WO2014141921A1 - Stratifié pour écran tactile et procédé de fabrication de ce stratifié - Google Patents

Stratifié pour écran tactile et procédé de fabrication de ce stratifié Download PDF

Info

Publication number
WO2014141921A1
WO2014141921A1 PCT/JP2014/055298 JP2014055298W WO2014141921A1 WO 2014141921 A1 WO2014141921 A1 WO 2014141921A1 JP 2014055298 W JP2014055298 W JP 2014055298W WO 2014141921 A1 WO2014141921 A1 WO 2014141921A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
laminate
touch panel
transparent electrode
film
Prior art date
Application number
PCT/JP2014/055298
Other languages
English (en)
Japanese (ja)
Inventor
伊藤　英明
漢那　慎一
後藤　英範
直樹 塚本
健司 勝田
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2014141921A1 publication Critical patent/WO2014141921A1/fr

Links

Images

Classifications

    • 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
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific 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
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

  • the present invention relates to a laminate for a touch panel and a method for producing a laminate for a touch panel.
  • Patent Document 1 a light-transmitting hard coat layer having a value obtained by multiplying the film thickness and the internal haze is 4 or more and the 10-point average roughness of the surface is 2 ⁇ m or less is attached to the glass surface. It is described that scattering of glass can be prevented.
  • Patent Document 2 discloses an adhesive sheet in which a hard coat layer, a transparent substrate film having a thickness of 25 to 70 ⁇ m, an adhesive layer, a polyester film having a thickness of 5 to 25 ⁇ m, and an adhesive layer are laminated in this order. It is described that glass scattering can be prevented by sticking to the surface of a glass plate.
  • Patent Document 3 describes a glass reinforced by a float process and having a Young's modulus of 71 to 74 GPa and a Poisson's ratio of 0.22 to 0.24. However, it does not describe that when glass is chemically strengthened, the glass can be prevented from scattering when it is damaged by external impact.
  • Patent Document 1 and Patent Document 2 By sticking a hard coat layer or an adhesive sheet to the surface of a glass plate as in Patent Document 1 and Patent Document 2, it is possible to prevent glass fragments from being scattered when damaged by receiving a certain external impact. However, as a result of investigations by the present inventors, it was found that this is insufficient.
  • the problem to be solved by the present invention is to provide a laminate for a touch panel that can prevent scattering of glass fragments when it is damaged by an external impact, and a method for manufacturing the same.
  • the present inventors have laminated a glass substrate, a transparent electrode layer, a protective layer, and a polymer layer in this order, and the glass substrate has potassium ions in the glass.
  • the present invention has been reached.
  • the present invention which is a specific means for solving the above problems, has the following configuration.
  • a glass substrate [1] a glass substrate; A transparent electrode layer; A protective layer covering the transparent electrode layer; A polymer layer; In this order, A laminate for a touch panel, wherein the glass substrate is subjected to a chemical strengthening treatment in which a part or all of ions having an ion radius smaller than that of potassium ions in the glass are replaced with potassium ions.
  • the touch panel laminate according to [1] further comprising a hard coat layer on the surface of the polymer layer opposite to the surface on which the protective layer is formed.
  • the laminate for a touch panel according to [2] having an easy adhesion layer between at least one of the protective layer and the polymer layer and between the polymer layer and the hard coat layer.
  • the refractive index difference between the refractive index of the easy adhesion layer between the protective layer and the polymer layer and the refractive index of the protective layer and the polymer layer adjacent to the easy adhesion layer is 0.
  • the refractive index difference between the refractive index of the easy adhesion layer between the polymer layer and the hard coat layer and the refractive index of the polymer layer and the hard coat layer adjacent to the easy adhesion layer is as follows: The laminate for a touch panel according to any one of [3] to [11], which is 0.02 or less. [13] The laminate for a touch panel according to any one of [1] to [12], wherein the polymer layer includes polyethylene terephthalate, polycarbonate, or a cycloolefin polymer. [14] The laminate for a touch panel according to any one of [1] to [13], wherein the retardation of the polymer layer is 3000 to 12000 nm.
  • the hydrolysis condensate of the alkoxysilane contained in the hard coat layer is any one of [5] to [19], which is a hydrolysis condensate of an epoxy group-containing alkoxysilane and an epoxy group-free alkoxysilane.
  • Laminate for touch panel [21] The touch panel laminate according to any one of [5] to [20], wherein the hard coat layer is formed by hydrolyzing alkoxysilane and condensing the hydrolyzed alkoxysilane.
  • [31] (1) The touch panel laminate according to any one of [1] to [30], which has a decorative layer.
  • the present invention it is possible to provide a laminated body for a touch panel that can prevent scattering of glass fragments when damaged by receiving an external impact, and a method for manufacturing the same.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the laminate for a touch panel of the present invention has a glass substrate, a transparent electrode layer, a protective layer covering the transparent electrode layer, and a polymer layer in this order, and the glass substrate is more than potassium ions in the glass. It is characterized in that it is subjected to a chemical strengthening treatment in which part or all of ions having a small ion radius are replaced with potassium ions.
  • FIG. 1 is a schematic cross-sectional view showing an example of a laminate for a touch panel of the present invention.
  • the laminate for a touch panel of the present invention comprises, from the outermost surface side (viewing side), the glass substrate 100, the transparent electrode layer 101, the protective layer 102 formed so as to cover the transparent electrode layer 101, and the polymer layer 103 in this order. Have in.
  • An easy adhesion layer 104 may be provided between the protective layer 102 and the polymer layer 103 as necessary.
  • the laminated body for touchscreens of this invention may have the hard-coat layer 105 in the surface on the opposite side to the surface by the side of the protective layer 102 of the polymer layer 103 as needed,
  • An easy-adhesion layer 106 may be provided between the polymer layer 103.
  • a decoration layer 107 may be provided at the end of the surface of the glass substrate 1 opposite to the surface on the viewing side.
  • an antireflection layer (not shown) may be provided between the transparent electrode layer 101 and the protective layer 102, and on the opposite side of the surface of the glass substrate 100 where the transparent conductive layer 101 is formed. You may have a hard-coat layer (not shown).
  • the thickness of the laminate for a touch panel of the present invention is preferably 0.3 to 1 mm, more preferably 0.5 to 1 mm, and further preferably 0.7 to 1 mm.
  • each member which comprises the laminated body for touchscreens of this invention is demonstrated.
  • the glass substrate used in the laminate for a touch panel of the present invention is subjected to a chemical strengthening treatment in which part or all of ions having an ion radius smaller than that of potassium ions in the glass are replaced with potassium ions.
  • the glass used in the present invention is not particularly limited, but the strain point temperature obtained by a method according to JIS R3103-2 (2001) is preferably 500 ° C. to 520 ° C. Further, it is preferable that the temperature near the temperature at which glass is likely to be deformed, that is, the temperature of the molten salt is 490 to 530 ° C.
  • the glass substrate used in the present invention is chemically strengthened on the surface of SiO 2 —Na 2 O—K 2 O—CaO—MgO—Al 2 O 3 glass, for example, so-called soda lime glass produced by a float process. It is preferable that the compression layer is formed by performing the treatment.
  • the chemical strengthening treatment is performed, for example, by immersing glass in a molten salt.
  • a chemical strengthening treatment sodium ions in the glass and potassium ions in the molten salt are exchanged to form a compressed layer.
  • the compressed layer has a compressive stress value of 200 to 650 MPa.
  • the temperature of the molten salt for immersion is 450 to 550 ° C. and the immersion time is 1 hour or more when chemically strengthening the glass so that the formed compressed layer has the value. 3 hours is preferable.
  • the thickness of the glass substrate is preferably 0.3 to 1.0 mm, and more preferably 0.4 to 0.8 mm. By setting the thickness of the glass substrate to 0.3 mm or more, insufficient strength can be solved.
  • the laminated body for touchscreens of this invention has a transparent electrode layer on a glass substrate, and is arrange
  • the transparent electrode layer preferably has a refractive index of 1.75 to 2.1.
  • the material for the transparent electrode layer is not particularly limited, and a known material can be used.
  • it can be made of a light-transmitting conductive metal oxide film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide).
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO 2 .
  • the film thickness of each element can be set to 10 to 200 nm.
  • the transparent electrode pattern is preferably an ITO film.
  • the transparent electrode pattern is preferably an ITO film having a refractive index of 1.75 to 2.1.
  • the thickness of the transparent electrode layer is preferably 10 to 200 nm, more preferably 20 to 150 nm, and even more preferably 30 to 100 nm.
  • the transparent electrode pattern is a first transparent electrode pattern and a second transparent electrode pattern in two directions substantially orthogonal to the row direction and the column direction, respectively.
  • the transparent electrode pattern in the laminate of the present invention may be the second transparent electrode pattern 4 or the pad portion 3 a of the first transparent electrode pattern 3.
  • the reference numeral of the transparent electrode pattern may be represented by “4”.
  • the transparent electrode pattern in the transparent laminate of the present invention is the static electrode of the present invention. It is not limited to the use for the second transparent electrode pattern 4 in the capacitive input device, but may be used as the pad portion 3a of the first transparent electrode pattern 3, for example.
  • the refractive index of the transparent electrode pattern is preferably 1.75 to 2.1.
  • the material for the transparent electrode pattern is not particularly limited, and a known material can be used.
  • ITO Indium Tin Oxide
  • IZO Indium It can be made of a light-transmitting conductive metal oxide film such as Zinc Oxide.
  • metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO 2 .
  • the film thickness of each element is 10-20. It can be 0 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced.
  • said 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, and the electroconductive element 6 mentioned later use the photosensitive film which has the photocurable resin layer using the said conductive fiber. It can also be manufactured.
  • the transparent electrode pattern is preferably an ITO film.
  • the transparent electrode pattern is preferably an ITO film having a refractive index of 1.75 to 2.1.
  • the laminated body for touch panels of this invention has a protective layer which covers a transparent electrode layer, and it is preferable that a protective layer has a function which prevents the corrosion of a transparent electrode layer.
  • the prevention of corrosion of the transparent electrode layer is preferably carried out by removing the halogen-containing compound, in particular by dehalogenating the photopolymerization initiator.
  • the protective layer preferably contains metal oxide particles, a resin (preferably an alkali-soluble resin), a polymerizable compound, a polymerization initiator, or a polymerization initiation system. Furthermore, an additive etc. are used, but it is not restricted to this.
  • the protective layer may be a transparent resin film or an inorganic film.
  • inorganic films used in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be used, which are described in these documents. From the viewpoint of controlling the refractive index, it is preferable to use an inorganic film having a laminated structure of a low refractive index material and a high refractive index material, or an inorganic film having a mixed film of a low refractive index material and a high refractive index material.
  • the inorganic layer may be a mixed layer of SiO 2 and Nb 2 O 5, and more preferably that case is a mixed film of SiO 2 and Nb 2 O 5 formed by sputtering.
  • the protective layer is preferably a transparent resin film.
  • a method for controlling the refractive index of the transparent resin film is not particularly limited, but a transparent resin film having a desired refractive index is used alone, or a transparent resin film to which fine particles such as metal fine particles and metal oxide fine particles are added is used. Can be used.
  • the resin composition used for the transparent resin film preferably contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a composition having a high refractive index and excellent transparency can be obtained.
  • the metal oxide particles preferably have a refractive index higher than that of a resin composition made of a material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is used. Particles of 1.50 or more are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles of 1.90 or more are particularly preferable.
  • the refractive index of light having a wavelength of 400 to 750 nm being 1.50 or more means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more.
  • the average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.
  • the metal of the metal oxide particles includes semimetals such as B, Si, Ge, As, Sb, and Te.
  • the light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb.
  • Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable.
  • Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium dioxide is most preferable. Titanium dioxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
  • the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm.
  • the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope.
  • the longest side is the diameter.
  • the said metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.
  • the content of the metal oxide particles in the resin composition may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, and the like.
  • the total solid content is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
  • the transparent resin film preferably has at least one of ZrO 2 particles and TiO 2 particles from the viewpoint of controlling the refractive index within the range of the refractive index of the antireflection layer, and more preferably ZrO 2 particles.
  • binder or polymer there are no particular restrictions on the resin (referred to as binder or polymer) and other additives used for the transparent resin film unless they are contrary to the spirit of the present invention.
  • an alkali-soluble resin As the resin (referred to as a binder or a polymer) used in the protective layer, an alkali-soluble resin is preferable.
  • the alkali-soluble resin include paragraph [0025] of JP 2011-95716 A and paragraph of JP 2010-237589 A.
  • the polymers described in [0033] to [0052] can be used.
  • the polymerizable compound the polymerizable compounds described in paragraphs [0023] to [0024] of Japanese Patent No. 4098550 can be used.
  • the polymerization initiator or polymerization initiation system the polymerizable compounds described in [0031] to [0042] described in JP2011-95716A can be used.
  • an additive may be used for the protective layer.
  • the additive include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraph [ And the other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.
  • the thickness of the protective layer is preferably 1 to 50 nm, more preferably 2 to 30 nm. Further, the refractive index of the protective layer is preferably 1.5 to 1.53, more preferably 1.5 to 1.52, and particularly preferably 1.51 to 1.52.
  • the laminated body for touchscreens of this invention has a polymer layer.
  • the effect of the present invention is achieved by having a polymer layer and adopting a predetermined stacking order.
  • the material of the polymer film used for the polymer layer is not particularly limited and is arbitrary.
  • examples thereof include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polystyrene, polyether ether ketone, polyphenylene sulfide, and cycloolefin polymer.
  • polycarbonate, polyester (particularly, polyethylene terephthalate), or cycloolefin polymer is exemplified as a particularly preferable material.
  • These resins are excellent in transparency and excellent in thermal and mechanical properties, and the retardation can be easily controlled by stretching.
  • polyesters typified by polyethylene terephthalate are the most suitable materials because they have a large intrinsic birefringence and relatively large retardation can be obtained relatively easily even when the film thickness is thin.
  • the polyester film in the present invention refers to a film whose main component is polyester, and usually refers to a film in which 98% by mass or more of the resin component is polyester, and preferably 90% by mass of the component constituting the polyester film is polyester. Is a film.
  • the kind in particular of polyester is not restrict
  • PET polyethylene terephthalate
  • the polymer film has a specific birefringence, it is desirable to use an oriented film.
  • the production method is not particularly limited as long as the film characteristics defined in the present invention are satisfied.
  • a non-oriented sheet obtained by melting polycarbonate and extruding it into a sheet is stretched in one direction (or two directions if necessary) at a temperature equal to or higher than the glass transition temperature to obtain an orientation having a specific retardation.
  • a polycarbonate film can be obtained.
  • the non-oriented polycarbonate sheet a commercially available product or a solution prepared by solution film formation can be suitably used.
  • a cycloolefin polymer a well-known cycloolefin polymer can be used and it is preferable to use the cycloolefin polymer which has specific retardation.
  • a non-oriented sheet obtained by melting a cycloolefin polymer and extruding it into a sheet is stretched in one direction (or two directions if necessary) at a temperature equal to or higher than the glass transition temperature, and a specific retardation is obtained.
  • An oriented cycloolefin polymer film having the following can be obtained.
  • the oriented cycloolefin polymer having a specific retardation commercially available ones may be used, and examples thereof include ZEON A FILM ZD14 manufactured by ZEON Corporation.
  • the non-oriented cycloolefin polymer a commercially available product or a solution prepared by solution casting can be suitably used.
  • a non-oriented polyester obtained by melting polyester and extruding into a sheet is subjected to heat treatment after transverse stretching with a tenter at a temperature equal to or higher than the glass transition temperature.
  • the transverse stretching temperature is preferably 80 to 130 ° C., particularly preferably 90 to 120 ° C.
