WO2004070737A1 - 透明導電性フィルム、透明導電板及びタッチパネル - Google Patents
透明導電性フィルム、透明導電板及びタッチパネル Download PDFInfo
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- WO2004070737A1 WO2004070737A1 PCT/JP2004/000987 JP2004000987W WO2004070737A1 WO 2004070737 A1 WO2004070737 A1 WO 2004070737A1 JP 2004000987 W JP2004000987 W JP 2004000987W WO 2004070737 A1 WO2004070737 A1 WO 2004070737A1
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- Prior art keywords
- film
- transparent conductive
- adhesive layer
- transparent
- thin film
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/048—Interaction techniques based on graphical user interfaces [GUI]
- G06F3/0487—Interaction techniques based on graphical user interfaces [GUI] using specific features provided by the input device, e.g. functions controlled by the rotation of a mouse with dual sensing arrangements, or of the nature of the input device, e.g. tap gestures based on pressure sensed by a digitiser
- G06F3/0488—Interaction techniques based on graphical user interfaces [GUI] using specific features provided by the input device, e.g. functions controlled by the rotation of a mouse with dual sensing arrangements, or of the nature of the input device, e.g. tap gestures based on pressure sensed by a digitiser using a touch-screen or digitiser, e.g. input of commands through traced gestures
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- Transparent conductive film, transparent conductive plate and touch panel Transparent conductive film, transparent conductive plate and touch panel
- the present invention relates to a touch panel, a transparent conductive film having a transparent conductive thin film formed on a high molecular weight film which can be advantageously used for the touch panel, and a transparent conductive plate having a transparent conductive thin film formed on a transparent substrate.
- a resistive touch panel has been used as a device for inputting by pressing a display screen such as a CRT or an LCD with a finger or drawing with a dedicated pen.
- touch panels are mainly used in ATMs and CDs of banks, ticket vending machines, personal digital assistants, personal computers, and input operation units of various industrial equipment.
- the resistive touch panel is an upper electrode made of a polymer film with an undercoat layer and a transparent conductive thin film formed on a lower electrode made of a transparent electrode formed on a thick substrate such as glass or plastic. Are stacked via a spacer (microdot spacer) so that the transparent conductive thin film faces each other.
- spacer microdot spacer
- JP-A-2-66609 discloses a laminate of a substrate Z, an adhesive, a substrate Z, and a transparent conductive layer, and describes a transparent conductive thin film in which stress is reduced by an adhesive. I have. [Summary of the Invention]
- the elasticity of the pressure-sensitive adhesive is 1 ⁇ 10 5 to 1 ⁇ 10 7 dyne / cm 2 (l ⁇ 10 4 to l ⁇ 10 6 Pa).
- Materials such as polyurethane and rubber
- these adhesives are easily plastically deformed, so that when the surface of the touch panel is pressed with a pen, the recessed shape is difficult to return to the original shape, which is a problem in appearance.
- these pressure-sensitive adhesive layers are pressure-sensitive adhesives that are mainly bonded together under pressure, in a severe environment, the adhesiveness may be reduced, and foaming and peeling may occur.
- the transparent electrode may crack or peel off or fall off from the polymer film with time. Due to damage, electrical properties such as uniformity of electrical resistance are lost, and superior durability cannot be obtained.
- the present invention solves such a problem, and almost no dent occurs when the surface of the touch panel is pressed with a pen, and peeling between the polymer film and the adhesive layer even after long-term use. It is an object of the present invention to provide a touch panel excellent in durability, in which no transparent conductive thin film is damaged, and a transparent conductive film and a transparent conductive plate useful for this touch panel.
- an adhesive layer that hardly leaves a depression when the surface of the touch panel is pressed with a pen or the like has a property that it can easily return to its original state even if it is slightly depressed when pressed with a pen. It was found that such an adhesive layer had a good feeling in use and was also good in terms of adhesiveness. That is, if the adhesive layer is too hard, the feeling of use and adhesion are poor, and if the adhesive layer is too soft, dents are likely to occur, and the durability is not sufficient.
- the present inventors have studied and found that in order to have such properties, it is necessary to increase the elastic deformation work (different from the elastic modulus and elastic modulus) of the adhesive layer. Reached.
- a first polymer film having a transparent conductive thin film provided on a surface thereof, and a second polymer film having a hard coat layer on a surface thereof are opposed to each other on a back surface on which the film or layer is not formed.
- a transparent conductive film bonded by an adhesive layer is not formed.
- the transparent conductive finolem is characterized in that the work of elastic deformation of the adhesive layer is 60% or more. [About the work of elastic deformation]
- the work of elastic deformation in the present invention is defined by the method described in A.8 Plastic and elastic parts oi the indentation relaxation of ISO 14457: 2002 (E). It is a value measured according to the above. This method is also described in DIN 50 359-1-1: 1977-10.
- the plastic part and the elastic part of the dent work are determined as follows.
- the mechanical work W t . tal is consumed as part ⁇ deformation work amount W p l ast.
- the remainder is defined as an elastic reverse deformation Wel ast.
- mechanical work ⁇ F dh (F: load, h: depth of penetration)
- the plastic part W P ] ast / W tota ⁇ is 100% -77 IT .
- the work of elastic deformation of the present invention corresponds to the elastic part.
- the elastic portion is measured using a Fischer scope commercially available from Helmut Fischer; H100 (a Pickers pyramid indenter with high dimensional accuracy is usually used).
- the load was 3.0 mN
- the load application time was 10 seconds
- the load removal time was 10 seconds.
- the adhesive layer is a cured film of a compound having an ester group. Curing of a compound having an ester group is generally curing by light or heat. It is preferable that the compound having an ester group is at least one (meth) acrylate ester and / or at least one (meth) acrylate monomer. It is particularly preferred that both are included.
- the adhesive layer may include a thermoplastic elastomer.
- a thermoplastic elastomer According to the above preferred embodiment, an adhesive layer having an elastic deformation work amount of 60% or more can be easily obtained.
- Photocuring of a compound having an ester group is generally performed using a photopolymerization initiator. This is performed using a peracid product.
- It is preferred elastic modulus of the adhesive layer is a l X 1 0 5 ⁇ l X 1 0 7 P a.
- the work of elastic deformation of the adhesive layer is preferably at least 80%. According to the preferred embodiment described above, the decrease in the dent amount is significantly reduced.
