CN1497304A - Transparent adhesive film for protecting liquid crystal polarization plate - Google Patents
Transparent adhesive film for protecting liquid crystal polarization plate Download PDFInfo
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- CN1497304A CN1497304A CNA031272908A CN03127290A CN1497304A CN 1497304 A CN1497304 A CN 1497304A CN A031272908 A CNA031272908 A CN A031272908A CN 03127290 A CN03127290 A CN 03127290A CN 1497304 A CN1497304 A CN 1497304A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- G02B1/14—Protective coatings, e.g. hard coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
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- General Physics & Mathematics (AREA)
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Abstract
Provided is a transparent adhesive film having excellent static electric resistant, breaking-resistant and contamination-resistant properties and possible to conduct fluoroscopic examination for defects of liquid crystal polar panel. The transparent film comprises a biaxial drawing transparent film; static electric-resistant layer and breaking-resistant layer laminated on one side of the biaxial film; and removable adhesive layer formed on the other side of the film. The static electric-resistant layer comprises 40-80 wt.% of tin oxide(II) and 60-20 wt.% of polyester resin. The breaking-resistant layer comprises curable resin layer such as thermosetting silicone resin. The adhesive layer comprises two-solution type curable urethane adhesive containing urethane adhesive cross-linked by polyisocyanate cross-linking agent.
Description
Technical field
The present invention relates to be used for to protect the adhesive film of the liquid crystal Polarizer that liquid crystal indicator uses, promptly directly be attached on the liquid crystal Polarizer, the transparent adhesive film of liquid crystal Polarizer protection that can fluoroscopic examination.
Background technology
For the liquid crystal Polarizer that uses in the liquid crystal indicator, damaging, pollute, adhere to foreign matter is fatal defective.Therefore, in manufacturing process, circulation operation and the assembling procedure of liquid crystal Polarizer, do not damage, do not pollute or non-cohesive foreign matter, take to attach the measure of protection adhesive film usually on the surface of liquid crystal Polarizer in order to make the liquid crystal Polarizer.The liquid crystal Polarizer that attaches the protection adhesive film will carry out defect inspection before being installed on the liquid crystal indicator.This inspection is carried out owing to attaching diaphragm, and therefore, claimed adhesive film has the high transparency.
And, in nearest checked operation and since on the protection adhesive film in spite of wound or the goods that pollute all handle as loss, therefore, also claimed adhesive film itself has anti-wound property and antistatic behaviour.For the wound of confirming the surface with pollute and whether to protect adhesive film itself, to wash with warm water or ethanol wiping sometimes, therefore, also must have water tolerance and resistance to chemical reagents.
When forming antistatic layer, for example, use and to contain anionic property antistatic agent or with the mix moisture prose style free from parallelism of the antistatic behaviour resin of its producing high-molecular, still with sulphonate-base etc., heatproof water-based and resistance to chemical reagents deficiency (for example, with reference to patent documentation 1 and patent documentation 2).The somebody has proposed for example adding non-response type silicone in the wearing layer, to improve the method for sliding etc. in order to improve the anti-wound property on stickability film surface, still, improves not enough.In patent documentation 1 and patent documentation 2, the method with ultraviolet isoreactivity energy line curing wearing layer is also disclosed.In the method, owing to when reaction, produce ozone gas etc., therefore, need exhaust equipment.
As the sticker that constitutes above-mentioned protection adhesive film, pay attention to the difficulty or ease of the transparency, clinging power control and non-polluting etc., therefore, using solvent-type acrylic usually is sticker (for example, referring to patent documentation 3).Because this protection adhesive film is peeled off in the way of LCD manufacturing process, therefore, the protection adhesive film must have the character of little stickability and releasable two aspects.But; under the situation of general little stickability sticker; exist in the circulation way of protection adhesive film under reeling condition and tunnel effect takes place (promptly; producing part between adhesion diaphragm and the stripping film peels off); perhaps on another face of the liquid crystal Polarizer that is pasted with this protection adhesive film, apply sticker again, the problem of tunnel effect or expansion takes place when drying easily.
Above-mentioned tunnel effect and expansion form the marking and manifest on adhering agent layer, have to cause to judge by accident in checking operation to be the problems such as reason of liquid crystal Polarizer defective.And, owing to have little stickability, therefore for example with the adherence deficiency of film base material such as Biaxially stretched clear polymer film and sticker, when peeling off, it is residual that pasty state takes place on liquid crystal Polarizer surface easily again.
As the stripping film used of protection adhesive film, use usually with face that sticker contacts on be coated with the film of remover.As this remover, use silicone-based remover and non-silicone-based remover.For example; for the silicone-based remover; though can design peeling force very light with the protection adhesive film; but exist owing to the mobile problem that causes that the liquid crystal Polarizer floats when pasting of silicone to the sticker aspect; and, also exist in order fully to carry out the high temperature that is solidified to form of silicone, film generation thermal shrinkage; cause the problem (for example, referring to patent documentation 4) of surface treatment obstacle by the pollution on liquid crystal Polarizer surface.
Patent documentation 1 spy opens flat 11-70629 communique (the 4th page)
Patent documentation 2 spies open flat 2000-168015 communique (the 4th~5 page)
Patent documentation 3 spies open flat 9-208910 communique (the 2nd page)
Patent documentation 4 spies open (the 2nd page) flat 2000-239623 number
Summary of the invention
The objective of the invention is, the transparent adhesive film that uses for being used to protect the liquid crystal display Polarizer solves above-mentioned prior art problems.