  • the transverse draw ratio is preferably 2.5 to 6.0 times, and particularly preferably 3.0 to 5.5 times. When the draw ratio is too high, the transparency of the resulting film tends to be lowered. On the other hand, if the draw ratio is too low, the draw tension is also small, so the birefringence of the resulting film is small, and the retardation is small, such being undesirable.
  • the treatment temperature is preferably from 100 to 250 ° C., particularly preferably from 180 to 245 ° C.
  • the stretching ratio, stretching temperature, and film thickness can be appropriately set.
  • the higher the stretching ratio, the lower the stretching temperature, and the thicker the film the higher the retardation.
  • the lower the stretching ratio, the higher the stretching temperature, and the thinner the film the lower the retardation.
  • the polymer layer preferably has a surface modification layer.
  • the surface modified layer is a layer formed on the surface layer of the polymer layer, and means a layer having an amorphous degree (non-crystalline degree / crystalline degree) of 5% or more.
  • the surface modification layer has a thickness from the surface of the polymer layer to any depth within the range of 40 to 330 nm.
  • the surface modification layer preferably has a thickness up to any depth within the range of 330 nm, more preferably within the range of 50 to 220 nm, and within the range of 50 to 200 nm. Further preferred.
  • the non-crystallinity indicates the ratio of the non-crystalline part to the total of the non-crystalline part and the crystal part (content ratio of the non-crystalline part).
  • the non-crystal part contains many Gauche crystal molecules, and the crystal part contains many trans-type crystal molecules. For this reason, the content rate of the non-crystal part and the crystal part can be calculated by the content rate of the crystal molecules.
  • the content ratio of the amorphous part and the crystalline part can be calculated by obtaining the spectrum of the surface modified layer by the ATR-IR method. A value obtained by dividing the amorphous degree (1175 cm ⁇ 1 ) by the spectrum of the crystallinity spectrum (1341 cm ⁇ 1 ) was defined as the amorphous degree (non-crystalline degree / crystalline degree).
  • the amorphousness (noncrystallinity / crystallinity) of the surface modification layer of the polymer layer is preferably 5% or more, more preferably 5 to 8.3%, and more preferably 5 to 8%. Further preferred. By setting the amorphous degree of the surface modified layer within the above range, it is possible to improve the oligomer block property and adhesion while preventing yellowing of the polymer layer.
  • the surface modified layer As described above on the surface of the polyester film.
  • the surface of the polyester film is subjected to the above-described treatment. It is more preferable to form such a surface modified layer.
  • a glow discharge treatment may be applied to the surface of the polymer layer in order to impart adhesion to the protective layer or the easy-adhesion layer and the hard coat layer.
  • the glow discharge treatment is a method called vacuum plasma treatment or glow discharge treatment, in which plasma is generated by discharge in a gas (plasma gas) in a low-pressure atmosphere to treat the substrate surface.
  • the low-pressure plasma used in the process of the present invention is a non-equilibrium plasma generated under conditions where the plasma gas pressure is low.
  • the treatment of the present invention is performed by placing a film to be treated in this low-pressure plasma atmosphere.
  • methods such as a method for generating plasma, methods such as direct current glow discharge, high frequency discharge, and microwave discharge can be used.
  • the power source used for discharging may be direct current or alternating current.
  • alternating current a range of about 30 Hz to 20 MHz is preferable.
  • alternating current a commercial frequency of 50 or 60 Hz may be used, or a high frequency of about 10 to 50 kHz may be used.
  • a method using a high frequency of 13.56 MHz is also preferable.
  • an inorganic gas such as oxygen gas, nitrogen gas, water vapor gas, argon gas, helium gas can be used, and in particular, oxygen gas or oxygen gas and argon gas
  • a method is also preferable in which a gas such as the air entering the processing container due to a leak or water vapor coming out of the object to be processed is used as the plasma gas without introducing the gas into the processing container.
  • the specific plasma gas pressure is preferably in the range of about 0.005 to 10 Torr, more preferably about 0.008 to 3 Torr.
  • the plasma output cannot be generally specified depending on the shape and size of the processing container, the shape of the electrode, and the like, but is preferably about 100 to 10,000 W, more preferably about 2000 to 10,000 W.
  • the treatment time of the glow discharge treatment of the present invention is preferably 0.05 to 100 seconds, more preferably about 0.5 to 30 seconds. If the treatment time is less than 0.05, the adhesion improving effect may be insufficient. Conversely, if the treatment time exceeds 100 seconds, problems such as deformation and coloring of the film to be treated may occur.
  • Discharge treatment intensity of the glow discharge treatment of the present invention will depend on the plasma power and treatment time, preferably in the range of 0.01 ⁇ 10kV ⁇ A ⁇ min / m 2, 0.1 ⁇ 7kV ⁇ A ⁇ min / m 2 Gayori preferable. Discharge treatment intensity that is sufficient adhesion improving effect of the 0.01 kV ⁇ A ⁇ min / m 2 or more is obtained, and such deformation and coloration of the processed film by a 10 kV ⁇ A ⁇ min / m 2 or less You can avoid problems.
  • the glow discharge treatment of the present invention it is preferable to heat a polymer layer that is a film to be treated in advance.
  • the surface of the polyester film is preferably subjected to glow discharge treatment at a temperature equal to or higher than Tg and then subjected to glow discharge treatment. That is, during the glow discharge treatment, the surface of the polymer layer is preferably heated to Tg (69 ° C.) or higher.
  • the surface of the polymer layer is more preferably heated within a temperature range of Tg to 200 ° C., and further preferably heated within a temperature range of Tg to 150 ° C.
  • Specific examples of the method for raising the temperature of the film to be processed in a vacuum include heating with an infrared heater and a heating method by contacting with a hot roll.
  • the b * value of the laminate for a touch panel of the present invention is preferably ⁇ 2.0 to 2.0, It is more preferably ⁇ 1.5 to 1.5, and further preferably ⁇ 1.2 to 1.2.
  • the degree of yellowish coloring is represented by a b * value in the CIE 1976 L * a * b * color system.
  • t represents the thickness ( ⁇ m) of the polymer layer.
  • the b * value of the polymer layer is preferably 1.75 or less, more preferably 1.6 or less, and even more preferably 1.45 or less.
  • the thickness of the polymer layer used in the present invention is not particularly limited, but when the thickness of the polymer layer is 10 to 100 ⁇ m, the b * value is preferably 1.2 or less. It is more preferably 0 or less, and further preferably 0.9 or less. Further, when the film thickness of the polymer layer is 100 to 150 ⁇ m, the b * value is preferably 1.45 or less, more preferably 1.3 or less, and further preferably 1.15 or less. . Further, when the film thickness of the polymer layer is 150 to 200 ⁇ m, the b * value is preferably 1.75 or less, more preferably 1.6 or less, and further preferably 1.45 or less. .
  • the amount of change in b * value after the b * value and a glow discharge treatment before the glow discharge treatment is performed is performed ([Delta] b) is 0.3 or less, is 0.2 or less More preferably, it is more preferably 0.1 or less.
  • a small change in the b * value before and after the glow discharge treatment indicates that no yellowing has occurred in the glow discharge treatment.
  • the polymer layer in which yellowing is suppressed can be obtained by setting the change amount of the b * value before and after the glow discharge treatment to be equal to or less than the above upper limit value.
  • the haze value of the laminated body for touchscreens of this invention is 2% or less, It is more preferable that it is 1.5% or less, It is further more preferable that it is 1% or less.
  • the polymer film used in the polymer layer preferably has a retardation of 3000 to 12000 nm (in-plane retardation, hereinafter also referred to as Re), more preferably has a retardation of 4500 to 10000 nm, and preferably 6000 to 8000 nm. More preferably, the phase difference is as follows.
  • Re in-plane retardation
  • the phase difference is as follows.
  • the polymer layer retardation is less than 3000 nm, when the screen is observed through a polarizing plate such as sunglasses, a strong interference color is exhibited. Therefore, the envelope shape is different from the emission spectrum of the light source, and good visibility cannot be ensured.
  • the Re of the polymer film used for the polymer layer is preferably in a range that allows it to function as a ⁇ / 4 plate, from the viewpoint of the visibility of the display image when a polarizing plate such as polarized sunglasses is used.
  • Re of the polymer film used for the polymer layer is preferably 100 to 200 nm, more preferably 120 to 180 nm, and further preferably 130 to 160 nm. If the Re of the polymer film used for the polymer layer falls outside this range, the polarization state of the display image of the liquid crystal display device cannot be made circularly polarized, and the display image when passing through a polarizing plate such as polarized sunglasses is displayed. The visibility is significantly deteriorated depending on the angle of the polarized sunglasses.
  • the ratio of the retardation in the in-plane direction to the thickness direction retardation (Re / Rth) of the polymer layer is preferably 0.200 or more, more preferably 0.500 or more, and further preferably 0.600 or more.
  • the ratio of the retardation in the in-plane direction to the retardation in the thickness direction (Re / Rth) is larger, rainbow unevenness when viewed with polarized sunglasses can be eliminated.
  • the ratio (Re / Rth) of retardation in the in-plane direction and thickness direction retardation of the polymer layer is preferably 1.2 or less, more preferably 1.0 or less. If it is larger than 1.2, the polymer film needs to be stretched more and the strength may be inferior.
  • Retardation (Re ( ⁇ ) and Rth ( ⁇ )) represents retardation in the in-plane direction (nm) and retardation in the thickness direction (nm), respectively, at the wavelength ⁇ .
  • Re ( ⁇ ) is measured by making light having a wavelength of ⁇ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).
  • Rth ( ⁇ ) is calculated by the following method.
  • Rth ( ⁇ ) is Re ( ⁇ ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film
  • the light is incident at a wavelength of ⁇ nm from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction of the rotation axis of KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
  • Re ( ⁇ ) represents a retardation value in a direction inclined by an angle ⁇ from the normal direction.
  • nx represents the refractive index in the slow axis direction in the plane
  • ny represents the refractive index in the direction perpendicular to nx in the plane
  • nz represents the refractive index in the direction perpendicular to nx and ny.
  • d represents a film thickness.
  • Rth ( ⁇ ) is calculated by the following method.
  • Rth ( ⁇ ) is from ⁇ 50 degrees to +50 degrees with respect to the normal direction of the film, with Re ( ⁇ ) as the slow axis (indicated by KOBRA 21ADH or WR) in the plane and the tilt axis (rotation axis).
  • Re ( ⁇ ) as the slow axis (indicated by KOBRA 21ADH or WR) in the plane and the tilt axis (rotation axis).
  • Re ( ⁇ ) as the slow axis (indicated by KOBRA 21ADH or WR) in the plane and the tilt axis (rotation axis).
  • KOBRA 21ADH or WR is calculated.
  • nx, ny, and nz can be calculated by KOBRA 21ADH.
  • the measurement wavelength is 550 nm unless otherwise specified.
  • the retardation of the polymer film By setting the retardation of the polymer film within the above range, it becomes possible to approximate the envelope shape of the spectrum of transmitted light to the emission spectrum of the light source with only a relatively simple configuration. That is, since the conventional technique uses a light source having a discontinuous emission spectrum, the visibility cannot be improved unless a birefringent body having an extremely high retardation (over 100,000 nm) is used. Using the property of a white LED light source having a spectrum, a unique effect of improving the visibility with a relatively simple configuration as described above is achieved.
  • the thickness of the polymer layer is preferably 20 to 150 ⁇ m, more preferably 30 to 125 ⁇ m, and even more preferably 50 to 100 ⁇ m.
  • the thickness is less than 20 ⁇ m, the anisotropy of the mechanical properties of the polymer film becomes remarkable, and tearing, tearing and the like are likely to occur, and the practicality as an industrial material is remarkably reduced.
  • it exceeds 150 ⁇ m the polymer film is very rigid, and the flexibility specific to the polymer film is lowered, and the practicality as an industrial material may also be lowered.
  • the refractive index of the polymer layer varies depending on the material used, but is preferably 1.60 to 1.75, more preferably 1.62 to 1.68, and 1.64 to 1.67. It is particularly preferred that When the refractive index is within the above range, it is possible to obtain a laminate for a touch panel having excellent rigidity as a support for the laminate for a touch panel and having excellent transparency.
  • the refractive index represents a measured value at a wavelength of 660 nm.
  • the polymer layer may contain other additives as long as they do not depart from the spirit of the present invention, and examples thereof include antioxidants and ultraviolet inhibitors.
  • the laminated body for touchscreens of this invention has a hard-coat layer in the surface on the opposite side to the surface in which the protective layer of a polymer layer is formed.
  • a hard coat layer not only the scattering property of glass but also haze, transparency, pencil hardness and the like can be improved.
  • the hard coat layer preferably contains a hydrolysis condensate of curable resin or alkoxysilane.
  • the hard coat layer is mainly composed of a curable resin having high chemical resistance and scratch resistance (50% by mass or more).
  • the hard coat layer may be formed by curing a curable resin by irradiation with ultraviolet rays or an electron beam, or may be formed by condensing and curing a hydrolyzate of alkoxysilane.
  • the curable resin includes an ionizing radiation curable resin, a thermosetting resin, a thermoplastic resin, and preferably a film forming operation.
  • Ionizing radiation curable resin As the ionizing radiation curable resin used for forming the hard coat layer, those having an acrylate functional group are preferable, and polyester acrylate or urethane acrylate is particularly preferable.
  • the polyester acrylate is composed of an oligomer (meth) acrylate of a polyester-based polyol.
  • the urethane acrylate is composed of an acrylated oligomer composed of a polyol compound and a diisocyanate compound.
  • a polyfunctional monomer can be used in combination.
  • Specific polyfunctional monomers include, for example, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, 1,6 hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
  • Polyester oligomers used to form the hard coat layer include adipic acid and glycol (ethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, polybutylene glycol, etc.) and triol (glycerin, trimethylolpropane, etc.) sebacic acid and glycol Examples thereof include polyadipate triol which is a condensation product with triol and polysebacate polyol. Note that a part or all of the aliphatic dicarboxylic acid may be substituted with another organic acid. In this case, as the other organic acid, isophthalic acid, terephthalic acid, phthalic anhydride, or the like is preferable because high hardness is expressed in the hard coat layer.
  • the polyurethane oligomer used for forming the hard coat layer can be obtained from a condensation product of polyisocyanate and polyol.
  • Specific polyisocyanates include adducts of methylene bis (p-phenylene diisocyanate), hexamethylene diisocyanate / hexane triol, hexamethylene diisocyanate, tolylene diisocyanate, tolylene diisocyanate trimethylolpropane, 1,5 Examples include naphthylene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate dimer, hydrogenated xylylene diisocyanate, tris (4-phenyl isocyanate) thiophosphate, Specific polyols include polyether polyols such as polyoxytate and methylene glycol, polyadipate polyols, and polycarbonate polyols
  • UV curable resins are used as the above ionizing radiation curable resins, photopolymerization of acetophenones, benzophenones, mifilabenzoylbenzoate, ⁇ -amyloxime esters, thioxanthones, etc. in these resins is started. It is preferable to use n-butylamine, triethylamine, tri-n-butylphosphine or the like as a photosensitizer mixed as a photosensitizer.
  • urethane acrylate is rich in elasticity and flexibility and excellent in workability (foldability), but has insufficient surface hardness, and it is difficult to obtain a pencil hardness of 2H or more.
  • the polyester acrylate can form a hard coat layer with extremely high hardness by selecting the constituent components of the polyester. Therefore, a hard coat layer in which 40 to 10 parts by mass of polyester acrylate is blended with 60 to 90 parts by mass of urethane acrylate is preferable because both high hardness and flexibility are easily achieved.
  • the thickness of the hard coat layer can be controlled by adjusting the coating amount of the aqueous composition.
  • the hard coat layer is formed by condensing a hydrolyzate of alkoxysilane.
  • Alkoxysilane has a hydrolyzable group, and when this hydrolyzable group is hydrolyzed in an acidic aqueous solution, silanol is generated, and silanols condense with each other, so that a hydrolyzed condensate of alkoxysilane ( Oligomer) is produced. That is, the hard coat layer contains a hydrolysis condensate of alkoxysilane.
  • the hard coat layer may contain a portion of alkoxysilane or a hydrolyzate thereof in addition to the alkoxysilane hydrolysis condensate.
  • the hard coat layer used in the present invention can be formed by applying an aqueous composition containing alkoxysilane and drying it.
  • the use of an aqueous composition is also preferable from the viewpoint of reducing environmental pollution caused by VOC (volatile organic compounds).
  • an epoxy group-containing alkoxysilane and an epoxy group-free alkoxysilane as the alkoxysilane.
  • Each of the epoxy group-containing alkoxysilane and the epoxy group-free alkoxysilane has a hydrolyzable group. Therefore, the hydrolyzable group is hydrolyzed in an acidic aqueous solution, and the resulting silanol is condensed to contain an epoxy group.
  • a hydrolysis condensate of alkoxysilane and epoxy group-free alkoxysilane is produced. That is, the hard coat layer used in the present invention includes a hydrolysis condensate of an epoxy group-containing alkoxysilane and an epoxy group-free alkoxysilane.
  • the ratio of the epoxy group-containing alkoxysilane to the total alkoxysilane is preferably 20 to 85% by mass.
  • the proportion of the epoxy group-containing alkoxysilane may be 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more.
  • the ratio for which an epoxy-group-containing alkoxysilane accounts may be 85 mass% or less, it is preferable that it is 80 mass% or less, and it is more preferable that it is 75 mass% or less.
