally the 0.001-5 micron, is preferably the 0.01-2 micron, more preferably the 0.01-1 micron.The thickness of tack coat is during greater than 5 microns, and the outward appearance of Polarizer is not good easily.
In Polarizer of the present invention, on the surface of diaphragm, can attach optically functional film by cementing agent.As optically functional film, can exemplify out the optical compensating film that on substrate material surface, applies liquid crystal compounds and be orientated gained, light by certain polarisation, and show the reflection polarisation reflection of light type light polarizing film of the character opposite with it, the phase-contrast film of making by polycarbonate resin, the phase-contrast film of making by the cyclic polyolefin hydrocarbon resin, the film that has concaveconvex structure from the teeth outwards with anti-dazzle function, implemented the film that anti-surface reflection is handled, the surface has the reflectance coating of reflection function, has reflection function simultaneously and sees through the Transflective film etc. of function.As with substrate material surface on apply liquid crystal compounds and be orientated the suitable commercially available product of optical compensating film of gained, comprise " the WV film " that description film Co., Ltd. of Fuji sells, " the NH film " and " NR film " (being trade name) that Shin Nihon Oil Co., Ltd sells etc.As with light by certain polarisation, and show and the suitable commercially available product of reflection polarisation reflection of light type light polarizing film of the character opposite to comprise " DBEF " (trade name) of Minnesota Mining and Manufacturing society (3M) (is Sumitomo ス リ-エ system Co., Ltd. in Japan) sale etc. with it.In addition, as the commercially available product suitable, comprise " ア ト Application ", " the エ ス シ-Na " that Sekisui Chemical Co., Ltd sells of ジ エ イ エ ス ア-Le Co., Ltd. sale, " ゼ オ ノ ア film " (being trade name) that オ プ テ ス Co., Ltd. sells etc. with the phase-contrast film of making by the cyclic polyolefin hydrocarbon resin.
Embodiment
Followingly the present invention is elaborated, but the invention is not restricted to these examples according to embodiment.In example, the % of expression content and use amount and part, the words that do not have to specify are weight basis.
Embodiment 1
Under dry conditions, with average degree of polymerization is about 2400, basicity is 99.9 moles more than the %, thickness is that 75 microns polyvinyl alcohol film uniaxial extension is to about 5 times, and further keep tense situation, after this direct dipping 1 minute in 60 ℃ pure water is at 28 ℃ of dippings 60 seconds down in 0.05/5/100 the aqueous solution in the weight ratio of iodine/potassium iodide/water.After this, be at 72 ℃ of dippings 300 seconds down in the aqueous solution of 8.5/8.5/100 in the weight ratio of potassium iodide/boric acid/water.After continuing to clean 20 seconds with 26 ℃ pure water, 65 ℃ dry down, prepare that absorption is orientated the light polarizing film that iodine is arranged on polyvinyl alcohol (PVA).
In addition, water-based emulsion (" the Ha イ De ラ Application AP-20 " that Dainippon Ink. ﹠ Chemicals Inc makes to 100 parts of polyesters ionomer type carbamate resins, the concentration of solid constituent not 30%, viscosity is 30mPa.sec) middle " CR-5L " that add 3 parts as Dainippon Ink. ﹠ Chemicals Inc's manufacturing of polyfunctional glycidyl ether, as cementing agent.At first; on two surfaces of the light polarizing film of gained, be 40 microns diaphragm (" ゼ オ ノ ア film " that オ プ テ ス Co., Ltd. makes) by the fit thickness of making by norbornene resin that carried out corona treatment of above-mentioned cementing agent; drying is 7 minutes under 80 ℃, makes Polarizer.After this, 1 week of maintenance at room temperature.On the surface of this Polarizer with the direction of the angle of film normal direction relative tilt 45 degree, to the blade that sees through direction of principal axis incision cutter, light polarizing film and this diaphragm are peeled off, still can not peel away fully.
Embodiment 2
Except change is fitted in diaphragm on the light polarizing film; the thickness that adopts the norbornene resin implemented corona treatment to make on its single face is 100 microns " ゼ オ ノ ア film "; the thickness that on its another surface, adopts the Triafol T implemented surperficial basification to make be 80 microns film (" Off ジ Star Network TD80 " film that description film Co., Ltd. of Fuji makes) in addition; adopt the mode the same to make Polarizer with embodiment 1; implement the disbonded test the same with embodiment 1 for the Polarizer of gained, still two surfaces all can not be peeled away fully.
Comparative example 1
Except " CR-5L " that in cementing agent, mismatch the polyfunctional glycidyl ether, adopt the mode the same to make Polarizer with embodiment 1, the diaphragm of gained Polarizer is peeled off easily.
Comparative example 2
Except waterborne polyurethane binders main agents (" EL-436A " that Japan モ-ト Application Co., Ltd. makes) and the 3 parts of polyisocyanate class hardening agent (" EL-436B " that Japan モ-ト Application Co., Ltd. makes) that 100 parts are made by polyester resin mix; with it as beyond the cementing agent; adopt the mode the same with embodiment 1 to make Polarizer, the diaphragm of gained Polarizer is peeled off easily.
Comparative example 3
Except main agents (" ダ イ ア ボ Application De DW901H " that ノ ガ ワ ケ ミ カ Le Co., Ltd. makes) and 3 parts of polyisocyanate class hardening agent (" HA-5A " that ノ ガ ワ ケ ミ カ Le Co., Ltd. makes) of 100 parts of waterborne polyurethane binders are mixed; with it as beyond the cementing agent; adopt the mode the same with embodiment 1 to make Polarizer, the diaphragm of gained Polarizer is peeled off easily.
