CN103492507B - Metal covering attaching adhesive sheet - Google Patents
Metal covering attaching adhesive sheet Download PDFInfo
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- CN103492507B CN103492507B CN201280019700.4A CN201280019700A CN103492507B CN 103492507 B CN103492507 B CN 103492507B CN 201280019700 A CN201280019700 A CN 201280019700A CN 103492507 B CN103492507 B CN 103492507B
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- adhesive sheet
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- acrylate
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J7/00—Adhesives in the form of films or foils
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention provides a kind of metal covering attaching adhesive sheet, this adhesive sheet is the adhesive sheet fitting in metal covering, wherein, this adhesive sheet has binder layer, described binder layer comprises the acrylic adhesive employing (methyl) acrylate copolymer, the content forming described (methyl) alkoxyalkyl acrylate monomer (A) in the monomer component of (methyl) acrylate copolymer is more than 50 quality %, to have carbonatoms be the content of (methyl) alkyl acrylate (B) of the acryl of 1 ~ 4 is 5 ~ 45 quality %, the content forming the monomer containing carboxyl in the monomer component of (methyl) acrylate copolymer is less than 1%, utilize this metal covering attaching adhesive sheet, the gonorrhoea under hot and humid condition and corrosion of metal can be reduced.
Description
Technical field
The present invention relates to a kind of adhesive sheet being attached at metal covering.
Background technology
In recent years, start touch sensor to be equipped on e-machine.In the touch sensor of e-machine, main lift-launch mainly utilizes pressure during input carry out the touch panel of the resistive film mode detected and utilize the electrostatic from human body during input to detect the touch panel of the electrostatic capacitance mode at input position, from the multifunctionality of input method, electrostatic capacitance mode becomes main flow just gradually.In touch panel, employ the transparent metal film being provided with conductive layer on transparent film base material or glass, in the touch panel of electrostatic capacitance mode, the layer on surface of metal of this transparent metal film is fixed by the mode contacted with the adhesive layer surface of double-sided adhesive sheet.
The metal that the metal layer of transparent metal film has high transparent and electroconductibility by evaporation tin indium oxide etc. is in this way formed, when carrying out stacked double-sided adhesive sheet in the mode making binder layer contact with the layer on surface of metal of this metallic membrane, there is the oxidizing reaction causing the metal caused by double-sided adhesive sheet, cause the problem of the reduction of conducting function.Thus, for the double-sided adhesive sheet that metal covering attaches, high preventing metal corrosion is needed.
As the double-sided adhesive sheet with preventing metal corrosion, because sour composition contained in binder layer is corrosion of metal, therefore the double-sided adhesive sheet (such as with reference to patent documentation 1 ~ 3) not containing sour composition was proposed.This double-sided adhesive sheet utilize not containing become the essential factor making metallic corrosion sour composition binder layer and there is preventing metal corrosion.But the wetting ability of the binder layer of the adhesive sheet not containing sour composition reduces, and thus has the problem that gonorrhoea can occur at hot and humid lower binder layer.
Patent documentation 1: Japanese Unexamined Patent Publication 2010-215794 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-79203 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-215923 publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, provides a kind of adhesive sheet, even if directly fit also can not corroding metal face for this adhesive sheet and metal covering, the reduction of the visibility caused by the gonorrhoea under hot environment also not easily occurs in addition.
For the method for dealing with problems
In the present invention, by using (methyl) acrylate copolymer of obtaining by (methyl) alkoxyalkyl acrylate monomer of specified quantitative and (methyl) the alkyl acrylate monomer copolymerization of alkyl with carbon number 1 ~ 4 in the binder layer of adhesive sheet, thus achieve the adhesive sheet that can not cause gonorrhoea under hot and humid condition and corrosion of metal.
Namely, the invention provides a kind of metal covering attaching adhesive sheet, it is the adhesive sheet fitting in metal covering, described adhesive sheet has binder layer, described binder layer comprises the acrylic adhesive employing (methyl) acrylate copolymer, described (methyl) acrylate copolymer contains (methyl) alkoxyalkyl acrylate monomer (A) and has carbon number is that (methyl) alkyl acrylate (B) of the acryl of 1 ~ 4 is as monomer component, the content forming described (methyl) alkoxyalkyl acrylate monomer (A) in the monomer component of (methyl) acrylate copolymer is more than 50 quality %, it is described that to have carbonatoms be the content of (methyl) alkyl acrylate (B) of the acryl of 1 ~ 4 is 5 ~ 45 quality %, the content forming the monomer containing carboxyl in the monomer component of (methyl) acrylate copolymer is less than 1%.
The effect of invention
Metal covering attaching adhesive sheet of the present invention is due within the adhesive layer containing (methyl) acrylate copolymer of obtaining by (methyl) alkoxyalkyl acrylate monomer of specified quantitative and (methyl) the alkyl acrylate monomer copolymerization of alkyl with carbon number 1 ~ 4, even if the content of the monomer therefore containing carboxyl is few, the wetting ability of binder layer is also very high, under hot and humid condition, binder layer can not gonorrhoea, can also prevent corrosion of metal.
Accompanying drawing explanation
Fig. 1 is the sketch chart of the configuration example representing the image display device applying metal covering attaching adhesive sheet of the present invention.
Fig. 2 is the sketch chart of the configuration example representing the image display device applying metal covering attaching adhesive sheet of the present invention.
Fig. 3 is the sketch chart of the configuration example representing the image display device applying metal covering attaching adhesive sheet of the present invention.
