CN105368335A - Surface protective film for transparent conductive membrane and transparent conductive membrane using same - Google Patents
Surface protective film for transparent conductive membrane and transparent conductive membrane using same Download PDFInfo
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- CN105368335A CN105368335A CN201510349770.1A CN201510349770A CN105368335A CN 105368335 A CN105368335 A CN 105368335A CN 201510349770 A CN201510349770 A CN 201510349770A CN 105368335 A CN105368335 A CN 105368335A
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- film
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- electrically conductive
- conductive film
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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
- 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
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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
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- Organic Chemistry (AREA)
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Abstract
The invention provides a surface protective film for transparent conductive membrane and a transparent conductive membrane using the same. The surface of the surface protective film is covered by an adhesive layer, and thus the surface of the surface protective film is smooth. The processing ability of the surface protective film is excellent even if the surface protective film is pasted on a transparent conductive membrane. During the process of manufacturing and processing, the defects on the appearance of the surface protective film are improved, and the yield is good when the surface protective film is used to produce transparent electrodes for touch control panels. The surface protective film (5) for transparent conductive membrane is pasted on one surface of a resin membrane, and the other surface of the resin membrane is covered by a transparent conductive membrane. An adhesive layer (2), which comprises an acrylic resin composition, a crosslinking agent, and a crosslinking catalyst, is laminated on one surface of a substrate membrane (1), the energy storage capacity of the adhesive layer is 4.0*10<5> Pa or more below 30 DEG C; the adhesive forces of the adhesive layer on PET membrane under the conditions: 15 minutes after drying and aging for 5 days at a temperature of 40 DEG C are defined as a and b respectively, and the relationship of a and b is as follows: 0.9=<a/b=<2.0.
Description
Technical field
The present invention relates to and fit to the transparent and electrically conductive film surface protection film that another surface of the resin molding being formed with nesa coating on a surface uses and the transparent and electrically conductive film using this surface protection film.In more detail; the invention provides a kind of transparent and electrically conductive film surface protection film and use the transparent and electrically conductive film of this surface protection film; in this transparent and electrically conductive film surface protection film; the bond layer formed maintains the smoothness on surface; even if fit on transparent and electrically conductive film and also there is excellent treatability; in the manufacture, complete processing of transparent and electrically conductive film; the macroscopic irregularity of surface protection film of resulting from is bad to improve, and productivity in contact panel transparency electrode manufacturing process is good.
Background technology
All the time, in the technical fields such as contact panel, Electronic Paper, electromagnetic shielding material, various sensor, liquid crystal panel, organic EL, solar cell, transparent and electrically conductive film (following, to be sometimes also only called " conductive film ") is widely used in the formation purposes of transparency electrode etc.This transparent and electrically conductive film is formed with the nesa coating be such as made up of ITO (indium tin oxide compound), AZO or GZO (being added with the compound of aluminium or gallium in ZnO (zinc oxide)) etc. on a surface of base material.
In addition, in the manufacturing process of contact panel transparency electrode, will through the operation of multiple heating process and agent treated, such as, to the transparent and electrically conductive film being formed with the nesa coating be made up of ITO, AZO or GZO etc. carry out the crystallization step of the metal oxide film of anneal, resist printing process, etch processes operation, utilize silver-colored thickener to form the operation of wired circuit, the printing process, blank operation etc. of insulation layer.In the manufacturing process of such transparency electrode, in order to prevent producing stained, damage on the surface being formed with the opposition side on the surface of nesa coating of transparent and electrically conductive film, laminating transparent and electrically conductive film surface protection film uses.
In the manufacturing process of transparency electrode, anneal, utilize the formation etc. of the wired circuit of silver-colored thickener at the temperature of about about 150 DEG C, carry out heat treated, therefore require that transparent and electrically conductive film protective membrane has thermotolerance.
About contact panel with etc., the transparent and electrically conductive film protective membrane that uses in the manufacturing process of transparency electrode, propose various scheme.Such as, in patent documentation 1, propose a kind of transparent and electrically conductive film surface protection film, the one side of its base material formed at the thermoplastic resin film by fusing point being more than 200 DEG C is provided with bond layer.Someone think its with use the polyolefin resin such as polyethylene, polypropylene as base material transparent and electrically conductive film surface protection film compared with, thermotolerance is good.
In addition; a kind of manufacture method of transparent and electrically conductive film surface protection film is proposed in patent documentation 2; wherein; on the one side of the base material film containing pet resin and/or PEN resin after coating adhesive, carry out drying with the temperature specified, the residence time, tensile stress.Someone thinks, the transparent and electrically conductive film surface protection film obtained by this manufacture method, after fitting on transparent and electrically conductive film, even if through heating process, also can not be produced large curling (curl).
A kind of resin molding with nesa coating and protective membrane is proposed in patent documentation 3, wherein, the one side of resin molding arranges nesa coating, the surface resin film contrary with the surface being provided with this nesa coating arranges protective membrane, said protection film is made up of the first film and the second film and from above-mentioned resin molding, sets gradually above-mentioned first film and the second film, this first film percent thermal shrinkage heated after 30 minutes at 150 DEG C is less than 0.5% on MD and TD direction, it is the linear expansivity of less than 40ppm/ DEG C that this second film has with the difference of the linear expansivity of the above-mentioned resin molding with nesa coating and protective membrane.If someone thinks apply this invention, then can not be there is the dimensional change caused by the thermal treatment in the complete processings such as contact panel and curling nesa coating.
