WO2010061851A1 - 被膜を持つシート及びその製造方法 - Google Patents
被膜を持つシート及びその製造方法 Download PDFInfo
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- WO2010061851A1 WO2010061851A1 PCT/JP2009/069871 JP2009069871W WO2010061851A1 WO 2010061851 A1 WO2010061851 A1 WO 2010061851A1 JP 2009069871 W JP2009069871 W JP 2009069871W WO 2010061851 A1 WO2010061851 A1 WO 2010061851A1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
-
- 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
- G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Definitions
- the present invention relates to a sheet having a coating and a method for producing the sheet.
- Polyester films are widely used in various optical applications such as base films for LCD members such as prism sheets, lens sheets, diffusers, reflectors, and touch panels, and antireflection and display explosion-proof base films.
- base films for LCD members such as prism sheets, lens sheets, diffusers, reflectors, and touch panels
- antireflection and display explosion-proof base films In order to obtain bright and clear images in these optical applications, the base film used as an optical film must have good transparency from its usage and must be free from defects such as foreign matter and scratches that affect the image. It becomes.
- Patent Document 1 a resistive touch panel transparent touch panel is arranged to face a fixed electrode support and is movable through a transparent shrinkable resin layer on the lower surface of a movable electrode film having a hard coat layer formed on the upper surface.
- Techniques for forming electrodes are disclosed.
- the oligomer that is a non-crosslinked component of the movable electrode film is precipitated on the movable electrode side, and becomes a whitened state and becomes transparent. It is lost and the appearance and visibility are prevented from deteriorating.
- the hard coat layer is formed on the upper surface of the movable electrode film, the hard coat layer prevents the oligomer from being deposited on the upper surface side of the movable electrode film from the inside of the movable electrode film.
- the problem to be solved by the invention is to provide a method for producing a sheet having a film that can prevent oligomer precipitation on the film surface by a simple method, and a sheet having a film using this method. . Moreover, it aims also at providing the laminated body containing this sheet
- seat (10) based on invention is a method of manufacturing the sheet
- the film (12) is formed by irradiating ultraviolet rays.
- an ultraviolet-ray can be irradiated with the exposure amount of 1500 mJ / cm ⁇ 2 > or more.
- ultraviolet rays can be irradiated in a plurality of times.
- a light beam having an emission wavelength range of 200 to 450 nm and a peak output characteristic at 360 to 370 nm can be used as the ultraviolet ray.
- the ultraviolet rays light rays having a wavelength range of 200 to 450 nm and peak output characteristics at 360 to 370 nm and 250 to 320 nm can be used.
- a transparent polyester film can be used as the film substrate (11). That is, by irradiating the film substrate (11) with ultraviolet rays to modify at least a part of the film substrate (11) to form a coating (12), oligomers on the surface of the film substrate (11) are formed. Precipitation can be prevented.
- the sheet (10) according to the invention has a coating (12) formed by modifying at least a part of the film substrate (11), and the coating (12) irradiates the film substrate (11) with ultraviolet rays. It is formed by these.
- the coating film (12) can have a Martens hardness of 200 N / mm 2 or more, an indentation elastic modulus of 4300 MPa or less, and a thickness of 0.1 ⁇ m or more.
- the value of a Martens hardness and an indentation elastic modulus can be measured on the conditions whose maximum test load is 1 mN.
- the laminate (20) according to the present invention has functional layers (22, 24) provided with various functions on the surface of any of the sheets (10).
- the functional layers (22, 24) are, for example, laminated on the side opposite to the coating layer (12) of the sheet (10) or the coating layer (12) of the sheet (10).
- a hard coat layer and the like can be included.
- the touch panel (5) includes a first electrode substrate (52) in which a first transparent conductive film (524) is formed on a first transparent substrate (522), and a second transparent conductive film (544). Has a second electrode substrate (54) formed on the second transparent substrate (542) so as to face the first transparent conductive film (524) with a predetermined gap. And any one movable side electrode board
- the film substrate is irradiated with ultraviolet rays to modify at least a part of the film substrate to form a film.
- the formed coating prevents oligomer precipitation from the inside of the film substrate. That is, according to the above-described invention, oligomer precipitation on the film surface can be prevented by a simple method without causing factors such as preparation of a separate paint, application, and other processes to deteriorate productivity as compared with the conventional method. be able to.
- FIG. 1 is a cross-sectional view showing a sheet according to the present embodiment.
- FIG. 2 is a cross-sectional view showing an example of a laminate having the sheet of FIG.
- FIG. 3 is a cross-sectional view showing another example of a laminate having the sheet of FIG. 4 is a cross-sectional view showing a touch panel having the laminate of FIG.
- FIG. 5 is an SEM image of the cross section of film a before ultraviolet irradiation.
- FIG. 6 is an SEM image of the cross section of film a after ultraviolet irradiation (1 pass).
- FIG. 7 is an SEM image of the cross section of film a after ultraviolet irradiation (2 pass).
- FIG. 8 is an SEM image of the cross section of film a after ultraviolet irradiation (3 pass).
- FIG. 9 is an SEM image of the cross section of film a after ultraviolet irradiation (10 pass).
- FIG. 10 is an SEM image of a cross section of film a after ultraviolet irradiation (20 pass).
- FIG. 11 is an SEM image of the cross section of film b before ultraviolet irradiation.
- FIG. 12 is an SEM image of the cross section of the film b after ultraviolet irradiation (3 pass).
- seat 10 which concerns on this embodiment has the film base materials 11, such as a transparent polyester film, for example.
- the coating 12 is formed here.
- the coating 12 serves to prevent oligomer precipitation from the inside of the film substrate 11 to the surface of the film substrate 11.
- the surface hardness of the coating 12 of this embodiment is appropriately adjusted. Specifically, the Martens hardness (HM) is adjusted to be larger than a specific value, and the indentation elastic modulus (EIT) is adjusted to be smaller than the specific value.
- HM Martens hardness
- EIT indentation elastic modulus
- Martens hardness represents the hardness (hardness of dent) of the coating 12 obtained from the test load and indentation surface area when the surface of the coating 12 is pressed with a Vickers indenter, and is an index of the hardness of the coating 12 surface. It becomes.
- the value of HM coating 12 can not be said sweepingly because varies depending on the material of the film substrate, preferably 200 N / mm 2 or more, and more preferably adjusted to 210N / mm 2 or more Yes.
- the inventors have found that by adjusting the HM of the coating 12 to a predetermined value or more, it becomes difficult to be damaged and the precipitation of the oligomer from the inside of the film substrate 11 to the outside can be effectively prevented. It was.
- the HM of the coating 12 is preferably adjusted to 350 N / mm 2 or less, more preferably 300 N / mm 2 or less. .
- the value of HM is determined by an ultra-micro hardness tester (Fischer Instruments, trade name: Fisher Scope HM2000) under an atmosphere of a temperature of 20 degrees and a relative humidity of 60%. It is a value obtained by measuring the hardness of the surface of the coating 12 by a method based on -14477-1. However, the maximum test load is a value measured at 1 mN.