Concrete, it is good to the invention provides antistatic behaviour, anti-wound property, soil resistance etc., and heatproof water-based, resistance to chemical reagents are also good, can be attached to that former state fluoroscopic examination liquid crystal Polarizer has the transparent adhesive film of flawless liquid crystal Polarizer protection on the liquid crystal Polarizer.
Other purposes of the present invention are, the suitable adhesion that keeps diaphragm and sticker is provided, with sticker when stripping film is peeled off, the adhesive film that peeling force is light and remover does not move.
The present invention includes each following invention.
(1) the transparent adhesive film of liquid crystal Polarizer protection; it is characterized in that on a surface of Biaxially stretched hyaline membrane, setting gradually antistatic layer and injury resistance layer; and another surface is provided with the liquid crystal Polarizer protection of exfoliated adhering agent layer with in the transparent adhesive film again; antistatic layer contains tin oxide, and injury resistance layer is made of curing resin layer.
(2) as described above transparent adhesive film is used in the liquid crystal Polarizer protection of (1) record, it is characterized in that above-mentioned curing resin layer is a thermosetting silicone resin layer.
(3) as described above transparent adhesive film is used in the liquid crystal Polarizer protection of (1) or (2) record, it is characterized in that above-mentioned antistatic layer contains tin oxide 40~80 quality % and polyester based resin 60~20 quality %.
(4) as described above transparent adhesive film is used in the protection of the liquid crystal Polarizer of any record of (1) to (3), it is characterized in that above-mentioned injury resistance layer contains non-response type silicone 0.1~10 quality %.
(5) as described above transparent adhesive film is used in the protection of the liquid crystal Polarizer of any record of (1) to (4), it is characterized in that the surface resistivity less than 1 * 10 of above-mentioned injury resistance layer
8Ω.
(6) as described above the protection of the liquid crystal Polarizer of any record of (1) to (5) is used transparent adhesive film; it is characterized in that above-mentioned exfoliated again adhering agent layer is that the two-solution curing type urethane of the crosslinked generation of crosslinking chemical is that sticker constitutes by being sticker with urethane with polyisocyanate; and the haze value of transparent adhesive film is below 3%.
(7) as described above the liquid crystal Polarizer protection of (6) record is used transparent adhesive film; it is characterized in that polyisocyanate be crosslinking chemical with respect to above-mentioned urethane is that the addition of sticker is, is that the solid portion of sticker solid portion 100 mass parts is 2~10 mass parts with respect to urethane.
(8) as the protection of liquid crystal Polarizer transparent adhesive film, wherein the lamination stripping film on the surface of above-mentioned exfoliated adhering agent layer again of any record of (1)~(7).
(9) use transparent adhesive film as the liquid crystal Polarizer protection of record in (8), wherein above-mentioned stripping film is the polyolefin mesentery.
(10) as (8) or (9) in the liquid crystal Polarizer protection of record use transparent adhesive film, wherein the surface potential of above-mentioned stripping film is less than 100V.
(11) as the transparent adhesive film of liquid crystal Polarizer protection of any record of (1)~(7); wherein above-mentioned liquid crystal Polarizer protection is being sticked on 23 ℃ of temperature with transparent adhesive film; on 3 hours the tri acetyl cellulose membrane of the following placement of the environment of humidity 50%RH; after 24 hours; by JIS-Z-0237 (here; " JIS " is the abbreviation of " Japanese Industrial Standard (Japanese Industrial Standards) "; " Z-0237 " is one of test method that is wherein comprised; the method is the test method of adhesive tape and sheet adhesive) 180 degree methods of tearing of defined measure, and clinging power is 3~30N/m.
(12) as the transparent adhesive film of liquid crystal Polarizer protection of any three records of (1)~(7); wherein above-mentioned liquid crystal Polarizer protection is being sticked on transparent adhesive film on the tri acetyl cellulose membrane of placing 3 hours under the environment of 23 ℃ of temperature, humidity 50%RH; through 24 hours; again after 90 ± 1 ℃ of temperature heat 2 hours down; the 180 degree method of tearing by the JIS-Z-0237 defined is measured, and clinging power is 3~30N/m.
The working of an invention scheme
Present inventors are in order to solve above-mentioned problem; carried out research with keen determination; found that; by on a surface of Biaxially stretched hyaline membrane, setting gradually the antistatic layer that contains tin oxide and as the curing resin layer of injury resistance layer; exfoliated again adhering agent layer is set on another face of above-mentioned Biaxially stretched hyaline membrane again; the transparent adhesive film that obtains therefrom has as the good characteristic of liquid crystal Polarizer protection with adhesive film, until finishing the present invention.
Antistatic layer of the present invention is that principal ingredient forms with tin oxide and binding resin.In electrically conductive microparticle, the excellent conductivity of tin oxide, whiteness is also high.The preferred tin oxide that uses the antimony pentoxide that mixed.The particle diameter of tin oxide preferably below 30nm, 5~25nm more preferably.If the problem that particle diameter greater than 30nm, exists mist degree to increase, on the other hand, when particle diameter is too small, difficulties in dispersion in coating sometimes.
The content of tin oxide in antistatic layer is preferably 40~80 quality %.If the content of tin oxide is less than 40 quality %, electrically conductive microparticle connection each other reduces the antistatic property deficiency.And, if the content of tin oxide more than 80 quality %, the binding resin deficiency, with the cohesiveness deficiency of base material, and, the mist degree height.
As antistatic property, the surface resistivity according to JIS C-2318 regulation of preferred injury resistance layer is wanted less than 1 * 10
8Ω is more preferably 7 * 10
7Below the Ω.In surface resistivity is 1 * 10
8Under the situation more than the Ω, transparent adhesive film adheres to impurity etc. on the surface easily.