In addition; a kind of transparent and electrically conductive film surface protection film is proposed in patent documentation 4; it is by using the stripping film of thickness and the stiffness (Gang Soft degree) specified, make the bond layer surface smoothing of surface protection film, macroscopic irregularity is bad to be improved.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-170535 publication
Patent documentation 2: Japanese Patent No. 4342775 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-268168 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2013-226676 publication
Summary of the invention
Invent problem to be solved
The bond layer that the invention provides surface protection film in the same manner as patent documentation 4 maintains smoothness, the bad improved transparent and electrically conductive film surface protection film of macroscopic irregularity on surface.The feature of the surface protection film of patent documentation 4 is that the stiffness employed at 40 DEG C is the stripping film of 0.30mN ~ 40mN, but the film with this stiffness exists, and thickness is thickening, the problem of cost up.In addition, when the manufacture of surface protection film or when user uses surface protection film, according to the specification of used processor, the roll up diameter of surface protection film is restricted sometimes.In this case; for employing the surface protection film of the thick stripping film of base material thickness; compared with the surface protection film of the stripping film thin with employing base material thickness; there are the following problems: to specify roll up diameter, (the volume I length of rolling of getting when り footpath is rolled shortens, and declines in the productivity of contact panel in transparency electrode manufacturing process.
The present invention completes in view of the foregoing, its problem is the transparent and electrically conductive film providing a kind of transparent and electrically conductive film surface protection film and use this surface protection film, this transparent and electrically conductive film surface protection film is from spool body (ロ ー Le body) under the state of uncoiling, the bond layer of transparent and electrically conductive film surface protection film maintains the smoothness on surface, even if fit on transparent and electrically conductive film and also there is excellent treatability, in the manufacture of transparent and electrically conductive film, in complete processing, the macroscopic irregularity of transparent and electrically conductive film surface protection film of resulting from is bad to improve, and productivity in contact panel transparency electrode manufacturing process is good.
For solving the means of problem
Transparent and electrically conductive film surface protection film manufactures by the following method: coating adhesive on base material film or stripping film, make the solvent evaporation in caking agent in drying process after, and laminating stripping film or base material film, and be rolled into bobbin shape.Present inventor has performed further investigation, found that, the dry solid state of bond layer started after 15 minutes is relevant to the concavo-convex distortion on the surface of bond layer.And then find; after drying starts, the caking agent solidified within 15 minutes, is there is by using bond layer; even if when stripping film thin for base material thickness being used for the laminating purposes of bond layer of transparent and electrically conductive film surface protection film; also can suppress to produce concavo-convex distortion in the to be fit of above-mentioned bond layer to the surface on adherend, thus complete the present invention.
In the manufacturing process of surface protection film; usually coating adhesive make it dry and after forming bond layer on base material film; under reel state, carry out maintenance, but between this preserving period in, the distortion of film can be peeling due to the impact of the rolling tightly of reel (volume I Parties り) etc.Therefore, after stripping film distortion when bond layer solidification, the transferring surface shape of stripping film to the surface of bond layer, through manufacture, the complete processing of transparent and electrically conductive film, the reason that this outward appearance that can become transparent and electrically conductive film is significantly deteriorated.
The technology of the present invention design is as follows: during transparent and electrically conductive film surface protection film is carried out maintenance with drum; the solidification of bond layer was carried out, thus, even if stripping film deforms before stripping film deforms; also can suppress the distortion on the surface of bond layer, thus maintain smoothness.
Namely; during transparent and electrically conductive film surface protection film involved in the present invention is carried out maintenance with drum; be subject at the bond layer being fitted with stripping film the distortion of stripping film tractive and before being out of shape; carry out the solidification of bond layer; prevent the surface fitting to the bond layer on adherend from producing concavo-convex, thus maintain smoothness.
The present inventor finds, by after 15 minutes are started to the drying of bond layer and aging (maintenance) complete after the bonding force of bond layer compare, that can grasp the solidification of bond layer carries out state.More particularly; after if the drying of bond layer starts 15 minutes and aging (maintenance) complete after bond layer to the ratio of the bonding force of PET film (bonding force after starting 15 minutes with the bonding force after aging completing divided by drying and obtain numerical value) within the limits prescribed; even if then when stripping film thin for base material thickness being used for the laminating purposes of bond layer of transparent and electrically conductive film surface protection film, also can suppress to produce concavo-convex distortion in the to be fit of above-mentioned bond layer to the surface on adherend.
In order to solve above-mentioned problem, the invention provides following transparent and electrically conductive film surface protection film.
A kind of transparent and electrically conductive film surface protection film, its another surface fitting to the resin molding being formed with nesa coating on a surface uses, it is characterized in that,
This transparent and electrically conductive film surface protection film uses the acrylic adhesive layer containing acrylic resin composition, linking agent and crosslinking catalyst to fold bond layer and forms on the one side of base material film, and the storage modulus of described bond layer at 30 DEG C is 4.0 × 10
5more than Pa, and the drying of described bond layer start 15 minutes after described bond layer the bonding force of PET film and the bonding force of described bond layer to PET film at 40 DEG C after aging 5 days are met to the relation of following formula (1).