- the indentation elastic modulus (EIT) corresponds to the Young's modulus and represents the ease of bending (flexibility) of the coating 12, and is an index of the brittleness of the coating 12.
- the EIT of the coating 12 is preferably adjusted to 4300 MPa or less, more preferably 4200 MPa or less, and even more preferably 4100 MPa or less.
- the EIT of the coating 12 is preferably adjusted to 3400 MPa or more, more preferably 3500 MPa or more.
- EIT is a value corresponding to the Young's modulus measured in accordance with ISO-14477-1 using the same apparatus as in the case of HM described above, and when the indenter is pushed into the coating 12. It is the Young's modulus of the coating 12 itself, which is calculated by measuring the ease of return of the indentation (elastic modulus). However, as with HM, it is a value measured with a maximum test load of 1 mN.
- the thickness (t) of the coating 12 of this embodiment is appropriately adjusted. Specifically, the thickness (t) is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more. This is because if the thickness is too thin, the effect of preventing oligomer precipitation cannot be exhibited. On the other hand, if the thickness is too thick, the planarity of the sheet 10 may be impaired. For this reason, the thickness t of the coating 12 is preferably 1.5 ⁇ m or less, more preferably 1.2 ⁇ m or less.
- the value of the bending resistance test (crack resistance 1) of the sheet 10 varies depending on the thickness t of the coating 12 and the type and thickness of the film substrate 11, but is preferably adjusted to 2 mm or less.
- the crack resistance of the coating 12 can be improved by adjusting the value of the bending resistance test to a predetermined value or less.
- the value of the bending resistance test is a value measured by a cylindrical mandrel method in accordance with JIS-K5600-5-1 (1999).
- the film 12 of this embodiment can be formed by irradiating the surface of the film substrate 11 with ionizing radiation at a predetermined exposure amount and modifying at least a part of the surface of the film substrate 11.
- ionizing radiation at a predetermined exposure amount
- the film substrate 11 is prepared.
- the film substrate 11 for example, a transparent polyester film or the like is used.
- the film substrate 11 may be subjected to an easy adhesion treatment on the surface thereof.
- the thickness of the film substrate 11 is not particularly limited.
- the prepared film substrate 11 is irradiated with ultraviolet rays.
- the ultraviolet irradiation surface may be the easy adhesion treatment surface of the film substrate 11 or a non-easy adhesion treatment surface.
- the inventors irradiate the film substrate 11 with ultraviolet rays at a predetermined exposure amount or more, whereby at least a part of the ultraviolet irradiation portion of the film substrate 11 is surface-modified. It was found that the coating film 12 for preventing oligomer precipitation from the outside to the outside can be formed as a coating film different from the film substrate 11.
- the “oligomer” is mainly composed of a trimer component of a polymer constituting the film substrate 11 among low molecular weight substances that crystallize after heat treatment and precipitate on the surface of the film substrate 11. It is defined as a thing. “Preventing oligomer precipitation” means that the film substrate 11 is heated at 150 ° C. for 1 hour, and then the surface of the film substrate 11 on which the film 12 is formed is observed with a 200 ⁇ microscope. This means that there are less than 50 precipitates, preferably 20 or less, more preferably 10 or less per field of view (area 0.5 mm 2 ) and equivalent circle diameter of 2 ⁇ m ⁇ or more.
- an ultraviolet lamp for example, ultraviolet rays are generated in an emission wavelength region of 100 to 500 nm, preferably 200 to 450 nm, and irradiated with a predetermined exposure amount.
- the ultraviolet lamp include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a carbon arc, a xenon arc, and a metal halide lamp.
- an ultraviolet lamp for example, a high-pressure mercury lamp, an electrodeless lamp, etc.
- a peak output at 250 to 320 nm in addition to 360 to 370 nm can be used. It is desirable to have a peak (maximum peak) at 360 to 370 nm that maximizes the lamp output (w / 10 nm) within the emission wavelength range described above, but it has a maximum peak at 250 to 320 nm. Also good. 360 to 370 nm and 250 to 320 nm include not only one peak but also two or more peaks. By using a light beam having a peak (including a maximum peak) in such a specific wavelength region, the effect of preventing precipitation of oligomers imparted to the formed film 12 is further improved.
- Integrated irradiation dose of ultraviolet rays at the exposure amount for example, 1500 mJ / cm 2 or more, preferably 2000 mJ / cm 2 or more, more preferably 2,500 mJ / cm 2 or more.
- irradiation preferably 30000mJ / cm 2 or less, more preferably 25000mJ / cm 2 following exposure can do. It is not necessary to irradiate this amount at a time, and it is possible to irradiate a small exposure amount in several degrees. By irradiating the predetermined exposure amount in several times, damage to the film substrate 11 can be reduced even when the integrated exposure amount is the same as compared with the case of irradiating a large exposure amount at a time.
- the ultraviolet irradiation may be performed only on one surface of the film substrate 11 or on both surfaces.
- the irradiation exposure amount may be changed for each surface.
- the film base 11 is irradiated with ultraviolet rays at a predetermined exposure amount or more. Thereby, at least a part of the ultraviolet irradiation portion of the film substrate 11 is modified, and the coating 12 is formed here. Since the formed coating 12 has an appropriate surface hardness and thickness as described above, precipitation of oligomers from the inside of the film base 11 to the surface of the film base 11 is effectively prevented. Therefore, according to this embodiment, compared with the conventional method including the factor which deteriorates productivity, such as preparation of a separate paint, application
- the surface hardness and thickness t of the coating 12 to be formed are appropriately adjusted, crack resistance and blocking resistance required when the sheet 10 of this embodiment is used as a base film for optical applications.
- various performances such as solvent resistance and wettability improvement can be satisfied.
- ⁇ Laminate> 2 and 3 each include the sheet 10 shown in FIG. 1 described above.
- the case where the film 10 has the coating film 12 on one surface of the film substrate 11 is illustrated as the sheet 10.
- a first functional layer 22 to which various functions are imparted is laminated on the surface opposite to the coating 12 of the sheet 10.
- the first functional layer 22 include a single layer film or a multilayer film such as a hard coat layer and an antireflection layer.
- the second functional layer 24 such as the above-described adhesive layer or transparent conductive layer is formed on the surface of the coating film 12 of the sheet 10.
- the first functional layer 22 shown in FIG. 2 may be further laminated on the surface of the sheet 10 opposite to the coating 12.
- the hard coat layer is provided to increase the surface hardness of the laminate 20 and prevent the surface from being scratched. Therefore, when a hard coat layer is used as the first functional layer 22, the surface hardness of the hard coat layer is preferably H or higher, more preferably 2H or higher, and further preferably 3H or higher.
- the value of the surface hardness is indicated by a pencil scratch value (pencil hardness) measured by a method according to JIS-K5400 (1990).
- the hard coat layer is made of a resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin.
- a resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin.
- an ionizing radiation curable resin because it can exhibit hard coat properties such as surface hardness.