Embodiment
Metal covering attaching adhesive sheet of the present invention is the adhesive sheet fitting in metal covering, the binder layer of described adhesive sheet comprises containing (methyl) alkoxyalkyl acrylate monomer (A) and has the binder layer of (methyl) alkyl acrylate monomer (B) as (methyl) acrylate copolymer of main monomer that carbon number is the alkyl of 1 ~ 4, wherein, the content forming (methyl) alkoxyalkyl acrylate monomer (A) in the monomer component of above-mentioned (methyl) acrylate copolymer is more than 50 quality %, to have carbon number be the content of (methyl) alkyl acrylate monomer (B) of the alkyl of 1 ~ 4 is 5 ~ 45 quality %, the content of the monomer containing carboxyl is below 1 quality %.
[(methyl) acrylate copolymer]
As (methyl) alkoxyalkyl acrylate monomer (A) forming (methyl) of the present invention acrylate copolymer, specifically, vinylformic acid 2-methoxy acrylate, vinylformic acid 2-ethoxy ethyl ester, vinylformic acid 2-methoxy triglycol ester, vinylformic acid 3-methoxyl group propyl ester, vinylformic acid 3-oxyethyl group propyl ester, vinylformic acid 4-methoxybutyl, vinylformic acid 4-Ethoxybutyl etc. can be enumerated.Wherein, particularly preferably vinylformic acid 2-methoxy acrylate, vinylformic acid 2-ethoxy ethyl ester.By using above-mentioned monomer, thus the required cohesive force for fixing metal film can be given to binder layer.
It should be noted that, in this specification sheets, vinylformic acid and methacrylic acid general name are labeled as (methyl) vinylformic acid, the derivative for them is stated similarly.
The content of (methyl) alkoxyalkyl acrylate monomer (A) is preferably 50 ~ 90 quality % relative to the whole monomer components 100 quality % forming (methyl) acrylate copolymer, be more preferably 60 ~ 90 quality %, more preferably 70 ~ 90 quality %, are particularly preferably 75 ~ 85 quality %.By being set to the content of (methyl) alkoxyalkyl acrylate monomer (A) within the scope of this, thus the wetting ability of binder layer can be improved, even if also can not gonorrhoea under hot and humid.
As (methyl) alkyl acrylate monomer (B) with the alkyl of carbon number 1 ~ 4 forming (methyl) of the present invention acrylate copolymer, it is (methyl) alkyl acrylate monomer beyond above-mentioned (methyl) alkoxyalkyl acrylate monomer (A), specifically, ethyl propenoate can be enumerated, n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate etc.
Wherein, particularly preferably n-butyl acrylate.By using n-butyl acrylate, thus can take into account for the resistance to gonorrhoea under the high adhesion of metal covering and hot and humid condition.
The content of (methyl) acrylate monomer (B) of carbon number 1 ~ 4 is preferably 5 ~ 45 quality % relative to the whole monomer components 100 quality % forming (methyl) acrylate copolymer, be more preferably 5 ~ 35 quality %, more preferably 5 ~ 25 quality %, are particularly preferably 10 ~ 25 quality %.By being set to the content of (methyl) acrylate monomer (B) within the scope of this, thus can take into account for the resistance to gonorrhoea under the high adhesion of metal covering and hot and humid condition.
As the monomer containing carboxyl of formation of the present invention (methyl) acrylate copolymer, be not particularly limited, but vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, β-crotonic acid, acrylic acid dimer, ethylene-oxide-modified succsinic acid acrylate etc. can be enumerated.Wherein, because versatility is high, therefore preferred vinylformic acid.
The usage quantity of the above-mentioned monomer containing carboxyl is preferably below the 1 quality % in the monomer component forming acrylic copolymer, and be more preferably below 0.5 quality %, more preferably below 0.1 quality %, does not particularly preferably contain in fact.By being set to the content of the monomer containing carboxyl within the scope of this, thus corrosion of metal can be prevented.
In addition, in order to improve the cohesive force of binder layer by carrying out crosslinking reaction rightly with linking agent, also preferably use the vinyl monomer with the functional group of reacting with linking agent.As the vinyl monomer with the functional group of reacting with linking agent, be not particularly limited, the vinyl monomer etc. containing hydroxyl such as vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 4-hydroxybutyl can be enumerated.
The above-mentioned usage quantity with the vinyl monomer of functional group is preferably 0.1 quality % ~ 10 quality % in the monomer component forming acrylic copolymer, is particularly preferably 0.5 ~ 5 quality %.
The weight-average molecular weight Mw of (methyl) acrylate copolymer is preferably 300,000 ~ 1,600,000, is more preferably 400,000 ~ 1,300,000, and more preferably 500,000 ~ 1,000,000.If the weight-average molecular weight Mw of (methyl) acrylate copolymer is within the scope of this, then can give the cementability for metal covering and the concavo-convex tracing ability for attached metal or display panel rightly.
In addition, the molecular weight distribution (weight-average molecular weight Mw/ number-average molecular weight Mn) of (methyl) acrylate copolymer is preferably 10 ~ 50, is more preferably 10 ~ 30, and more preferably 10 ~ 20.If the molecular weight distribution of (methyl) acrylate copolymer (weight-average molecular weight Mw/ number-average molecular weight Mn) is within the scope of this, then can give the concavo-convex tracing ability for attached metal or display panel, at display frame part not easily residual bubble, can suppress in addition from peeling off metal covering.