Comparative example 4
Except in 100 parts of water, adding 3 parts of carboxylic acid group's modified polyethylene alcohol (" Network ラ レ Port バ-Le KL318 " that Network ラ レ Co., Ltd. makes) and 1.5 parts of water soluble polyamide epoxy resin (" ス ミ レ-ズ レ ジ Application 650 " (solid constituent are 30% aqueous solution) that Sumitomo Chemical Company Ltd makes; and with it as beyond the cementing agent; adopt the mode the same with embodiment 1 to make Polarizer, the diaphragm of gained Polarizer is peeled off easily.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the method that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, but every content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (5)
1. Polarizer, it is the Polarizer that forms by adhesive layer stacked ring olefine kind resin film at least one surface of the light polarizing film that polyvinyl alcohol resin forms, it is characterized in that this adhesive layer is formed by polyesters ionomer type carbamate resins and the compound that contains glycidoxypropyl.
2. Polarizer according to claim 1 is characterized in that stacked cycloolefin based resin film on a surface of light polarizing film, stacked cellulose acetate class film on another surface.
3. Polarizer according to claim 1 is characterized in that stacked cycloolefin based resin film on two surfaces of light polarizing film.
4. the manufacture method of a Polarizer, it is characterized in that on the light polarizing film that polyvinyl alcohol resin forms, by comprising polyesters ionomer type carbamate resins and the aqueous binders that contains the compound of glycidoxypropyl, come stacked ring olefine kind resin film.
5. polarizing plate making method according to claim 4 is characterized in that wherein said aqueous binders does not contain organic solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003209260 | 2003-08-28 | ||
| JP2003209260A JP4827369B2 (en) | 2003-08-28 | 2003-08-28 | Manufacturing method of polarizing plate |
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| Publication Number | Publication Date |
|---|---|
| CN1591056A CN1591056A (en) | 2005-03-09 |
| CN100410694C true CN100410694C (en) | 2008-08-13 |
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| CNB2004100571146A Expired - Fee Related CN100410694C (en) | 2003-08-28 | 2004-08-24 | Polarizing plate and its mfg method |
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| Country | Link |
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| JP (1) | JP4827369B2 (en) |
| KR (1) | KR20050021307A (en) |
| CN (1) | CN100410694C (en) |
| TW (1) | TW200510788A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5348580B2 (en) * | 2008-01-31 | 2013-11-20 | 住友化学株式会社 | Manufacturing method of polarizing plate |
| JP2010250104A (en) * | 2009-04-16 | 2010-11-04 | Dainippon Printing Co Ltd | Optical functional film, method for manufacturing optical functional film, and polarizing plate |
| JP2012018383A (en) * | 2010-06-08 | 2012-01-26 | Sumitomo Chemical Co Ltd | Optical film, anti-glare film, and polarizing plate |
| JP2013254153A (en) * | 2012-06-08 | 2013-12-19 | Nitto Denko Corp | Activation treatment method and manufacturing method of optical film, optical film, and image display device |
| KR102457408B1 (en) | 2013-08-09 | 2022-10-24 | 스미또모 가가꾸 가부시키가이샤 | Optical film |
| CN104345372B (en) | 2013-08-09 | 2018-04-10 | 住友化学株式会社 | Optical film |
| CN104345368B (en) | 2013-08-09 | 2018-10-16 | 住友化学株式会社 | Elliptical polarization plate |
| TW201510586A (en) | 2013-08-09 | 2015-03-16 | Sumitomo Chemical Co | Optical film |
| TWI653149B (en) | 2013-08-09 | 2019-03-11 | 住友化學股份有限公司 | Optical film |
| JP6477499B2 (en) | 2013-12-27 | 2019-03-06 | 日本ゼオン株式会社 | Multilayer film, polarizing plate, and method for producing multilayer film |
| US11061175B2 (en) * | 2016-05-17 | 2021-07-13 | Nitto Denko Corporation | Polarizing film, method for producing same, optical film, image display device, and adhesion improvement-treated polarizer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0651117A (en) * | 1991-07-22 | 1994-02-25 | Nippon Zeon Co Ltd | Polarizing film for liquid crystal display |
| CN1220735A (en) * | 1997-03-19 | 1999-06-23 | 可乐丽股份有限公司 | Polarizing film |
| JP2000321430A (en) * | 1999-05-14 | 2000-11-24 | Gunze Ltd | Polarizing plate and its production |
| JP2001343526A (en) * | 2000-06-01 | 2001-12-14 | Konica Corp | Optical film excellent in durability |
-
2003
- 2003-08-28 JP JP2003209260A patent/JP4827369B2/en not_active Expired - Fee Related
-
2004
- 2004-07-29 TW TW093122689A patent/TW200510788A/en unknown
- 2004-08-24 CN CNB2004100571146A patent/CN100410694C/en not_active Expired - Fee Related
- 2004-08-26 KR KR1020040067467A patent/KR20050021307A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0651117A (en) * | 1991-07-22 | 1994-02-25 | Nippon Zeon Co Ltd | Polarizing film for liquid crystal display |
| CN1220735A (en) * | 1997-03-19 | 1999-06-23 | 可乐丽股份有限公司 | Polarizing film |
| JP2000321430A (en) * | 1999-05-14 | 2000-11-24 | Gunze Ltd | Polarizing plate and its production |
| JP2001343526A (en) * | 2000-06-01 | 2001-12-14 | Konica Corp | Optical film excellent in durability |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050021307A (en) | 2005-03-07 |
| CN1591056A (en) | 2005-03-09 |
| JP4827369B2 (en) | 2011-11-30 |
| TW200510788A (en) | 2005-03-16 |
| JP2005070140A (en) | 2005-03-17 |
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