- thermoplastic resins and thermosetting resins include polyester resins, acrylic resins, acrylic urethane resins, polyester acrylate resins, polyurethane acrylate resins, epoxy acrylate resins, urethane resins, and epoxy resins.
- ionizing radiation curable resin a photopolymerizable prepolymer that is crosslinked and cured by irradiation with ionizing radiation (ultraviolet rays or electron beams) can be used.
- ionizing radiation ultraviolet rays or electron beams
- a photopolymerizable prepolymer described later may be used alone, or two or more kinds may be used in combination.
- the photopolymerizable prepolymer includes a cationic polymerization type and a radical polymerization type.
- Examples of the cationic polymerization type photopolymerizable prepolymer include epoxy resins and vinyl ether resins.
- Examples of the epoxy resin include bisphenol epoxy resin, novolac epoxy resin, alicyclic epoxy resin, and aliphatic epoxy resin.
- an acrylic prepolymer (hard prepolymer) having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is hard coat property. It is particularly preferably used from the viewpoint of
- acrylic prepolymers examples include urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate, and silicone acrylate.
- the urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate by reaction with (meth) acrylic acid.
- polyester acrylate-based prepolymer include esterification of a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or a polyvalent carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to an acid with (meth) acrylic acid.
- the epoxy acrylate prepolymer can be obtained, for example, by esterification by a reaction of an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac epoxy resin with (meth) acrylic acid.
- the acrylic prepolymer can be used alone, it is preferable to add a photopolymerizable monomer in order to impart various performances such as improvement of cross-linking curability and adjustment of curing shrinkage.
- photopolymerizable monomer examples include monofunctional acrylic monomers (for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate, etc.), bifunctional acrylic monomers (for example, 1,6-hexanediol diacrylate).
- monofunctional acrylic monomers for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate, etc.
- bifunctional acrylic monomers for example, 1,6-hexanediol diacrylate
- Neopentyl glycol diacrylate diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, etc.
- trifunctional or higher acrylic monomers eg dipentaerythritol hexaacrylate, trimethylpropane triacrylate, pentaerythritol tris
- Acrylate includes not only acrylate but also methacrylate. These photopolymerizable monomers may be used alone or in combination of two or more.
- the hard coat layer is formed by being cured by irradiation with ultraviolet rays
- a photopolymerization initiator in addition to the above-mentioned photopolymerizable prepolymer and photopolymerizable monomer, a photopolymerization initiator, a photopolymerization accelerator, and ultraviolet sensitization are used. It is preferable to add additives such as an agent.
- photopolymerization initiator for radical polymerization type photopolymerizable prepolymers and photopolymerizable monomers, for example, acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, ⁇ -acyloxime ester, thioxanthones, etc. Is mentioned.
- Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions, and aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, The compound which consists of anions, such as hexafluoroarsenate, is mentioned. These may be used alone or in combination of two or more.
- Examples of the photopolymerization accelerator include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.
- Examples of the ultraviolet sensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
- the blending amount of these additives is usually selected in the range of 0.2 to 10 parts by weight with respect to the total of 100 parts by weight of the above-mentioned photopolymerizable prepolymer and photopolymerizable monomer.
- an additive component may be appropriately blended as necessary.
- additive components include surface conditioners, lubricants, colorants, pigments, dyes, fluorescent brighteners, flame retardants, antibacterial agents, fungicides, UV absorbers, light stabilizers, heat stabilizers, and antioxidants. , Plasticizers, leveling agents, flow regulators, antifoaming agents, dispersants, storage stabilizers, crosslinking agents, silane coupling agents, and the like.
- the thickness of the hard coat layer is preferably about 0.1 to 30 ⁇ m. More preferably, it is 0.5 to 15 ⁇ m, and further preferably 2 to 10 ⁇ m. By setting the thickness to 0.1 ⁇ m or more, sufficient surface hardness (hard coat property) can be exhibited also on the hard coat layer side.
- the antireflection layer is provided on the surface of the hard coat layer, and is provided to reduce reflection on the surface portion of the hard coat layer and to improve the total light transmittance of the entire laminate 20.
- the refractive index of the hard coat layer it is conceivable to design the refractive index of the hard coat layer to be small.
- the surface of the hard coat layer has a refractive index lower than that of the hard coat layer. It is preferable to form the antireflection layer with a small thickness.
- the antireflection layer may be made of a material having a lower refractive index than that of the hard coat layer.
- a material having a lower refractive index than that of the hard coat layer For example, silicon-based resin, fluorine-based resin, metal oxide sol, and metal oxide fine particles, preferably porous or hollow. In which fine metal oxide particles are added. Moreover, what added the said metal oxide microparticles
- the metal oxide sol examples include silica and alumina sol.
- silica sol is preferably used from the viewpoint of refractive index, fluidity, and cost.
- the metal oxide sol refers to a material in which the Tyndall phenomenon cannot be observed due to the presence of the metal oxide, and refers to a so-called uniform solution. For example, even a material generally called colloidal silica sol is not included in the metal oxide sol in this embodiment as long as the Tyndall phenomenon is observed.
- Such a metal oxide sol can be prepared by hydrolyzing a metal alkoxide such as tetraethoxysilane, methyltrimethoxysilane, zirconia propoxide, aluminum isopropoxide, titanium butoxide, titanium isopropoxide.
- a metal alkoxide such as tetraethoxysilane, methyltrimethoxysilane, zirconia propoxide, aluminum isopropoxide, titanium butoxide, titanium isopropoxide.
- the solvent for the metal oxide sol include methanol, ethanol, isopropanol, butanol, acetone, and 1,4-dioxane.
- the metal oxide fine particles are those obtained by pulverizing the above-mentioned metal oxide, and examples thereof include silica fine particles and alumina fine particles. Among these, silica fine particles are preferably used from the viewpoint of refractive index, fluidity, and cost. Further, the shape of the metal oxide fine particles is not particularly limited, but porous or hollow metal oxide fine particles having a low refractive index are preferably used.
- the average particle diameter of the metal oxide fine particles is not particularly limited as long as the above conditions are satisfied, but is preferably in the range of 40 to 100 nm.
- the average particle diameter of the metal oxide fine particles is more preferably in the range of 40 to 70 nm.
- the mixing ratio of the metal oxide sol and the metal oxide fine particles is not particularly limited, but the metal oxide fine particles are preferably 5 parts by weight with respect to 100 parts by weight of the metal oxide component in the metal oxide sol. Above, more preferably 20 parts by weight or more, preferably 200 parts by weight or less, more preferably 100 parts by weight or less.
- the thickness of the antireflection layer preferably satisfies the following equation based on the theory of antireflection of light.
- [Expression 1] d (a + l) ⁇ / 4n
- d is the thickness (unit: “nm”) of the antireflection layer
- a is 0 or a positive even number
- ⁇ is the center wavelength of the light to be prevented from being reflected
- n is the refractive index of the antireflection layer.
- it is preferably about 2 ⁇ m or less, more preferably 1 ⁇ m or less, further preferably 0.8 ⁇ m or less, particularly preferably 0.5 ⁇ m or less, and most preferably 0.3 ⁇ m or less.