It should be noted that, in the present invention, the weight-average molecular weight Mw that should contain (methyl) acrylate copolymer (A) of carboxyl can utilize gel permeation chromatography (GPC) to measure.More particularly, as GPC determinator, TOSOH Co., Ltd's system " SC8020 " can be used, utilize polystyrene conversion value, carry out measuring under following GPC condition determination and obtain.
(condition determination of GPC)
■ sample concentration: 0.5 quality % (tetrahydrofuran solution)
■ sample injection rate: 100 μ L
■ elutriant: tetrahydrofuran (THF) (THF)
■ flow velocity: 1.0mL/min
■ column temperature (mensuration temperature): 40 DEG C
■ chromatographic column: TOSOH Co., Ltd's system " TSKgelGMHHR-H "
■ detector: differential refractometer
The polymerization process of (methyl) acrylate copolymer used in the present invention is not particularly limited, suitably can use known various polymerization process, the thermal polymerization such as solution polymerization process, emulsion polymerization method, mass polymerization can be adopted, irradiate light or radioactive rays isoreactivity energy-ray and the polymerization process etc. that carries out.Considering from the viewpoint such as operability, quality stability, preferably can adopt solution polymerization process, can be any one in the disposable feeding mode whole amount of monomer component supplied in reaction vessel once, the dropping mode that supplies continuously or in batches etc.
As solvent used in solution polymerization, the various organic solvents used in solution polymerization can be used in, wherein preferably use non-toluene system organic solvent.As preferred organic solvent, ethyl acetate, hexane, hexanaphthene, methylcyclohexane, Virahol etc. can be exemplified.As other the organic solvent that can preferably use, n-butyl alcohol, sec-butyl alcohol, the trimethyl carbinol, t-butyl methyl ether, methylethylketone, methyl ethyl diketone, 1,2-ethylene dichloride etc. can be exemplified.
[binder composition]
The binder composition forming the binder layer of metal covering attaching adhesive sheet of the present invention is the binder composition containing above-mentioned (methyl) acrylate copolymer, in the composition, as the composition beyond above-mentioned multipolymer, in order to improve the cohesive force of binder layer, preferably containing linking agent.
As used linking agent, isocyanate-based linking agent, epoxy linking agent, chelating system linking agent, aziridine system linking agent, polyfunctional acrylic ester system etc. can be enumerated.Wherein, the reactive isocyanate-based linking agent with the composition of (methyl) acrylic copolymer is preferably imbued with.
The use level of adding the linking agent in the binder layer of this adhesive sheet to is preferably 0.05 ~ 2 mass parts, is more preferably 0.07 ~ 1.5 mass parts, more preferably 0.1 ~ 1 mass parts.By being set to the content of the linking agent of this scope, be easy to the percent gel of binder layer to be adjusted to suitable scope.
Above-mentioned (methyl) acrylate copolymer and linking agent are preferably dissolved or dispersed in the binder composition in solvent by binder composition of the present invention, as this solvent, can preferably use with solvent phase used in above-mentioned solution polymerization with solvent.
In binder composition of the present invention, beyond above-mentioned, as required, also can containing other general additive, such as UV light absorber, photostabilizer, protective agent, stripping conditioning agent, tackifier, softening agent, tenderizer, weighting agent, tinting material (pigment or dyestuff etc.), tensio-active agent etc.
[metal covering attaching adhesive sheet]
Metal covering attaching adhesive sheet of the present invention by have comprise above-mentioned binder composition binder layer as binder layer, thus gonorrhoea and the corrosion of metal of the binder layer under hot and humid condition can be suppressed.
Metal covering attaching adhesive sheet of the present invention both can be the adhesive sheet with film base material, also can be the adhesive sheet not having film base material and be only made up of binder layer.In addition, binder layer both can be made up of simple layer, also can be stacked multilayer.In addition, according to use-pattern, both can be the form of one side adhesive sheet, also can be the form of double-sided adhesive sheet.
When adhesive sheet of the present invention is used as fixing between parts with adhesive sheet; such as when have as the surface protection panel on image display device surface and ito film or glass etc. the fixing of the component on metal covering surface or by have to fix between the parts fix between the component on metal covering surface use with adhesive sheet; preferably can use the form of double-sided adhesive sheet; wherein; from the viewpoint of the guaranteeing of the transparency, product having shape-following-up properties, preferably not there is base material and the adhesive sheet be only made up of binder layer.The component that the double-sided adhesive sheet of this form is particularly suitable for a side is the situation that the surface protection panel etc. with the printing step discrepancy in elevation has the component of surface unevenness profile.In addition; when being used as the breaking or be used for the anti-splashing adhesive sheet preventing splashing when breaking of panel after preventing the surface of the panel that surface protection panel is integrated with ito glass or effects on surface protection panel to be applied with ITO process; preferably can use the form of the adhesive sheet with film base material, the form that the one side being simultaneously provided with the film base material of hard coat is provided with the one side adhesive sheet of binder layer can be preferably used in especially.
When metal covering attaching adhesive sheet of the present invention has film base material, transparent film base material can be used as this base material.As this transparent substrate, such as polyethylene terephthalate can be enumerated, polybutylene terephthalate, PEN, polyethylene film, polypropylene screen, glassine paper, diacetyl cellulose film, tri acetyl cellulose membrane, cellulose acetate butyrate film, polychloroethylene film, polyvinylidene chlorida film, polyvinyl alcohol film, Ethylene vinyl accetate copolymer film, Polystyrene Film, polycarbonate membrane, polymethylpentene film, polysulfone membrane, polyether-ether-ketone film, poly (ether sulfone) film, polyetherimde films, polyimide film, fluororesin film, nylon membrane, acrylic resin film etc.Wherein, the polyethylene terephthalate of preferably transparent, smoothness excellence.