0.9≤a/b≤2.0 formula (1)
(herein, a is that the drying of described bond layer starts the described bond layer after 15 minutes to the bonding force of PET film, and b is that described bond layer at 40 DEG C after aging 5 days is to the bonding force of PET film)
In addition, the invention provides a kind of transparent and electrically conductive film, it is another transparent and electrically conductive film obtained on the surface above-mentioned transparent and electrically conductive film surface protection film being fitted to the resin molding being formed with nesa coating on a surface.
The effect of invention
The invention provides a kind of transparent and electrically conductive film surface protection film and use the transparent and electrically conductive film of this surface protection film; transparent and electrically conductive film surface protection film of the present invention is under the state from spool body uncoiling; the bond layer formed maintains the smoothness on surface; even if fit on transparent and electrically conductive film and also there is excellent treatability; in the manufacture, complete processing of transparent and electrically conductive film; the macroscopic irregularity of surface protection film of resulting from is bad to improve, and productivity in contact panel transparency electrode manufacturing process is good.
In addition, in recent years, along with the slimming of the housing of the contour function portable terminal device of smart mobile phone, the slimming of the transparent and electrically conductive film used constantly is in progress.Transparent and electrically conductive film surface protection film of the present invention in the manufacturing process of contact panel transparency electrode, even if under the state on the transparent and electrically conductive film fitting to slimming after heating process, generation curling also very little.Thereby, it is possible to significantly improve workability (workability), the production efficiency of the manufacturing process of contact panel transparency electrode.
Accompanying drawing explanation
Fig. 1 is the sectional view of the example representing transparent and electrically conductive film surface protection film of the present invention.
Fig. 2 represents sectional view transparent and electrically conductive film surface protection film of the present invention being fitted to the example on transparent and electrically conductive film.
Fig. 3 is the schematic diagram of an example of the manufacture method representing transparent and electrically conductive film surface protection film of the present invention.
Embodiment
Below, based on embodiment, the present invention is described in detail.
Fig. 1 is the sectional view of the example representing transparent and electrically conductive film surface protection film of the present invention.This transparent and electrically conductive film surface protection film 5 is laminated with bond layer 2 on the transparent one side with flexual base material film 1.For the protection of bond layer surface, the stripping film 3 that carried out lift-off processing is stacked in the to be fit on the surface on adherend of bond layer 2 by the upper layer that it has carried out lift-off processing.
As base material film 1, use and transparent there is flexual plastic film.Thereby, it is possible to transparent and electrically conductive film surface protection film of the present invention laminating to be bonded to the visual inspection directly carrying out conductive film under the state be formed with on a surface of base material on another surface of the transparent and electrically conductive film of nesa coating.As the plastic film being used as base material film 1, can preferably enumerate the polyester films such as polyethylene terephthalate, PEN, polyethylene glycol isophthalate, polybutylene terephthalate.In addition, except polyester film, as long as there is required intensity and there is the plastic film of optics adaptive, then also can use the plastic film of other resin types.Base material film 1 is unstretching film, unidirectional or biaxial stretching film etc., be not particularly limited, but the heat shrink rate of preferred substrates film is low.
In addition, the thickness of the base material film 1 of transparent and electrically conductive film surface protection film involved in the present invention is not particularly limited, and selects according to used transparent and electrically conductive film.More than used transparent conductivity thickness to 100 μm, the treatability of transparent and electrically conductive film itself can not be too poor, and therefore, surface protection film is mainly conceived to protect the surface of transparent and electrically conductive film.Therefore, the thickness of the base material film 1 of surface protection film can be used to be the surface protection film of about 25 ~ 75 μm.
On the other hand, when used transparent and electrically conductive film is as thin as below 50 μm, the treatability of transparent and electrically conductive film itself is poor, therefore, also will consider the treatability of surface protection film, preferably uses the transparent and electrically conductive film that the thickness of base material film is thick.As the thickness of concrete base material film, be preferably about 100 ~ 188 μm.
In addition, can be stacked to prevent the stain-proofing layer for the purpose of surface smut, antistatic layer, oligopolymer preventing layer, atraumatic hard coat or to carry out the process of Corona discharge Treatment, easy-adhesion such as anchoring coating process etc. on the surface being laminated with the opposition side on the surface of bond layer 2 of base material film 1 as required.
The bond layer 2 of transparent and electrically conductive film surface protection film involved in the present invention is preferably acrylic-based adhesives.Be particularly preferably the binary liquid shape caking agent carrying out acrylic-based adhesives and linking agent to prepare (cooperation) before being about to use.
As acrylic-based adhesives, preferably in (methyl) acrylic polymers (acrylic resin composition), be added with linking agent and be added with the caking agent of tackifiers as required.(methyl) acrylic polymers is generally the polymkeric substance of functional monomer's copolymerization such as the comonomer such as principal monomer and vinyl cyanide, vinyl acetate, methyl methacrylate, ethyl propenoate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hy-droxybutyl, glycidyl methacrylate, N-methylol methacrylamide such as n-butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, vinylformic acid ester in the different ninth of the ten Heavenly Stems.Preferred (methyl) acrylic monomer of monomer composition forming (methyl) acrylic polymers is more than 50%, and (methyl) acrylic monomer also can be 100%.