  • the epoxy group-containing alkoxysilane is an alkoxysilane having an epoxy group. Any epoxy group-containing alkoxysilane may be used as long as it has one or more epoxy groups in one molecule, and the number of epoxy groups is not particularly limited. In addition to the epoxy group, the epoxy group-containing alkoxysilane may further have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxyl group.
  • epoxy group-containing alkoxysilane used in the present invention 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxy) Cyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Examples thereof include glycidoxypropyltriethoxysilane. Examples of commercially available products include KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the epoxy group-free alkoxysilane is an alkoxysilane having no epoxy group.
  • the epoxy group-free alkoxysilane may be an alkoxysilane having no epoxy group, and may have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxyl group. good.
  • the epoxy group-free alkoxysilane is preferably tetraalkoxysilane, trialkoxysilane, or a mixture thereof. It is preferably a mixture of tetraalkoxysilane or trialkoxysilane, and contains a mixture of tetraalkoxysilane and trialkoxysilane, so that when a hard coat layer is formed, while having appropriate flexibility, Sufficient hardness can be obtained.
  • the molar ratio of tetraalkoxysilane and trialkoxysilane is preferably 25:75 to 85:15, and 30:70 to 80:20 is more preferable, and 30:70 to 65:35 is even more preferable.
  • the tetraalkoxysilane is a tetrafunctional alkoxysilane, more preferably one having 1 to 4 carbon atoms in each alkoxy group. Of these, tetramethoxysilane and tetraethoxysilane are particularly preferably used.
  • the hydrolysis rate of tetraalkoxysilane when mixed with acidic water does not become too slow, and the time required for dissolution until a uniform aqueous solution is shortened. Thereby, the manufacturing efficiency at the time of manufacturing a hard-coat layer can be improved.
  • Examples of commercially available products include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the trialkoxysilane is a trifunctional alkoxysilane represented by the following general formula (1).
  • RSi (OR 1 ) 3 (1)
  • R is an organic group having 1 to 15 carbon atoms that does not contain an amino group
  • R 1 is an alkyl group having 4 or less carbon atoms such as a methyl or ethyl group.
  • the trifunctional alkoxysilane represented by the general formula (1) does not contain an amino group as a functional group. That is, this trifunctional alkoxysilane has an organic group R having no amino group.
  • R has an amino group, if it is mixed with a tetrafunctional alkoxysilane and hydrolyzed, dehydration condensation is promoted between the produced silanols. For this reason, an aqueous composition becomes unstable and is not preferable.
  • R in the general formula (1) may be an organic group having a molecular chain length in the range of 1 to 15 carbon atoms.
  • the number of carbon atoms By setting the number of carbon atoms to 15 or less, the flexibility when the hard coat layer is formed is not excessively increased, and sufficient hardness can be obtained.
  • the carbon number of R By setting the carbon number of R within the above range, a hard coat layer with improved brittleness can be obtained.
  • the adhesiveness of other films, such as a support body, and a hard-coat layer can be improved.
  • the organic group represented by R may have a heteroatom such as oxygen, nitrogen, or sulfur.
  • a heteroatom such as oxygen, nitrogen, or sulfur.
  • trialkoxysilane examples include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, propyltrimethoxysilane, Phenyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-ureidopropyltriethoxysilane, methyltriethoxysilane, methyl Trimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, fluorine
  • the hard coat layer used in the present invention may contain a metal complex as a curing agent.
  • a metal complex composed of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf and Zr is preferable, and these can be used in combination.
  • metal complexes can be easily obtained by reacting a metal alkoxide with a chelating agent.
  • chelating agents include ⁇ -diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and ⁇ -keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.
  • the metal complex include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetyl)
  • Magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), zirconium tetraacetylacetate Narate, zirconium tributoxyacetylacetonate, zirconium Chill acetonate bis (ethyl acetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate and titanium
  • aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), and zirconium tetraacetylacetonate are preferred, and storage stability Considering availability, aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate), which are aluminum chelate complexes, are particularly preferable.
  • Examples of commercially available products include aluminum chelate A (W), aluminum chelate D, aluminum chelate M (manufactured by Kawaken Fine Chemical Co., Ltd.), and the like.
  • the proportion of the metal complex is preferably 17 to 70 mol% with respect to the epoxy group-containing alkoxysilane.
  • the proportion occupied by the metal complex may be 17% or more, and more preferably 20% or more.
  • the content rate of a metal complex should just be 70% or less, it is preferable that it is 65% or less, and it is more preferable that it is 60% or less.
  • the metal complex when the metal complex is contained in the above lower limit value or more, excellent alkali resistance can be obtained when the hard coat layer is formed. Moreover, by setting it as the said upper limit or less, the dispersibility in aqueous solution can be made favorable, and manufacturing cost can be suppressed.
  • the hard coat layer used in the present invention may contain inorganic fine particles.
  • the inorganic fine particles are added for the purpose of adjusting the refractive index of the hard coat layer to a preferable range and for increasing the alkali resistance of the hard coat layer.
  • a preferable example of the inorganic fine particles is a transparent and insulating metal oxide.
  • fine silica particles from the viewpoint of crosslinking with alkoxysilane.
  • silica fine particles dry powdery silica produced by combustion of silicon tetrachloride can be used, but colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water is more preferable.
  • colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water is more preferable.
  • Specific examples include, but are not limited to, Snowtex series manufactured by Nissan Chemical Industries, Ltd. such as Snowtex O-33.
  • the average particle size of colloidal silica is 3 nm to 50 nm, preferably 4 nm to 50 nm, more preferably 4 nm to 40 nm, and particularly preferably 5 nm to 35 nm.
  • the average particle diameter can be determined from a photograph obtained by observing dispersed inorganic fine particles with a transmission electron microscope.
  • the projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, and the average particle size (average primary particle size) is obtained.
  • the average particle diameter of the inorganic fine particles can be calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter.
  • the colloidal silica is more preferably adjusted to have a pH of 2 to 7 when added to the aqueous composition.
  • the pH is 2 to 7
  • the stability of silanol, which is a hydrolyzate of alkoxysilane is better than when the pH is less than 2 or greater than 7, and the dehydration condensation reaction of the silanol proceeds faster. It is possible to suppress an increase in the viscosity of the coating liquid due to this.
  • x is the ratio (unit: mass%) of the inorganic fine particles to the total solid content contained in the aqueous composition.
  • x is preferably 1 or more, and more preferably 3 or more.
  • x should just be 80 or less, it is preferable that it is 70 or less, and it is more preferable that it is 65 or less.
  • the ratio (unit: mass%) of the epoxy group-containing alkoxysilane to the total alkoxysilane is x, where x is the ratio (unit: mass%) of the inorganic fine particles to the total solid content in the aqueous composition.
  • x is the ratio (unit: mass%) of the inorganic fine particles to the total solid content in the aqueous composition.
  • the inorganic fine particles preferably have an average aspect ratio of 30 to 5000.
  • the aspect ratio of the inorganic fine particles may be 30 or more, preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.
  • the aspect ratio of the inorganic fine particles may be 5000 or less, preferably 3000 or less, more preferably 1500 or less, and further preferably 800 or less.
  • a hard coat layer with higher hardness can be formed by setting the average aspect ratio of the inorganic fine particles within the above range.
  • the average aspect ratio means that the average minor axis of the inorganic fine particles in the thickness direction perpendicular to the major axis direction of the inorganic fine particles is r (nm), and the average major axis of the inorganic fine particles in the major axis direction of the inorganic fine particles is L (nm). ) Means the L / r ratio. That is, the aspect ratio can be calculated by observing inorganic fine particles contained in the aqueous composition and dividing the long diameter of the inorganic fine particles by the short diameter.
  • the average minor axis r (nm) of the inorganic fine particles is preferably 1 to 20 nm.
  • the average minor axis r (nm) is preferably 1 nm or more, and more preferably 2 nm or more.
  • the average minor axis r (nm) is preferably 20 nm or less, more preferably 15 nm or less, and further preferably 10 nm or less.
  • the average major axis L (nm) is preferably 100 to 10000 nm.
  • the average major axis L (nm) is The thickness is preferably 100 nm or more, more preferably 300 nm or more, and further preferably 700 nm or more.
  • the average major axis L (nm) is preferably 10000 nm or less, more preferably 8000 nm or less, and further preferably 5000 nm or less.
  • the average aspect ratio of the inorganic fine particles can be within a preferable range.
  • the length of the inorganic fine particles described above can be measured using an optical microscope or an electron microscope. For example, using a scanning electron microscope (SEM), select 100 arbitrary inorganic particles having a major axis of 100 nm or more present in a cross section perpendicular to the longitudinal direction of the hard coat layer and a cross section parallel to the longitudinal direction.
  • SEM scanning electron microscope
  • the aspect ratio can be obtained by measuring the major axis and minor axis of the inorganic particles. The major axis and minor axis are measured for every 100 inorganic particles, and the average aspect ratio can be calculated from these aspect ratios.
  • the hard coat layer may contain an ultraviolet absorber.
  • an ultraviolet absorber As a result, UV degradation of the laminated film and the colorant (particularly dye-based) can be prevented, and visibility and explosion-proof properties can be maintained for a long time.
  • the kind of ultraviolet absorber is not specified.
  • the addition amount is preferably 0.1 to 10% by mass with respect to the resin forming the hard coat layer. By setting the content to 0.1% by mass or more, the effect of preventing UV deterioration is sufficiently exhibited, and by setting the content to 10% by mass or less, it is possible to more effectively suppress a decrease in wear resistance and scratch resistance.
  • the addition method is preferably used by dispersing in a solvent.
  • a surfactant may be added to the hard coat layer for the purpose of reducing friction on the coating film surface or improving the coating property.
  • the hard coat layer may be colored by dispersing pigments, dyes, and other fine particles.
  • an ultraviolet absorber, an antioxidant or the like may be added.
  • surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, manufactured by BASF) 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 90 1,904,150R1, Pionein D-6512, D-6414, D-6112, D-6115, D-6120, D-6131, D-6108-W, D-6112-W, D-6115-W, D -6115-W,
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and sanded BL (manufactured by Sanyo Chemical Industries, Ltd.).
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • an aliphatic wax can be contained.
  • the aliphatic wax include plant-based waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin modified wax, cucumber wax, sugar cane wax, esparto wax, and bark wax.
  • Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, and fishertro push wax
  • synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax.
  • carbana wax, paraffin wax, and polyethylene wax are particularly preferable because of easy adhesion to a hard coat layer and a pressure-sensitive adhesive and good lubricity.
  • These are also preferably used as aqueous dispersions because they can reduce the environmental burden and are easy to handle. Examples of commercially available products include Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.).
  • either organic or inorganic fine particles can be used.
  • polymer fine particles such as polystyrene, polymethyl methacrylate, silicone resin, and benzoguanamine resin
  • inorganic fine particles such as silica, calcium carbonate, magnesium oxide, and magnesium carbonate
  • polystyrene, polymethylmethacrylate, and silica are preferably used from the viewpoints of a slip improvement effect and cost.
  • These particles may be used alone or as a colloid dispersed in a dispersion medium such as water, such as colloidal silica.
  • Examples of commercially available products include Snowtex XL (manufactured by Nissan Chemical Industries, Ltd.), Seahoster KE-P250 (manufactured by Nippon Shokubai Co., Ltd.), and the like. Two or more kinds of matting agents may be included.
  • the thickness of the hard coat layer is not particularly limited, but is preferably in the range of 1 to 15 ⁇ m.
  • the refractive index of the hard coat layer is preferably 1.50 to 2.10, more preferably 1.60 to 2.00, and further preferably 1.62 to 1.95.
  • the laminated body for touchscreens of this invention may have an easily bonding layer between at least one between a protective layer and a polymer layer, and between a polymer layer and a hard-coat layer.
  • the refractive index n of the easy-adhesion layer is preferably
  • the refractive index difference between the refractive index of the hard coat layer and the refractive index of the easy adhesion layer at least one is preferably 0.02 or less, more preferably 0.015 or less, and More preferably, it is 01 or less.
  • the refractive index difference between the refractive index of the easy adhesion layer between the protective layer and the polymer layer and the refractive index of the protective layer and the polymer layer adjacent to the easy adhesion layer is 0.02 or less. It is preferable.
  • the refractive index difference between the refractive index of the easy adhesion layer between the polymer layer and the hard coat layer and the refractive index of the polymer layer adjacent to the easy adhesion layer and the hard coat layer is 0. 02 or less is preferable.
  • the refractive index n of the easy-adhesion layer used in the present invention is preferably 1.63 or more and 1.69 or less, and more preferably 1.63 or more and 1.66 or less. By setting it as the said range, it can be made easy to adjust a refractive index with respect to another layer.
  • the thickness of the easy adhesion layer used in the present invention is 200 nm or less.
  • the thickness of the easy-adhesion layer used in the present invention is determined by required optical performance, easy adhesion, and the like.
  • the thickness of the easy adhesion layer used in the present invention is preferably 50 nm or more, and more preferably 80 nm or more.
  • the thickness of the easy-adhesion layer used in the present invention is preferably 180 nm or less, and more preferably 150 nm or less.
  • the easy-adhesion layer used in the present invention preferably contains a polyester having a naphthalene skeleton.
  • the polyester having a naphthalene skeleton represents that a monomer having a naphthalene skeleton is included as a monomer constituting the polyester.
  • the monomer having a naphthalene skeleton is preferably contained as a dicarboxylic acid component, and examples thereof include 2,6-naphthalenedicarboxylic acid.
  • a monomer having no naphthalene skeleton can be included as necessary, such as adjustment of the refractive index.
  • examples of the dicarboxylic acid component include terephthalic acid and isophthalic acid
  • examples of the diol component include ethylene glycol and diethylene glycol.
  • the structural unit derived from the monomer having a naphthalene skeleton is preferably from 50 mol% to 100 mol%, more preferably from 60 mol% to 80 mol% in the dicarboxylic acid component. .
  • the number average molecular weight of the polyester having a naphthalene skeleton is preferably 15000 to 40000, more preferably 17000 to 30000, and further preferably 18000 to 25000.
  • the number average molecular weight of the polyester having a naphthalene skeleton used in the present invention within the above range, the adhesion between the polymer layer and the polyester film, particularly the adhesion after wet heat aging can be enhanced.
  • the number average molecular weight represents the number average molecular weight measured by GPC (Gel Permeation Chromatography) as a standard material as polystyrene.
  • the refractive index of the polyester having a naphthalene skeleton is preferably 1.60 or more and 1.75 or less, and more preferably 1.60 or more and 1.70 or less.
  • the content of the polyester having a naphthalene skeleton in the polymer layer is preferably 5% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 60% by mass or less with respect to the total solid content in the polymer layer.
  • the easy-adhesion layer used in the present invention may contain particles.
  • the particles used in the present invention can easily adjust the refractive index of the easy-adhesion layer. There may be only one type of particles used in the present invention, or two or more types.
  • the refractive index of the particles is preferably 1.60 or more and 3.00 or less, more preferably 1.80 or more and 2.80 or less, and further preferably 1.90 or more and 2.60 or less. By setting it as the said range, it can be made easy to adjust the refractive index of an easily bonding layer.
  • the average particle diameter of the particles is preferably 0.65 times or less with respect to the thickness of the easy adhesion layer. It is more preferably 0.50 times or less, and further preferably 0.40 times or less. By setting it as the said range, an unevenness
  • the average particle size of the particles was measured using a laser diffraction / scattering particle size distribution analyzer LA910 (manufactured by Horiba, Ltd.) using an aqueous dispersion of particles, and expressed in median size. Moreover, after manufacturing the laminated body of this invention, the average particle diameter of the particle
  • the particles are preferably contained in an amount of 40% by mass to 80% by mass with respect to the solid content of the easy adhesion layer. It is preferably 45 to 75% by mass, and more preferably 50 to 70% by mass. By setting it as the said range, while making it easy to adjust the refractive index of an easily bonding layer, particle
  • the particles include conductive metal particles and metal oxide particles, and metal oxide particles are preferable.
  • Examples of the conductive metal particles include particles of antimony, selenium, titanium, tungsten, tin, zinc, indium and the like.
  • the metal oxide particles include particles containing any one of tin oxide, zirconium oxide and titanium oxide as a main component.