- each constituent component and other components as necessary are blended, and further, dissolved or dispersed in an appropriate solvent to prepare a coating solution, and the coating is performed.
- the liquid is applied to the sheet 10 by a known method such as roll coating, bar coating, spray coating, air knife coating, die coating, blade coating, spin coating, gravure coating, flow coating, or screen printing. It can be formed by applying and drying sequentially and, if necessary, curing by a necessary curing method.
- the adhesive layer examples include natural rubber-based, recycled rubber-based, chloroprene rubber-based, nitrile rubber-based, elastomer-based adhesives such as styrene / butadiene-based, acrylic-based, polyester-based, epoxy-based, urethane-based, cyanoacrylate-based, etc.
- the synthetic resin adhesive it can be composed of a known adhesive such as an emulsion adhesive.
- the pressure-sensitive adhesive layer generally has a thickness of 5 ⁇ m or more in order to exert adhesiveness.
- Such an adhesive layer is prepared by preparing an adhesive layer coating solution by dissolving or dispersing an adhesive component and, if necessary, a crosslinking agent and other additives in a solvent, and is similar to the above-described antireflection layer. It can be produced by applying and drying on the film 12 of the sheet 10 by a conventionally known coating method. Alternatively, the adhesive layer coating liquid may be applied to a separator or the like, dried, and then laminated on the coating film 12 of the sheet 10.
- the first functional layer 22 described above can have an ultraviolet absorption performance.
- the light transmittance in the range of 350 to 380 nm is about 0.1% to 70%
- weather resistance can be imparted while maintaining the hard coat property.
- an ionizing radiation curable resin is used for the hard coat layer, by adjusting the ultraviolet region where the ionizing radiation curable resin is cured and the absorbing ultraviolet region, the ultraviolet ray is not affected without affecting the curing of the hard coat layer.
- Absorbability can be imparted.
- the transparent conductive layer can be composed of, for example, a generally widely known transparent conductive material or organic conductive material.
- the transparent conductive material include transparent conductive materials such as indium oxide, tin oxide, indium tin oxide, gold, silver, and palladium.
- the organic conductive material include conductive polymers such as polyparaphenylene, polyacetylene, polyaniline, polythiophene, polyparaphenylene vinylene, polypyrrole, polyfuran, polyselenophene, and polypyridine.
- the transparent conductive material which is excellent in transparency and electroconductivity, and which has as a main component any of the indium oxide, tin oxide, or indium tin oxide obtained by comparatively low cost.
- the transparent conductive layer can be formed in a thin film state using the above-described conductive material by a dry process (for example, vacuum deposition method, sputtering method, ion plating method) or a wet process (for example, solution coating method). it can.
- a dry process for example, vacuum deposition method, sputtering method, ion plating method
- a wet process for example, solution coating method
- the thickness of the transparent conductive layer varies depending on the applied material, it cannot be generally stated, but the surface resistivity is set to 1000 ⁇ or less, preferably 500 ⁇ or less. For example, it is preferably 10 nm or more, and more preferably 20 nm or more. In consideration of economy, a range of 80 nm or less, preferably 70 nm or less is suitable. In such a thin film, visible light interference fringes due to uneven thickness of the transparent conductive layer are unlikely to occur. Further, the total light transmittance is usually preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
- a first functional layer 22 in which a transparent hard coat layer and an antireflection layer are sequentially laminated is formed on the opposite side of the sheet 10 from the coating 12, and the first functional layer 22 is transparent on the surface side of the coating 12.
- the laminate 20 having a structure in which the second functional layer 24 composed of a conductive layer is formed can be used as an electrode substrate for an antistatic film, an infrared shielding film, an antireflection film, an electromagnetic shielding film, a touch panel, or the like.
- a first functional layer 22 in which a transparent hard coat layer and an antireflection layer are sequentially laminated is formed on the opposite side of the sheet 10 from the coating 12, and a transparent conductive layer is formed on the surface side of the coating 12.
- a transparent conductive layer is formed on the surface side of the coating 12.
- the touch panel 5 shown in FIG. 4 is a resistive film type touch panel mounted on the front surface of a display element 9 such as a liquid crystal provided in various electronic devices (for example, a mobile phone, a car navigation system, etc.). Each function of the device can be switched by visually checking and selecting the characters, symbols, patterns, and the like displayed on the display element 9 on the rear surface through the touch panel 5 and pressing them with a finger, a dedicated pen, or the like.
- the touch panel 5 of this embodiment includes an upper electrode substrate (first electrode substrate) 52 and a lower electrode substrate (second electrode substrate) 54.
- the upper electrode substrate 52 includes an upper transparent substrate (first transparent substrate) 522.
- An upper transparent conductive film (first transparent conductive film) 524 is formed on the lower surface of the upper transparent substrate 522.
- the lower electrode substrate (second electrode substrate) 54 includes a lower transparent substrate (second transparent substrate) 542.
- a lower transparent conductive film (second transparent conductive film) 544 is formed on the upper surface of the lower transparent substrate 542.
- either the upper electrode substrate 52 side or the lower electrode substrate 54 side may be a movable electrode.
- the upper electrode substrate 52 is a movable electrode and the lower electrode substrate 54 is fixed (not fixed). The case of using a movable electrode is illustrated.
- the outer peripheral portions of the lower surface of the upper electrode substrate 52 and the upper surface of the lower electrode substrate 54 are bonded together via a substantially frame-shaped spacer 56.
- the upper transparent conductive film 524 of the upper electrode substrate 52 and the lower transparent conductive film 544 of the lower electrode substrate 54 are arranged to face each other with a predetermined gap.
- a plurality of dot-like spacers 58 are arranged at predetermined intervals as necessary. Note that the spacer 58 may be disposed as necessary, and a configuration in which the spacer 58 is not disposed is also possible.
- a pair of electrodes are formed on both ends of the upper and lower transparent conductive films 524 and 544, respectively.
- a pair of upper electrodes (not shown) formed on the upper transparent conductive film 524 and a pair of lower electrodes (not shown) formed on the lower transparent conductive film 544 are arranged in a direction crossing each other. Has been.
- a separator (not shown) may be attached to the lower surface of the lower electrode substrate 54 via the adhesive layer 7.
- the separator (not shown) of the touch panel 5 of this embodiment is peeled to expose the adhesive layer 7 and the display element 9. Make contact with the front face. Thereby, a color liquid crystal display element with a touch panel can be formed.
- this liquid crystal display element with a touch panel when the user presses the upper surface of the upper electrode substrate 52 with a finger or a pen while visually recognizing the display of the display element 9 disposed on the back surface of the touch panel 5, the upper electrode substrate 52 bends.
- the upper transparent conductive film 524 in contact with the pressed portion contacts the lower transparent conductive film 544.
- the pressed position is detected by electrically detecting this contact via the pair of upper and lower electrodes described above.
- the second functional layer 24 (transparent conductive layer) of the stacked body 20 corresponds to the upper transparent conductive film 524.
- the lower transparent substrate 542 of the lower electrode substrate 54 as a fixed electrode is made of, for example, glass.