As linking agent, isocyanate compound, epoxy compounds, melamine compound, metal chelate compound etc. can be enumerated, wherein preferred isocyanate compound.The preferred polyisocyanate compound in a part with isocyanic ester (NCO) base of more than at least 2 or 3 further.
Polyisocyanate compound is divided into fatty family isocyanic ester, fragrant family isocyanic ester, non-ring type system isocyanic ester, ester ring type system isocyanic ester etc., can be any one.As the concrete example of the isocyanate compound of two senses, the fatty family isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI) can be enumerated; The fragrant family isocyanate compounds such as diphenylmethanediisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenation of benzene dimethylene diisocyanate (H6XDI), dimethyl two phenylene diisocyanate (TOID), tolylene diisocyanate (TDI).
As isocyanate compound more than trifunctional, the biuret form modifier of diisocyanates (there is the compound of 2 NCO bases in a part), isocyanuric acid ester type modifier can be enumerated; With the affixture (polyalcohol modified thing) etc. of polyvalent alcohol (there is the compound of more than at least 3 OH bases in a part) more than the trivalents such as TriMethylolPropane(TMP) (TMP), glycerine.
The addition of linking agent considers that the kind, the polymerization degree, amount of functional groups etc. of (methyl) acrylic polymers are determined, be not particularly limited, relative to (methyl) acrylic polymers 100 weight part, linking agent is usually made to be about 0.5 ~ 10 weight part.
In addition; transparent and electrically conductive film surface protection film involved in the present invention is during carrying out maintenance with drum; need before stripping film distortion, bond layer to be cured; therefore; in order to promote the crosslinking reaction of (methyl) acrylic polymers and linking agent, preferably add crosslinking catalyst.As long as crosslinking catalyst plays the material of catalyst action to the reaction (crosslinking reaction) of (methyl) acrylic polymers and linking agent, when using polyisocyanate compound as linking agent, the organometallic compounds etc. such as the amine compounds such as tertiary amine, organo-tin compound, organo-lead compound, organic zinc compound, organoiron compound can be enumerated.
As tertiary amine, trialkylamine, N, N, N can be enumerated ', N '-tetra, N, N-dialkyl amido alcohol, Triethylene Diamine, morpholine derivative, bridged piperazine derivatives etc.
As organo-tin compound, dialkyltin, the soap of dialkyl tin, the soap etc. of sub-tin can be enumerated.
The addition of crosslinking catalyst considers that the kind, addition etc. of the kind of (methyl) acrylic polymers, the polymerization degree, amount of functional groups, crosslinking catalyst are determined, be not particularly limited, relative to acrylic polymers 100 weight part, about being generally 0.01 ~ 0.5 weight part.
In addition, the shelf lives of the excessive viscosity rising of the adhesive composite after preparing to suppress linking agent, gelation, prolongation adhesive composite, crosslinking delay agent can be contained as required.
As crosslinking delay agent; the beta-diketons such as the 'beta '-ketoesters such as methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid grease, lauryl acetoacetate, etheric acid stearyl ester, methyl ethyl diketone, 2,4-hexanedione, benzoylacetone can be enumerated.Be particularly preferably more than at least one in the compound group being selected from and being made up of methyl ethyl diketone, methyl aceto acetate.These crosslinking delay agent are keto-enol tautomerism compound, using polyisocyanate compound as in the adhesive composite of linking agent, by the isocyanate group that sealant retention rate has, the excessive viscosity of the adhesive composite after linking agent can be suppressed to prepare rises, gelation, can extend the shelf lives of adhesive composite.
The addition of crosslinking delay agent is not particularly limited, relative to (methyl) acrylic polymers 100 weight part, about usually adding 1.0 ~ 5.0 weight parts.
In addition, tackifiers can be added as required in caking agent.As tackifiers, rosin series, cumarone indenes system, terpenic series, petroleum, phenol system etc. can be enumerated.
In addition, in the bond layer 2 of transparent and electrically conductive film surface protection film involved in the present invention, static inhibitor can be mixed as required.As static inhibitor, the dispersiveness preferably in (methyl) acrylic polymers or the static inhibitor good with (methyl) acrylic polymers consistency.As spendable static inhibitor, tensio-active agent system, ionic liquid, an alkali metal salt, metal oxide, metal particle, electric conductive polymer, carbon, carbon nanotube etc. can be enumerated.From the transparency, with affinity angularly of (methyl) acrylic polymers, preferred surfactant system, ionic liquid, an alkali metal salt etc.Static inhibitor relative to the addition of caking agent can consider static inhibitor kind, suitably determine with the consistency of base polymer.In addition, stripping voltage required when considering transparent and electrically conductive film surface protection film involved in the present invention to peel off from transparent and electrically conductive film, the contaminative, bonding force etc. of adherend specifically set kind, the addition of static inhibitor.
In addition, the thickness of the bond layer 2 of transparent and electrically conductive film surface protection film involved in the present invention is not particularly limited, such as, be preferably the thickness of about 5 ~ 50 μm, the more preferably thickness of about 5 ~ 30 μm.When the thickness of bond layer 2 is more than 50 μm, the cost manufacturing transparent and electrically conductive film surface protection film increases, and therefore damages competitive power.When the thickness of bond layer 2 is less than 5 μm, there are the following problems: reduce the adaptation of transparent and electrically conductive film, or when being mixed into foreign matter when being fitted on transparent and electrically conductive film by surface protection film, transparent and electrically conductive film is significantly out of shape.