As the binding resin that uses in the antistatic layer, can enumerate polyester based resin, acrylic resin, ethylene-vinyl acetate acrylic copolymer resin, polyvinyl alcohol resin, polystyrene resin, iolon usually is that resin, nylon are resin, polyolefin-based resins, polyurethane series resin etc.The content of the binding resin in the antistatic layer is preferably 20~60 quality %.For example, when transparent adhesive film base material is Biaxially stretched transparent polyester film, consider from the connectivity aspect, the preferred polyester based resin that uses, as polyester based resin, can enumerate the solution and the dispersion liquid of unsaturated polyester resin, can add wax addition type and non-wax addition type castor-oil plant wet goods drying oil, also can add fluorine is auxiliary agent.Wherein, the polyester based resin of preferred organic solvent soluble, and, from wetting state, the transparency of filming, and and then the anti-adhesive aspect after apply consider that preferred to add fluorine be auxiliary agent.
The thickness of antistatic layer is preferably 0.05~5.00 micron, more preferably 0.10~2.00 micron.If 0.05 micron of Film Thickness Ratio is thin, the antistatic property deficiency, on the other hand, if thickness surpasses 5.00 microns, mist degree increases, and effect is saturated, and is uneconomical.
The curing resin layer that is arranged on the antistatic layer is that injury resistance layer applies curable resin liquid through solidifying to form.As curable resin, thermoset resin, uv curing resin, electronics line curable resin are arranged, use with the form of solvent solution, aqueous dispersions, solvent-free monomer or the oligomer liquid of this resin.
In the curable resin, it is preferred that thermoset resin does not produce when solidifying aspect the ozone.In thermoset resin, preferred soil resistance, the good thermosetting silicone resin of sliding.The dehydration condensation that the thermosetting silicone resin is undertaken by heating solidifies, and therefore, has the ternary crosslinked configuration.As an example, the common poly-alkylsiloxane compound that has the OH base with end is a principal ingredient with terminal potpourri with poly-alkylsiloxane of hydrogen, and as poly-alkylsiloxane, representational is dimethyl silicone polymer.
As required, the commodity that contain catalyzer such as solvent, tin also can be commonly referred to as the hard paint of thermosetting silicone.
As the hard paint of heat curing-type silicone, can enumerate " SHC900 " GE (trade name) of Toshiba's silicone system for example etc.For the stickability of further raising, can also contain alkyd resin and melamine resin etc. with antistatic layer.
As uv curing resin, can use the solvent-free liquid, solvent solution, aqueous dispersions of acrylic monomer or oligomer etc., consider preferred ultra-violet solidified silicone resin from soil resistance, sliding aspect.
For diaphragm itself is difficult for polluting, perhaps when polluting, also remove easily and depollute, preferably in anti-wound property film, add non-response type silicone, non-response type silicone can import straight chain dimethyl polysiloxane, phenyl and senior alkyl.As non-response type silane, can enumerate for example upright ダ ウ コ in east-ニ Application グ. " BY-24-842 ADDITIVE " (trade name) of silicone (strain) system etc.
The addition of the non-response type silicone in the injury resistance layer is preferably 0.1~10 quality %, more preferably 0.1~5.0 quality %, preferred especially 0.5~5.0 quality %.If addition is less than 0.1 quality %, the soil resistance deficiency, on the other hand, if more than 10 quality %, diaphragm is adding man-hour with coiling form, and silicone moves to the back side sometimes, and is therefore not preferred.And, preferred 0.1~10 micron of the thickness of injury resistance layer, more preferably 0.3~5 micron.If 0.1 micron of Film Thickness Ratio is thin, anti-wound property and resistance to chemical reagents deficiency, if than 10 micron thickness, the antistatic property variation, and mist degree improves.
In the present invention, use Biaxially stretched hyaline membrane, consider from the transparency, resistance to chemical reagents and thermotolerance aspect as the substrate sheets that transparent adhesive film is used, for example can enumerate by being selected from polyester system, polyolefin such as tygon, polypropylene, polystyrene, polyvinylidene chloride system, ethylene-ethenol system, polyvinyl chloride, polycarbonate-based, polyamide-based, polyimide system, acrylic acid series, the Biaxially stretched hyaline membrane of at least a formation in the various resins of acetic acid esters system, polyethersulfone system.The Biaxially stretched clear polymer film of preferred use.The operation of coating injury resistance layer particularly described later, drying, heat curing is owing to be high temperature, and therefore, in order to prevent thermal shrinkage or wrinkling etc., the base material of using as transparent adhesive film need have thermotolerance etc.The thickness of Biaxially stretched hyaline membrane of the present invention is preferably 6~300 microns, more preferably 10~100 microns.Can impose known surface treatments such as Corona discharge Treatment to Biaxially stretched hyaline membrane.
For adhering agent layer of the present invention; good with the adherence of base material films such as Biaxially stretched clear polymer film; good with the fissility of stripping film; and; remover does not move, and does not pollute adhering agent layer, therefore yet; in the process with the reeling condition circulation before transparent adhesive film attaches on the liquid crystal Polarizer; tunnel effect does not take place, and, on the another side of the liquid crystal Polarizer that attaches the protection adhesive film; apply again and during dry sticker; tunnel effect and expansion do not take place yet, and possess the little stickability and the releasable that are attached on the liquid crystal Polarizer, and; after peeling off again, do not have residual paste yet and stay on the surface of liquid crystal Polarizer.