- the first and second polymer films are made of polyethylene terephthalate. This is advantageous in terms of transparency.
- the transparent conductive thin film is preferably made of at least one compound selected from indium oxide, tin oxide, zinc oxide, indium-doped tin oxide (ITO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide. This is advantageous in terms of transparency and conductivity.
- an undercoat layer is formed between the first polymer film and the transparent conductive thin film.
- the adhesiveness of the transparent conductive thin film is improved.
- a protective layer is provided on the transparent conductive thin film.
- the present invention provides a transparent substrate and a polymer film provided with a transparent conductive thin film, wherein the surface of the transparent substrate and the surface on which the film is not formed face each other, and are bonded together by an adhesive layer.
- a transparent conductive plate
- the transparent conductive plate When the transparent conductive plate is used for a touch panel, even if the transparent conductive film is not used, the pressing of the pen is indirectly buffered, which can contribute to the reduction of the depression caused by the pen. -Regarding the preferred embodiment of the adhesive layer, the description of the transparent conductive film can be applied as it is.
- the polymer film is preferably made of polyethylene terephthalate. This is advantageous in terms of transparency.
- the transparent substrate is generally a glass plate or a plastic plate (eg, an attaryl resin (particularly, polymethyl methacrylate) plate, a polycarbonate plate).
- a first polymer film having a transparent conductive thin film on the surface and a second polymer film having a hard coat layer on the surface are adhered to each other with a bonding agent layer facing each other on the back side.
- An upper electrode, a transparent substrate, and a polymer film having a transparent conductive thin film provided on the surface thereof are bonded together with an adhesive layer, with the surface of the transparent substrate facing the surface on which the film is not formed.
- a touch panel, wherein the upper electrode is the transparent conductive film, wherein the lower electrode is a transparent electrode.
- a first polymer film provided with a transparent conductive thin film on the surface and a second polymer film having a hard coat layer on the surface are bonded to each other with an adhesive layer facing the back sides.
- a touch panel, wherein the lower electrode is a transparent electrode, and the lower electrode is the transparent conductive plate. is there.
- FIG. 2 is a cross-sectional view illustrating an example of the transparent conductive film of the present invention.
- FIG. 3 is a cross-sectional view illustrating an example of the touch panel of the present invention using the transparent conductive plate of the present invention as a lower electrode of the touch panel.
- FIG. 2 is a cross-sectional view showing one example of the transparent conductive film of the present invention.
- the transparent conductive film of the present invention comprises a polymer film 12 (second polymer film) having a hard coat layer 11 on the surface and a transparent conductive thin film 16 via an undercoat layer 15 on the surface.
- the polymer film 14 (first polymer film) on which is formed is adhered via an adhesive layer 13 with the back surfaces (the side without the formed film) facing each other.
- the adhesive layer 13 of the present invention has an elastic deformation work of 60% or more.
- the adhesive layer 13 of the present invention has such a property that almost no dent is left when the surface of the touch panel is pressed with a pen or the like, and even if the surface is slightly dented when pressed with a pen, it easily returns to the original state.
- Such an adhesive layer has a good feeling in use and also has a good adhesive property.
- FIG. 3 is a cross-sectional view showing an example of a touch panel using the transparent conductive film of the present invention for an upper electrode.
- the transparent conductive film of the present invention shown in FIG. 2 is used for the upper electrode, and the upper electrode, the transparent conductive thin film 18 and the microdot spacer 20 on the transparent substrate 19 are arranged in this order.
- the lower electrode provided in the above is laminated with the transparent conductive thin films facing each other to form a touch panel.
- the adhesive layer 13 of the present invention which is excellent in preventing dents and bonding, is provided. The durability is improving.
- the upper electrode is particularly large compared to the lower electrode when input to the touch panel with a pen or finger, and is deformed by the force. If the dent remains, the appearance will be poor, and if it is deformed, The transparent conductive thin film is liable to fall off or peel off due to the load.
- the adhesive layer of the present invention By providing the adhesive layer of the present invention, this poor appearance can be effectively prevented, and the load can be reduced. Therefore, the adhesiveness between the adhesive layer and the plastic substrate or the polymer film can be reduced by this load. There is almost no lowering.
- the adhesive layer of the present invention has such a buffering action, does not cause dents, and can maintain the adhesion between the adhesive layer and the polymer film.
- the above-mentioned touch panel of the present invention using the transparent conductive film having the adhesive layer of the present invention for the upper electrode has a good external appearance over a long period of time, and does not cause a transparent conductive thin film, falling off, peeling, or peeling between layers. It has durability.
- FIG. 4 is a sectional view showing an example of the transparent conductive plate of the present invention.
- a polymer film 27 having a transparent conductive thin film 28 on the surface is provided on a transparent substrate 29 via an adhesive layer 23.
- a microdot spacer 30 is generally provided on the transparent conductive thin film 28.
- a spacer is necessary when bonding to the upper electrode to make a touch panel.
- the adhesive layer 23 of the present invention has a work of elastic deformation of 60% or more. That is, when the adhesive layer 23 of the present invention is used for the upper electrode, the depression when the surface of the touch panel is pressed with a pen or the like hardly remains, and when the pressure is pressed with the pen. It has the property of easily returning to its original state even if it is slightly dented. Therefore, such an adhesive layer has a good usability even when used for the lower electrode, and is also effective in improving the adhesiveness.
- FIG. 5 is a cross-sectional view showing an example of a touch panel using the transparent conductive plate of the present invention for a lower electrode.
- the transparent conductive plate of the present invention shown in FIG. 4 is used for a lower electrode, and the lower electrode has a hard coat layer 21 on one surface and a transparent film via an undercoat layer 25 on the other surface.
- the polymer film 22 on which the conductive thin film 26 is provided is bonded to the upper electrode serving as a force so that the transparent conductive thin films are opposed to each other, thereby forming a touch panel.
- the present invention provides an adhesive layer 23 that has a buffering effect and a dent prevention effect against the pressing of a pen or the like, and has an excellent adhesive property, thereby improving appearance and durability. are doing.
- the touch panel according to the present invention has a mode in which an adhesive layer is provided on one of the upper and lower electrodes as shown in FIGS. 3 and 5, it is also possible to provide an adhesive layer on both electrodes. Needless to say.