  • the particle containing any one of tin oxide, zirconium oxide and titanium oxide as the main component in the present invention means that the compounding amount of any one of tin oxide, zirconium oxide and titanium oxide contained in the particle is 80% by mass or more. A certain particle. Among these, it is preferable to use tin oxide or zirconium oxide.
  • tin oxide As the tin oxide, tin (IV) oxide having a SnO 2 composition is preferably used.
  • tin oxide the use of tin oxide doped with antimony or the like has the effect of reducing the surface resistivity of the laminated film and preventing impurities such as dust from adhering because of its conductivity. Since it is obtained, it is preferable.
  • antimony-doped tin oxide commercially available products can also be used. FS-10D, SN-38F, SN-88F, SN-100F, TDL-S, TDL-1 (all of which are Ishihara Sangyo) Etc.).
  • inorganic oxide fine particles having no conductivity may be preferably used.
  • tin oxide prepared so that tin oxide is not doped with antimony or the like and the surface resistance is not lowered can be suitably used.
  • tin oxide doped with phosphorus for example, EP SPDL-2 manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd., an aqueous dispersion of P-doped SnO 2 having a particle size of 130 nm
  • Zirconium oxide has a composition of ZrO 2 , for example, NZS-20A, NZS-30.
  • A, OZ-S30K (all manufactured by Nissan Chemical Industries, Ltd.) and SZR-CW (manufactured by Sakai Chemical Industry Co., Ltd.) can be mentioned, and these can also be suitably used in the present invention.
  • titanium oxide (IV) having a composition of TiO 2 is preferably used. Titanium oxide has a rutile type (tetragonal high-temperature type), anatase type (tetragonal low-temperature type), etc. depending on the difference in crystal structure, but is not particularly limited. Further, titanium oxide subjected to surface treatment may be used. Examples of the titanium oxide used in the present invention include IT-S, IT-O, IT-W (all manufactured by Idemitsu Kosan Co., Ltd.), TTO-W-5 (manufactured by Ishihara Sangyo Co., Ltd.), and the like. And can also be suitably used in the present invention.
  • the shape of the particles used in the present invention may be acicular or spherical, but is preferably spherical.
  • the average particle diameter of the particles can be measured by the above-described method.
  • the diameter of a circle circumscribing such shaped particles can be determined as the particle diameter in the present invention.
  • the easily bonding layer used for this invention may contain members other than the member mentioned above as needed. An example will be described below.
  • the easy-adhesion layer used in the present invention may further contain a second polyester in addition to the above-described polyester having a naphthalene skeleton.
  • the glass transition temperature Tg 1 of the polyester having a naphthalene skeleton is set to 80 to 130 ° C.
  • the glass transition temperature Tg 2 of the second polyester is set to 0 to 80 ° C. It is also preferable to do.
  • Tg 1 and Tg 2 are set in the above range, adhesion between the polymer layer and other layers, particularly a hard coat layer described later, can be improved.
  • Tg 1 is preferably 90 to 120 ° C., and more preferably 100 to 115 ° C.
  • Tg 2 is preferably 20 to 70 ° C., more preferably 30 to 60 ° C.
  • Tg 1 -Tg 2 is preferably 20 ° C. or higher, and more preferably 40 ° C. or higher. By setting Tg 1 -Tg 2 to be equal to or more than the above lower limit value, the adhesion can be more effectively improved.
  • the glass transition temperature represents a glass transition temperature measured by DSC (Differential Scanning Calibration) as follows. Weigh 10 mg of polyester and set in an aluminum pan. At a rate of temperature increase of 10 ° C./min, the temperature is raised from room temperature to 300 ° C., rapidly cooled, and again heated at 10 ° C./min to obtain a DSC curve. The temperature at which the obtained DSC curve is bent is defined as the glass transition temperature.
  • DSC Different Scanning Calibration
  • the second polyester may contain one or more of terephthalic acid, isophthalic acid and sodium sulfoisophthalate as the acid component.
  • the second polyester resin may contain triethylene glycol as a diol component. Triethylene glycol can enhance the adhesiveness of the easy-adhesion layer formed using the second polyester.
  • the content of triethylene glycol is 10 to 50 mol% with respect to the total diol component of the second polyester resin.
  • the content of triethylene glycol may be 10 to 50 mol%, preferably 15 to 45 mol%, and more preferably 20 to 40 mol%.
  • the number average molecular weight of the second polyester is preferably 15000 to 40000.
  • the number average molecular weight of the second polyester is preferably 17000 to 30000, and more preferably 18000 to 25000.
  • the easy-adhesion layer used in the present invention may contain polyolefin, acrylic, polyurethane, rubber-based resin or the like as a binder in order to further improve the adhesion to the polyester film.
  • content in the easily bonding layer of the binder used for this invention 0.5 to 40 mass% is preferable with respect to the total solid of an easily bonding layer, and 1.5 to 30 mass% is preferable. Is more preferable.
  • the polyolefin preferably has a polar group such as a carboxyl group as an ionomer of the polyolefin having a polar group. It may be used by dissolving in an organic solvent, or an aqueous dispersion may be used. However, since the environmental load is small, it is preferable to attach with an aqueous system using an aqueous dispersion.
  • a commercially available product may be used as the aqueous dispersion and is not particularly limited. Examples of those that can be preferably used in the present invention include Chemipearl S75N (manufactured by Mitsui Chemicals), Arrow Base SE1200.
  • Arrowbase SB1200 (above, manufactured by Unitika Ltd.), Hitech S3111, S3121 (above, produced by Toho Chemical Co., Ltd.), and the like. Only one type of polyolefin may be included, or two or more types may be included.
  • acrylic acrylic containing methacrylate and ethyl acrylate and other copolymerization components is preferable, and those described in paragraphs [0145] to [0146] of JP2012-101449A can be used.
  • Commercially available products may also be used, and specific examples include AS-563A manufactured by Daicel Finechem Co., Ltd. (product name) and the like.
  • Acrylic has a glass transition temperature of preferably ⁇ 50 to 120 ° C., and more preferably ⁇ 30 to 100 ° C.
  • the weight average molecular weight of acrylic is preferably 3000 to 1000000.
  • the polyurethane is preferably composed of polyol, polyisocyanate, chain extender, cross-linking agent, etc., and those described in paragraph [0035] of JP2012-056220A can be used.
  • the easy-adhesion layer used in the present invention may contain a crosslinking agent.
  • the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
  • a carbodiimide type crosslinking agent and an oxazoline type crosslinking agent are preferable.
  • a compound having a plurality of carbodiimide structures in the molecule is preferable.
  • a compound having a plurality of carbodiimide groups in the molecule can be used without particular limitation.
  • Polycarbodiimide is usually synthesized by condensation reaction of organic diisocyanate, but the organic group of the organic diisocyanate used in this synthesis is not particularly limited, either aromatic or aliphatic, or a mixture thereof It can be used. From the viewpoint of reactivity, an aliphatic type is particularly preferable.
  • organic isocyanate organic diisocyanate, organic triisocyanate and the like are used.
  • organic isocyanate those described in paragraph [0024] of JP2009-220316A can be used.
  • the carbodiimide-based crosslinking agent used in the present invention may be a commercially available product, and specific examples include Carbodilite V-02-L2 manufactured by Nisshinbo Co., Ltd.
  • JP 2012-231029 A As the oxazoline-based crosslinking agent, those described in paragraph [0078] of JP 2012-231029 A can be used. Commercial products may also be used, such as Epochros K2010E, K2020E, K2030E, WS500, WS500, and WS700 manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
  • the cross-linking agent used in the present invention is preferably added in the range of 0.5 to 50% by mass, more preferably in the range of 1 to 30% by mass, with respect to the total solid content of the easy-adhesion layer. That is.
  • the addition amount 1% by mass or more, the particles contained in the easy-adhesion layer can be effectively prevented from peeling off.
  • the addition amount is 50% by mass or less, the surface shape tends to be further improved.
  • Two or more types of crosslinking agents may be included, and when two or more types are included, the total amount is preferably within the above range.
  • the easy-adhesion layer used in the present invention may contain a matting agent for improving the slipperiness of the laminated film.
  • a matting agent for improving the slipperiness of the laminated film.
  • the matting agent either organic or inorganic fine particles can be used.
  • polymer fine particles such as polystyrene, polymethyl methacrylate, silicone resin, and benzoguanamine resin
  • inorganic fine particles such as silica, calcium carbonate, magnesium oxide, and magnesium carbonate can be used.
  • polystyrene, polymethyl methacrylate, and silica are preferable from the viewpoint of the effect of improving the slipperiness and cost.
  • These particles may be used alone or as a colloid dispersed in a dispersion medium such as water, such as colloidal silica.
  • a dispersion medium such as water, such as colloidal silica.
  • examples of commercially available products include Snowtex XL (manufactured by Nissan Chemical Industries, Ltd.). Two or more kinds of matting agents may be included.
  • the average particle size of the matting agent is preferably 0.03 to 1 ⁇ m, more preferably 0.05 to 0.5 ⁇ m.
  • the average particle size of the matting agent is 0.03 ⁇ m or more, the effect of improving the slip property is effectively exhibited, and when the average particle size is 1 ⁇ m or less, the laminated film is incorporated into a display device such as a touch panel. There is a tendency to suppress the deterioration of display quality.
  • the average particle size of the matting agent is preferably 0.65 times or less the thickness of the easy-adhesion layer, like the average particle size of the particles of the polymer layer. It is more preferably 0.50 times or less, and further preferably 0.40 times or less. By setting it as the said range, an unevenness
  • the average particle diameter of the matting agent in the present invention is a value measured by the same method as the average particle diameter of the particles included in the polymer layer.
  • the easy-adhesion layer used in the present invention may have a surfactant to reduce repellency and the like when a functional layer such as a hard coat layer is applied to the surface of the easy-adhesion layer.
  • a surfactant the above-described surfactants can be used.
  • the easy-adhesion layer used in the present invention may have an antistatic agent to prevent the easy-adhesion layer from being charged by static electricity or the like.
  • the type of the antistatic agent is not particularly limited.
  • an electron conductive polymer such as polyaniline and polypyrrole, an ion conductive polymer having a carboxyl group or a sulfonic acid group in the molecular chain, conductive fine particles, etc. Is mentioned.
  • the conductive tin oxide fine particles described in JP-A-61-20033 can be preferably used from the viewpoints of conductivity and transparency.
  • the addition amount of the antistatic agent is preferably added so that the surface resistivity of the easy adhesion layer measured in an atmosphere of 25 ° C. and 30% relative humidity is 1 ⁇ 10 5 ⁇ or more and 1 ⁇ 10 13 ⁇ or less.
  • the surface resistivity can be suppressed 1 ⁇ 10 and a 5 Omega or lower the amount of the antistatic agent tends to improve transparency of the laminate, by the following 1 ⁇ 10 13 Omega, dust It tends to be less likely to adhere.
  • the easy-adhesion layer used in the present invention preferably contains an aliphatic wax as a slipping agent in order to obtain the lubricity of the layer surface.
  • aliphatic wax examples include plant-based waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin modified wax, cucumber wax, sugar cane wax, esparto wax, and bark wax.
  • Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, and fishertro push wax
  • synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax.
  • carnauba wax, paraffin wax, and polyethylene wax are particularly preferable because they are easy to adhere to a hard coat layer and a pressure-sensitive adhesive and have good lubricity.
  • These are also preferably used as aqueous dispersions because they can reduce the environmental burden and are easy to handle.
  • Examples of commercially available products include Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.).
  • the laminate for a touch panel of the present invention may have an antireflection layer between the transparent electrode layer and the protective layer. By having the antireflection layer, the pattern visibility of the transparent electrode layer is improved.
  • the refractive index of the antireflection layer is preferably 1.6 or more, more preferably 1.65 or more. Although there is no restriction
  • the antireflection layer preferably contains metal oxide particles, a resin (preferably an alkali-soluble resin), a polymerizable compound, a polymerization initiator, or a polymerization initiation system. Furthermore, an additive etc. are used, but it is not restricted to this.
  • the antireflection layer may be a transparent resin film or an inorganic film.
  • inorganic films used in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be used, which are described in these documents. From the viewpoint of controlling the refractive index, it is preferable to use an inorganic film having a laminated structure of a low refractive index material and a high refractive index material, or an inorganic film having a mixed film of a low refractive index material and a high refractive index material.
  • the inorganic layer may be a mixed layer of SiO 2 and Nb 2 O 5, and more preferably that case is a mixed film of SiO 2 and Nb 2 O 5 formed by sputtering.
  • the antireflection layer is preferably a transparent resin film.
  • the method for controlling the refractive index of the antireflection layer that is the transparent resin film is not particularly limited, but a transparent resin film having a desired refractive index is used alone, or fine particles such as metal fine particles and metal oxide fine particles are added. A transparent resin film that has been used can be used.
  • the antireflection layer preferably contains particles, and more preferably contains metal oxide particles.
  • the resin composition used for the antireflection layer which is the transparent resin film preferably contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a composition having a high refractive index and excellent transparency can be obtained.
  • the metal oxide particles preferably have a refractive index higher than the refractive index of the resin composition made of a material excluding the particles.
  • the antireflection layer has a wavelength of 400 to 750 nm. It is preferable to include particles having a refractive index of 1.60 to 3.00 in the light having, preferably including particles having a refractive index of 1.70 or more, and more preferably including particles of 1.90 or more.
  • the refractive index of light having a wavelength of 400 to 750 nm being 1.60 or more means that the average refractive index of light having a wavelength in the above range is 1.60 or more. It is not necessary that the refractive index of all light having a wavelength is 1.60 or more.
  • the average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.
  • the metal of the metal oxide particles includes semimetals such as B, Si, Ge, As, Sb, and Te.
  • the light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb.
  • Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc.
  • titanium oxide, titanium composite oxide, zinc oxide, tin oxide, oxidation Zirconium, indium / tin oxide and antimony / tin oxide particles are more preferred, titanium oxide, titanium composite oxide, tin oxide and zirconium oxide particles are more preferred, and zirconium oxide particles are most preferred.
  • the surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
  • the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm.
  • the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
  • the said metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.
  • the content of the metal oxide particles in the antireflection layer that is the transparent resin film may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, and the like.
  • the content of the antireflection layer, which is the transparent resin film can be 5 to 95% by mass, preferably 5 to 80% by mass, and more preferably 40 to 80% by mass. preferable.
  • the antireflection layer that is the transparent resin film preferably has at least one of ZrO 2 particles and TiO 2 particles from the viewpoint of controlling the refractive index within the range of the refractive index of the antireflection layer, and the ZrO 2 particles are more preferable.
  • the resin (referred to as binder and polymer) used for the antireflection layer which is a transparent resin film and other additives are not particularly limited as long as they are not contrary to the gist of the present invention.
  • the antireflection layer is a transparent resin film, components other than the particles of the antireflection layer can be the same as those of the protective layer.
  • an alkali-soluble resin As the resin (referred to as binder or polymer) used in the antireflection layer, an alkali-soluble resin is preferable.
  • the alkali-soluble resin include paragraphs [0025] of JP2011-95716A and JP2010-237589A.
  • the polymers described in paragraphs [0033] to [0052] can be used.
  • the polymerizable compound the polymerizable compounds described in paragraphs [0023] to [0024] of Japanese Patent No. 4098550 can be used.
  • the polymerization initiator or polymerization initiation system the polymerizable compounds described in [0031] to [0042] described in JP2011-95716A can be used.
  • an additive may be used in the antireflection layer.
  • the additive include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraph [ And the other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.
  • the thickness of the antireflection layer is preferably 500 nm or less, and more preferably 100 nm or less.
  • the thickness of the antireflection layer is particularly preferably from 55 to 100 nm, more preferably from 60 to 90 nm, even more preferably from 70 to 90 nm.
  • the manufacturing method of the laminated body for touchscreens of this invention is a laminated body for touchscreens of this invention, Comprising: A front layer board with a transparent electrode layer which has a glass substrate and a transparent electrode layer has a protective layer and a polymer layer in this order. Including a step of laminating a laminated material such that the surface on the transparent electrode layer side and the surface on the protective layer side face each other, wherein the glass substrate is a part of ions having an ion radius smaller than potassium ions in glass or It is characterized by being subjected to a chemical strengthening treatment that replaces all with potassium ions.
  • the manufacturing method of the laminated body for touchscreens of this invention can be manufactured by laminating
  • the said transfer process is a process of laminating
  • Lamination (bonding) of the protective layer and the polymer layer to the surface of the glass substrate is performed by stacking the protective layer and the polymer layer on the surface of the transparent electrode pattern, and applying pressure and heating.