Adhering agent layer of the present invention is that the two-solution curing type urethane of the crosslinked generation of crosslinking chemical is that sticker constitutes by being sticker with urethane with polyisocyanate preferably, as urethane is that sticker is preferred, is that to cooperate polyisocyanate in the polyurethane-type polyvalent alcohol of crosslinking chemical reaction and the molecular weight 10000~300000 that generates be that the solvent-borne type urethane of crosslinking chemical is a sticker using catalyzer to make for example polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone type polyvalent alcohol and polyisocyanate.This sticker is that crosslinking chemical is crosslinked by polyisocyanate, forms adhering agent layer.In this application, the two-solution curing type urethane is that sticker is compared with common two-solution curing type sticker (for example acrylate host/epoxy hardener etc.), have with respect to the polyolefin mesentery good from mould.
As polyisocyanate is crosslinking chemical, can enumerate known aromatic poly-isocyanate, aliphatic poly carbimide, aromatic-aliphatic polyisocyanate and alicyclic polymeric isocyanate etc.These crosslinking chemicals can suitably be controlled the cross-linking density that urethane is a sticker, even in the heat treated (90 ℃, 2 hours) after the liquid crystal Polarizer attaches, the clinging power when peeling off does not change yet.And, can also improve the adherence of sticker and Biaxially stretched hyaline membrane, and, can obtain Polarizer is possessed the transparent adhesive film of liquid crystal Polarizer protection of little stickability and releasable, therefore preferably.
At polyisocyanate is in the crosslinking chemical, and the preferred polyfunctional poly isocyanate compound with the fast fulminuric acid ester ring of cross-linking reaction that adopts is that sticker is cross-linked to form as crosslinking chemical with urethane.For example, preferred to use the polyisocyanate with at least one fulminuric acid ester ring that is made of the tripolymer of polyfunctional poly isocyanate compound be crosslinking chemical, even when peeling off after heat treated, clinging power is also almost constant.
Polyisocyanate fat crosslinking chemical of the present invention is that the addition of sticker is to be preferred solid portion 1.5~11 mass parts of sticker solid portion 100 mass parts, more preferably 2~10 mass parts with respect to urethane with respect to urethane.If less than 1.5 mass parts, the degree of crosslinking deficiency, clinging power, particularly the clinging power after the heating strengthens, from the releasable variation of liquid crystal Polarizer.On the other hand, if more than 11 mass parts, degree of crosslinking excessively increases, and clinging power reduces, and the little stickability deficiency with respect to Polarizer perhaps, is in state of saturation, hinders crosslinked, cohesive force reduction, releasable variation.
The thickness of adhering agent layer is preferably 5~50 microns, more preferably 20~30 microns.If 5 microns of the thickness deficiencies of adhering agent layer, to the clinging power deficiency of to-be-adhered object, and if surpassed 50 microns, clinging power is saturated, and is uneconomical, sticker overflows, and becomes the reason that aggegation when peeling off destroys.
The transmittance of the transparent adhesive film of the present invention is subjected to the influence of each composition of layer such as substrate sheets, antistatic layer, injury resistance layer and adhering agent layer, and preferred haze value is below 3%, can be attached to that former state fluoroscopic examination liquid crystal Polarizer has zero defect on the liquid crystal Polarizer.
As the formation method of liquid crystal Polarizer protection of the present invention with transparent adhesive film, by at substrate being the face side coating antistatic layer of Biaxially stretched hyaline membrane, and carry out drying, then, apply injury resistance layer, and it is dry, applying the two-solution curing type urethane on the inside side of the Biaxially stretched hyaline membrane of antistatic behaviour that obtains is sticker, carries out drying, forms adhering agent layer, then, the method for applying stripping film on this adhering agent layer; Perhaps, apply this sticker on stripping film, carry out drying, form after the adhering agent layer, by adhering agent layer, side applying stripping film prepares in the inside of the Biaxially stretched hyaline membrane of antistatic behaviour.
Antistatic layer, the injury resistance layer of lamination can form on the single face of Biaxially stretched transparent polyester film by present known method thereon.For example, adopt coating units such as comma applicator, ripple applicator, curtain coating device, reverse roll applicator, scraper applicator, excellent applicator, slit die applicator, air knife coaters, reverse gravure applicator, direct gravure applicator, fine gravure applicator, can adopt the method that Biaxially stretched hyaline membrane is applied.Coating can be carried out simultaneously by curtain formula applicator or slit die applicator etc. are two-layer, and can adopt above-mentioned any one method to carry out successively.
For adhering agent layer, same with above-mentioned antistatic layer, injury resistance layer, can adopt the method that on the surface of the Biaxially stretched hyaline membrane of antistatic behaviour, directly applies by known method, perhaps, after stripping film applies, it is transferred to method on the Biaxially stretched transparent polyester film of antistatic behaviour etc.And the operation of lamination antistatic layer and injury resistance layer also can be after forming above-mentioned adhering agent layer.
As stripping film of the present invention, be the stripping film of (1) plastic foil system, (2) other stripping films.
As (1) plastic foil is stripping film, (a) polyolefin mesentery is arranged, (b) other plastic foils.
As (a) polyolefin mesentery, the resin laminated composite membrane with tygon, polypropylene, polybutylene, polymethylpentene, ethylene-propylene copolymer resin, their mixed with resin more than two kinds is arranged.Wherein, can apply or mix fluororesin and silicone resin, even the polyolefin mesentery has advantage in the coating of not carrying out silicone etc. aspect also operable.
(b) as other plastic foils, can enumerate fluororesin-coated or silicone resin etc. on plastic foils such as polyethylene terephthalate, polyamide, make it count 0.1~3.0g/m with dry mass
2About, by heat curing or ionizing radiation curing etc., peeling agent layer is set, perhaps, in film, mix fluororesin or silicone resin etc.