- polyester polyethylene terephthalate (PET), polybutylene terephthalate, polymethinolemethacrylate (PMMA), Acrylic resin, polycarbonate (PC), polystyrene, triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene monoacetate copolymer, polyvinyl butyral, metal ion bridged ethylene, Examples thereof include methacrylic acid copolymer, polyurethane, and cellophane.
- PET, PC, PMMA, TAC, and especially PET are preferable in terms of strength.
- the thickness of the first and second polymer films 12 and 14 varies depending on the use of the transparent conductive film and the like, but for the use as an upper electrode of a touch panel, it is usually 13 m to 0. It is about 5mm. If the thickness of the polymer film is less than 13 ⁇ , sufficient durability as the upper electrode cannot be obtained.If the thickness exceeds 0.5 mm, the obtained touch panel becomes thicker. Flexibility is also impaired, which is not desirable.
- the second polymer film 2 is set thicker than the first polymer film. Generally, it is in the range of 1 3 ⁇ ; ⁇ to 0.2 mm. Polymer fill The thickness of the rooms 22 and 27 can be set similarly.
- the transparent substrates 19 and 29 in the present invention are generally glass plates or plastic substrates.
- the material for the plastic substrate include an acrylic resin (particularly, polymethyl methacrylate), a polycarbonate resin, a polystyrene resin, a polyolefin resin, and an amorphous polyolefin resin. Its thickness is generally in the range of 50 ⁇ to 0.5111111, preferably 50:01 to 0.5 mm.
- the transparent conductive thin films 16, 18, 26, 28 formed on the polymer films 14, 22 or the transparent substrates 19, 29 include ITO (tin-doped indium oxide), ATO (tin-doped antimony oxide), ZnO, A1 the doped ZnO, but include acid I arsenide-based transparent conductive film such as S N_ ⁇ 2, in particular I tO is preferred.
- Transparent conductive thin films 1, 6, 18, 26, and 28 cannot obtain sufficient conductivity if the thickness is too small, and if the thickness is excessively large, the conductivity does not improve and the film formation cost increases. It is not preferable that the thickness of the transparent conductive film is too large. For this reason, the thickness of the transparent conductive thin film is preferably 1 to 500 nm, particularly preferably 5 to 100 nm.
- the transparent conductive thin film can be formed by an ordinary method, but is generally preferably formed by a sputtering method.
- a second polymer film having a hard coat layer is attached to the back side of the first polymer film having the transparent conductive thin film via the adhesive layer of the present invention.
- the back side of the polymer film having the transparent conductive thin film is attached to the surface of the transparent substrate via the adhesive layer of the present invention.
- the adhesive layer of the present invention is a layer having a work of elastic deformation of 60% or more, preferably 70% or more, particularly preferably 80% or more. ⁇
- the work of the sexual deformation is described above.
- the elastic modulus of the adhesive layer is 1 ⁇ 10 5 to 1 ⁇ 10 7 Pa. That is, it is particularly preferable to have the specific elastic modulus while having the specific elastic deformation work. Thereby, the dent prevention property and the adhesiveness are further improved.
- the adhesive layer of the present invention is preferably a cured film of a compound having an ester group.
- the curing of a compound having an ester group is generally curing by light or heat, It is preferably three-dimensionally cured by a polymerization initiator or an organic peroxide. It is preferred that the compound having an ester group is a mixture of at least one (meth) acrylate monomer and at least one (meth) acrylate monomer. Instead of a mixture, only the respective monomers and oligomers may be used.
- Examples of (meth) acrylate copolymers include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyester methacrylate, and acrylyl resin.
- (Meth) acrylate and the like can be mentioned, and urethane acrylate, epoxy acrylate and polyester acrylate are preferable.
- a mixture of acrylate oligomer and methacrylate oligomer, or acrylate methacrylate oligomer can also be used.
- examples of urethane (meth) acrylates include polyol compounds (for example, ethylene glycol, propylene glycol, neopentyl glycol,
- Polyols such as diethylene glycolone, dipropylene glycolone, polypropylene glycolone, 1,4-dimethylone resin, hexane, bisphenoleno A-polyethoxydiol, and polytetramethylene glycol;
- Polybasic acids such as acid, maleic acid, itaconic acid, adipic acid, hydrogenated dimer acid, phthalic acid, isophthalic acid, terephthalic acid, or polyester polyols which are reaction products with these acid anhydrides;
- Polycaprolactone polyols which are reactants with ⁇ -force prolactone; reactants of the polyols with the above-mentioned polybasic acids or ⁇ -caprolactones of these acid anhydrides; polycarbonates Polyols, polymer polyols, etc.) and organic polyisocyanates (for example, Li range iso Xia sulfonates, isophorone iso Xia sulf
- the weight average molecular weight of the above oligomer is generally from 300 to 500, preferably from 300 to 300.
- the compounding amount is preferably from 20 to 80% by mass of the mixture, particularly preferably from 20 to 70% by mass.
- Acrylate monomers and methacrylate monomers play a role in improving the adhesion to various polymer films and controlling the elastic modulus, and are also necessary for adjusting the viscosity of the adhesive coating solution.
- the amount is determined by appropriately adjusting the amount of the oligomer used. Generally, 10 to 80% by weight of the above mixture is preferred, especially 20 to 70% by weight.
- the molecular weight of the above monomer is generally 50 to 500, preferably 50 to 300.
- Examples of the above monomers include 2-hydroxyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutynole (meth) phthalate, 2-ethylhexylpolyethoxy (meth) acrylate Rate, benzyl (meth) acrylate, isobornyl (meth) acrylate, phenoxicetyl (meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopente-loxoxetyl (meth) acrylate, tetrahydrofurfurinole (meta) acrylate , Morpholine acrylate (atariloyl morpholine), N-vinylcaprolactam, 2-hydroxy_3-phenoxypropyl * pill (meth) ac Mono-functional monomers such as acrylate, o-pheninolepheninoleoxyethyl (meta) acrylate, isobono-ole (
- Examples of preferred (meth) acrylate monomers include morpholine acrylate, phenoxyacrylate, tetrahydrofurfurylacrylate, 2-hydroxyshetyl acrylate, isobornyl acrylate, phenylidari Monofunctional acrylic monomers such as sigil ether terephthalate; bifunctional acrylyl monomers such as 1.6-hexanediol atalylate, dimethylol tricyclodecane diatalylate, and neopentyl dalicol diacrylate Multifunctional acryl monomers such as pentaerythritol tonole retaryl acrylate, pentaerythritol tonole pentaacrylate, dipenta erythritol hexacrylate, and methacrylic monomers of the same type (that is, acrylate converted to methacrylate). Rukoto can.