  • known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • a surface treatment can be applied to the non-contact surface of the glass substrate (front plate) in advance.
  • the surface treatment it is preferable to perform a surface treatment (silane coupling treatment) using a silane compound.
  • silane coupling agent those having a functional group that interacts with the photosensitive resin are preferable.
  • a silane coupling solution N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a heating tank may be used, and the reaction can be promoted by preheating the substrate of the laminator.
  • the transparent electrode pattern is formed by using the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 forming method in the description of the capacitive input device of the present invention described later.
  • a method using a photosensitive film that can be formed on a glass substrate is preferred.
  • the transfer step includes the first photocurable resin layer for etching and the second photocurable resin layer for etching (hereinafter collectively referred to as photocurable resin layer) of the transfer film from which the protective film has been removed, which will be described later. Is also transferred onto the transparent electrode layer.
  • a method including a step of removing the temporary support after laminating the photocurable resin layer of the transfer film on the transparent electrode pattern is preferable.
  • Transfer (bonding) of the photocurable resin layer to the surface of the base material is performed by overlaying the photocurable resin layer on the surface of the transparent electrode pattern, and applying pressure and heating.
  • known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the transfer film has a temporary support and the first photocurable resin layer for etching or the second photocurable resin layer for etching.
  • a temporary support a material that is flexible and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heating can be used.
  • Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.
  • the thickness of the temporary support is not particularly limited and is generally in the range of 5 to 200 ⁇ m, and in the range of easy handling and versatility, the range of 10 to 150 ⁇ m is particularly preferable.
  • the temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like. Further, the temporary support can be imparted with conductivity by the method described in JP-A-2005-221726.
  • Thermoplastic resin layer >> The transfer film is preferably provided with a thermoplastic resin layer between the temporary support and the first photocurable resin layer for etching or the second photocurable resin layer for etching.
  • thermoplastic resin layer is preferably alkali-soluble.
  • the thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness of the base surface (including unevenness due to already formed images, etc.), and according to the unevenness of the target surface. It is preferable to have a property that can be deformed.
  • the thermoplastic resin layer preferably includes an organic polymer substance described in JP-A-5-72724 as a component.
  • the Vicat method specifically, a polymer obtained by American Material Testing Method ASTM D1235
  • polyolefins such as polyethylene and polypropylene, ethylene copolymers with ethylene and vinyl acetate or saponified products thereof, copolymers of ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride and vinyl chloride, Vinyl chloride copolymer with vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer with styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, Vinyl toluene copolymer of vinyl toluene and (meth) acrylic acid ester or saponified product thereof, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer weight of butyl (meth) acrylate and vinyl acetate, etc.
  • the layer thickness of the thermoplastic resin layer is preferably 3 to 30 ⁇ m.
  • the thickness of the thermoplastic resin layer is more preferably 4 to 25 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
  • the thermoplastic resin layer can be formed by applying a preparation liquid containing a thermoplastic organic polymer, and the preparation liquid used for the application can be prepared using a solvent.
  • the solvent is not particularly limited as long as it can dissolve the polymer component constituting the layer, and examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, 2-propanol and the like.
  • thermoplastic resin layer and photocurable resin layer The viscosity of the thermoplastic resin layer measured at 100 ° C. is in the region of 1000 to 10,000 Pa ⁇ sec, the viscosity of the photocurable resin layer measured at 100 ° C. is in the region of 2000 to 50000 Pa ⁇ sec, and the following formula ( It is preferable to satisfy A).
  • the viscosity of each layer can be measured as follows.
  • the solvent is removed from the coating solution for the thermoplastic resin layer or the photocurable resin layer by drying under atmospheric pressure and reduced pressure to obtain a measurement sample.
  • Vibron DD-III type: manufactured by Toyo Baldwin Co., Ltd.
  • Vibron Can be used under the conditions of a measurement start temperature of 50 ° C., a measurement end temperature of 150 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz / deg, and a measurement value of 100 ° C.
  • the transfer film further includes an intermediate layer between the photo-curable resin layer and the thermoplastic resin, from the viewpoint of preventing mixing of components when applying a plurality of layers and during storage after application. ,preferable.
  • an oxygen-blocking film having an oxygen-blocking function which is described as “separation layer” in JP-A No. 5-72724, is preferable. And productivity is improved.
  • the transfer film is preferably further provided with a protective film (protective release layer) or the like on the surface of the photocurable resin layer.
  • the transfer film can be produced according to the method for producing a photosensitive transfer material described in paragraphs [0094] to [0098] of JP-A-2006-259138.
  • JP-A-2006-23696 As examples of the exposure step, the development step, and other steps, the methods described in paragraph numbers [0035] to [0051] of JP-A-2006-23696 can be preferably used in the present invention.
  • the exposure step is a step of exposing the photocurable resin layer transferred onto the transparent electrode layer.
  • a predetermined mask is disposed above the photocurable resin layer formed on the transparent electrode layer, and then the light is applied from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer.
  • Examples thereof include a method of exposing the curable resin layer, and a method of exposing the entire surface of the photocurable resin layer through a thermoplastic resin layer and an intermediate layer without using a mask.
  • the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photocurable resin layer (for example, 365 nm, 405 nm, etc.).
  • the exposure amount is usually about 5 to 200 mJ / cm 2 , preferably 10 to 100 m. It is about J / cm 2 .
  • the developing step is a step of developing the exposed photocurable resin layer for etching.
  • the developing step is not a developing step in a narrow sense in which the pattern-exposed photocurable resin layer is pattern-developed with a developer, but only the thermoplastic resin layer and the intermediate layer are removed after the entire surface exposure.
  • the photo-curable resin layer itself is a developing step that includes a case where a pattern is not formed.
  • the development can be performed using a developer.
  • the developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used.
  • the developer in the case where the photo-curable resin layer itself does not form a pattern preferably has a development behavior that does not dissolve the non-alkali development type colored composition layer.
  • a small amount of an organic solvent miscible with water may be added to the developer.
  • organic solvents miscible with water examples include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ⁇ -caprolactone, ⁇ -butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ⁇ -caprolactam, N-methylpyrrolidone and the like.
  • the concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
  • a known surfactant can be added to the developer.
  • the concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
  • the development method may be any of paddle development, shower development, shower & spin development, dip development, and the like.
  • shower development will be described.
  • An uncured portion can be removed by spraying a developer onto the photocurable resin layer after exposure.
  • an alkaline solution having a low solubility of the photocurable resin layer is sprayed by a shower or the like before development to remove the thermoplastic resin layer or the intermediate layer. It is preferable to keep it.
  • it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
  • the pH of the developer is preferably 8 to 13.
  • the manufacturing method of the capacitance-type input device may have other processes such as a post-exposure process and a post-bake process.
  • a post-exposure process When the first photocurable resin layer for etching and the second photocurable resin layer for etching are thermosetting transparent resin layers, it is preferable to perform a post-bake process.
  • patterning exposure and whole surface exposure may be performed after peeling the temporary support, or may be performed before peeling the temporary support, and then the temporary support may be peeled off. Exposure through a mask or digital exposure using a laser or the like may be used.
  • the capacitance-type input device of the present invention has the laminate of the present invention.
  • the capacitive input device of the present invention has a transparent electrode pattern, an antireflection layer disposed adjacent to the transparent electrode pattern, and a protective layer disposed adjacent to the antireflection layer,
  • the refractive index of the antireflection layer is preferably higher than the refractive index of the protective layer, and the refractive index of the antireflection layer is preferably 1.6 or more.
  • the capacitance-type input device of the present invention includes at least the following (3) to (5), (7) on the front plate (corresponding to the glass substrate in the laminate of the present invention) and the non-contact side of the front plate. And it is preferable to have the laminated body of this invention.
  • the antireflection layer corresponds to the antireflection layer in the laminate of the invention.
  • the (8) protective layer corresponds to the protective layer in the laminate of the present invention.
  • the protective layer is preferably a so-called transparent protective layer in a generally known capacitance type input device.
  • the (4) second electrode pattern may be a transparent electrode pattern or a transparent electrode pattern, but is preferably a transparent electrode pattern.
  • the capacitive input device of the present invention may further have the following element (6).
  • (6) A conductive element that is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern and is different from the first transparent electrode pattern and the second transparent electrode pattern
  • the first transparent electrode pattern is It corresponds to the transparent electrode pattern in the laminate.
  • the (3) first transparent electrode pattern and the (7) second electrode pattern At least one of the electrode patterns corresponds to the transparent electrode pattern in the laminate of the present invention.
  • the second electrode pattern is not a transparent electrode pattern but has (6) another conductive element
  • (3) the first transparent electrode pattern and (6) another conductive element At least one of them corresponds to the transparent electrode pattern in the laminate of the present invention.
  • the second electrode pattern is a transparent electrode pattern and (6) has another conductive element
  • (3) the first transparent electrode pattern, (7) the second electrode pattern At least one of the other conductive elements (6) corresponds to the transparent electrode pattern in the transparent laminate of the present invention.
  • the capacitance-type input device of the present invention preferably further has (1) a mask layer and / or a decoration layer as necessary.
  • the mask layer is provided as a black frame around the area touched by a finger or a touch pen so that the transparent wiring of the transparent electrode pattern cannot be seen from the contact side or is decorated.
  • the decoration layer is provided for decoration, for example, it is preferable to provide a white decoration layer.
  • the (1) mask layer and / or the decorative layer may comprise (2) the transparent film and the front plate, (3) the first transparent electrode pattern and the front plate, and (4) the second transparent electrode pattern. And the front plate or (6) another conductive element and the front plate.
  • the (1) mask layer and / or decorative layer is more preferably provided adjacent to the front plate.
  • the capacitance-type input device of the present invention includes such various members, the antireflection layer disposed adjacent to the transparent electrode pattern and the antireflection layer disposed adjacent to the transparent electrode pattern.
  • the transparent electrode pattern can be made inconspicuous, and the visibility problem of the transparent electrode pattern can be improved.
  • the transparent electrode pattern is sandwiched between the transparent film having the refractive index of 1.6 to 1.78 and the film thickness of 55 to 110 nm and the antireflection layer, thereby further transparent. The problem of the visibility of the electrode pattern can be improved.
  • FIG. 2 is a cross-sectional view showing a preferred configuration of the capacitive input device of the present invention.
  • the capacitive input device has the laminate of the present invention. Specifically, the front plate 1, the decorative layer 2a, the mask layer 2b, the first transparent electrode pattern 3, The second transparent electrode pattern 4, the insulating layer 5, the conductive element 6, and the transparent protective layer 7 are included.
  • a transparent protective plate 7 has a polymer layer (not shown) on the opposite side of the front plate 1 side.
  • a mask layer 2 b is provided on the non-contact surface of the front plate 1.
  • the mask layer 2b is a frame-like pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so as not to show the lead wiring or the like.
  • the capacitance type input device of the present invention is provided with a mask layer 2 so as to cover a part of the front plate 1 (a region other than the input surface in FIG. 1).
  • the front plate 1 can be provided with an opening 8 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 8.
  • a plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in the first direction via connection portions;
  • a plurality of second transparent electrode patterns 4 made of a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction, the first transparent electrode pattern 3 and the second An insulating layer 5 that electrically insulates the transparent electrode pattern 4 is formed.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and the conductive element 6 to be described later those mentioned as the material for the transparent electrode pattern in the laminate of the present invention can be used.
  • a membrane is preferred.
  • At least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 extends over both the non-contact surface of the front plate 1 and the region of the mask layer 2 opposite to the front plate 1.
  • FIG. 2 a diagram is shown in which the second transparent electrode pattern is disposed across both the non-contact surface of the front plate 1 and the area of the mask layer 2 opposite to the front plate 1. Yes.
  • an expensive film such as a vacuum laminator can be used by using a photosensitive film having a specific layer structure to be described later. Even without the use of equipment, it is possible to perform lamination without generating bubbles at the boundary of the mask portion with a simple process.
  • FIG. 4 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention.
  • the first transparent electrode pattern 3 is formed such that the pad portion 3a extends in the first direction via the connection portion 3b.
  • the second transparent electrode pattern 4 is electrically insulated by the first transparent electrode pattern 3 and the insulating layer 5 and extends in a direction intersecting the first direction (second direction in FIG. 4). It is constituted by a plurality of pad portions that are formed.
  • the pad portion 3a and the connection portion 3b may be manufactured as one body, or only the connection portion 3b is manufactured and the pad portion 3a and the second portion 3b are formed.
  • the transparent electrode pattern 4 may be integrally formed (patterned).
  • the pad portion 3a and the second transparent electrode pattern 4 are manufactured (patterned) as a single body (patterning), a part of the connection part 3b and a part of the pad part 3a are connected as shown in FIG.
  • Each layer is formed so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by 5.
  • a conductive element 6 is provided on the side of the mask layer 2 opposite to the front plate 1.
  • the conductive element 6 is electrically connected to at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4, and is different from the first transparent electrode pattern 3 and the second transparent electrode pattern 4. Is another element.
  • FIG. 2 shows a diagram in which the conductive element 6 is connected to the second transparent electrode pattern 4.
  • the protective layer 7 is installed so that all of each component may be covered.
  • the protective layer 7 may be configured to cover only a part of each component.
  • the insulating layer 5 and the protective layer 7 may be made of the same material or different materials. As the material constituting the insulating layer 5, those mentioned as the material for the antireflection layer or protective layer in the laminate of the present invention can be preferably used.
  • FIG. 5 is a top view showing an example of the tempered glass 11 in which the opening 8 is formed.
  • FIG. 6 is a top view showing an example of the front plate on which the mask layer 2 is formed.
  • FIG. 7 is a top view showing an example of the front plate on which the first transparent electrode pattern 3 is formed.
  • FIG. 8 is a top view showing an example of a front plate on which the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are formed.
  • FIG. 9 is a top view showing an example of a front plate on which conductive elements 6 different from the first and second transparent electrode patterns are formed.
  • a laminate material is used to form a surface on the front plate 1 on which each element is arbitrarily formed. It can be formed by laminating the antireflection layer.
  • At least one element of the mask layer 2, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, and the conductive element 6 is: It is preferable to form using the said photosensitive film which has a temporary support body and a photocurable resin layer in this order.
  • the said photosensitive film which has a temporary support body and a photocurable resin layer in this order.
  • the photosensitive film Using the photosensitive film, permanent materials such as the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element when the mask layer, the insulating layer, and the conductive photocurable resin layer are used are formed.
  • the photosensitive film is laminated on the substrate and then exposed in a pattern as necessary.