(2), be to press the film of stating (1) on fabric upper stratas such as paper, synthetic paper and nonwoven fabrics as other stripping films.Under the situation of synthetic paper, also can be thereon direct silicone-coating resin etc.
Even the said polyolefins mesentery does not use removers such as silicone, also have fissility, therefore, preferably use as stripping film, remover does not move to the sticker aspect.
And polyolefin mesentery and urethane are a little less than the peeling force of sticker, because of the adverse effect that causes that moves of remover, do not have cheap and transparent advantages of higher.
Wherein, the surface potential that preferred especially peeling force is stable is less than the Biaxially stretched polypropylene screen of 100V.And then, preferably peel off adhesive film from stripping film of the present invention after, the not enough 100V of the surface potential of stripping film.
For the outward appearance and the transparency of not damaging the sticker after peeling off, preferably according to the snotter table of Finance Ministry printing office distribution, the above flake number of major diameter 0.05mm contained in the polyolefin mesentery is 0.1/m
2Below, and the maximum height of the surface roughness of JIS-B-0601 regulation is the stripping film below 2 microns.
Liquid crystal Polarizer protection of the present invention is attached on 3 hours tri acetyl cellulose membrane of placement under the environment of 23 ± 2 ℃ of temperature, humidity 50 ± 3%RH with transparent adhesive film; after 24 hours; the clinging power (A) that the 180 degree methods of stipulating according to JIS-Z-0237 of tearing draw is preferably 3~30N/m, more preferably 5~20N/m.If the not enough 3N/m of this clinging power, the clinging power deficiency lacks as the adaptability that requires little adhesive liquid crystal Polarizer protection with transparent adhesive film.On the other hand, if this clinging power surpasses 30N/m, clinging power is strong excessively, lacks as the adaptability of the liquid crystal Polarizer protection that requires releasable with adhesive film.
And; liquid crystal Polarizer protection of the present invention is attached on 3 hours tri acetyl cellulose membrane of placement under the environment of 23 ± 2 ℃ of temperature, humidity 50 ± 3%RH with transparent adhesive film; after 24 hours; again after heating 2 hours under 90 ℃ ± 1 ℃; the clinging power (B) that the 180 degree methods of stipulating according to JIS-Z-0237 of tearing draw is preferably 3~30N/m, more preferably 5~20N/m.If the not enough 3N/m of this clinging power, the clinging power deficiency lacks as the adaptability that requires little adhesive liquid crystal Polarizer protection with transparent adhesive film.On the other hand, if this clinging power surpasses 30N/m, clinging power is strong excessively, lacks as the adaptability of the liquid crystal Polarizer protection that requires releasable with adhesive film.
Particularly; the preferred clinging power (A) and (B) that satisfies simultaneously when measuring under these conditions; from the liquid crystal Polarizer automatically or the hand merit peel off the operating process of protection adhesive film, the distortion of liquid crystal Polarizer does not take place or adhere to polluter such as starchiness residue.
According to being sticker with urethane with polyisocyanate is that the crosslinked two-solution curing type urethane of crosslinking chemical is (6) of the invention described above of constituting of sticker, can satisfy above-mentioned clinging power (A) and (B) simultaneously.
[embodiment]
Be elaborated based on embodiment below.Among below the embodiment and comparative example, unless special restriction is arranged, " part " is " mass parts ", and " % " is " quality % ".
Embodiment 1
At base material is on Biaxially stretched polyethylene terephthalate (PET) film (trade name " T-100C ", Mitsubishi Chemical's polyester film (strain) system, 25 microns of thickness, full transmittance 88%, haze value 3.0%), the mass ratio that applies tin oxide/alkyd resin with fine gravure applicator is 2/1 antistatic agent (trade name " マ イ Network ロ ソ Le バ-Rmd142 ", (strain) ソ Le ペ Star Network ス system, tin oxide mean grain size 20nm, fluorine-containing be auxiliary agent), so that count 0.3g/m with dry mass
2, drying is 30 seconds under 100 ℃, forms antistatic layer.
On this antistatic layer, as thermoset resin, mix non-response type silicone (trade name " BY-24-842ADDITIVE ", the upright ダ ウ コ in east-ニ Application グ silicone (strain) system, solid portion 50%) 1 part (being converted into solid portion) with respect to the hard paint of silicone (trade name " SHC900 ", GE Toshiba silicone (strain) system, solid portion 30%) 100 parts (being converted into solid portion), adjust coating liquid, apply with fine gravure applicator, so that count 0.5g/m with dry mass
2, drying is 30 seconds under 120 ℃, forms injury resistance layer, obtains the Biaxially stretched transparent polyester film of antistatic behaviour.
In addition, at urethane is in the sticker (trade name " サ イ ア バ イ Application SH-101 ", Toyo Ink manufacturing (strain) system) 100 parts (being converted into solid portion), adding is as 10 parts of the tripolymers of the hexamethylene diisocyanate of crosslinking chemical (trade name " コ ロ Woo-ト 2030 ", Japanese polyurethane industry (strain) system), carry out crosslinkedly, make the adhering agent layer coating liquid.
This adhering agent layer is coated on the one side opposite with the antistatic layer of the Biaxially stretched transparent polyester film of above-mentioned antistatic behaviour with the comma applicator with coating liquid, and makes with dry mass and count 2Sg/m
2, drying is 1 minute under 100 ℃, forms adhering agent layer; as stripping film, adopting surface potential is the Biaxially stretched polypropylene screen (trade name " E-200 ", Oji Paper (strain) system, thickness is 25 microns) of 5V; be attached on the adhering agent layer, make the transparent adhesive film of liquid crystal Polarizer protection.