- the above-described laminate 20 in addition to the movable electrode, can also be used for the fixed electrode (lower electrode substrate 54). Thereby, it can be set as the lighter, thinner, and hard-to-break touch panel.
- the prepared film a was sent out at a speed of 2 m / min, and ultraviolet rays (light emission wavelength) generated at an output of 120 W / cm 2 using a high-pressure mercury lamp to the surface of the easy-adhesion layer of the film a being sent out.
- ultraviolet rays light emission wavelength
- Peak wavelength 360 to 370 nm (maximum)
- 250 to 260 nm, 300 to 320 nm was irradiated for about 6 seconds
- irradiation exposure dose about 960 mJ / cm 2 ).
- This irradiation cycle was set to “1 pass”, and ultraviolet rays were passed in the number of passes shown in Table 1 to obtain a film sample.
- the cross section of the obtained film sample was observed using SEM (Scanning Electron Microscope, scanning electron microscope). 5 to 10 show SEM images before ultraviolet irradiation (0 pass), after 1 pass, after 2 pass, after 3 pass, after 10 pass, and after 20 pass. As shown in FIGS. 6 to 10, it was confirmed that a film was formed on the ultraviolet irradiation surface of the film a when the ultraviolet rays were irradiated. In addition, as shown in FIG. 5, before irradiating with an ultraviolet-ray, naturally the film is not formed in the film a.
- FIG. 11 and FIG. 12 show SEM images before ultraviolet irradiation (0 pass) and after 3 passes.
- FIG. 12 when ultraviolet rays were irradiated, it was confirmed that a film was formed on the ultraviolet irradiation surface of the film b.
- FIG. 11 before irradiating with an ultraviolet-ray, naturally the film is not formed in the film b.
- HM Martens hardness
- EIT indentation elastic modulus
- Blocking resistance As in (2) above, a hard coat layer was formed on the film sample. Next, the ultraviolet irradiation surface of the film sample prepared separately was superimposed on the hard coat layer surface of the film sample on which the hard coat layer was formed. Next, both film samples were sandwiched between glass plates, and a weight of about 2 kg was placed and left in an atmosphere at 50 ° C. for 24 hours. Next, the overlapping surface was visually observed to confirm the occurrence of Newton rings, and then both were peeled off.
- the refractive index at 633 nm at 25 ° C. was measured using an automatic wavelength scanning ellipsometer (M-150, manufactured by JASCO Corporation) on the ultraviolet-irradiated surface of the film sample.
- a 125 ⁇ m thick PET film (A4350, manufactured by Toyobo Co., Ltd., with an easy adhesive layer)
- a 125 ⁇ m thick PET film (O300E, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., with an easy adhesive layer)
- a thickness A 125 ⁇ m thick PET film (OFW, manufactured by Teijin Limited, with an easy-adhesion layer) was irradiated with ultraviolet rays in the same manner as in Experimental Examples 1 to 18 described above, and the same evaluation was observed. It could be confirmed.
- electrodeless lamps A to D were used instead of the high pressure mercury lamp as the ultraviolet irradiation source, and the ultraviolet rays were irradiated under the same conditions as in the above experimental examples 1 to 18, and the same evaluation was performed. As a result, a high pressure mercury lamp was used. It was confirmed that there was a tendency similar to the case.
- the ultraviolet rays generated using each lamp were as follows.
- Lamp A emission wavelength range: 220 to 440 nm, peak wavelength: 360 to 370 nm (maximum), 250 to 270 nm, 310 to 320 nm
- lamp B emission wavelength range: 200 to 440 nm, peak wavelength: 360 to 370 nm (maximum)) 250 to 260 nm, 310 to 320 nm
- lamp C emission wavelength range: 250 to 450 nm, peak wavelength: 350 to 390 nm (maximum), 390 to 450 nm
- lamp D emission wavelength range: 250 to 450 nm, peak wavelength: 360 to 370 nm (maximum), 400 to 410 nm (maximum)).
- Example 19 First, an ultraviolet curable acrylic hard coat layer having a thickness of 6 ⁇ m was formed on the surface opposite to the ultraviolet irradiation surface of the film sample obtained in Experimental Example 4 (ultraviolet 3 pass irradiation). Next, an antireflection layer (refractive index: 1.36) having a thickness of about 0.1 ⁇ m was formed on the hard coat layer so as to have a minimum reflectance near a wavelength of 550 nm. Next, an ITO film having a thickness of about 20 nm was formed on the ultraviolet irradiation surface of the film sample by a sputtering method.
- the upper electrode substrate 52 shown in FIG. 4 was configured with the first laminate sample thus obtained.
- the second laminate sample as the lower electrode substrate 54 shown in FIG. It was produced by cutting out into a size (rectangle of 87.3 mm length ⁇ 64.0 mm width).
- an ionizing radiation curable resin (DotCure TR5903: Taiyo Ink Co., Ltd.) is printed as a spacer coating solution on the surface of the second laminate sample having the ITO film by screen printing, and then irradiated with ultraviolet light using a high-pressure mercury lamp. Irradiation was performed, and spacers 58 having a diameter of 50 ⁇ m and a height of 8 ⁇ m were arranged at intervals of 1 mm.
- the first laminate sample and the second laminate sample in which the spacers 58 are arranged are arranged so that the ITO films of both samples face each other with a predetermined gap, and both surfaces are bonded to each other with a thickness of 30 ⁇ m and a width of 3 mm.
- the edge was adhere
- the bonded portion of both samples was outside the display surface area of the touch panel sample.
- the interference unevenness was not noticeable, and as a result, it was confirmed that the operation could be performed satisfactorily.