In addition, that the bond layer 2 of transparent and electrically conductive film surface protection film involved in the present invention is preferably about 0.05 ~ 0.5N/25mm to the stripping strength on adherend surface, that there is slight cementability micro-bond layer.By making the transparent and electrically conductive film surface protection film with so micro-bond layer, the operability of the excellence easily peeled off from adherend can be obtained.
In addition, the material of the stripping film 3 of transparent and electrically conductive film surface protection film involved in the present invention is not particularly limited.As the material of spendable stripping film, the polyolefin films such as polyethylene film, polypropylene screen, polymethylpentene film can be enumerated, on the surface of the films such as polyester film, use the strippers such as polysiloxane series stripping agent to implement the stripping film, fluororesin film, polyimide film etc. of lift-off processing.In addition, also can for by the film of more than 2 use joint compound be laminated film, on film, melt extrude resin and the stacked film be laminated.These unitary films or stacked film use the strippers such as polysiloxane series stripping agent implement lift-off processing, obtain stripping film.
In addition, the thickness of the stripping film 3 of transparent and electrically conductive film surface protection film involved in the present invention is not particularly limited, and selects the stripping film of wieldy thickness.Usually the stripping film of 19 μm ~ about 75 μm mostly is.
When making stripping film 3 thick, in the spool body of identical coil diameter being rolled into drum, the total length of transparent and electrically conductive film surface protection film shortens, manufacturing cost increases, and therefore, makes stripping film 3 be suitable thickness.In addition, stripping film 3 preferably lift-off processing is carried out to single-layer polyester film and obtain stripping film, lift-off processing is implemented to the film using joint compound to be built up by polyester film multilayer layer and the stripping film that obtains.
In addition, the method that base material film 1 stacks gradually bond layer 2 and stripping film 3 is undertaken by known method, is not particularly limited.Specifically, can be on base material film 1 coating adhesive layer 2 and dry after laminating stripping film 3 method, on stripping film 3 coating adhesive layer 2 and dry after laminating base material film 1 method etc. in any one method.
In addition, base material film 1 forms bond layer to be undertaken by known method.Specifically, known coating process such as reverse coating method, comma coating method, woodburytype, slot coating processes, Meyer rod coating method, air knife coating method etc. can be adopted.
In addition, method stripping film 3 being implemented to lift-off processing is undertaken by known method.Specifically, on the one side of stripping film 3, be coated with stripper by woodburytype, coating process such as Meyer rod coating method, air knife coating method etc. and by heating or uviolizing etc., stripper carried out drying, solidified.Also can carry out corona treatment in advance to the film that will carry out lift-off processing as required, pre-treatment that Cement Composite Treated by Plasma, anchoring coating (ア ン カ ー コ ー ト) etc. make stripper improve the adaptation of film.
In addition, Fig. 2 is the schematic pie graph representing example transparent and electrically conductive film surface protection film of the present invention being fitted to the stacked film 11 on transparent and electrically conductive film.
This stacked film 11 is utilized by adhesive film 4 its bond layer 2 to fit to the stacked film on the surface of transparent and electrically conductive film 10, and this adhesive film 4 peels stripping film 3 from transparent and electrically conductive film surface protection film 5 of the present invention and obtains.Transparent and electrically conductive film 10 is formed with nesa coating 7 on a surperficial 6a of resin molding 6.Adhesive film 4 is fitted on another surperficial 6b of resin molding 6.
As transparent and electrically conductive film 10, polyethylene terephthalate (PET) film of the nesa coating being formed with ITO, AZO or GZO etc. can be enumerated, be formed with the cyclic polyolefin film etc. of the nesa coating of ITO, AZO or GZO etc.Such transparent and electrically conductive film is widely used in the formation purposes of transparency electrode etc. in the technical fields such as contact panel, Electronic Paper, electromagnetic shielding material, various sensor, liquid crystal panel, organic EL, solar cell.
Transparent and electrically conductive film surface protection film of the present invention plays following excellent effect: in the manufacturing process of the transparency electrode of contact panel etc.; can significantly improve workability, production efficiency; even the transparent and electrically conductive film of slimming, workability, treatability also can not be made to reduce.
In addition, Fig. 3 is the schematic diagram of an example of the manufacture method representing transparent and electrically conductive film surface protection film of the present invention.
The spool body 22 that the spool body 21 reeled from the stripping film 3 having carried out lift-off processing and base material film 1 reel constantly releases stripping film 3 and base material film 1 respectively.On a surface of base material film 1, utilize caking agent apparatus for coating 23 coating adhesive.By dry in drying oven 24 for the base material film 1 being coated with caking agent, form adhesive film 4.The surface of the lift-off processing that made the surface being formed with bond layer of adhesive film 4 with the carrying out of stripping film 3 is relative, uses crimping roller 25,26 to crimp, obtains transparent and electrically conductive film surface protection film 5.Transparent and electrically conductive film surface protection film 5 is rolled as spool body 27.Usually, transparent and electrically conductive film surface protection film 5 preservation, transport and carry out with the state of spool body 27.When fitting on transparent and electrically conductive film 10, transparent and electrically conductive film with surface protection film 5 from uncoiling spool body 27.