Embodiment 2
Except the mass ratio that uses tin oxide/vibrin as antistatic agent is 1/1 antistatic agent (trade name " マ イ Network ロ ソ Le バ-Rmd112 ", (strain) ソ Le ベ ッ Network ス system); similarly to Example 1, make the transparent adhesive film of liquid crystal Polarizer protection.
Embodiment 3
Except the solid portion that uses non-response type silicone (trade name " BY-24-842 ADDITIVE ", the upright ダ ウ コ in east-ニ Application グ silicone (strain) system, solid portion 50%) is 4 parts; similarly to Example 1, make the transparent adhesive film of liquid crystal Polarizer protection.
Embodiment 4
Except the solid portion that uses non-response type silicone (trade name " BY-24-842 ADDITIVE ", the upright ダ ウ コ in east-ニ Application グ silicone (strain) system, solid portion 50%) is 0.5 part; similarly to Example 1, make the transparent adhesive film of liquid crystal Polarizer protection.
Embodiment 5
Except making at urethane is in sticker (trade name " サ イ ア バ イ Application SH-101 ", Toyo Ink manufacturing (strain) system) 100 mass parts (being converted into solid portion); tripolymer (trade name " コ ロ Woo-ト 2030 ", poly-urethane industry (strain) system of Japan) as the hexamethylene diisocyanate of crosslinking chemical is outside 7 parts; similarly to Example 1, make the transparent adhesive film of liquid crystal Polarizer protection.
Embodiment 6
Except use ultraviolet hardening surface treatment colloidal silica coating (trade name " UVHC1105 ", GE Toshiba silicone (strain) system, solid portion 100%) as curable resin, is 98/2 to mix with non-response type silicone (trade name " BY-24-842 ADDITIVE ", the upright ダ ウ コ in east-ニ Application グ silicone (strain) system, solid portion 50%) with the solid portion ratio, apply with fine gravure applicator, so that count 3.0g/m with dry mass
2, after under 120 ℃ dry 30 seconds, with 300m.J/cm
2The irradiation ultraviolet radiation lamp is made outside the injury resistance layer, similarly to Example 1, makes the transparent adhesive film of liquid crystal Polarizer protection.
Comparative example 1
Except the formation of omitting antistatic layer and injury resistance layer; similarly to Example 1; on the single face of Biaxially stretched polyethylene terephthalate (PET) film (trade name " T-100C ", Mitsubishi Chemical's polyester film (strain) system, 25 microns of thickness, full transmittance 88%, haze value 3.0%), form adhesive coating; the applying stripping film is made the transparent adhesive film of liquid crystal Polarizer protection.
Comparative example 2
Except use the acrylic acid ammonium salt as antistatic agent is the antistatic agent (trade name " go-セ Off ア イ マ-C670 ", Japanese synthetic chemistry (strain) system), similarly to Example 1, makes the transparent adhesive film of liquid crystal Polarizer protection.
Estimate
Carry out following evaluation for the liquid crystal Polarizer protection that obtains in each embodiment and the comparative example with transparent adhesive film, the result represents at table 1.
(assessment item)
[surface resistivity of injury resistance layer (Ω)]
Use East Asia electric wave industry (strain) system " numeral insulation meter DSM-8103 ",, under the atmosphere of 23 ℃ of temperature, humidity 50%RH, place sample, apply the voltage of 100V according to JISC-2318, with the surface resistance of charging after 40 seconds as surface resistivity (Ω).
[full transmittance]
For the transparent adhesive film of liquid crystal Polarizer protection of the stripping film of tearing, measure meter (form name " NDH2000 ", Japanese electric look industry (strain) system) with mist degree and measure.
[anti-wound property evaluation]
Use and learn the formula fastness frictional testing machine (Feitian appliance industry (strain) system) that shakes, cellulosic nonwoven fabric (trade name " BENCOT ", Asahi Chemical Industry's (strain) system) is wound on the metallic arc plate pressure head of 20mm * 40mm, under the state of load 500g, rubs back and forth 10 times.Then, observing the surface, for good, is bad when injury resistance layer comes off when injury resistance layer does not change substantially, estimates.
[evaluation of heatproof water-based]
Use and learn the formula fastness frictional testing machine (Feitian appliance industry (strain) system) that shakes, cellulosic nonwoven fabric (trade name " BENCOT ", Asahi Chemical Industry's (strain) system) is wound on the dull and stereotyped pressure head of metallic of 20mm * 40mm, infiltrate 50 ℃ warm water 1ml, under the state of load 500g, rub back and forth 10 times.Then, the observation surface, injury resistance layer is zero when not having variation and surface resistivity also not to reduce substantially, injury resistance layer does not come off, but albefaction takes place, and is △ when perhaps the table of discovery surface resistivity reduces, when coming off be *, estimate.
[resistance to chemical reagents evaluation]
Use and learn the formula fastness frictional testing machine (Feitian appliance industry (strain) system) that shakes, cellulosic nonwoven fabric (trade name " BENCOT ", Asahi Chemical Industry's (strain) system) is wound on the dull and stereotyped pressure head of metallic of 20mm * 40mm, infiltrate ethanol 1ml, under the state of load 500g, rub back and forth 10 times.Then, the observation surface, injury resistance layer is zero when not having variation and surface resistivity also not to reduce substantially, injury resistance layer does not come off, but albefaction takes place, and is △ when perhaps the table of discovery surface resistivity reduces, when coming off be *, estimate.
[sticker tack]
On the surface of injury resistance layer, coat the acrylic acid series sticker, estimate having or not of sticker tack.