In film base material used in metal covering attaching adhesive sheet of the present invention, based on improving the object with the adaptation of binder layer, the surface treatment such as oxide treatment by surfaces such as the further provided for contouring process on the surface of sand-blast or solvent treatment method etc. or Corona discharge Treatment, chromic acid process, flame treating, hot blast process, ozone ■ uviolizing process can be implemented.
The film base material of metal covering attaching adhesive sheet of the present invention, in order to prevent the scar that is mixed in production process or beat the macroscopic irregularitys such as trace, also preferably makes the hard coat film at least in one side with hard coat.Wherein, the hard coat preferably containing acrylic resin.By containing acrylic resin, thus the cementability for hard coated face can be guaranteed.In addition, the metal covering attaching adhesive sheet one side of this hard coat film being provided with binder layer can be suitable for use as anti-splashing adhesive sheet.
Metal covering attaching adhesive sheet of the present invention is the metal covering attaching adhesive sheet being provided with binder layer in the one side of hard coat film, when this adhesive sheet is used as anti-splashing adhesive sheet, the surperficial pencil hardness of the hard coating surface of hard coat film is more than B, is preferably more than F.In addition, preferably the thickness of hard coat is set to 1 ~ 5 μm.
Metal covering attaching of the present invention is flooded the 24 little percent gel represented with following formula constantly with the binder layer of adhesive sheet and is preferably 30 ~ 80 quality % in toluene, is more preferably 30 ~ 70 quality %, most preferably is 35 ~ 55 quality %.If the percent gel of binder layer is in above-mentioned scope, then metal covering fixing in easily suppress through time peel off, in addition, the concavo-convex tracing ability for attached metal or display panel can be given, not easily remain bubble in display frame part.
Percent gel (quality %)=[(after the toluene dipping of binder layer quality)/(before the toluene dipping of binder layer quality)] × 100
For the store elastic modulus of 70 DEG C of the dynamic viscoelastic spectrogram recorded under frequency 1Hz for the binder layer of metal covering attaching adhesive sheet of the present invention, store elastic modulus preferably is contained in 4.0 × 10
4~ 9.0 × 10
5scope in, more preferably 4.0 × 10
4~ 8.0 × 10
4, most preferably 4.0 × 10
4~ 7.0 × 10
4.By store elastic modulus is comprised in this range, can take into account the mobility of following step discrepancy in elevation part with to the suppression of peeling off caused because of warpage.
The dynamic viscoelastic of binder layer of the present invention can by using test for viscoelastic machine (Rheometrics Inc., trade(brand)name: ARES2KSTD), test film is sandwiched same trier as determination part parallel disk between, measure store elastic modulus under frequency 1Hz (G ') and loss Young's modulus (G ") and obtain.The tackiness agent of thick 0.5 ~ 2.5mm both can be clipped between parallel disk by test film individually, also base material can be clipped between parallel disk with after the duplexer multilayer ground overlap of tackiness agent.It should be noted that, in the latter case, adjusted according to the mode only making the thickness of tackiness agent reach above-mentioned scope.
For the transparency of metal covering attaching adhesive sheet of the present invention, preferably total light penetration is more than 80%, turbidity is less than 1.0%, and more preferably total light penetration is more than 90%, turbidity is less than 0.5%.If the transparency of nesa coating is in above-mentioned scope, then easily guarantee the transparency of the indicating meter being equipped with the touch-panel device employing this bonding film.
For being pasted with the metal of metal covering attaching adhesive sheet of the present invention, being not particularly limited, specifically, tin indium oxide, Indium sesquioxide, stannic oxide, zinc oxide, Cadmium oxide, gallium oxide, titanium oxide etc. can being enumerated.
By metal covering attaching adhesive sheet of the present invention under the environment of temperature 23 DEG C, relative humidity 50%RH, for metal, use 2kg roller, be once that reciprocal mode crimps to crimp number of times, the 180 ° of peeling adhesion forces left standstill under the 300mm/min after 1 hour are preferably respectively 5 ~ 20N/25mm relative to metal.If in above-mentioned scope, be then easy to suppress from peeling off end face at the fixing middle of nesa coating, in addition, for the laminating substandard products in manufacturing process, the stripping of adhesive sheet can be realized.
As long as the thickness of metal covering attaching adhesive sheet of the present invention is suitably selected according to used mode, but be preferably 5 ~ 500 μm.Wherein, when bonding on even surface, by being adjusted to 10 ~ 250 μm, thus easily by touch-panel device slimming.In addition, when attach to have on the step discrepancy in elevation or concavo-convex face, preferably the thickness of binder layer is set to more than 20 μm, is particularly preferably set to 25 ~ 150 μm.
Metal covering attaching adhesive sheet of the present invention can utilize the method generally used to make.Such as, can on film base material or release sheet, form binder layer and manufacture.Specifically, following method etc. can be utilized to manufacture, namely, the composition of tackiness agent to be directly coated on base material film and to make its dry or solidification ■ polymerization, or to be temporarily coated on release sheet and to make its dry or solidification ■ polymerization, after forming binder layer, fit on similarly made on release sheet binder layer or base material film.