[embodiment]
Below, based on embodiment, the present invention will be described further.
(making of the transparent and electrically conductive film surface protection film of embodiment 1)
At thickness be the polyester film after the two-way stretch of 25 μm one side on, by Meyer rod method coating composition, the thickness of dried polysiloxane film is made to be 0.1 μm, the coating of this coating for being obtained with the dilution of toluene/ethyl acetate 1:1 mixed solvent by addition reaction-type polysiloxane (name of an article TorayDowCorning manufactures: be added with platinum catalyst SRX-2121 weight part in SRX-211100 weight part).And then, in the heated air circulation type baking oven of temperature 120 DEG C, carry out drying, the solidification of 1 minute, obtain the stripping film of embodiment 1.
In addition, bond layer uses adhesive composite to be formed, this adhesive composite is be add HDI system linking agent (Japanese polyurethane industrial manufactures, the name of an article: CORONETHX) 4 weight parts in acrylic polymers 100 weight part of 40%, as dibutyl tin laurate 0.03 weight part of crosslinking catalyst and the adhesive composite be obtained by mixing at the solids component of ethyl acrylate and the copolymerization of vinylformic acid-2-hydroxyl ethyl ester.Being that the polyethylene terephthalate film of 125 μm is coated with above-mentioned adhesive composite at thickness, making the thickness of dried bond layer be 20 μm, is make caking agent in the heated air circulation type baking oven of 130 DEG C dry 1 minute in temperature.Then, polysiloxane (silicone) the treated side laminating layer of the stripping film of the embodiment 1 of above-mentioned making is laminated on the surface of bond layer, obtains the transparent and electrically conductive film surface protection film of embodiment 1.
(making of the transparent and electrically conductive film surface protection film of embodiment 2)
Except making the addition of linking agent be except 6 weight parts relative to acrylic polymers 100 weight part, obtain the transparent and electrically conductive film surface protection film of embodiment 2 similarly to Example 1.
(making of the transparent and electrically conductive film surface protection film of embodiment 3)
Except making the addition of linking agent be except 8 weight parts relative to acrylic polymers 100 weight part, obtain the transparent and electrically conductive film surface protection film of embodiment 3 similarly to Example 1.
(making of the transparent and electrically conductive film surface protection film of comparative example 1)
Except making the drying temperature of bond layer be except 100 DEG C, obtain the transparent and electrically conductive film surface protection film of comparative example 1 similarly to Example 1.
(making of the transparent and electrically conductive film surface protection film of comparative example 2)
Except the solids component being used in butyl acrylate, ethyl acrylate and acrylic acid copolymer is add epoxy linking agent in acrylic polymers 100 weight part of 40% (gas chemical company of Mitsubishi manufactures; the name of an article: TETRAD-C) 4 weight parts the adhesive composite be obtained by mixing as beyond adhesive composite, obtain the transparent and electrically conductive film surface protection film of comparative example 2 similarly to Example 1.
(making of the transparent and electrically conductive film surface protection film of comparative example 3)
Except being used in ethyl acrylate, the solids component of butyl acrylate and the copolymerization of vinylformic acid-2-hydroxyl ethyl ester is add HDI system linking agent in acrylic polymers 100 weight part of 40% (Japanese polyurethane industrial manufactures; the name of an article: CORONETHX) 1 weight part, as dibutyl tin laurate 0.03 weight part of crosslinking catalyst and the adhesive composite be obtained by mixing as beyond adhesive composite, obtain the transparent and electrically conductive film surface protection film of comparative example 3 similarly to Example 1.
(making of the transparent and electrically conductive film surface protection film of comparative example 4)
Except not adding the dibutyl tin laurate as crosslinking catalyst, obtain the transparent and electrically conductive film surface protection film of comparative example 4 similarly to Example 1.
Below, the method and test result of evaluation test is shown.Herein, use " hard coating process PET film " as an example of transparent and electrically conductive film base material (film).
(mensuration of storage modulus)
For the sample obtained in embodiment, comparative example, determination of viscoelasticity device (ABM company manufactures, Measurement of Dynamic Viscoelasticity device Reogel-E4000) is used to be determined at the storage modulus of the bond layer of maintenance after 5 days at 30 DEG C under 40 DEG C of environment.
(mensuration to the bonding force of PET film)
For the sample obtained in embodiment, comparative example, measure the drying of bond layer to start after 15 minutes and under the environment of 40 DEG C the bond layer of maintenance after 5 days to the bonding force of PET film.
By making the rubber rollers round trip of 2kg, sample being fitted to thickness is on the two-way stretch polyethylene terephthalate film (DIAMONDFOILT100 that Mitsubishi Plastics Inc manufactures) of 38 μm.23 DEG C, place 1 hour under the environment of 50%RH after, use small desk testing apparatus (EZ-L that company of Shimadzu Seisakusho Ltd. manufactures), measure bonding force when to peel off PET film along the direction of 180 ° with the peeling rate of 300mm/ minute.