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Abstract
Description
上記発明において、紫外線を複数回に分けて照射することができる。
上記発明において、紫外線として、波長域が200~450nmで、360~370nm及び250~320nmにピーク出力特性を持つ光線を用いることができる。
上記発明において、マルテンス硬さ及び押し込み弾性率の値は、最大試験荷重が1mNの条件での測定することができる。
図1に示すように、本実施形態に係るシート10は、例えば透明ポリエステルフィルムなどのフィルム基材11を有する。本実施形態では、フィルム基材11表面の少なくとも一部が改質されており、ここに被膜12が形成されている。この被膜12が、本実施形態ではフィルム基材11の内部からフィルム基材11表面へのオリゴマーの析出を防止する機能を司る。
本実施形態の被膜12は、フィルム基材11の表面に電離放射線を所定の露光量で照射し、フィルム基材11表面の少なくとも一部を改質させることによって形成することができる。以下では、電離放射線として紫外線を用いる場合を例示し、シート10の製造方法の一例を説明する。
本実施形態では、発光波長域が上述した範囲にあり、少なくとも360~370nmにピーク出力(ピーク強度)を発生させる紫外線ランプを用いることが望ましい。また、発光波長域が上述した範囲にあり、360~370nmに加えて、さらに250~320nmにもピーク出力を発生させる紫外線ランプ(例えば高圧水銀灯、無電極ランプなど)を用いることもできる。360~370nmに、上述した発光波長域内でのランプ出力(w/10nm)が最大となるピーク(最大ピーク)を有することとなるものが望ましいが、250~320nmに最大ピークを有するものであってもよい。360~370nmや250~320nmには存在すべきピークは1つに限らず、2つ以上の場合も含まれる。こうした特定の波長域にピーク(最大ピークを含む)を持つ光線を用いることにより、形成される被膜12に対して付与されるオリゴマーの析出防止効果が一層向上する。
図2及び図3に示す積層体20は、何れも、上述した図1に示すシート10を有する。以下の説明では、シート10として、フィルム基材11の一方の面に被膜12を有する場合を例示する。
ハードコート層は、積層体20の表面硬度を高くし、表面に傷が発生することを防止するために設けられる。従って、第1機能層22としてハードコート層を用いる場合の当該ハードコート層の表面硬度は、好ましくはH以上、より好ましくは2H以上、さらに好ましくは3H以上である。表面硬度の値は、JIS-K5400(1990)に準拠した方法で測定した鉛筆引っかき値(鉛筆硬度)で示される。
反射防止層は、ハードコート層の表面に設けられ、ハードコート層の表面部分での映り込みを減少させ、積層体20全体の全光線透過率を向上させるために設けられる。表面部分での映り込みを防止するためにハードコート層の屈折率を小さく設計することも考えられる。ところが、屈折率が小さくなるようにハードコート層を設計すると、ハードコート層のハードコート性が低下することがあるので、ハードコート層の表面に、ハードコート層の屈折率より低い屈折率を持つ反射防止層を薄い厚みで形成することが好ましい。
[数1] d=(a十1)λ/4n
ここで、dは反射防止層の厚み(単位は「nm」)、aは0又は正の偶数、λは反射を防止しようとする光の中心波長、nは反射防止層の屈折率である。具体的には、例えば2μm程度以下が好ましく、より好ましくは1μm以下、さらに好ましくは0.8μm以下、特に好ましくは0.5μm以下、最も好ましくは0.3μm以下である。反射防止層の厚みが厚くなると、厚みムラに起因する干渉ムラが発生し難くなる反面、下面に設けられるハードコート層のハードコート性が発揮され難くなる。
粘着層としては、例えば、天然ゴム系、再生ゴム系、クロロプレンゴム系、ニトリルゴム系、スチレン・ブタジエン系などのエラストマー粘着剤、アクリル系、ポリエステル系、エポキシ系、ウレタン系、シアノアクリレート系などの合成樹脂粘着剤のほか、エマルジョン系粘着剤などの公知の粘着剤で構成することができる。粘着層は、粘着性を発揮させるために厚み5μm以上にするのが一般的である。このような粘着層は、粘着性成分、および必要に応じて加えた架橋剤や他の添加剤を溶剤に溶解または分散して粘着層用塗布液を調製し、上述した反射防止層と同様の従来公知のコーティング方法により、シート10の被膜12上に塗布、乾燥することにより作製することができる。また、上記粘着層用塗布液をセパレーター等に塗布、乾燥した後、シート10の被膜12上にラミネートすることにより作製することもできる。
透明導電層としては、例えば一般的に広く知られた透明導電性材料や有機導電性材料などで構成することができる。透明導電性材料としては、例えば、酸化インジウム、酸化錫、酸化インジウム錫、金、銀、パラジウムなどの透明導電性物質が挙げられる。有機導電性材料としては、例えばポリパラフェニレン、ポリアセチレン、ポリアニリン、ポリチオフェン、ポリパラフェニレンビニレン、ポリピロール、ポリフラン、ポリセレノフェン、ポリピリジン等の導電性高分子が挙げられる。中でも、透明性と導電性に優れ、比較的低コストに得られる酸化インジウム、酸化錫又は酸化インジウム錫のいずれかを主成分とした透明導電性材料で構成されていることが好ましい。
図4に示すタッチパネル5は、各種電子機器(例えば携帯電話やカーナビ等)に設けられる液晶等の表示素子9の前面に装着される抵抗膜方式のタッチパネルである。このタッチパネル5を通して背面の表示素子9に表示された文字や記号、絵柄等の視認や選択を行い、指や専用ペン等で押圧操作することによって、機器の各機能の切換えを行うことができる。
まず、フィルム基材11として、厚さ125μmのPETフィルム(U34、東レ社製、易接着層あり。以下「フィルムa」とする)を準備する。
フィルム基材11として、厚さ100μmのPETフィルム(T-60、東レ社製、易接着層なし。以下「フィルムb」とする)を用いた以外は、実験例1~6と同様の条件で紫外線照射を行い、フィルム試料を得た。
フィルム基材11として、厚さ125μmのPETフィルム(A4300、東洋紡績社製、易接着層あり。以下「フィルムc」とする)を用いた以外は、実験例1~6と同様の条件で紫外線照射を行い、フィルム試料を得た。
上記実験例1~18により得られたフィルム試料について、下記特性を評価した。結果を表1に示す。
いずれも超微小硬さ試験装置(フィッシャー・インストルメンツ社、商品名:フィッシャー・スコープ・HM2000)を用い、ISO-14577-1に準拠した方法により後述の測定条件で、得られたフィルム試料に形成された被膜の表面(紫外線照射をしていない試料の場合はフィルム面)の硬さやヤング率を測定した。HM及びEITの何れも測定条件を、圧子形状:ビッカース圧子(a=136°)、測定環境:温度20℃・相対湿度60%、最大試験荷重:1mN、荷重速度:1mN/20秒、最大荷重クリープ時間:5秒、除荷速度:1mN/20秒、とした。
まず、得られたフィルム試料の紫外線照射面とは反対面に、厚さ6μmの紫外線硬化型アクリル系ハードコート層を形成した。次に、ハードコート層を形成したフィルム試料を150℃のオーブンに投入し、1時間後に取り出した。次に、取り出したフィルム試料の紫外線照射面(紫外線照射をしていない試料の場合はフィルム面)を顕微鏡(200倍)で観察し、10視野当たり(面積0.5mm2 )に、円相当径で2μmφ以上の析出物が10個以下であった(オリゴマーの析出が全く認められなかった)ものを「○」、上記析出物が20個を超え50個未満であった(オリゴマーの析出がやや認められたが問題なしと考えられる)ものを「△」、上記析出物が50個を超えた(オリゴマーの析出が認められた)ものを「×」として評価した。
まず、上記(2)と同様に、得られたフィルム試料にハードコート層を形成した。次に、ハードコート層を形成したフィルム試料に対し、ヘーズメーター(NDH2000、日本電色社)を用いてヘーズ値「%」(JIS-K7136:2000)を測定した。その後、ヘーズ値測定後のフィルム試料を上記(2)と同様に150℃のオーブンに投入して1時間後に取り出した。次に、取り出したフィルム試料に対して上記同様にヘーズ値を測定した。
(4-1)マンドレル
JIS-K5600-5-1(1999)に準拠した耐屈曲性(円筒形マンドレル法)に基づき、直径が2mmの鉄棒に、フィルム試料を被膜が外側になるように巻き付け、その巻き付けた部分の被膜にクラックを生じるか否かを目視で観察する。その結果、クラックが確認できなかったものを「○」、クラックを確認できたものを「×」として評価した。
(4-2)折り曲げ
フィルム試料を被膜が外側になるように2つに折り曲げ、その折り曲げた部分の被膜にクラックを生じるか否かを目視で観察する。その結果、クラックが確認できなかったものを「○」、クラックを確認できたものを「×」として評価した。