[for the clinging power (A) of liquid crystal Polarizer]
The liquid crystal Polarizer is protected with transparent adhesive film (size: 25mm * 100mm) take a sample; be attached to 23 ℃ of temperature; (trade name " Off ジ ッ Network " on the tri acetyl cellulose membrane of 3 hours Polarizer of placement under the environment of humidity 50%RH; 38 microns of thickness; Fuji's photographic plat (strain) system); adopt the pressure roller of 2kg to carry out 1 back and forth; after 24 hours; according to the 180 degree methods of stipulating among the JIS-Z-0237 (peeling off method) of tearing, the clinging power (A) when tearing with the speed of draw speed 300mm/ branch with Tan Xilun cupping machine ((strain) オ リ エ Application テ ッ Network system RTC-1210) mensuration.
[generation of ozone gas]
The mensuration of ozone gas is to gather discarded air in the injury resistance layer coating, and adopting the ozone ph test paper ph is that potassium iodide starch test paper is checked ozone.
[to the clinging power (B) of liquid crystal Polarizer]
The liquid crystal Polarizer is protected with transparent adhesive film (size: 25mm * 10mm) take a sample; be attached to 23 ℃ of temperature; (trade name " Off ジ ッ Network " on the tri acetyl cellulose membrane of 3 hours liquid crystal Polarizer of placement under the environment of humidity 50%RH; 38 microns of thickness; Fuji's photographic plat (strain) system); adopt the pressure roller of 2kg to carry out 1 back and forth; after 24 hours; under 90 ℃, carry out 2 hours heat treated again; then; according to the 180 degree methods of stipulating among the JIS-Z-0237 (peeling off method) of tearing, the clinging power (B) when tearing with the speed of draw speed 300mm/ branch with Tan Xilun cupping machine ((strain) オ リ エ Application テ ッ Network system RTC-1210) mensuration.
[peeling force of peeling off from stripping film]
The liquid crystal Polarizer is protected with transparent adhesive film (size: 25mm * 100mm) take a sample; after attaching the two sides adhesive tape on whole of the anti-wound property face of film; two sides adhesive tape side is attached on the corrosion resistant plate; according to the 180 degree methods of stipulating among the JIS-Z-0237 (peeling off method) of tearing, the clinging power when tearing with the speed of draw speed 300mm/ branch with Tan Xilun cupping machine ((strain) オ リ エ Application テ ッ Network system RTC-1210) mensuration stripping film.
[sticking with paste having or not of peeling off] from transparent adhesive film
When the liquid crystal Polarizer is measured clinging power; visual assessment has not to be had owing to the protection of liquid crystal Polarizer is protected the state of peeling off with transparent adhesive film with the bad sticker (paste) that makes of the adherence of transparent adhesive film and adhesive coating from the liquid crystal Polarizer; be zero when sticker is not peeled off, sticker peel off for *.
[impurity tack]
The starch powder that is scattered on the liquid crystal Polarizer protection surface with the injury resistance layer of transparent adhesive film is inverted film, estimates remaining starch and falls afterwards starch and have or not and adhere to.
Table 1
Surface resistivity Ω | Mist degree % | Anti-wound property | The heatproof water-based | Resistance to chemical reagents | The sticker tack | |
Embodiment 1 | 1.00×10 7 | 2.4 | Well | ○ | ○ | Do not have |
Embodiment 2 | 5.00×10 7 | 1.8 | Well | ○ | ○ | Do not have |
Embodiment 3 | 1.00×10 7 | 2.4 | Well | ○ | ○ | Do not have |
Embodiment 4 | 1.00×10 7 | 2.4 | Well | ○ | ○ | Do not have |
Embodiment 5 | 1.00×10 7 | 2.4 | Well | ○ | ○ | Do not have |
Embodiment 6 | 1.00×10 7 | 2.4 | Well | ○ | ○ | Do not have |
Comparative example 1 | 1.00×10 8 | 5.0 | Bad | × | × | Have |
Comparative example 2 | 7.00×10 8 | 1.8 | Well | △ | △ | Do not have |
(the continuous table of table 1)
Clinging power (A) N/m | Clinging power (B) N/m | Ozone gas produces | The peeling force N/m that peels off from stripping film | Having the mould of having no way of adhering to take place to stick with paste peels off | The impurity tack | |
Embodiment 1 | 12 | 15 | Do not have | 2 | ○ | Do not have |
Embodiment 2 | 12 | 15 | Do not have | 2 | ○ | Do not have |
Embodiment 3 | 12 | 15 | Do not have | 2 | ○ | Do not have |
Embodiment 4 | 12 | 15 | Do not have | 2 | ○ | Do not have |
Embodiment 5 | 13 | 18 | Do not have | 2 | ○ | Do not have |
Embodiment 6 | 12 | 15 | Have | 2 | ○ | Do not have |
Comparative example 1 | 12 | 15 | Do not have | 2 | ○ | Have |
Comparative example 2 | 12 | 15 | Do not have | 2 | ○ | Have |
As shown in table 1; protect with transparent adhesive film for the liquid crystal Polarizer that embodiment 1~6 obtains; surface resistivity and mist degree are enough low; anti-wound property, heatproof water-based, resistance to chemical reagents are good; non-cohesive sticker and impurity on the surface; with the clinging power fit of liquid crystal Polarizer, do not take place to peel off from the paste of the Biaxially stretched transparent polyester film of antistatic behaviour yet, also very light from the peeling force of stripping film.And in embodiment 1~5, when making the Biaxially stretched transparent polyester film of antistatic behaviour, do not produce ozone.In embodiment 6, apply injury resistance layer, when being cured, produce ozone by irradiation ultraviolet radiation.