- oligomer and the monomer known materials used as ultraviolet curable resins and the like can be used in addition to the above materials.
- the composition of the adhesive layer forming material containing the above mixture as a main component is preferably cured by using a photopolymerization initiator and by using an organic peroxide.
- a photopolymerization initiator it is preferable to use and cure the photopolymerization initiator.
- thermoplastic elastomer is used.
- Such thermoplastic elastomers include polystyrene-based block copolymers, such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-butadiene.
- Styrene block copolymer SBS
- SEBS styrene-ethylene-butadiene-styrene block copolymer
- SPBS styrene-propylene-butadiene-styrene block copolymer
- SEB S is preferred.
- the polystyrene-based block copolymer is obtained by, for example, sequentially polymerizing styrene, butadiene and the like in the presence of an alkyllithium catalyst to obtain a block copolymer.
- SEBS is generally obtained by hydrogenation of SBS.
- the thermoplastic elastomer is preferably used in an amount of 5 to 800%, especially 20 to 500% by mass based on the total amount of the ester group-containing compound.
- Any organic peroxide can be used as long as it decomposes at a temperature of 70 ° C. or higher to generate radicals.
- the organic peroxide is generally selected in consideration of the film formation temperature, composition preparation conditions, curing temperature, heat resistance of the adherend, and storage stability. In particular, those having a decomposition temperature of 50 ° C or more with a half-life of 10 hours are preferred.
- this organic peroxide examples include 2,5-dimethylhexane_2,5-dihydroxypropoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-1,3 t-butyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-1,2,5-di (t-ptinoleperoxy) hexane, dicumyl peroxide, a, hi, 1-bis (t-butylpyroxyisopropyl) benzene, n-butyl-4,4-bis (t-butylpyroxy) norrelate, 1,1-bis (t-butynoleoxy) cyclohexane, 1,1-bis (t-butynoleoxy) 1,3,3,5-trimethylcyclohexane, t-butyl peroxybe Benzoate, benzoyl peroxide, t -butylperoxyacetate, methyle
- the organic peroxides may be used alone or in combination of two or more.
- the content of the organic peroxide is preferably in the range of 0.1 to 10% by mass based on the ester group-containing compound.
- a photosensitizer light
- the polymerization initiator is generally used in an amount of 0.1 to 10.0% by mass based on the ester group-containing compound.
- any known photopolymerization initiator can be used, but one having good storage stability after compounding is desirable.
- radical photopolymerization initiators are generally used, for example, benzophenone, o-methylbenzoylbenzoate, 4-benzoylyl 4'-methyldiphenylsulfide, isopropylthioxanthone, getyl Hydrogen abstraction initiators such as thioxanthone and methyl 4- (ethylamino) benzoate; Intramolecular cleavage initiation such as benzoin ether, benzoyl propyl ether, and benzyl dimethyl ketal; lj; 2-hydroxy-2-methylinole 1-Phenylpropane-1-one, 1-hydroxy ⁇ -hydroxyalkylphenone type such as xylcyclohexylphenyl ketone, anolexynolephenyldalioxylate,
- the adhesive layer of the present invention can contain a silane coupling agent as an adhesion promoter.
- silane coupling agents include bierethoxysilane, vinyltris (
- ⁇ _ (methacryloxypropyl) trimethoxysilane is particularly preferred.
- These silane coupling agents may be used alone or in combination of two or more.
- the content of the above compound is preferably 0.01 to 10% by mass based on the ester group-containing compound.
- an epoxy group-containing compound may be contained as an adhesion promoter.
- Epoxy group-containing compounds include tridalicydyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1, 6-hexane diol diglycidyl ether, aryl glycidyl ether, and 2-ethylhexanol.
- Glycidyl ether phenyldaricidyl ether, phenol (ethyleneoxy) 5 -glycidinoleate, ⁇ -t-butynolepheninoleglycidinoleate, diglycidinole adipate, diglycidyl phthalate, glycidyl Examples thereof include methacrylate and butyldaricidyl ether. These may be used alone or in combination of two or more. The content of the above compound is preferably 0.1 to 20% by mass based on the ester group-containing compound.
- a cross-linking aid and a tackifier are applied. It may contain auxiliaries, plasticizers, ultraviolet absorbers, antioxidants and the like. Further, in order to improve the mechanical strength, other compounds other than the ester group-containing compound, such as an acryloxy group-containing compound, a methacryloxy group-containing compound and / or an aryl group-containing compound, may be included.
- the above-mentioned acryloxy group-containing compound and methacryloxy group-containing compound are generally acrylic acid or methacrylic acid derivatives, and examples thereof include esters and amides of acrylic acid or methacrylic acid.
- ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, etc., hexahexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyshetyl group, Examples thereof include a 3-hydroxypropyl group and a 3-chloro-2-propyl group.
- esters of acrylic acid or methacrylic acid with polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolone bread, and pentaerythritol can also be mentioned.
- amides examples include diacetone acrylamide.
- crosslinking aid examples include glycerin, trimethylolpropane, pentaerythritol, and the like, which are obtained by esterifying a plurality of acrylic or methacrylic acids, triallyl cyanurate, triallyl isocyanurate, diaryl phthalate, diaryl isophthalate. And diaryl maleate.
- These compounds having an acryloxy group or the like may be used alone or as a mixture of two or more kinds, generally in an amount of 0.1 to 50% by mass, preferably 0.5 to 3% by mass based on the ester group-containing compound. It is used in an amount of 0% by weight. If the amount exceeds 50% by mass, the workability or applicability during preparation of the adhesive may be reduced. If the amount is less than 0.1% by mass, the effect of adding these compounds cannot be obtained.
- hydrocarbon resin is added to the adhesive for factory purposes such as Can be added.
- the hydrocarbon resin to be added may be either a natural resin type or a synthetic resin type.
- Rosin, rosin derivatives, and terpene resins are preferably used as the natural resin.