まず、上記(2)と同様に、フィルム試料にハードコート層を形成した。次に、ハードコート層を形成したフィルム試料のハードコート層面に、別途用意したフィルム試料の紫外線照射面を重ね合わせた。次に、両フィルム試料をガラス板で挟み込み、約2kgの重りを載せて50℃の雰囲気下に24時間放置した。次に、重ね合わせ面を目視により観察しニュートンリングの発生状況を確認した後、両者を剥離した。その結果、剥離前はニュートンリングが発生しておらず、剥離時には剥離音を立てずに軽く剥離されるものを「○」、剥離前は一部ニュートンリングが発生しており、剥離時には小さな剥離音を立てながら剥離されるものを「△」、剥離前は全面にニュートンリングが発生しており、剥離時には大きな剥離音を立てて剥離されるものを「×」として評価した。
フィルム試料の紫外線照射面に対し、自動波長走査型エリプソメーター(M-150、日本分光社製)を用い、25℃における633nmでの屈折率を測定した。
まず、上記(2)と同様に、フィルム試料にハードコート層を形成した。次に、ハードコート層を形成したフィルム試料の紫外線照射面を、メチルエチルケトンをしみ込ませた綿布で往復30回擦った。次に、上記(2)と同様にフィルム試料の紫外線照射面を顕微鏡で観察し、オリゴマーの析出が、上記(2)の評価と同程度であったものを「○」、上記(2)の評価よりも悪くなったものを「×」として評価した。なお、各フィルム基材の0pass、1passについては、後述するように、上記(2)の評価が「×」であったため、ここでは評価しなかった。
(8)耐熱耐湿性(オリゴマー析出防止性、顕微鏡)
まず、実験例13~18で得られたフィルム試料に、上記(2)と同様にしてハードコート層を形成した。
次に、ポリエステルフィルムの一方の面にハードコート層、もう一方の面にアンチブロッキング層を有するハードコートフィルム(KBフィルムGSAB:きもと社)のアンチブロッキング層上に、乾燥厚み約20μmとなるようにアクリル系粘着剤層を設けた。次いで、当該粘着剤層とハードコート層を形成した実験例13~18のフィルム試料の被膜面とを貼り合わせ、150℃の環境に2時間放置した後、60℃、95%RHの環境(恒温恒湿器)に240時間放置し、取り出した。そして、ハードコートフィルム側から、上記(2)と同様にして顕微鏡で観察し同様の評価を行った。
なお、被膜の上層に、粘着層を有する場合でも、紫外線を2pass以上照射した場合には、高温高湿環境においてもオリゴマーの析出を防止する効果が確認された。
また、紫外線照射源として、高圧水銀灯に代え、無電極ランプA~Dを用い、上述した実験例1~18と同条件で紫外線照射を行い、同様の評価を行ったところ、高圧水銀灯を用いた場合と同様の傾向があることが確認できた。
各ランプを用いて発生させた紫外線は以下のとおりであった。ランプA(発光波長域:220~440nm、ピーク波長:360~370nm(最大)、250~270nm、310~320nm)、ランプB(発光波長域:200~440nm、ピーク波長:360~370nm(最大)、250~260nm、310~320nm)、ランプC(発光波長域:250~450nm、ピーク波長:350~390nm(最大)、390~450nm)、ランプD(発光波長域:250~450nm、ピーク波長:360~370nm(最大)、400~410nm(最大))。
まず、実験例4(紫外線3pass照射)で得られたフィルム試料の紫外線照射面とは反対面に、厚さ6μmの紫外線硬化型アクリル系ハードコート層を形成した。次に、ハードコート層の上に、波長550nmの付近で最小反射率となるように厚さ約0.1μmの反射防止層(屈折率:1.36)を形成した。次に、フィルム試料の紫外線照射面に、厚み約20nmのITO膜をスパッタリング法で形成した。
Claims (14)
- フィルム基材の少なくとも一部が改質されてなる被膜を持つシートを製造する方法であって、前記フィルム基材に紫外線を照射し、前記被膜を形成させることを特徴とするシートの製造方法。
- 請求項1記載のシートの製造方法において、
前記紫外線を1500mJ/cm2 以上の露光量で照射することを特徴とするシートの製造方法。 - 請求項2記載のシートの製造方法において、
前記紫外線を複数回に分けて照射することを特徴とするシートの製造方法。 - 請求項1~3の何れか一項記載のシートの製造方法において、
前記紫外線として、発光波長域が200~450nmであり、360~370nmにピーク出力特性を持つ光線を用いることを特徴とするシートの製造方法。 - 請求項4記載のシートの製造方法において、
前記紫外線は、さらに250~320nmにピーク出力特性を持つことを特徴とするシートの製造方法。 - 請求項1~5の何れか一項記載のシートの製造方法において、
前記フィルム基材として、透明ポリエステルフィルムを用いることを特徴とするシートの製造方法。 - フィルム基材表面へのオリゴマーの析出を防止する方法であって、前記フィルム基材に紫外線を照射し、前記フィルム基材の少なくとも一部を改質させ、被膜を形成させることを特徴とするオリゴマーの析出防止方法。
- フィルム基材の少なくとも一部が改質されてなる被膜を持つシートであって、
前記被膜は、前記フィルム基材に紫外線を照射することにより形成されることを特徴とするシート。 - 請求項8記載のシートにおいて、
前記被膜は、マルテンス硬さが200N/mm2 以上、押し込み弾性率が4300MPa以下、厚みが0.1μm以上であることを特徴とするシート。 - 請求項8又は9記載のシートにおいて、
前記マルテンス硬さ及び前記押し込み弾性率の値は、最大試験荷重が1mNの条件での測定値であることを特徴とするシート。 - 請求項8~10の何れか一項記載のシートの表面に機能層を有する積層体。
- 請求項11記載の積層体において、
前記機能層が、前記シートの前記被膜側に積層された粘着層を含むことを特徴とする積層体。 - 請求項11記載の積層体において、
前記機能層が、前記シートの前記被膜とは反対側に積層されたハードコート層を含むことを特徴とする積層体。 - 第1の透明導電膜が第1の透明基板に形成された第1の電極基板と、
第2の透明導電膜が前記第1の透明導電膜と所定の間隙を空けて対向するように第2の透明基板に形成された第2の電極基板とを、有するタッチパネルであって、
前記第1の透明基板及び前記第2の透明基板のうち何れか一方の可動側電極基板が、請求項13記載の積層体を含むことを特徴とするタッチパネル。
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CN200980153179.1A CN102300910B (zh) | 2008-11-28 | 2009-11-25 | 具有被膜的片材及其制造方法 |
US13/129,142 US20110216029A1 (en) | 2008-11-28 | 2009-11-25 | Sheet with reformed layer and manufacturing method thereof |
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JP (1) | JP5872770B2 (ja) |
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WO (1) | WO2010061851A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2013237157A (ja) * | 2012-05-11 | 2013-11-28 | Kuraray Co Ltd | 樹脂成形体の製造方法、樹脂成形体、およびモールド |
JP2016031558A (ja) * | 2014-07-25 | 2016-03-07 | 大日本印刷株式会社 | 多層基材及びタッチパネル画像表示装置 |
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5464573A (en) * | 1977-11-01 | 1979-05-24 | Agency Of Ind Science & Technol | Method of treating the surface of molded product of vinyl chloride resin |
JPS57174322A (en) * | 1981-04-21 | 1982-10-27 | Teijin Ltd | Production of crosslinked polyester molding |
JPS60245643A (ja) * | 1984-05-21 | 1985-12-05 | Shin Etsu Chem Co Ltd | 表面改質合成樹脂成形品 |