  • the non-exposed part In the case of negative type material, the non-exposed part is exposed, and in the case of positive type material, the exposed part is developed and removed. By doing so, a pattern can be obtained.
  • the thermoplastic resin layer and the photocurable layer may be developed and removed with separate liquids, or may be removed with the same liquid. You may combine well-known image development facilities, such as a brush and a high pressure jet, as needed. After the development, post-exposure and post-bake may be performed as necessary.
  • the photosensitive film other than the transfer film which is preferably used when manufacturing the capacitive input device of the present invention, will be described.
  • the photosensitive film preferably has a temporary support and a photocurable resin layer, and preferably has a thermoplastic resin layer between the temporary support and the photocurable resin layer. If a mask layer or the like is formed using the photosensitive film having the thermoplastic resin layer, bubbles are not easily generated in the element formed by transferring the photocurable resin layer, and image unevenness occurs in the image display device. Therefore, excellent display characteristics can be obtained.
  • the photosensitive film may be a negative type material or a positive type material.
  • production method- As the temporary support and the thermoplastic resin layer in the photosensitive film, the same materials as those used in the transfer film of the present invention can be used. Also, as the method for producing the photosensitive film, the same method as the method for producing the transfer film can be used.
  • the said photosensitive film adds an additive to a photocurable resin layer according to the use. That is, when using the said photosensitive film for formation of a mask layer, a coloring agent is contained in a photocurable resin layer. Moreover, when the said photosensitive film has an electroconductive photocurable resin layer, an electroconductive fiber etc. contain in the said photocurable resin layer.
  • the photocurable resin layer preferably contains an alkali-soluble resin, a polymerizable compound, a polymerization initiator, or a polymerization initiation system. Furthermore, conductive fibers, colorants, other additives, and the like are used, but are not limited thereto.
  • a solid structure or a hollow structure is preferable.
  • the fiber having a solid structure may be referred to as “wire”, and the fiber having a hollow structure may be referred to as “tube”.
  • a conductive fiber having an average minor axis length of 5 nm to 1,000 nm and an average major axis length of 1 ⁇ m to 100 ⁇ m may be referred to as “nanowire”.
  • a conductive fiber having an average minor axis length of 1 nm to 1,000 nm, an average major axis length of 0.1 ⁇ m to 1,000 ⁇ m, and having a hollow structure may be referred to as “nanotube”.
  • the material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. However, at least one of metal and carbon is preferable, and among these, The conductive fiber is particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.
  • the material of the metal nanowire is not particularly limited.
  • at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is preferable.
  • at least one metal selected from Group 2 to Group 14 is selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14.
  • At least one metal selected from the group is more preferable, and it is particularly preferable to include it as a main component.
  • Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. And alloys thereof. Among these, in view of excellent conductivity, those mainly containing silver or those containing an alloy of silver and a metal other than silver are preferable. Containing mainly silver means that the metal nanowire contains 50% by mass or more, preferably 90% by mass or more. Examples of the metal used in the alloy with silver include platinum, osmium, palladium and iridium. These may be used alone or in combination of two or more.
  • the shape of the metal nanowire is not particularly limited and can be appropriately selected depending on the purpose. In applications where high transparency is required, a cylindrical shape and a cross-sectional shape with rounded polygonal corners are preferred.
  • the cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the corner of the cross section of the metal nanowire means a peripheral portion of a point that extends each side of the cross section and intersects with a perpendicular drawn from an adjacent side. Further, “each side of the cross section” is a straight line connecting these adjacent corners.
  • the ratio of the “outer peripheral length of the cross section” to the total length of the “each side of the cross section” was defined as the sharpness.
  • the sharpness can be represented by the ratio of the outer peripheral length of the cross section indicated by the solid line and the outer peripheral length of the pentagon indicated by the dotted line.
  • a cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape having rounded corners.
  • the sharpness is preferably 60% or less, and more preferably 50% or less. If the sharpness exceeds 75%, the electrons may be localized at the corners, and plasmon absorption may increase, or the transparency may deteriorate due to yellowing or the like. Moreover, the linearity of the edge part of a pattern may fall and a shakiness may arise.
  • the lower limit of the sharpness is preferably 30%, more preferably 40%.
  • the average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 150 nm or less, more preferably 1 nm to 40 nm, and more preferably 10 n m to 40 nm is more preferable, and 15 nm to 35 nm is particularly preferable.
  • the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated.
  • the average minor axis length is more than 150 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are times when you can't.
  • the average minor axis length of the metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis length of was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the shortest axis.
  • the average major axis length (sometimes referred to as “average length”) of the metal nanowire is preferably 1 ⁇ m to 40 ⁇ m, more preferably 3 ⁇ m to 35 ⁇ m, and even more preferably 5 ⁇ m to 30 ⁇ m. If the average major axis length is less than 1 ⁇ m, it may be difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 ⁇ m, the metal nanowires are too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
  • the average major axis length of the metal nanowires is, for example, observed with 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average major axis length of the wire was determined. In addition, when the said metal nanowire was bent, the circle
  • the thickness of the conductive photocurable resin layer is preferably from 0.1 to 20 ⁇ m, and preferably from 0.5 to 18 ⁇ m, from the viewpoint of process suitability such as coating solution stability, drying during coating, and development time during patterning. Further preferred is 1 to 15 ⁇ m.
  • the content of the conductive fiber based on the total solid content of the conductive photocurable resin layer is preferably 0.01 to 50% by mass, and 0.05 to 30% by mass from the viewpoints of conductivity and coating solution stability. % Is more preferable, and 0.1 to 20% by mass is particularly preferable.
  • a coloring agent can be used for a photocurable resin layer.
  • a coloring agent can be used for a photocurable resin layer.
  • known colorants organic pigments, inorganic pigments, dyes, etc.
  • a mixture of pigments such as red, blue, and green can be used.
  • the photocurable resin layer is used as a black mask layer, it is preferable to include a black colorant from the viewpoint of optical density.
  • the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.
  • white pigments described in paragraphs [0015] and [0114] of JP-A-2005-7765 can be used.
  • pigments or dyes described in paragraphs [0183] to [0185] of Japanese Patent No. 4546276 may be mixed and used.
  • the colorants described in paragraph numbers [0080] to [0088] of JP-A-2005-17521 can be suitably used.
  • the colorant preferably a pigment, more preferably carbon black
  • This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the colorant and the pigment dispersant in an organic solvent (or vehicle) described later.
  • the vehicle is a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds to the pigment to form a coating film (binder) and dissolves and dilutes it.
  • Component organic solvent
  • the disperser used for dispersing the pigment is not particularly limited.
  • the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438 Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.
  • the colorant preferably has a number average particle size of 0.001 ⁇ m to 0.1 ⁇ m, more preferably 0.01 ⁇ m to 0.08 ⁇ m, from the viewpoint of dispersion stability.
  • the “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a large number of particles, This 100 average value is said.
  • the layer thickness of the photocurable resin layer containing the colorant is preferably 0.5 to 10 ⁇ m, more preferably 0.8 to 5 ⁇ m, and particularly preferably 1 to 3 ⁇ m, from the viewpoint of thickness difference from other layers.
  • the content of the colorant in the solid content of the colored photosensitive resin composition is not particularly limited, but is preferably 15 to 70% by mass from the viewpoint of sufficiently shortening the development time, and preferably 20 to 60%. More preferably, it is more preferably 25 to 50% by mass.
  • the total solid content as used in this specification means the total mass of the non-volatile component remove
  • the layer thickness of the photocurable resin layer is preferably from 0.1 to 5 ⁇ m, more preferably from 0.3 to 3 ⁇ m from the viewpoint of maintaining insulation. 0.5 to 2 ⁇ m is particularly preferable.
  • the photosensitive film is a negative type material
  • the photosensitive film may be a positive type material.
  • the photosensitive film is a positive type material, for example, a material described in JP-A-2005-221726 is used for the photocurable resin layer, but the material is not limited thereto.
  • thermoplastic resin layer -Viscosity of thermoplastic resin layer and photocurable resin layer-
  • the viscosity of the thermoplastic resin layer measured at 100 ° C. is in the region of 1000 to 10,000 Pa ⁇ sec
  • the viscosity of the photocurable resin layer measured at 100 ° C. is in the region of 2000 to 50000 Pa ⁇ sec
  • the viscosity of each layer can be measured as follows.
  • the solvent is removed from the coating solution for the thermoplastic resin layer or the photocurable resin layer by drying under atmospheric pressure and reduced pressure to obtain a measurement sample.
  • Vibron DD-III type: manufactured by Toyo Baldwin Co., Ltd.
  • Vibron Can be used under the conditions of a measurement start temperature of 50 ° C., a measurement end temperature of 150 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz / deg.
  • the mask layer 2 and the insulating layer 5 can be formed by transferring a photocurable resin layer to the front plate 1 or the like using the photosensitive film.
  • the black photocurable resin is formed on the surface of the front plate 1 using the photosensitive film having a black photocurable resin layer as the photocurable resin layer. It can be formed by transferring the layer.
  • the front plate 1 on which the first transparent electrode pattern is formed using the photosensitive film having an insulating photocurable resin layer as the photocurable resin layer It can be formed by transferring the photocurable resin layer to the surface.
  • the photosensitive film having the specific layer structure including the thermoplastic resin layer between the photocurable resin layer and the temporary support is used. Generation of bubbles during lamination can be prevented, and a high-quality mask layer 2 and the like having no light leakage can be formed.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 may be formed by using the photosensitive film having an etching treatment or a conductive photocurable resin layer, or using a photosensitive film. It can be formed using as a lift-off material.
  • the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are formed by etching, first, on the non-contact surface of the front plate 1 on which the mask layer 2 and the like are formed.
  • a transparent electrode layer such as ITO is formed by sputtering.
  • an etching pattern is formed by exposure and development using the photosensitive film having an etching photocurable resin layer as the photocurable resin layer on the transparent electrode layer.
  • the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first transparent electrode pattern 3 and the like can be formed.
  • etching pattern when the photosensitive film is used as an etching resist (etching pattern), a resist pattern can be obtained in the same manner as in the above method.
  • etching etching or resist stripping can be applied by a known method described in paragraphs [0048] to [0054] of JP 2010-152155 A.
  • an etching method there is a commonly performed wet etching method of dipping in an etching solution.
  • an acid type or an alkaline type may be appropriately selected according to an object to be etched.
  • acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done.
  • the acidic component a combination of a plurality of acidic components may be used.
  • alkaline type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate.
  • a mixed aqueous solution of a salt such as A combination of a plurality of alkali components may be used as the alkali component.
  • the temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower.
  • the resin pattern used as an etching mask (etching pattern) in the present invention is formed by using the above-described photocurable resin layer, so that it is particularly suitable for acidic and alkaline etching solutions in such a temperature range. Excellent resistance. Therefore, the resin pattern is prevented from peeling off during the etching process, and the portion where the resin pattern does not exist is selectively etched.
  • a cleaning process and a drying process may be performed as necessary to prevent line contamination.
  • the cleaning process is performed by cleaning the substrate with pure water for 10 to 300 seconds at room temperature, for example, and the air blowing pressure (about 0.1 to 5 kg / cm 2 ) is appropriately adjusted using an air blow for the drying process. Just do it.
  • the method of peeling the resin pattern is not particularly limited, and examples thereof include a method of immersing the substrate in a peeling solution being stirred at 30 to 80 ° C., preferably 50 to 80 ° C. for 5 to 30 minutes.
  • the resin pattern used as an etching mask in the present invention exhibits excellent chemical resistance at 45 ° C. or lower as described above, but exhibits a property of swelling by an alkaline stripping solution when the chemical temperature is 50 ° C. or higher. . Due to such properties, when the peeling process is performed using a peeling solution of 50 to 80 ° C., there are advantages that the process time is shortened and the resin pattern peeling residue is reduced.
  • the resin pattern used as an etching mask in the present invention exhibits good chemical resistance in the etching process, while in the peeling process. Good peelability will be exhibited, and both conflicting properties of chemical resistance and peelability can be satisfied.
  • the stripping solution examples include inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these. What was melt
  • dissolved in this mixed solution is mentioned. You may peel by the spray method, the shower method, the paddle method etc. using the said peeling liquid.
  • the front plate 1 It can be formed by transferring the conductive photocurable resin layer to the surface.
  • the first transparent electrode pattern 3 or the like is formed using a photosensitive film having the conductive photocurable resin layer, there is no leakage of resist components from the opening portion even on a substrate (front plate) having an opening portion. Without contaminating the back side of the substrate, it is possible to manufacture a touch panel having a merit of thin layer / light weight by a simple process.
  • the first transparent electrode pattern 3 or the like is formed by using the photosensitive film having a specific layer structure including a thermoplastic resin layer between the conductive photocurable resin layer and the temporary support. It is possible to prevent the generation of bubbles when laminating the conductive film, and to form the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 with excellent conductivity and low resistance.
  • a 1st transparent electrode layer, a 2nd transparent electrode layer, and another electroconductive member can also be formed using the said photosensitive film as a lift-off material.
  • a transparent conductive layer is formed on the entire surface of the base material, and then the desired transparent conductive layer is formed by dissolving and removing the photocurable resin layer together with the deposited transparent conductive layer. A pattern can be obtained (lift-off method).
  • the touch panel of this invention contains the laminated body of this invention mentioned above.
  • the touch panel of the present invention can be used as an input device by being incorporated in a display device such as a liquid crystal display, a plasma display, an organic EL display, a CRT display, and electronic paper.
  • a display device such as a liquid crystal display, a plasma display, an organic EL display, a CRT display, and electronic paper.
  • occurrence of interference unevenness can be suppressed and a touch panel with good color can be obtained.
  • Capacitance type input devices have the advantage of simply forming a light-transmitting conductive film on a single substrate. A capacitance type is preferred.
  • a capacitance-type input device for example, when the electrode pattern is extended in a direction intersecting each other as the transparent electrode layer and a finger or the like comes into contact, it is detected that the capacitance between the electrodes changes.
  • a type that detects the input position can be preferably used.
  • descriptions in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be referred to.
  • thermoplastic film layer having a dry film thickness of 15.1 ⁇ m, the intermediate layer having a dry film thickness of 1.6 ⁇ m, and the dry film thickness so that the optical density is 4.0 are formed on the temporary support.
  • a 2.2 ⁇ m black photocurable resin layer was provided, and finally a protective film (12 ⁇ m thick polypropylene film) was pressure-bonded.
  • a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black photocurable resin layer were integrated was prepared, and the sample name was designated as a decorative pattern forming photosensitive film K1. .
  • Propylene glycol monomethyl ether acetate 79.53 mass%
  • R pigment dispersion 1 (the following composition): 3.3 parts by mass MMPGAc (manufactured by Daicel Chemical Industries): 6.2 parts by mass Methyl ethyl ketone (Tonen Chemical) (Manufactured by Co., Ltd.): 34.0 parts by mass / cyclohexanone (manufactured by Kanto Denka Kogyo Co., Ltd.):
  • ⁇ Decorative pattern formation on glass substrate> For a glass substrate (thickness 0.7 mm, Gorilla glass, manufactured by Corning) that has been subjected to a chemical strengthening treatment in which part or all of ions having a smaller ion radius than potassium ions in the glass are replaced with potassium ions, Silane coupling treatment was performed. A glass cleaner solution adjusted to 25 ° C. is sprayed with a rotating brush having nylon bristles while sprayed for 20 seconds in a shower. After pure water shower cleaning, a silane coupling solution (N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxy) is washed.
  • a silane coupling solution N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxy
  • Silane 0.3% by mass aqueous solution trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.
  • This substrate was heated at 140 ° C. for 2 minutes with a substrate preheating device.
  • the surface of the black photocurable resin layer exposed to the silane coupling-treated glass substrate obtained by removing the cover film from the decorative film-forming photosensitive film K1 obtained from the above and the silane coupling is removed.
  • the surface of the treated glass substrate is overlapped with each other, and the substrate heated at 140 ° C.
  • the laminator manufactured by Hitachi Industries (Lamic II type)
  • a rubber roller temperature of 130 ° C. a wire Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
  • the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support.
  • the substrate and the exposure mask (quartz exposure mask with a frame pattern) were set up vertically with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. In this state, the distance between the exposure mask surface and the black light curable resin layer was set to 200 ⁇ m, and pattern exposure was performed at an exposure amount of 70 mJ / cm 2 (i-line).
  • a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 33 ° C. for 60 seconds
  • shower development was performed at a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer and the intermediate layer.
  • air was blown onto the upper surface of the glass base material to drain the liquid, and then pure water was sprayed for 10 seconds by a shower, pure water shower washing was performed, and air was blown to reduce the liquid pool on the base material.
  • the shower pressure was reduced to 0.1 MPa at 32 ° C. using a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) diluted 5 times with pure water). It was set, developed for 45 seconds, and washed with pure water.
  • a sodium carbonate / sodium hydrogen carbonate developer trade name: T-CD1 (manufactured by FUJIFILM Corporation) diluted 5 times with pure water. It was set, developed for 45 seconds, and washed with pure water.
  • ⁇ Formation of transparent electrode pattern> ⁇ Formation of transparent electrode layer >> The substrate on which the decorative pattern was formed was introduced into a vacuum chamber, and DC magnetron sputtering (conditions) was performed using an ITO target (indium: tin 95: 5 (molar ratio)) with a SnO 2 content of 10% by mass. : A base material temperature of 250 ° C., an argon pressure of 0.13 Pa, an oxygen pressure of 0.01 Pa) was used to form an ITO thin film having a thickness of 40 nm to obtain a substrate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 80 ⁇ / ⁇ .
  • first transparent electrode pattern (Formation of first transparent electrode pattern) Similarly to the formation of the decorative pattern, the substrate on which the transparent electrode layer was formed was washed, and the etching photosensitive film E1 from which the cover film was removed was laminated (base material temperature: 130 ° C., rubber roller temperature 120 ° C., wire Pressure 100 N / cm, conveyance speed 2.2 m / min). After peeling off the temporary support, the distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the photocurable resin layer for etching is set to 200 ⁇ m, and the exposure amount is 50 mJ / cm 2 (i-line). ) For pattern exposure.
  • a triethanolamine developer (containing 30% by mass of triethanolamine, a trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 25 ° C. for 100 seconds
  • a surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was treated at 33 ° C. for 20 seconds, using a rotating brush and an ultra-high pressure cleaning nozzle. The residue was removed, and a post-bake treatment at 130 ° C. for 30 minutes was further performed to obtain a substrate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
  • the substrate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched light.
  • ITO etchant hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.
  • the transparent electrode layer in the exposed region not covered with the curable resin layer was dissolved and removed to obtain a substrate with a transparent electrode layer pattern having a photocurable resin layer pattern for etching.
  • a substrate with a transparent electrode layer pattern with a photocurable resin layer pattern for etching is applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465, Nissin Chemical Industry Co., Ltd.) immersed in a resist stripping tank containing a liquid temperature of 45 ° C., treated for 200 seconds, removed the photo-curable resin layer for etching, and the mask layer and the first transparent electrode pattern A formed substrate was obtained.
  • a resist stripping solution N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465, Nissin Chemical Industry Co., Ltd.) immersed in a resist stripping tank containing a liquid temperature of 45 ° C., treated for 200 seconds, removed the photo-curable resin layer for etching, and the mask layer and the first transparent electrode pattern A formed substrate was obtained.
  • the front plate with the first transparent electrode pattern was washed, treated with silane coupling, and laminated with the insulating film forming photosensitive film W1 from which the cover film was removed (base temperature). : 100 ° C., rubber roller temperature 120 ° C., linear pressure 100 N / cm, transport speed 2.3 m / min).
  • the distance between the exposure mask (quartz exposure mask having the insulating layer pattern) surface and the photocurable resin layer for etching is set to 100 ⁇ m, and the exposure dose is 30 mJ / cm 2 (i Line).
  • a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 33 ° C. for 60 seconds, Sodium carbonate / bicarbonate developer (trade name: T-CD1 (Fuji Film Co., Ltd.) diluted 5-fold with pure water) at 25 ° C. for 50 seconds, surfactant-containing cleaning solution (trade name) : T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water for 20 seconds at 33 ° C, and the residue is removed with a rotating brush and ultra-high pressure washing nozzle.
  • a post-baking treatment for 60 minutes was performed to obtain a substrate on which a decorative pattern, a first transparent electrode pattern, and an insulating layer pattern were formed.
  • Second Transparent Electrode Pattern (Formation of transparent electrode layer)
  • the front plate on which the first transparent electrode pattern and the insulating layer pattern were formed was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa).
  • An ITO thin film having an oxygen pressure of 0.01 Pa and a thickness of 80 nm was formed to obtain a substrate on which a transparent electrode layer was formed.
  • the surface resistance of the ITO thin film was 110 ⁇ / ⁇ .
  • the first transparent electrode pattern, the insulating layer pattern, the transparent electrode layer, and the photocurable resin layer pattern for etching are formed using the etching photosensitive film E1.
  • the obtained front plate was obtained (post-baking treatment; 130 ° C. for 30 minutes).
  • the decorative pattern the first are obtained by etching (30 ° C. for 50 seconds) and removing the photocurable resin layer for etching (45 ° C. for 200 seconds).
  • a substrate on which a transparent electrode pattern, an insulating layer pattern, and a second transparent electrode pattern were formed was obtained.
  • the front plate on which the first transparent electrode pattern, the insulating layer pattern, and the second transparent electrode pattern were formed was subjected to DC magnetron sputtering treatment to a thickness of 200 nm.
  • a front plate on which an aluminum (Al) thin film was formed was obtained.
  • the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the photocuring for etching are performed using the etching photosensitive film E1.
  • a front plate on which a conductive resin layer pattern was formed was obtained.
  • the decorative pattern the first are obtained by etching (30 ° C. for 50 seconds) and removing the photocurable resin layer for etching (45 ° C. for 200 seconds).
  • a substrate on which a conductive element different from the transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns was formed was obtained.
  • Tin oxide fine particle dispersion 8 parts by mass (average particle size 60 nm) as solid content 2.8 parts by mass of polyurethane (manufactured by Mitsui Chemicals, Takelac WS-5100)
  • Cross-linking agent 4.2 parts by mass (manufactured by Nisshinbo Chemical Co., Ltd., 10% diluted solution of Carbodilite V-02-L2)
  • Surfactant A 0.2 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 10% aqueous solution of sanded BL, anionic)
  • Surfactant B 0.2 parts by mass (Sanyo Chemical Industry Co., Ltd., 10% diluted solution of NAROACTY CL-95, nonionic) 84.6 parts by weight of water
  • the above formulation is adjusted so that the refractive index of the easy-adhesion layer after coating and drying is 1.58.
  • An easy-adhesion layer coating solution was applied to the surface of the PET film subjected to the glow discharge treatment by a bar coating method. And this was dried at 150 degreeC for 2 minutes. A laminated film having an easy-adhesion layer applied on both sides of the PET film was obtained.
  • the film thickness of the easy-adhesion layer was measured by observing the laminated film at a magnification of 200,000 using a transmission electron microscope (JEM2010 (manufactured by JEOL Ltd.)). The film thickness was 100 nm.
  • the following formulation was used for the aqueous composition.
  • Acetic acid aqueous solution 100 parts by mass (manufactured by Daicel Chemical Industries, Ltd., 1% aqueous solution of industrial acetic acid) 80 parts by mass of 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-403) 20 parts by mass of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04)
  • Aluminum chelate complex 22.1 parts by mass made by Kawaken Fine Chemicals, aluminum chelate D
  • 200 parts by mass of inorganic fine particles manufactured by Nissan Chemical Industries, Snowtex O-33
  • Surfactant A 0.2 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 10% aqueous solution of sanded BL, anionic)
  • Surfactant B 0.2 parts by mass (Sanyo Chemical Industry Co.,
  • Preparation was performed according to the following procedure. 3-Glycidoxypropyltriethoxysilane (KBE-403) was added to 100 parts by mass of 1% acetic acid and sufficiently hydrolyzed, and then tetraalkoxysilane (KBE-04) was added. A necessary part by mass of the aluminum chelate complex with respect to the epoxy group-containing alkoxysilane was added, and inorganic fine particles (Snowtex O-33) were added thereto.
  • KBE-403 3-Glycidoxypropyltriethoxysilane
  • KBE-04 tetraalkoxysilane
  • a necessary part by mass of the aluminum chelate complex with respect to the epoxy group-containing alkoxysilane was added, and inorganic fine particles (Snowtex O-33) were added thereto.
  • the protective layer coating solution prepared by the following composition is adjusted to a film thickness of 10 ⁇ m while changing the coating amount, and coated and dried to form a protective layer. Then, a cover film (12 ⁇ m thick polypropylene film) was pressure-bonded.
  • the adjusted glass cleaner solution was washed with a rotating brush having nylon bristles while spraying the glass cleaner solution for 20 seconds by showering, and after pure water shower washing, a silane coupling solution (N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane.
  • a 3% by weight aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd. was sprayed for 20 seconds with a shower and washed with pure water.
  • the substrate was heated at 140 ° C. for 2 minutes with a base material preheating device.
  • the surface of the curable transparent resin layer exposed after the removal of the cover film from the above-mentioned laminated material with an anti-scattering function, which has been cut into a desired shape of the substrate in advance to the obtained silane coupling treatment substrate, and the silane cup The substrate was heated so as to be in contact with the surface of the ring-treated substrate, and the substrate heated at 140 ° C.
  • Example 2 After the protective layer was formed, UV lamp irradiation (exposure amount 300 mJ / cm 2 , methane halide lamp) was irradiated. Thereafter, an antireflection layer was formed on the protective layer with a coating solution (refractive index: 1.72) having the composition of the following material-8 so as to have a film thickness of 52 nm. A laminated material was produced in the same manner as in Example 1 except for this.
  • Example 3 A laminate was produced in the same manner as in Example 1 except that the PET film of Example 1 was changed to a TAC film having a thickness of 80 ⁇ m (Fuji Film, Fujitac).
  • Example 4 A laminate was prepared in the same manner as in Example 1 except that the PET film of Example 1 was changed to a TAC film having a thickness of 40 ⁇ m (Fujifilm, Fujitac).
  • Example 7 A laminate was prepared in the same manner as in Example 1 except that the PET film of Example 1 was replaced with a 66 ⁇ m thick polycarbonate film (manufactured by Kaneka Corporation, Elmec).
  • Example 8 In Example 1, a laminate was produced in the same manner as in Example 1 except that a laminate material without a hard coat layer was used.
  • Example 9 A laminate was produced in the same manner as in Example 1 except that a laminate material having a hard coat layer containing an acrylic resin produced as follows was used. In the table below, “acrylic” was indicated.
  • the solvent was distilled off under reduced pressure to obtain a curable multi-branched polymer (RHB-1).
  • the OH value of the curable multi-branched polymer (RHB-1) was 434 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 15 mol%.
  • ⁇ Adjustment of coating solution 40 parts by mass of the polymer (RHB-1) DPHA (dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.) 10 parts by mass Irgacure 907 (manufactured by BASF) 2.5 parts by mass Methyl ethyl ketone 20 parts by mass Methyl isobutyl ketone 30 parts by mass
  • each well-mixed solution was filtered and adjusted with a polypropylene filter having a pore size of 30 ⁇ m.
  • ⁇ Coating of hard coat layer> It is applied by a bar coating method so as to have a film thickness of 1 ⁇ m, dried at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds, and further irradiated with 160 W / cm 2 of UV under a nitrogen purge to cure the coating film, A hard coat layer was formed on the polymer layer.
  • Example 10 A laminate was produced in the same manner as in Example 1 except that a laminate material without an easy-adhesion layer was used.
  • Example 11 Using a hard coat layer having a refractive index of 1.64 containing zirconium formed by the following method as a hard coat layer, and forming an easy adhesion layer having a refractive index of 1.65 prepared from a coating solution having the composition shown in the following table The difference between the refractive index difference with the hard coat layer is 0.02 or less, and the difference between the refractive index difference with the polymer layer is 0.02 or less and a laminated material having an easy-adhesion layer is used. A laminate was produced in the same manner.
  • a hard coat layer coating solution having the following composition was applied by a bar coating method to a WET thickness of about 2 ⁇ m. After drying at 90 ° C. for 1 minute, the resin was cured by irradiating ultraviolet rays at a dose of 1600 mJ / cm 2 using a high-pressure mercury lamp. This produced the hard-coat layer on the surface of the easily bonding layer described below.
  • the hard coat layer had a thickness of 1 ⁇ m and a refractive index of 1.64.
  • UV curable resin manufactured by JSR Corporation, Z7410B
  • Inorganic fine particles zirconium oxide manufactured by Nissan Chemical Industries, Ltd. OZ-S30K 20 parts by mass
  • Example 12 A laminate was produced in the same manner as in Example 1 except that the PET film of Example 1 was changed to a cycloolefin polymer film (Zeon Corporation, Zeon film ZD14) having a thickness of 60 ⁇ m and a retardation of 140 nm.
  • the transparent laminate is placed on a liquid crystal display device (a liquid crystal cell is sandwiched between two polarizing plates) with an absorption axis of the polarizing plate and a slow axis of the polymer film of 45 degrees. Visibility was good when the image was viewed through a polarizing plate such as sunglasses.
  • a protective layer having the same composition as that used in Example 1 was formed by coating, and an easy-adhesion layer was coated using a bar coater so as to have a film thickness described in the table. It was formed by partial drying, and the hard coat layer was applied by a bar coating method to a thickness of 1 ⁇ m and dried at 150 ° C. for 2 minutes to form a laminate.
  • ⁇ Haze> The amount of change of the haze before and after the heat treatment at 150 ° C. for 10 minutes was measured on the laminated material before being transferred to the glass substrate, and the measurement result was evaluated. Haze was measured according to JIS-K-7105 using a haze meter (NDH-2000, Nippon Denshoku Industries Co., Ltd.). Regarding the amount of change in haze before and after heat treatment (unit:%), the haze before and after the heat treatment under a predetermined condition (that is, no heat treatment) was measured, and the haze before the heat treatment was determined as H1. When the haze after heat treatment is H2,
  • the heat treatment in the haze measurement was performed by placing the sample in an oven whose internal temperature was set to 150 ° C. and holding it for 10 minutes. In addition, the haze measurement after heat processing was implemented after cooling the sample taken out from oven.
  • ⁇ Transparency (transmittance)> The transmittance of 440 nm was evaluated for the laminated material before being transferred to the glass substrate. Measurement was performed using a spectrophotometer (UV2100, manufactured by Shimadzu Corporation). A: (Good): 95% or more B: (Preferably usable): 90 to less than 95% C: (Useable): Less than 90%
  • ⁇ Transparent electrode pattern visibility> The transparent laminated body of each Example and Comparative Example was bonded to the transparent laminated body and the black PET material via a transparent adhesive tape (trade name, OCA tape 8171CL, manufactured by 3M), and the entire substrate was shielded from light.
  • the visibility of the transparent electrode pattern was performed by making light incident on the fluorescent lamp (light source) and the prepared substrate from the glass surface side and visually observing reflected light from the glass surface obliquely in a dark room.
  • B The transparent electrode pattern is slightly visible but hardly visible.
  • C A transparent electrode pattern is visible (unclear).
  • D Although a transparent electrode pattern can be seen, it is practically acceptable.
  • E The transparent electrode pattern is clearly visible (easy to understand).
  • ⁇ Interference unevenness> Irradiate the surface of the laminate opposite to the glass substrate with the diffused light of the three-wavelength fluorescent lamp through the milky white acrylic plate from the transparent laminated body of each Example and Comparative Example on a desk with a black doskin cloth laminated The generated reflected light was visually observed. And by visually observing the rainbow-colored interference unevenness observed at this time, ranking was performed according to the following evaluation criteria, and the interference unevenness of the laminate was evaluated. In addition, when visually observing, each laminate was subjected to a blackening treatment as a compulsory condition, and a 500 nm light transmittance adjusted to 1% or less was separately evaluated.
  • the laminated body for touchscreens of this invention can prevent glass scattering. Moreover, in the preferable embodiment of the laminated body for touchscreens of this invention, it turns out that the property which is excellent also in haze, transparency, pencil hardness, and visibility was given.