- rosin gum-based resins, tall oil-based resins, and wood-based resins can be used.
- rosin derivative rosin obtained by hydrogenation, heterogeneity, polymerization, esterification, and metal salting can be used.
- terpene-based resin a terpene-based resin such as ⁇ -pinene and ⁇ -pinene can be used.
- dammar, corval and shellac may be used as other natural resins.
- petroleum-based resins, phenol-based resins, and xylene-based resins are preferably used for synthetic resins.
- the petroleum resin aliphatic petroleum resin, aromatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, hydride oil resin, pure monomer petroleum resin, and cumarone indene resin can be used.
- the phenolic resin an alkylphenol resin or a modified phenol resin can be used.
- xylene-based resin a xylene resin or a modified xylene resin can be used.
- the amount added to the ester group-containing compound such as the hydrocarbon resin is appropriately selected, but is preferably from 1 to 200% by mass, more preferably from 5 to 50% by mass, based on the ester group-containing compound. It is.
- the above-mentioned (crosslinked type) adhesive layer forming material For shellfish with ester-containing compounds.
- the adhesive forming material is applied to a first polymer film (for example, using a knife coater, a mouth coater, a bar coater, or the like), and dried as necessary. And the first polymer film are bonded together.
- Lamination may be performed by force rendering, roll, die extrusion, inflation, or the like, or lamination may be performed by heating and pressing these layers with a roll or the like. After the lamination, it is preferable to perform degassing by heating under pressure and deaeration by heating under reduced pressure in order to remove air bubbles in the adhesive layer.
- the pressurized degassing is performed by putting the laminated film in a pressurized heating chamber such as an autoclave and degassing. After degassing, Cured by heating or light irradiation.
- the thermal curing differs depending on the type of the organic peroxide to be used, but is generally 70 to: L 50 ° (preferably at a temperature of 70 to 130 ° C., generally for 10 seconds to 120 minutes, The curing can be preferably performed for a time of 20 seconds to 60 minutes
- many light sources that emit light in the ultraviolet to visible region can be used, for example, ultra-high pressure, high pressure, low pressure mercury lamps, Chemical lamps, xenon lamps, halogen lamps, mercury-halogen lamps, power-bon-arc lamps, incandescent lamps, laser light, etc.
- the irradiation time is generally determined by the type of lamp and the intensity of the light source. However, it is about several seconds to several minutes
- the laminate may be heated to 40 to 120 ° C. in advance and irradiated with ultraviolet rays.
- the pressing force at the time of bonding by the adhesive layer can be appropriately set, and generally a pressure of 0 to 50 kg / cm 2 , particularly preferably 0 to 30 kg / cm 2 is preferable.
- the thickness of the adhesive layer formed as described above is generally 5-100 tm.
- the transparent conductive plate of the present invention can be produced in the same manner as in the production of the above-mentioned conductive film. That is, an adhesive layer forming material (ester-containing compound, etc.) is applied on a transparent substrate (for example, using a knife coater, a roll coater, a bar coater, etc.), dried if necessary, and then transparent through this coating layer. Attach the substrate and the polymer film. Thermal curing or light curing is performed as described above. As the hard coat on the second polymer film, the laminate may be manufactured without the hard coat, and then the hard coat may be provided.
- a protective layer can be provided on the transparent conductive thin film of the present invention.
- the protective layer is preferably a thin layer made of, for example, SiCx, SiCXOy, SiCxNy, SiCxOyNz (x, y, and z are integers).
- the thickness of the protective layer is appropriately determined according to the material used, the light transmittance required for the transparent conductive film, the required durability, and the like.
- the protective effect of the transparent conductive thin film due to the formation of the layer cannot be sufficiently obtained. Conversely, if the thickness is excessively large, the transparency is reduced, or the conductivity of the transparent conductive thin film is reduced. In addition, the thickness of the transparent conductive film itself also increases, which is not preferable. Therefore, the protective layer is 1 ⁇ :! OOO nm thickness, especially:! Preferably, it is ⁇ 100 nm.
- the protective layer may be made of a polymer.
- the transparent conductive film of the present invention may be a pen or a polymer film on the surface of the second polymer film 12 opposite to the surface on the side of the adhesive layer 13 or on the surface of the polymer film 22.
- the hard coat layers 11 and 21 are formed to protect against finger input.
- the hard coat layer can be formed using a conventionally used ultraviolet curable resin or thermosetting silane.
- the hard coat layer is formed of, for example, an acrylic resin layer, an epoxy resin layer, a urethane resin layer, a silicone resin layer, or the like. Usually, its thickness is about 1 to 50 ⁇ .
- the transparent conductive thin film may be formed directly on the first polymer film or the transparent substrate, or an undercoat layer may be interposed between the polymer film or the transparent substrate and the transparent conductive thin film, By forming such an undercoat, the adhesiveness of the transparent conductive thin film to the polymer film or the transparent substrate can be enhanced, and peeling of the transparent conductive thin film can be prevented.
- the undercoat layer can be formed by vapor deposition using the material used for the protective layer. Alternatively, it can be formed by applying a resin layer of, for example, an acrylic resin, a urethane resin, an epoxy resin, or a hydrolyzate of an organic silicon compound.
- the undercoat layer is formed by coating a polymer film with a coating solution having a desired composition, for example, using a bar coater. Prior to the formation of the undercoat layer on the polymer film, the surface of the polymer film is subjected to plasma treatment, edge treatment, solvent cleaning, etc. according to the usual method to increase the adhesive strength of the formed thin film. May be performed.
- the surface of the hard coat layer may be subjected to anti-glare processing or AR processing for the purpose of improving the optical properties of the transparent conductive film.
- An anti-reflection layer can be provided on the surface of the hard coat layers 11 and 21.
- the antireflection layer for example, the following can be used.
- Three layers are alternately laminated in the order of high-refractive-index transparent thin film / low-refractive-index transparent thin film, for a total of six layers.
- the high-refractive-index transparent thin film I TO (indium tin oxide) or Zn_ ⁇ , ZnO doped with A1, T i 0 2, Sn_ ⁇ 2, sigma 1: 0 refractive index such as 1.8
- the above thin film can be adopted.