(mensuration of the initial bonding force of transparent and electrically conductive film surface protection film)
Be used in one side that thickness is polyester film after the two-way stretch of 50 μm implements hard coating process, also for the PET film (KIMOTO company manufactures, the name of an article: KB film #50G01) after the hard coating process of ito film.By be cut into the wide transparent and electrically conductive film surface protection film of 25mm and fit to PET film the surface implementing hard coating process on after, 23 DEG C, preserve 1 hour under the environment of 50%RH, make the working sample of initial bonding force.Then, use tensile testing machine, measure with the peeling rate of 300mm/ minute along 180 ° direction peel off transparent and electrically conductive film surface protection film time intensity, it can be used as initial bonding force (N/25mm).
The small desk testing apparatus that the model that determinator uses company of Shimadzu Seisakusho Ltd. to manufacture is EZ-L.
The mensuration > of bonding force after the heating of < transparent and electrically conductive film surface protection film
Implementing after on the hard surface being coated with process of PET film is fitted to by being cut into the wide transparent and electrically conductive film surface protection film of 25mm; preserve 1 hour under 150 DEG C of environment; as the working sample of bonding force after heating; in addition; measure in the same manner as the mensuration of initial bonding force, it can be used as the rear bonding force (N/25mm) of heating.
The small desk testing apparatus that the model that determinator uses company of Shimadzu Seisakusho Ltd. to manufacture is EZ-L.
When transparent and electrically conductive film surface protection film (fit in hard coating process PET film the confirmation method of treatability)
Use and the sample of visual inspection has been carried out as following transparent and electrically conductive film surface protection film to transparent and electrically conductive film surface protection film.The hard coating treated side of the PET film (KIMOTO company manufactures, the name of an article: KB film #50G01) after hard coating process to be fitted transparent and electrically conductive film surface protection film, then stacked product are cut into A4 size.Arrest 1 angle in 4 angles of cutting the sample obtained, before and after the mode of agitating to use face, come and go vibration 20 times aloft.Then, process PET film is firmly coated with or without bending, distortion by visual confirmation.By be firmly coated with process PET film on not have bend, distortion sample be evaluated as (zero), by exist bending or be out of shape sample be evaluated as (×).
(method of the visual inspection of transparent and electrically conductive film surface protection film)
Use test coating machine makes the reel product (400mm wide × 100m roll up long) of transparent and electrically conductive film surface protection film, and in the baking oven of 40 DEG C, insulation 5 days, carries out the maintenance of caking agent.Then, observed by the outward appearance of the visual sample to the position apart from end 50m (apart from roughly equidistant position, two ends) from the transparent and electrically conductive film surface protection film after reel product uncoiling.The sample of the surface smoothing of bond layer is evaluated as (zero), the surface at bond layer is created weak concavo-convex sample and be evaluated as (△), the surface at bond layer is created sample concavo-convex by force and is evaluated as (×).
(method of the visual inspection of hard coating process film)
Use and the sample of visual inspection has been carried out as following transparent and electrically conductive film surface protection film to transparent and electrically conductive film surface protection film.The hard coating treated side of hard coating process PET film (KIMOTO company manufactures, the name of an article: KB film #50G01) to be fitted transparent and electrically conductive film surface protection film, then, at 150 DEG C, carry out the heat treated of 1 hour.After being peeled off with surface protection film by transparent and electrically conductive film, be firmly coated with the condition of surface of process PET film by visual observation.Sample level and smooth for the outward appearance being firmly coated with process PET film is evaluated as (zero), the sample creating concavo-convex weak distortion is evaluated as (△), the sample creating concavo-convex severe deformation is evaluated as (×).
Table 1 will be shown in for each sample tests result.In table 1, " polymer A " acrylic polymers for recording in embodiment 1, " polymer B " acrylic polymers for recording in comparative example 2, " polymkeric substance C " acrylic polymers for recording in comparative example 3, " linking agent 1 " HDI system linking agent for recording in embodiment 1 and comparative example 3, " linking agent 2 " epoxy linking agent for recording in comparative example 2.In addition, about the value of the storage modulus in table 1, represented, such as, by 4.0 × 10 by the form recording mantissa and index in the front and back of E
5be designated as 4.0E+05.
[table 1]
Measurement result as shown in Table 1 makes following judgement.
In embodiment 1 ~ 2; the bond layer used in transparent and electrically conductive film surface protection film, " drying of bond layer start after 15 minutes with the ratio to the bonding force of PET film after aging 5 days at 40 DEG C " (a/b) be 1.4 ~ 1.6; the change of the bonding force after dry beginning completed with aging (maintenance) after 15 minutes is little, and bond layer surface is concavo-convex very little.The outward appearance employing the hard coating process PET film of this surface protection film is good.In addition, treatability when being fitted to by the transparent and electrically conductive film surface protection film of embodiment 1 ~ 2 in hard coating process PET film is also very good.
About embodiment 3, " drying of bond layer starts the ratio after 15 minutes and to the bonding force of PET film after aging 5 days at 40 DEG C " (a/b) is 2.0, compared with embodiment 1 ~ 2, the concavo-convex of bond layer surface increases slightly, but the concaveconvex shape on bond layer surface can not be transferred in hard coating process PET film, obtain the hard coating process PET film that outward appearance is good.