[use form]
Metal covering attaching adhesive sheet of the present invention is due to can not corroding metal face, there is good whitening resistance, therefore, when the component that the metal wiring film etc. the surface at glass or film being provided with the ito glass of tin indium oxide (ITO) or ito film or being provided with the distribution of silver or copper on the surface of glass or film has metal covering surface is fixed, can use suitably.Especially go for requiring high transparent and the electroconductibility that will aspire for stability have the component on metal covering surface fixing in.In addition, metal covering attaching adhesive sheet of the present invention due to good step discrepancy in elevation tracing ability can be realized, even if therefore the component fixed be have surface unevenness profile component, such as being provided with the component of the printing step discrepancy in elevation, also can use suitably.
As the suitable configuration example being suitable for metal covering attaching adhesive sheet of the present invention, such as, in touch sensor that go for requiring high transparent and stable electroconductibility, that use in the image displaying part of e-machine, an evaporation have the fixing of the polyethylene terephthalate film of ITO and surface protection panel or have at an evaporation between the polyethylene terephthalate film of ITO fixing.As the concrete example of the image display device that this kind is formed, formation as shown in Figure 1 preferably can be exemplified.Application examples in Fig. 1 is the purposes utilizing the metal covering attaching adhesive sheet 1 of the present invention without base material to be fixed with the ito film 4 on transparent resin film 4a with ITO surface 4b the surface protection panel 2 with the printing step discrepancy in elevation 3, and adhesive sheet of the present invention can suitably in this purposes.In addition, can also suitably in following purposes, namely, in housing 5, there is the image display such as LCD module 6, the transparent resin film 4a side of this housing and ito film 4 ' is fixed by the adhesive member such as adhesive tape or jointing tape 7, the ITO of this ito film 4 ' surface 4b ' and the transparent resin film 4a surface of above-mentioned ito film 4 is fixed by metal covering attaching adhesive sheet ' 1 of the present invention without base material.
In addition, can also be used suitably as the bonding film for following object, that is, by the touch sensor used in the image displaying part of e-machine, have the fixing of the glass of tin indium oxide and surface protection panel at an evaporation; Or splashing when preventing glass breakage.As the concrete example of the image display device that this kind is formed, can preferably exemplify the formation shown in Fig. 2 and Fig. 3.
Application examples in Fig. 2 is following example; namely; in one side, there is the ITO surface 14 after ITO process; be provided with the ITO surface 14 of the surface protection panel 12 of the printing step discrepancy in elevation 13 on this surface, the metal covering attaching adhesive sheet 11 of the present invention that the one side being useful in hard coat film 16 has a binder layer 15 is used as the anti-splashing adhesive sheet of this surface protection panel.In this formation, the hard coat film 16 of metal covering attaching adhesive sheet 11 is fixed by adhesive member 19 with the housing 17 with the image display such as LCD module 18.In addition; application examples in Fig. 3 to have the surface protection panel 22 of the printing step discrepancy in elevation 23 and the purposes of ito glass 24 by fixing without the metal covering attaching adhesive sheet 21 of the present invention of base material on transparent glass 24a with ITO surface 24b and 24c, can be identical with the mode of above-mentioned Fig. 1 apply adhesive sheet of the present invention suitably.In addition, as the anti-splashing adhesive sheet of this ito glass 24, the one side that can also be used in hard coat film 25 has the metal covering attaching adhesive sheet 21 ' of the present invention of binder layer 26.In this formation, the hard coat film 25 of metal covering attaching adhesive sheet 21 ' is fixed by adhesive member 29 with the housing 27 with the image display such as LCD module 28 identically with Fig. 2.
Embodiment
To embodiment and comparative example be utilized to carry out more specific description to the present invention below.
< acrylic copolymer (1) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using vinylformic acid 2-methoxy acrylate 75 quality %, n-butyl acrylate 24 quality %, Hydroxyethyl Acrylate 1 quality % and as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (1) that weight-average molecular weight is 700,000.
< acrylic copolymer (2) >
Except vinylformic acid 2-methoxy acrylate being set to 85 quality %, n-butyl acrylate being set to except 14 quality %, operate in the same manner with acrylate copolymer (1), obtain the acrylate copolymer (2) that weight-average molecular weight is 700,000.
< acrylic copolymer (3) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using vinylformic acid 2-methoxy acrylate 70 quality %, vinylformic acid 2 ethylhexyl 29 quality %, Hydroxyethyl Acrylate 1 quality % and as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (3) that weight-average molecular weight is 1,000,000.
< acrylic copolymer (4) >
Except vinylformic acid 2-methoxy acrylate being set to 50 quality %, n-butyl acrylate being set to except 49 quality %, operate in the same manner with acrylate copolymer (1), obtain the acrylate copolymer (4) that weight-average molecular weight is 1,000,000.
< acrylic copolymer (5) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using n-butyl acrylate 80 quality %, methyl methacrylate 19 quality %, Hydroxyethyl Acrylate 1 quality % and as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (5) that weight-average molecular weight is 800,000.
< acrylic copolymer (6) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using n-butyl acrylate 80 quality %, vinylformic acid 19 quality %, Hydroxyethyl Acrylate 1 quality % and as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (6) that weight-average molecular weight is 700,000.
< acrylic copolymer (7) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using vinylformic acid 2-methoxy acrylate 75 quality %, n-butyl acrylate 16 quality %, methyl methacrylate 8 quality %, Hydroxyethyl Acrylate 1 quality % and as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (7) that weight-average molecular weight is 700,000.