- the low-refractive Oriritsu transparent thin S i 0 2, Mg F 2, A l 2 O 3, acrylic resins, urethane resins, silicone resins, the refractive index such as a fluorine resin used 1.6 following film be able to. Further, it can also be obtained by applying an organic binder-based paint (refractive index: 1.5 or less) containing the above-mentioned inorganic fine powder having a low refractive index.
- the thickness of these high and low refractive index films is appropriately determined in order to reduce the reflectance in the visible light region due to light interference, but this depends on the number of layers in the laminated film, the material used, and the center wavelength. Depends on For example, in the case of a four-layer structure, the high refractive index film of the first layer on the transparent substrate side is 5 to 50 nm, the low refractive index film of the second layer is 5 to 50 nm, and the high refractive index film of the third layer is 50 to 50 nm. It is preferable that the low refractive index film of the fourth layer is in the range of 50 to 150 nm. Further, a contamination prevention film may be further formed on such an antireflection film to improve the contamination resistance of the surface. As the contamination prevention film, a fluorine-based resin thin film or a silicon-based resin thin film (thickness 1 to 1000 nm) is preferable.
- Examples of the material of the spacers 20 and 30 include a photocurable resin and a thermosetting resin, and are formed, for example, by printing on a transparent conductive thin film.
- the transparent conductive film of the present invention can be effectively used not only as an upper electrode of a touch panel, but also as a transparent switching device and other various optical transparent conductive films. Further, the transparent conductive plate of the present invention can be effectively used not only as a lower electrode of a touch panel, but also as a transparent switching device and various other optical transparent conductive films. [Example 1]
- 1-Hydroxycyclohexyl phenyl ketone 2 parts by mass The above mixture is uniformly stirred and mixed, and the mixture is applied to the surface of a PET (polyethylene terephthalate) film (for second polymer film) with a thickness of ⁇ ⁇ ⁇ ⁇ . It is applied using a knife coater (layer thickness 25 ⁇ ), and is coated on the back of a 38 ⁇ thick PET film (for the first polymer film) with a 30 nm thick ITO transparent conductive film on the surface. The coating layer was bonded. The coating layer was irradiated with ultraviolet light from a surface of a PET film having a thickness of 100 ⁇ for 5 seconds by a metal halide lamp (20 OmW / cm 2 ).
- an adhesive layer was formed, and the two PET films were bonded.
- a UV-curable acrylic resin hard coat (layer thickness 5 ⁇ ), a cured layer of ITO-containing UV-curable acrylic resin (80 nm thick) and a UV-curable acrylic A three-layer laminated film (the hard coat layer was the lowermost layer) consisting of a cured resin layer (thickness: 100 nm) was formed to obtain a transparent conductive film for the upper electrode.
- the following formulation was polymerized in ethyl acetate to obtain a polymer.
- An isocyanate compound (specific name) was added to 100 parts by mass of the obtained polymer. 1 part by mass of isocyanate) was added and reacted to obtain a pressure-sensitive adhesive.
- Urethane acrylate (UV3000B, manufactured by Nippon Synthetic Chemical Co., Ltd.) 50 parts by mass Isobol acrylate 25 parts by mass Neopentyl glycol diacrylate 25 parts by mass
- Urethane atarilate (UV2000 B, manufactured by Nippon Synthetic Chemical Co., Ltd.) 50 parts by mass phenylglycidinoleate ether epoxyacrylate
- Example 2 (Irgacure 184; manufactured by Ciba Geigy Co., Ltd.) 1 part by weight In Example 1, except that the above-mentioned composition was used as the material (formulation) for forming the adhesive layer Similarly, a transparent conductive film for an upper electrode was obtained.
- a transparent conductive film for an upper electrode was obtained in the same manner as in Example 1, except that the above composition was used as the material (formulation) for forming the adhesive layer.
- a transparent conductive film for an upper electrode was obtained in the same manner as in Example 1 except that the above-mentioned composition was used as a material (formulation) for forming an adhesive layer.
- Urethane acrylate (UV2000B, manufactured by Nippon Synthetic Chemical Co., Ltd.) 50 parts by weight morpholine acrylate (RM-1001; Nippon Kayaku Co., Ltd.) 15 parts by mass phenoxshetyl acrylate
- a transparent conductive film for an upper electrode was obtained in the same manner as in Example 1 except that the above-mentioned composition was used as a material (composition) for forming an adhesive layer.
- Example 2 300 parts by mass of toluene
- the above composition was used as the material (formulation) for forming the adhesive layer, and the surface of a 100 ⁇ thick PET film (for the second polymer film) was applied using a knife coater.
- a transparent conductive film for an upper electrode was obtained in the same manner except that the solvent was evaporated (layer thickness: 25 ⁇ ) to evaporate the solvent. [Evaluation method of transparent conductive film]
- An adhesive layer (thickness 25 ⁇ ) was placed on a glass plate under the same conditions as in the example or comparative example. A sample was obtained. The surface of the adhesive layer of the sample was measured using a micro hardness tester (Fischer scope H100) commercially available from Helmut Fischer, with a load of 3. OmN, load application time: 10 seconds, and subsequent load removal time : Pressed in 10 seconds.
- the elastic deformation work was obtained from the load (F) vs. indentation depth (h) curve as shown in Fig. 1.
- a sample of the adhesive layer formed into a cylindrical shape having a diameter of 12 mm and a thickness of 2 mm was distorted using a rheometrics viscoelasticity measuring device (RDS-—).
- the viscoelasticity was measured under the conditions of%, frequency 1 Hz.
- Example 2 Example 3 Example 4 Example 5 Example 6 Work of elastic deformation (%) 8 9. 7 85.5 5 8. 7. 8 2.5 5.80 5 Modulus of elasticity (Pa) 8.09 X10 5 8.72X1058 .56 X10 5 1.04 X10 6 1.03 X10 6 Depression after sliding test m) 0.1 0. 6 0.6. 0. 7 0. 1 After sliding test! 2! Tee (%) 0.30 3 0. 5 0. 4 0.
- the transparent conductive film formed using the adhesive layer having the specific work of elastic deformation according to the present invention has almost no dents and has a problem of deterioration of electrical characteristics. And also had excellent durability when used as the upper electrode of a touch panel.
- a transparent conductive plate for a lower electrode having such an adhesive layer was similarly manufactured. However, like the transparent conductive film, it had an effect of preventing dents and was excellent in durability.