On the other hand; for comparative example 1 ~ 2; " drying of bond layer starts the ratio after 15 minutes and to the bonding force of PET film after aging 5 days at 40 DEG C " (a/b) is 2.3 ~ 8.5, and transparent and electrically conductive film surface protection film creates concavo-convex on the surface of bond layer.Therefore, to firmly be coated with process stacked product that PET film fit carry out heat treated time, the concaveconvex shape on the surface of bond layer is transferred in hard coating process PET film, is firmly coated with the outward appearance decline processing PET film.
In addition, in comparative example 3, the storage modulus of bond layer is low to moderate and is less than 4.0 × 10
5pa, " drying of bond layer starts the ratio after 15 minutes and to the bonding force of PET film after aging 5 days at 40 DEG C " (a/b) is 1.5.But the transparent and electrically conductive film surface protection film of comparative example 3 creates concavo-convex on the surface of bond layer.Therefore, to firmly be coated with process stacked product that PET film fit carry out heat treated time, the concaveconvex shape on the surface of bond layer is transferred in hard coating process PET film, is firmly coated with the outward appearance decline processing PET film.
For the comparative example 4 not adding crosslinking catalyst, in evaluating the bonding force of PET film after the drying of bond layer starts 15 minutes, cohesion occurs bond layer destroys, and transparent and electrically conductive film surface protection film creates concavo-convex on the surface of bond layer.Therefore, to firmly be coated with process stacked product that PET film fit carry out heat treated time, the concaveconvex shape on the surface of bond layer is transferred in hard coating process PET film, is firmly coated with the outward appearance decline processing PET film.
[industrial applicability]
Transparent and electrically conductive film surface protection film of the present invention in the manufacturing process of contact panel transparency electrode, even if under the state on the transparent and electrically conductive film fitting to slimming after heating process, generation curling also very little.Thereby, it is possible to significantly improve workability, the production efficiency of the manufacturing process of contact panel transparency electrode.In addition, transparent and electrically conductive film surface protection film of the present invention can as use in the technical fields such as contact panel, Electronic Paper, electromagnetic shielding material, various sensor, liquid crystal panel, organic EL, solar cell, the manufacture of transparent and electrically conductive film, processing surface protection film widely use.
[explanation of symbol]
1 ... base material film, 2 ... bond layer, 3 ... stripping film, 4 ... adhesive film, 5 ... transparent and electrically conductive film surface protection film, 6 ... resin molding, 6a ... a surface of resin molding, 6b ... another surface of resin molding, 7 ... nesa coating, 10 ... transparent and electrically conductive film, 11 ... stacked film, 21 ... the spool body of stripping film, 22 ... the spool body of base material film, 23 ... caking agent apparatus for coating, 24 ... drying oven, 25, 26 ... crimping roller, 27 ... the spool body of transparent and electrically conductive film surface protection film.
Claims (2)
1. a transparent and electrically conductive film surface protection film, its another surface fitting to the resin molding being formed with nesa coating on a surface uses, it is characterized in that,
This transparent and electrically conductive film surface protection film uses the acrylic adhesive layer containing acrylic resin composition, linking agent and crosslinking catalyst to fold bond layer and forms on the one side of base material film, and the storage modulus of described bond layer at 30 DEG C is 4.0 × 10
5more than Pa, and the drying of described bond layer start 15 minutes after described bond layer the bonding force of PET film and the bonding force of described bond layer to PET film at 40 DEG C after aging 5 days are met to the relation of following formula (1),
0.9≤a/b≤2.0 formula (1)
Herein, a is that the drying of described bond layer starts the described bond layer after 15 minutes to the bonding force of PET film, and b is that described bond layer at 40 DEG C after aging 5 days is to the bonding force of PET film.
2. a transparent and electrically conductive film, it is another transparent and electrically conductive film obtained on the surface transparent and electrically conductive film surface protection film according to claim 1 being fitted to the resin molding being formed with nesa coating on a surface.
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| JP2014161803A JP6218332B2 (en) | 2014-08-07 | 2014-08-07 | Method for producing roll body of surface protective film for transparent conductive film |
| JP2014-161803 | 2014-08-07 |
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| KR101766117B1 (en) | 2016-02-17 | 2017-08-07 | 현대자동차주식회사 | One Body Hot-Stamping Body Frame Structure |
| JP2020111622A (en) * | 2017-03-29 | 2020-07-27 | 三井化学東セロ株式会社 | Adhesive laminated film and structure |
| WO2018181453A1 (en) * | 2017-03-29 | 2018-10-04 | 三井化学東セロ株式会社 | Adhesive laminated film and structure |
| JP2019185164A (en) | 2018-04-03 | 2019-10-24 | 富士通コンポーネント株式会社 | Tactile presentation device |
| JP7039674B2 (en) * | 2020-11-05 | 2022-03-22 | リンテック株式会社 | Laminates and protective films |
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| TWI681032B (en) | 2020-01-01 |
| KR20160018348A (en) | 2016-02-17 |
| JP6218332B2 (en) | 2017-10-25 |
| CN105368335B (en) | 2021-03-26 |
| KR101756737B1 (en) | 2017-07-12 |
| KR101837940B1 (en) | 2018-03-13 |
| JP2016037557A (en) | 2016-03-22 |
| KR20170081633A (en) | 2017-07-12 |
| TW201610080A (en) | 2016-03-16 |
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