< acrylic copolymer (8) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using vinylformic acid 2-methoxy acrylate 75 quality %, n-butyl acrylate 24 quality, vinylformic acid 4 hydroxybutyl 1 quality % and as 2 of polymerization starter, 2 ' Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (8) that weight-average molecular weight is 700,000.
< acrylate copolymer (9) >
Except n-butyl acrylate being set to 22 quality %, Hydroxyethyl Acrylate being set to except 3 quality %, operate in the same manner with acrylate copolymer (1), obtain the acrylate copolymer (9) that weight-average molecular weight is 700,000.
< acrylate copolymer (10) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using vinylformic acid 2-methoxy acrylate 40 quality %, n-butyl acrylate 24 quality %, 2-EHA 35 quality %, Hydroxyethyl Acrylate 1 quality % and as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (10) that weight-average molecular weight is 700,000.
< acrylic copolymer (11) >
Prepare in the reaction vessel of stirrer, reflux cooler, thermometer, dropping funnel and nitrogen inlet what possess acrylic copolymer, using vinylformic acid 2-methoxy acrylate 70 quality %, n-butyl acrylate 24 quality %, Hydroxyethyl Acrylate 1 quality %, vinylformic acid 5 quality % and as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate 0.2 part is dissolved in ethyl acetate 100 quality %, after carrying out nitrogen replacement, be polymerized 8 hours at 80 DEG C and obtain the acrylate copolymer (11) that weight-average molecular weight is 700,000.
< binder composition (a) >
By aforesaid propylene acid ester copolymer (1) diluted ethyl acetate, obtain the binder composition (a) that resin solid content is 30 quality %.
< binder composition (b) >
By aforesaid propylene acid ester copolymer (2) diluted ethyl acetate, obtain the binder composition (b) that resin solid content is 30 quality %.
< binder composition (c) >
By aforesaid propylene acid ester copolymer (3) diluted ethyl acetate, obtain the binder composition (c) that resin solid content is 30 quality %.
< binder composition (d) >
By aforesaid propylene acid ester copolymer (4) diluted ethyl acetate, obtain the binder composition (d) that resin solid content is 30 quality %.
< binder composition (e) >
By aforesaid propylene acid ester copolymer (5) diluted ethyl acetate, obtain the binder composition (e) that resin solid content is 30 quality %.
< binder composition (f) >
By aforesaid propylene acid ester copolymer (6) diluted ethyl acetate, obtain the binder composition (f) that resin solid content is 30 quality %.
< binder composition (g) >
By aforesaid propylene acid ester copolymer (7) diluted ethyl acetate, obtain the binder composition (g) that resin solid content is 30 quality %.
< binder composition (h) >
By aforesaid propylene acid ester copolymer (8) diluted ethyl acetate, obtain the binder composition (h) that resin solid content is 30 quality %.
< binder composition (i) >
By aforesaid propylene acid ester copolymer (9) diluted ethyl acetate, obtain the binder composition (i) that resin solid content is 30 quality %.
< binder composition (j) >
By aforesaid propylene acid ester copolymer (10) diluted ethyl acetate, obtain the binder composition (j) that resin solid content is 30 quality %.
< binder composition (k) >
By aforesaid propylene acid ester copolymer (11) diluted ethyl acetate, obtain the binder composition (k) that resin solid content is 30 quality %.
(embodiment 1)
Isocyanate-based linking agent (Japanese polyurethane Inc. CoronateHX, solids component are 75%) 0.1 mass parts is added and after stirring 15 minutes in above-mentioned binder composition (a) 100 mass parts, on the polyester film (following #75 stripping film) of thick 50 μm after lift-off processing having been carried out to one side with silicone compounds, be coated with in the mode making dried thickness reach 50 μm, drying 5 minutes at 75 DEG C.The adhesive sheet of gained is fitted to the polyester film (following #38 stripping film) that one side has carried out thick 38 μm after lift-off processing with silicone compounds.Thereafter slaking 7 days at 23 DEG C, obtain thick 50 μm, the adhesive sheet without base material of percent gel 50%.
(embodiment 2)
Except isocyanate-based linking agent is set to except 0.08 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 40%.
(embodiment 3)
Except binder composition (a) 100 mass parts is set to except binder composition (b) 100 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 50%.
(embodiment 4)
Except binder composition (a) 100 mass parts is set to binder composition (b) 100 mass parts, is set to except 0.08 mass parts by isocyanate-based linking agent, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 40%.
(embodiment 5)
Except binder composition (a) 100 mass parts is set to except binder composition (g) 100 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 50%.
(embodiment 6)
Except binder composition (a) 100 mass parts is set to except binder composition (h) 100 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 50%.
(embodiment 7)
Except binder composition (a) 100 mass parts is set to except binder composition (i) 100 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 55%.
(comparative example 1)
Except binder composition (a) 100 mass parts is set to except binder composition (c) 100 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 60%.
(comparative example 2)
Except binder composition (a) 100 mass parts is set to except binder composition (d) 100 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 60%.
(comparative example 3)
Except binder composition (a) 100 mass parts is set to except binder composition (e) 100 mass parts, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 60%.
(comparative example 4)
Isocyanate-based linking agent (Japanese polyurethane Inc. CoronateL-45, solids component are 45%) 0.1 mass parts is added and after stirring 15 minutes in above-mentioned binder composition (f) 100 mass parts, on the polyester film (following #75 stripping film) of thick 50 μm after lift-off processing having been carried out to one side with silicone compounds, be coated with in the mode making dried thickness reach 50 μm, drying 5 minutes at 75 DEG C.The adhesive sheet of gained is fitted to the polyester film (following #38 stripping film) that one side has carried out thick 38 μm after lift-off processing with silicone compounds.Thereafter slaking 7 days at 23 DEG C, obtain thick 50 μm, the adhesive sheet without base material of percent gel 70%.