JPS60245644A (ja) * | 1984-05-21 | 1985-12-05 | Shin Etsu Chem Co Ltd | 塩化ビニル系樹脂成形品 |
JPS63308042A (ja) * | 1987-03-16 | 1988-12-15 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニー | 半結晶性ポリマーの表面改質方法および該改質表面を有する半結晶性ポリマー物品 |
JPH0713695A (ja) * | 1993-04-28 | 1995-01-17 | Nissha Printing Co Ltd | 透明タッチパネル |
JP2002103504A (ja) * | 2000-10-03 | 2002-04-09 | Nitto Denko Corp | 透明導電性フィルム |
JP2004181707A (ja) * | 2002-12-02 | 2004-07-02 | Mitsubishi Polyester Film Copp | 積層ポリエステルフィルム |
JP2005132897A (ja) * | 2003-10-29 | 2005-05-26 | Nitto Denko Corp | ハードコートフィルム |
JP2006053424A (ja) * | 2004-08-13 | 2006-02-23 | Fuji Xerox Co Ltd | 半導電性ローラ及びそれを用いた画像形成装置 |
JP2006117804A (ja) * | 2004-10-21 | 2006-05-11 | Kokuritsu Iyakuhin Shokuhin Eisei Kenkyusho | 軟質プラスティック材料の表面改質方法及び表面を改質した軟質プラスティック材料 |
WO2007052485A1 (ja) * | 2005-10-31 | 2007-05-10 | Nitto Denko Corporation | 導電性積層フィルム、タッチパネル用電極板、タッチパネルおよび導電性積層フィルム用粘着剤 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6080132A (ja) * | 1983-10-07 | 1985-05-08 | Fuji Photo Film Co Ltd | フレキシブル磁気デイスク保護層の形成方法 |
US4879176A (en) * | 1987-03-16 | 1989-11-07 | Minnesota Mining And Manufacturing Company | Surface modification of semicrystalline polymers |
JP2574009B2 (ja) * | 1988-09-05 | 1997-01-22 | 工業技術院長 | プラスチック成形品の表面改質法 |
JP3569715B2 (ja) * | 1996-07-29 | 2004-09-29 | アークレイ株式会社 | 液状試料を分析するための用具とその製造方法 |
JP4232387B2 (ja) * | 2001-05-29 | 2009-03-04 | 東レ株式会社 | ハードコートフィルム用ポリエステルフィルム |
JP2003237822A (ja) * | 2002-02-15 | 2003-08-27 | Sekisui Jushi Co Ltd | 熱可塑性樹脂バンドおよびその製造方法 |
JP2005135586A (ja) * | 2003-10-28 | 2005-05-26 | Nitto Denko Corp | 透明積層導電性フィルムとその製造方法 |
-
2009
- 2009-11-25 JP JP2010540493A patent/JP5872770B2/ja not_active Expired - Fee Related
- 2009-11-25 KR KR1020117014576A patent/KR20110095915A/ko not_active Application Discontinuation
- 2009-11-25 CN CN200980153179.1A patent/CN102300910B/zh not_active Expired - Fee Related
- 2009-11-25 WO PCT/JP2009/069871 patent/WO2010061851A1/ja active Application Filing
- 2009-11-25 US US13/129,142 patent/US20110216029A1/en not_active Abandoned
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5464573A (en) * | 1977-11-01 | 1979-05-24 | Agency Of Ind Science & Technol | Method of treating the surface of molded product of vinyl chloride resin |
JPS57174322A (en) * | 1981-04-21 | 1982-10-27 | Teijin Ltd | Production of crosslinked polyester molding |
JPS60245643A (ja) * | 1984-05-21 | 1985-12-05 | Shin Etsu Chem Co Ltd | 表面改質合成樹脂成形品 |
JPS60245644A (ja) * | 1984-05-21 | 1985-12-05 | Shin Etsu Chem Co Ltd | 塩化ビニル系樹脂成形品 |
JPS63308042A (ja) * | 1987-03-16 | 1988-12-15 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニー | 半結晶性ポリマーの表面改質方法および該改質表面を有する半結晶性ポリマー物品 |
JPH0713695A (ja) * | 1993-04-28 | 1995-01-17 | Nissha Printing Co Ltd | 透明タッチパネル |
JP2002103504A (ja) * | 2000-10-03 | 2002-04-09 | Nitto Denko Corp | 透明導電性フィルム |
JP2004181707A (ja) * | 2002-12-02 | 2004-07-02 | Mitsubishi Polyester Film Copp | 積層ポリエステルフィルム |
JP2005132897A (ja) * | 2003-10-29 | 2005-05-26 | Nitto Denko Corp | ハードコートフィルム |
JP2006053424A (ja) * | 2004-08-13 | 2006-02-23 | Fuji Xerox Co Ltd | 半導電性ローラ及びそれを用いた画像形成装置 |
JP2006117804A (ja) * | 2004-10-21 | 2006-05-11 | Kokuritsu Iyakuhin Shokuhin Eisei Kenkyusho | 軟質プラスティック材料の表面改質方法及び表面を改質した軟質プラスティック材料 |
WO2007052485A1 (ja) * | 2005-10-31 | 2007-05-10 | Nitto Denko Corporation | 導電性積層フィルム、タッチパネル用電極板、タッチパネルおよび導電性積層フィルム用粘着剤 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013237157A (ja) * | 2012-05-11 | 2013-11-28 | Kuraray Co Ltd | 樹脂成形体の製造方法、樹脂成形体、およびモールド |
JP2016031558A (ja) * | 2014-07-25 | 2016-03-07 | 大日本印刷株式会社 | 多層基材及びタッチパネル画像表示装置 |
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US20110216029A1 (en) | 2011-09-08 |
JP5872770B2 (ja) | 2016-03-01 |
KR20110095915A (ko) | 2011-08-25 |
CN102300910A (zh) | 2011-12-28 |
JPWO2010061851A1 (ja) | 2012-04-26 |
CN102300910B (zh) | 2014-05-07 |
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