- the transparent conductive film, the transparent conductive plate, and the touch panel having the same according to the present invention are such that the surface of the transparent conductive thin film (upper electrode) is depressed even when pen and finger input are repeated. And the transparent electrode hardly cracks or peels off or falls off from the high molecular film with the passage of time.Therefore, the electrical characteristics such as uniformity of the electrical resistance value are maintained, and the durability is improved. Is an excellent one.
Abstract
Description
Claims
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0266811A (ja) * | 1988-08-31 | 1990-03-06 | Nitto Denko Corp | 透明導電性積層体の製造法 |
JPH0266809A (ja) * | 1988-08-31 | 1990-03-06 | Nitto Denko Corp | 透明導電性積層体 |
JPH02129808A (ja) * | 1988-11-07 | 1990-05-17 | Nitto Denko Corp | 透明導電性積層体 |
JP2000182473A (ja) * | 1998-12-16 | 2000-06-30 | Nitto Shinko Kk | 面状スイッチ |
JP2001332132A (ja) * | 2000-05-22 | 2001-11-30 | Nitto Denko Corp | 保護フィルム付き透明導電性フィルムとその使用方法 |
JP2002245858A (ja) * | 2001-02-16 | 2002-08-30 | Hs Planning:Kk | 透明導電性積層体 |
JP2003151356A (ja) * | 2001-11-16 | 2003-05-23 | Bridgestone Corp | 透明導電性フィルム及びタッチパネル |
JP2003151357A (ja) * | 2001-11-16 | 2003-05-23 | Bridgestone Corp | 透明導電板、その製造方法及びタッチパネル |
Family Cites Families (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8814705D0 (en) * | 1988-06-21 | 1988-07-27 | Ciba Geigy Ag | Method |
US5448037A (en) * | 1992-08-03 | 1995-09-05 | Mitsui Toatsu Chemicals, Inc. | Transparent panel heater and method for manufacturing same |
TW250618B (ja) * | 1993-01-27 | 1995-07-01 | Mitsui Toatsu Chemicals | |
US5310835A (en) * | 1993-09-30 | 1994-05-10 | National Starch And Chemical Investment Holding Corporation | Transparent two-part acrylic adhesive composition and the method of use thereof |
JPH08148036A (ja) * | 1994-11-18 | 1996-06-07 | Nitto Denko Corp | 透明導電性フィルム |
TW415888B (en) * | 1998-02-17 | 2000-12-21 | Nippon Kayaku Kk | Transparent sheet or film |
US6629833B1 (en) * | 1998-05-15 | 2003-10-07 | Toyo Boseki Kabushiki Kaisha | Transparent conductive film and touch panel |
WO1999064950A1 (fr) * | 1998-06-08 | 1999-12-16 | Kaneka Corporation | Ecran tactile a film resistif pour afficheur a cristaux liquides et afficheur a cristaux liquides equipe dudit ecran tactile |
WO1999066391A1 (fr) * | 1998-06-18 | 1999-12-23 | Kaneka Corporation | Ecran tactile transparent et affichage a cristaux liquides avec ecran tactile transparent |
JP2000207128A (ja) * | 1999-01-18 | 2000-07-28 | Matsushita Electric Ind Co Ltd | 透明タッチパネルおよびそれを用いた電子機器 |
DE60045758D1 (de) * | 1999-08-31 | 2011-05-05 | Teijin Ltd | Transparenten leitender mehrschichtkörper und damit versehener berührungsempfindlicher bildschirm |
US6495253B1 (en) * | 1999-09-17 | 2002-12-17 | Kimoto Co., Ltd. | Support film for a transparent conductive thin film |
ATE362843T1 (de) * | 2000-03-28 | 2007-06-15 | Toyo Boseki | Transparenter leitender film, transparentes leitendes blatt und berührungsempfindliche tafel |
AU4884801A (en) * | 2000-05-18 | 2001-11-26 | Bridgestone Corporation | Display panel, and electromagnetic shielding light transmitting window material manufacturing method |
WO2001087590A1 (fr) * | 2000-05-19 | 2001-11-22 | Tdk Corporation | Film fonctionnel avec couche fonctionnelle et article dote d'un tel film |
JP3995141B2 (ja) * | 2000-06-12 | 2007-10-24 | 日東電工株式会社 | 透明導電性フィルムおよびタッチパネル電極 |
US6372074B1 (en) * | 2000-06-14 | 2002-04-16 | Avery Dennison Corporation | Method of forming a protective coating for color filters |
WO2002029830A1 (fr) * | 2000-09-29 | 2002-04-11 | Matsushita Electric Industrial Co., Ltd. | Substrat transparent a revetement anti-reflet conducteur multicouches, |
JP4151818B2 (ja) * | 2000-10-03 | 2008-09-17 | 日東電工株式会社 | 透明導電性フィルム |
TW539704B (en) * | 2000-12-08 | 2003-07-01 | Toyo Boseki | Coating film for optical application |
JP4004025B2 (ja) * | 2001-02-13 | 2007-11-07 | 日東電工株式会社 | 透明導電性積層体およびタッチパネル |
WO2002074532A1 (fr) * | 2001-03-15 | 2002-09-26 | Mitsui Chemicals Inc. | Corps lamine et dispositif d'affichage utilisant ce corps lamine |
KR20010094773A (ko) * | 2001-03-16 | 2001-11-03 | 장광식 정윤철 | 편광판 일체형 터치 패널 및 터치 패널 일체형 평판디스플레이 그리고 적층 방법 |
US20040137222A1 (en) * | 2001-03-30 | 2004-07-15 | Welke Siegfried K. | Transparent pressure-sensitive adhesive layer |