(comparative example 5)
Except binder composition (a) 100 mass parts is set to binder composition (j) 100 mass parts, is set to except 0.3 mass parts by isocyanate-based linking agent, operate identically with embodiment 1, obtain the adhesive sheet of percent gel 80%.
(comparative example 6)
Except binder composition (f) 100 mass parts is set to binder composition (k) 100 mass parts, is set to except 0.12 mass parts by isocyanate-based linking agent, operate identically with comparative example 4, obtain the adhesive sheet of percent gel 80%.
For the adhesive sheet obtained in above-described embodiment and comparative example, carry out following evaluation.The result of gained is shown in table 1 ~ 2.
(hot and humid condition transfers the resistance to gonorrhoea of postpone)
Order according to polyethylene terephthalate film, glass makes adhesive sheet fit, the test sample prepared thus is placed 250 hours under 60 DEG C of 90%RH conditions, uses color technical institute system " HR-100 type " in (strain) village to determine the turbidity after just being taken out from above-mentioned condition by test sample.
Zero: turbidity is less than 1.0%
△: turbidity is 1.0% ~ 3.0%
×: turbidity is more than 3.O%
(resistance value of indium tin oxides film measures)
After the one side of adhesive sheet and polyethylene terephthalate film (100 μm) are fitted, sanction is cut as 50mm × 50mm, makes the evaporation of itself and 100mm × 100mm have the tin indium oxide face of the polyethylene terephthalate film of tin indium oxide to fit.The two ends of the adhesive sheet after laminating, use resistance value measuring machine Mitsubishi Chemical (strain) system " LORESTAGP ", measure the resistance value (R1) at initial stage.The evaporation of fitting adhesive sheet is had the polyethylene terephthalate film of tin indium oxide 60 DEG C, place 250 hours under 90%RH condition, 23 DEG C, place 1 hour under 50%RH condition after, determine with preliminary phase with the resistance value (R2) at position.Following formula is utilized to calculate the resistance change rate of tin indium oxide (ITO) film.
Resistance change rate (%)=((R2-R1)/R1) × 100 of ito film
Zero: resistance change rate is 90 ~ 110%
×: resistance change rate is less than 90% or be more than 110%
(printing step discrepancy in elevation tracing ability evaluates 1)
The stripping film of the side of made adhesive sheet is peeled off, make its with decorate with picture frame shape thick 15 μm, thick 100 μm of the printed layers of wide 5mm, long 50mm, wide 40mm polyethylene terephthalate film fit.The stripping film of the residue side of the test film of gained is peeled off, makes it and fit at the sheet glass of thick 1mm, long 50mm, wide 40mm, under 5 normal atmosphere, the condition of 70 DEG C, 20 minutes, carry out heating and pressurizing process.Place 1 day at 23 DEG C after heating and pressurizing process, overall near the ornamental portion after utilizing microscope (multiplying power 300 times) to observe printing, be confirmed whether alveolate being mixed into.The metewand that bubble is mixed into is as follows.
Zero: the bubble not having diameter more than 5 μm
△: the bubble not having diameter 30 more than μ μm
×: the bubble or the stripping that have diameter more than 30 μm
[table 1]
[table 2]
The simple symbol of the cooperation in table is as follows.
MEA: methoxyethyl acrylate
BA: butyl acrylate
2EHA: 2-EHA
HEA: Hydroxyethyl Acrylate
MA: methyl methacrylate
AA: vinylformic acid
The stripping film of the side of the adhesive sheet made in embodiment 1 is peeled off, adhesive sheet is fitted with the face of hard coat that do not have being provided with the hard coat film of hard coat in the one side of polyethylene terephthalate film, obtains the anti-splashing adhesive sheet in the one side of the base material with hard coat with binder layer.To the anti-splashing adhesive sheet of gained, carry out following evaluation.The result of gained is shown in Table 3.
(printing step discrepancy in elevation tracing ability evaluates 2)
The stripping film of the residue side of the adhesive sheet of gained is peeled off, make it and decorate the thick 1mm of printed layers, long 50mm with picture frame shape, the sheet glass of wide 40mm fits, under 5 normal atmosphere, the condition of 70 DEG C, 20 minutes, carry out heating and pressurizing process.After just carrying out heating and pressurizing process, overall near the ornamental portion after utilizing microscope (multiplying power 300 times) to observe printing, be confirmed whether alveolate being mixed into.The metewand that bubble is mixed into is as follows.
Zero: the bubble not having diameter more than 5 μm
△: the bubble not having diameter more than 30 μm
×: the bubble or the stripping that have diameter more than 30 μm
[table 3]
As shown in the above Table, the adhesive sheet of embodiment 1 ~ 7 is even without the monomer containing carboxyl, and under hot and humid condition, turbidity also can not raise, and confirms do not have gonorrhoea.In addition, the adhesive sheet of embodiment 1 ~ 4 is also very excellent for following of the printing step discrepancy in elevation, also has good printing step discrepancy in elevation tracing ability when using the hard coat film being provided with hard coat as base material.On the other hand, although employ the methoxyethyl acrylate that wetting ability is high, but be in the comparative example 5 that the content of the comparative example 2 of 49 quality %, the comparative example 3 of high containing wetting ability alkoxyalkyl acrylate monomer and alkoxyalkyl acrylate monomer is low at the content employing comparative example 1 that carbon number is the 2-EHA of 8, carbon number is the n-butyl acrylate of 4, under hot and humid condition, turbidity raises, and confirms gonorrhoea.In addition, just have as with regard to acrylic acid comparative example 4 of the monomer containing carboxyl and the adhesive sheet of comparative example 6, although can not gonorrhoea under hot and humid condition, but confirm the rising of the resistance value of ITO.