On the other hand, the transparent adhesive film of preparation does not have injury resistance layer in comparative example 1, and therefore, anti-wound property, heatproof water-based and the resistance to chemical reagents on surface are poor, and antistatic behaviour is also poor, and then, confirm to adhere to impurity.The heatproof water-based of the transparent adhesive film of preparation and resistance to chemical reagents reduce in comparative example 2, and antistatic behaviour is also poor, confirm to adhere to impurity.
The invention effect
Transparent adhesive film for protecting liquid crystal polarization plate of the present invention forms the antistatic layer that contains tin oxide on the surface; the curing resin layer (preferred silicone hard-coat) that contains non-response type silicone is set thereon as required; can obtain good surface resistivity and the transparency; and, can access the Biaxially stretched transparent polyester film of antistatic behaviour that has both good scratch resistance and heatproof water-based and resistance to chemical reagents.
And then, by will urethane be add in the sticker as the adhering agent layer of the polyisocyanate compounds of crosslinking agent and stripping film that silicone moves few alkene mesentery combined, the adherence of adhering agent layer and the Biaxially stretched transparent polyester film of antistatic behaviour is good, and, do not occur in the tunnel-effect that in the process of circulation under the reeling condition, produces easily before being attached on the liquid crystal polarization plate. When further applying sticker and carrying out drying on another face of the liquid crystal polarization plate that attaches Transparent adhesive film of the present invention, tunnel-effect and foaming do not occur yet. And Transparent adhesive film of the present invention occurs to be adhered to by the dust that static causes hardly, and the bad marking that causes of sticker is few, therefore, has the excellent results of the fluoroscopic examination that can easily carry out liquid crystal polarization plate etc.
Claims (12)
1, the transparent adhesive film of liquid crystal Polarizer protection; it is for setting gradually antistatic layer and injury resistance layer on a surface of Biaxially stretched hyaline membrane; and the transparent adhesive film of liquid crystal Polarizer protection of exfoliated adhering agent layer is set on another surface again; it is characterized in that antistatic layer contains tin oxide, injury resistance layer is made of curing resin layer.
2, transparent adhesive film is used in the liquid crystal Polarizer protection of claim 1 record, it is characterized in that above-mentioned curing resin layer is a thermosetting silicone resin layer.
3, the liquid crystal Polarizer protection of claim 1 or 2 records uses transparent adhesive film, wherein above-mentioned antistatic layer to contain tin oxide 40~80 quality % and polyester based resin 60~20 quality %.
4, the liquid crystal Polarizer protection of claim 1 or 2 records uses transparent adhesive film, wherein above-mentioned injury resistance layer to contain non-response type silicone 0.1~10 quality %.
5, the protection of liquid crystal Polarizer transparent adhesive film, wherein the surface resistivity less than 1 * 10 of above-mentioned injury resistance layer of claim 1 or 2 records
8Ω.
6, the transparent adhesive film of liquid crystal Polarizer protection of claim 1 or 2 records; wherein above-mentioned exfoliated again adhering agent layer is that the two-solution curing type urethane of the crosslinked generation of crosslinking chemical is that sticker constitutes by being sticker with urethane with polyisocyanate; and the haze value of transparent adhesive film is below 3%.
7, the transparent adhesive film of liquid crystal Polarizer protection of claim 6 record; wherein polyisocyanate be crosslinking chemical with respect to above-mentioned urethane is that the addition of sticker is, is that the solid portion of sticker solid portion 100 mass parts is 2~10 mass parts with respect to urethane.
8, the protection of liquid crystal Polarizer transparent adhesive film, wherein the lamination stripping film on the surface of above-mentioned exfoliated adhering agent layer again of claim 1 or 2 records.
9, transparent adhesive film is used in the liquid crystal Polarizer protection of claim 8 record, and wherein above-mentioned stripping film is the polyolefin mesentery.
10, transparent adhesive film is used in the liquid crystal Polarizer protection of claim 8 record, and wherein the surface potential of above-mentioned stripping film is less than 100V.
11, the transparent adhesive film of liquid crystal Polarizer protection of claim 1 or 2 records; wherein above-mentioned liquid crystal Polarizer protection is being sticked on transparent adhesive film on the tri acetyl cellulose membrane of placing 3 hours under the environment of 23 ℃ of temperature, humidity 50%RH; after 24 hours, the clinging power of measuring by the 180 degree method of tearing of JIS-Z-0237 defined is 3~30N/m.
12, the transparent adhesive film of liquid crystal Polarizer protection of claim 1 or 2 records; wherein above-mentioned liquid crystal Polarizer protection is being sticked on transparent adhesive film on the tri acetyl cellulose membrane of placing 3 hours under the environment of 23 ℃ of temperature, humidity 50%RH; after 24 hours; 90 ± 1 ℃ heating is after 2 hours down in temperature again, and the clinging power of measuring by the 180 degree method of tearing of JIS-Z-0237 defined is 3~30N/m.
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- 2003-09-30 CN CNB031272908A patent/CN100373226C/en not_active Expired - Fee Related
- 2003-10-06 KR KR1020030069254A patent/KR101058358B1/en not_active IP Right Cessation
- 2003-10-06 TW TW092127631A patent/TWI284764B/en not_active IP Right Cessation
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Also Published As
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TW200413790A (en) | 2004-08-01 |
CN100373226C (en) | 2008-03-05 |
KR20040032058A (en) | 2004-04-14 |
TWI284764B (en) | 2007-08-01 |
KR101058358B1 (en) | 2011-08-22 |
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