US6896981B2 (en) * | 2001-07-24 | 2005-05-24 | Bridgestone Corporation | Transparent conductive film and touch panel |
JP2003045234A (ja) * | 2001-07-26 | 2003-02-14 | Dainippon Printing Co Ltd | 透明導電性フィルム |
TW565799B (en) * | 2001-08-30 | 2003-12-11 | Nissha Printing | Mounting structure of detachable transparent touch panel and mounting sheet used therefor |
JP2003114764A (ja) * | 2001-10-04 | 2003-04-18 | Matsushita Electric Ind Co Ltd | タッチパネルおよびこれを用いた電子機器 |
WO2003032332A1 (fr) * | 2001-10-05 | 2003-04-17 | Bridgestone Corporation | Film transparent electroconducteur, son procede de fabrication, et ecran tactile y relatif |
JP4213887B2 (ja) * | 2001-10-26 | 2009-01-21 | 日東電工株式会社 | 透明性粘着剤組成物とその粘着シート |
TW200428268A (en) * | 2002-07-15 | 2004-12-16 | Fuji Photo Film Co Ltd | Internal touch panel, and process for producing it and display device |
JP4342775B2 (ja) * | 2002-07-31 | 2009-10-14 | 日東電工株式会社 | 透明導電性フィルム用表面保護フィルム及びその製造方法並びに表面保護フィルム付き透明導電性フィルム |
JP4137551B2 (ja) * | 2002-08-09 | 2008-08-20 | 日東電工株式会社 | 透明導電性基板用表面保護フィルム及び表面保護フィルム付き透明導電性基板 |
EP1591554A4 (en) * | 2003-01-24 | 2010-04-07 | Bridgestone Corp | THIN FILM OF TIN OXIDE AND INDIUM (ITO), PROCESS FOR FORMING THE FILM, TRANSPARENT CONDUCTIVE FILM AND TOUCH SCREEN |
JP3907611B2 (ja) * | 2003-06-23 | 2007-04-18 | 日東電工株式会社 | 粘着剤組成物及び粘着製品 |
-
2004
- 2004-02-02 CN CNB2004800033688A patent/CN100397531C/zh not_active Expired - Fee Related
- 2004-02-02 JP JP2005504809A patent/JP4646131B2/ja not_active Expired - Fee Related
- 2004-02-02 WO PCT/JP2004/000987 patent/WO2004070737A1/ja active Application Filing
-
2005
- 2005-08-02 US US11/194,848 patent/US7438978B2/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0266811A (ja) * | 1988-08-31 | 1990-03-06 | Nitto Denko Corp | 透明導電性積層体の製造法 |
JPH0266809A (ja) * | 1988-08-31 | 1990-03-06 | Nitto Denko Corp | 透明導電性積層体 |
JPH02129808A (ja) * | 1988-11-07 | 1990-05-17 | Nitto Denko Corp | 透明導電性積層体 |
JP2000182473A (ja) * | 1998-12-16 | 2000-06-30 | Nitto Shinko Kk | 面状スイッチ |
JP2001332132A (ja) * | 2000-05-22 | 2001-11-30 | Nitto Denko Corp | 保護フィルム付き透明導電性フィルムとその使用方法 |
JP2002245858A (ja) * | 2001-02-16 | 2002-08-30 | Hs Planning:Kk | 透明導電性積層体 |
JP2003151356A (ja) * | 2001-11-16 | 2003-05-23 | Bridgestone Corp | 透明導電性フィルム及びタッチパネル |
JP2003151357A (ja) * | 2001-11-16 | 2003-05-23 | Bridgestone Corp | 透明導電板、その製造方法及びタッチパネル |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006099247A (ja) * | 2004-09-28 | 2006-04-13 | Nippon Sheet Glass Co Ltd | 薄型タッチパネル及びその製造方法 |
US8604335B2 (en) * | 2004-10-13 | 2013-12-10 | Teijin Dupont Films Japan Limited | Laminate for dye-sensitized solar cell, electrode for dye-sensitized solar cell and method for producing it |
JP2008184538A (ja) * | 2007-01-30 | 2008-08-14 | Bridgestone Corp | 紫外線硬化樹脂組成物 |
JP5644104B2 (ja) * | 2007-03-16 | 2014-12-24 | 三菱瓦斯化学株式会社 | 光透過型電磁波シールド積層体およびその製造方法、光透過型電波吸収体並びに接着剤組成物 |
US8889570B2 (en) | 2007-03-16 | 2014-11-18 | Mitsubishi Gas Chemical Company, Inc | Light-transmitting electromagnetic-shielding laminate and method for producing the same, light-transmitting radio wave absorber, and adhesive composition |
JP2010224902A (ja) * | 2009-03-24 | 2010-10-07 | Fujitsu Component Ltd | タッチパネル |
JP2012091370A (ja) * | 2010-10-26 | 2012-05-17 | Nippon Steel Chem Co Ltd | 4層積層体及びその製造方法 |
KR101233241B1 (ko) | 2011-05-19 | 2013-02-14 | 주식회사 에프피 | 터치 패널용 자외선 경화형 전도성 페이스트 조성물, 이를 포함하는 터치 패널 및 이 조성물의 제조 방법 |
JP2013094984A (ja) * | 2011-10-28 | 2013-05-20 | Nitto Denko Corp | 透明導電性フィルム |
WO2013114945A1 (ja) * | 2012-01-31 | 2013-08-08 | 東レフィルム加工株式会社 | 透明導電性フィルム、タッチパネルおよび表示装置 |
JP2014044934A (ja) * | 2012-08-01 | 2014-03-13 | Nitto Denko Corp | 透明導電性積層フィルム、その製造方法及びタッチパネル |
WO2014207952A1 (ja) * | 2013-06-24 | 2014-12-31 | 日東電工株式会社 | 透明導電性積層フィルム、その製造方法及びタッチパネル |
JP2018502332A (ja) * | 2015-03-20 | 2018-01-25 | 歐浦登(順昌)光學有限公司 | 一体型全密閉液晶スクリーンとその製造方法 |
WO2018179893A1 (ja) * | 2017-03-30 | 2018-10-04 | 富士フイルム株式会社 | 光学フィルムならびにこれを有する画像表示装置の前面板、画像表示装置、画像表示機能付きミラ-、抵抗膜式タッチパネルおよび静電容量式タッチパネル |
JPWO2018179893A1 (ja) * | 2017-03-30 | 2019-11-07 | 富士フイルム株式会社 | 光学フィルムならびにこれを有する画像表示装置の前面板、画像表示装置、画像表示機能付きミラ−、抵抗膜式タッチパネルおよび静電容量式タッチパネル |
Also Published As
Publication number | Publication date |
---|---|
CN100397531C (zh) | 2008-06-25 |
US7438978B2 (en) | 2008-10-21 |
CN1745439A (zh) | 2006-03-08 |
US20060008665A1 (en) | 2006-01-12 |
JPWO2004070737A1 (ja) | 2006-05-25 |
JP4646131B2 (ja) | 2011-03-09 |
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