Nomenclature
1,1 ', 11,21,21 ': metal covering attaching adhesive sheet
2,12,22: surface protection panel
3,13,23: the printing step discrepancy in elevation
4,4 ': ito film
4a, 4a ': transparent resin film
4b、4b’：ITO
5,17,27: housing
6,18,28: image display
7,19,29: adhesive member
14：ITO
15,25: binder layer
16,26: hard coat film
24:ITO glass
25a: transparent glass
25b、25c：ITO
Claims (3)
1. a metal covering attaching adhesive sheet, is characterized in that, is the adhesive sheet fitting in metal covering,
Described adhesive sheet has binder layer, and described binder layer comprises the acrylic adhesive employing (methyl) acrylate copolymer,
Described (methyl) acrylate copolymer contains (methyl) alkoxyalkyl acrylate monomer (A) and has carbon number is that (methyl) alkyl acrylate (B) of the alkyl of 1 ~ 4 is as monomer component
The content forming described (methyl) alkoxyalkyl acrylate monomer (A) in the monomer component of (methyl) acrylate copolymer is more than 50 quality %, it is described that to have carbonatoms be the content of (methyl) alkyl acrylate (B) of the alkyl of 1 ~ 4 is 5 ~ 45 quality %
The content forming the monomer containing carboxyl in the monomer component of (methyl) acrylate copolymer is below 1 quality %,
The summation forming the content of each monomer component of (methyl) acrylate copolymer is 100 quality %,
The weight-average molecular weight of described (methyl) acrylate copolymer is 400,000 ~ 1,600,000.
2. metal covering attaching adhesive sheet according to claim 1, wherein,
It is described that to have carbonatoms be (methyl) alkyl acrylate (B) of the alkyl of 1 ~ 4 is n-butyl acrylate.
3. metal covering attaching adhesive sheet according to claim 1 and 2, wherein,
The percent gel of described binder layer is 30 ~ 80 quality %,
Described percent gel is that the binder layer of described metal covering attaching with adhesive sheet floods the 24 little percent gel represented with following formula constantly in toluene,
Percent gel (quality %)=[(after the toluene dipping of binder layer quality)/(before the toluene dipping of binder layer quality)] × 100.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011-204533 | 2011-09-20 | ||
| JP2011204533 | 2011-09-20 | ||
| PCT/JP2012/073792 WO2013042648A1 (en) | 2011-09-20 | 2012-09-18 | Adhesive sheet for metal surface bonding |
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| Publication Number | Publication Date |
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| CN103492507A CN103492507A (en) | 2014-01-01 |
| CN103492507B true CN103492507B (en) | 2015-11-25 |
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| CN201280019700.4A Active CN103492507B (en) | 2011-09-20 | 2012-09-18 | Metal covering attaching adhesive sheet |
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| JP (1) | JP5278628B1 (en) |
| KR (1) | KR101522231B1 (en) |
| CN (1) | CN103492507B (en) |
| TW (1) | TWI598420B (en) |
| WO (1) | WO2013042648A1 (en) |
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| JP5671485B2 (en) * | 2012-01-11 | 2015-02-18 | 綜研化学株式会社 | Adhesive tape for conductive film and laminate for touch panel |
| JP5732434B2 (en) * | 2012-06-06 | 2015-06-10 | 綜研化学株式会社 | Adhesive sheet for conductive film, laminate, and touch panel having the laminate |
| JP6291679B2 (en) * | 2014-03-31 | 2018-03-14 | リンテック株式会社 | Method for producing surface protective film for transparent conductive substrate, surface protective film for transparent conductive substrate, and laminate |
| JP2016084438A (en) * | 2014-10-28 | 2016-05-19 | Dic株式会社 | Adhesive film, information display device and portable electronic terminal |
| JP6452483B2 (en) * | 2015-02-16 | 2019-01-16 | 日東電工株式会社 | Optical film with adhesive and image display device |
| JP6554344B2 (en) * | 2015-06-30 | 2019-07-31 | リンテック株式会社 | Adhesive sheet and display |
| US12012529B2 (en) | 2018-04-18 | 2024-06-18 | Dic Corporation | Adhesive tape and article |
| KR102476457B1 (en) * | 2019-07-26 | 2022-12-09 | 주식회사 엘지화학 | Adhesive film, protective film for optical member comprising same, optical member comprising same and liquid crystal display device comprising same |
| KR20220003033U (en) | 2021-06-18 | 2022-12-28 | 임환석 | Tatoo sticker |
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| Publication number | Publication date |
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| KR101522231B1 (en) | 2015-05-21 |
| TWI598420B (en) | 2017-09-11 |
| WO2013042648A1 (en) | 2013-03-28 |
| TW201333137A (en) | 2013-08-16 |
| JP5278628B1 (en) | 2013-09-04 |
| JPWO2013042648A1 (en) | 2015-03-26 |
| KR20130106434A (en) | 2013-09-27 |
| CN103492507A (en) | 2014-01-01 |
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