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Position Input By Displaying (AREA)

Abstract

L'invention concerne un stratifié pour écran tactile, constitué successivement d'un substrat en verre, d'une couche électrode transparente, d'une couche protectrice couvrant la couche électrode transparente, et d'une couche polymère. La réalisation de ce substrat de verre implique un traitement de consolidation chimique consistant en une substitution, par des ions de potassium, de tout ou partie des ions qui se trouvent dans le verre et dont le rayon ionique est inférieur à celui d'un ion de potassium.
PCT/JP2014/055298 2013-03-15 2014-03-03 Stratifié pour écran tactile et procédé de fabrication de ce stratifié WO2014141921A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-052749 2013-03-15
JP2013052749A JP6121204B2 (ja) 2013-03-15 2013-03-15 タッチパネル用積層体およびタッチパネル用積層体の製造方法

Publications (1)

Publication Number Publication Date
WO2014141921A1 true WO2014141921A1 (fr) 2014-09-18

Family

ID=51536594

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/055298 WO2014141921A1 (fr) 2013-03-15 2014-03-03 Stratifié pour écran tactile et procédé de fabrication de ce stratifié

Country Status (2)

Country Link
JP (1) JP6121204B2 (fr)
WO (1) WO2014141921A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108025537A (zh) * 2015-09-29 2018-05-11 富士胶片株式会社 转印薄膜、静电电容型输入装置的电极保护膜、层叠体及静电电容型输入装置

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0367449A (ja) * 1989-08-04 1991-03-22 Akashi Biimu Technol Kk 粒子線装置の絞り清浄化方法および装置
JP6471406B2 (ja) * 2013-12-18 2019-02-20 大日本印刷株式会社 光学積層体
JP6639098B2 (ja) * 2015-03-20 2020-02-05 富士フイルム株式会社 タッチパネル部材、タッチパネル及びタッチパネル表示装置
JP6581200B2 (ja) 2015-09-30 2019-09-25 富士フイルム株式会社 静電容量型入力装置の電極保護膜用の組成物、静電容量型入力装置の電極保護膜、転写フィルム、積層体、静電容量型入力装置および画像表示装置。
JP6474713B2 (ja) * 2015-12-09 2019-02-27 富士フイルム株式会社 転写材料、転写材料の製造方法、タッチパネルの製造方法およびタッチパネル
JP6716912B2 (ja) * 2015-12-25 2020-07-01 大日本印刷株式会社 表示装置用基材
WO2021166652A1 (fr) * 2020-02-21 2021-08-26 富士フイルム株式会社 Procédé de formation d'un motif électro-conducteur, motif électro-conducteur, film de transfert et écran tactile

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011054122A (ja) * 2009-09-04 2011-03-17 Dainippon Printing Co Ltd 基板および基板の製造方法
JP2012025158A (ja) * 2010-06-25 2012-02-09 Gunze Ltd 透明面状体及び透明タッチパネル
WO2012023359A1 (fr) * 2010-08-20 2012-02-23 シャープ株式会社 Dispositif d'entrée de position, dispositif d'affichage et procédé de fabrication de dispositifs d'entrée de position
WO2012099394A2 (fr) * 2011-01-19 2012-07-26 Lg Innotek Co., Ltd. Écran tactile et son procédé de fabrication
JP5051328B1 (ja) * 2012-01-27 2012-10-17 大日本印刷株式会社 光学積層体、偏光板及び画像表示装置
JP2013015989A (ja) * 2011-07-04 2013-01-24 Daiwa Sangyo:Kk 静電容量型タッチパネルとその製造方法
JP5133449B1 (ja) * 2011-11-04 2013-01-30 Ｓｍｋ株式会社 透明タッチパネル
JP2013023611A (ja) * 2011-07-22 2013-02-04 Adeka Corp 水系ポリウレタン樹脂組成物、これを塗布してなる易接着性ポリエステルフィルム

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5203072B2 (ja) * 2008-07-07 2013-06-05 東洋紡株式会社 タッチパネル用上部電極
KR20100084252A (ko) * 2009-01-16 2010-07-26 삼성모바일디스플레이주식회사 터치 스크린 패널

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011054122A (ja) * 2009-09-04 2011-03-17 Dainippon Printing Co Ltd 基板および基板の製造方法
JP2012025158A (ja) * 2010-06-25 2012-02-09 Gunze Ltd 透明面状体及び透明タッチパネル
WO2012023359A1 (fr) * 2010-08-20 2012-02-23 シャープ株式会社 Dispositif d'entrée de position, dispositif d'affichage et procédé de fabrication de dispositifs d'entrée de position
WO2012099394A2 (fr) * 2011-01-19 2012-07-26 Lg Innotek Co., Ltd. Écran tactile et son procédé de fabrication
JP2013015989A (ja) * 2011-07-04 2013-01-24 Daiwa Sangyo:Kk 静電容量型タッチパネルとその製造方法
JP2013023611A (ja) * 2011-07-22 2013-02-04 Adeka Corp 水系ポリウレタン樹脂組成物、これを塗布してなる易接着性ポリエステルフィルム
JP5133449B1 (ja) * 2011-11-04 2013-01-30 Ｓｍｋ株式会社 透明タッチパネル
JP5051328B1 (ja) * 2012-01-27 2012-10-17 大日本印刷株式会社 光学積層体、偏光板及び画像表示装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108025537A (zh) * 2015-09-29 2018-05-11 富士胶片株式会社 转印薄膜、静电电容型输入装置的电极保护膜、层叠体及静电电容型输入装置
CN108025537B (zh) * 2015-09-29 2019-12-03 富士胶片株式会社 转印薄膜、静电电容型输入装置的电极保护膜、层叠体及静电电容型输入装置

Also Published As

Publication number Publication date
JP6121204B2 (ja) 2017-04-26
JP2014178922A (ja) 2014-09-25

Similar Documents

Publication Publication Date Title
JP6121204B2 (ja) タッチパネル用積層体およびタッチパネル用積層体の製造方法
US10336043B2 (en) Transfer film, transparent laminate, method for producing transparent laminate, capacitive input device, and image display device
TWI498212B (zh) 光學積層體及硬質塗膜
JP5857013B2 (ja) 加飾材付き基材およびその製造方法、タッチパネルならびに情報表示装置
JP6225053B2 (ja) 感光性積層体、転写材料、パターン化された感光性積層体及びその製造方法、タッチパネル、並びに画像表示装置
WO2015133599A1 (fr) Substrat de montage de matériau décoratif et procédé de fabrication associé, panneau tactile et dispositif d'affichage d'informations
CN107710123B (zh) 带透明电极的复合体、转印薄膜、带透明电极的复合体的制造方法及静电电容型输入装置
JP5935802B2 (ja) 防眩性フィルムの製造方法
KR20130031910A (ko) 점착제층이 형성된 수지 필름, 적층 필름 및 터치 패널
WO2014175312A1 (fr) Matériau de transfert, substrat doté d'une couche de transfert, écran tactile, procédés de fabrication de ceux-ci et dispositif d'affichage d'informations
KR20120117646A (ko) 점착제층이 형성된 투명 수지 필름, 적층 필름 및 터치 패널
TWI537130B (zh) The manufacturing method of laminated film
CN108367560B (zh) 装饰膜、图像显示装置、触摸面板以及装饰膜的制造方法
TW201736135A (zh) 硬塗膜及其應用
JPWO2012124323A1 (ja) 防眩性フィルム、防眩性フィルムの製造方法、防眩性反射防止フィルム、偏光板、及び画像表示装置
WO2014115415A1 (fr) Corps stratifié transparent et son procédé de fabrication
CN108351722B (zh) 薄膜触控传感器
JP2009185282A (ja) ハードコートフィルム、ハードコートフィルムの製造方法、光学素子および画像表示装置
TW201518093A (zh) 硬塗薄膜、透明導電性薄膜及靜電容觸控面板
TW201806764A (zh) 保護膜、光學膜、積層體、偏光板、影像顯示裝置及偏光板之製造方法
KR101544163B1 (ko) 디스플레이용 필름
TWI582469B (zh) 圖案非可見性優異的透明導電性光學片
JP2010143213A (ja) ハードコートフィルム、ハードコートフィルムの製造方法、透明導電性積層体、光学素子および電子機器
JP2006030837A (ja) 反射防止積層フィルムおよびそれを用いた表示媒体
JP2014100882A (ja) 両面塗布フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14765630

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14765630

Country of ref document: EP

Kind code of ref document: A1