JP2015168601A - Glass substrate, touch panel sensor substrate, and image display device with coordinate detection function - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass substrate excellent in impact resistance without reducing productivity, a cover glass-integrated touch panel sensor substrate using the glass substrate, and an image display device with a coordinate detection function, which mounts the touch panel sensor substrate.SOLUTION: A transparent glass substrate 1 has a chemically reinforced layer 2 on top and back surfaces, and a DLC film 3 formed at an end cross section of the substrate. The touch panel sensor substrate includes a display region having transparent electrodes in at least an X-axis direction and a Y-axis direction, and a decorative frame region for blocking light in an outer periphery of the display region, both formed on one surface of the glass substrate 1.

Description

  The present invention relates to a glass substrate for a cover glass for an electronic device, an image display device for an electronic device, an electronic device, and a method for strengthening the glass substrate for the cover glass for an electronic device.

  In recent years, a touch panel has been adopted as an operation unit of an electronic device such as a mobile phone or a portable information terminal. Touch panel sensors that perform position detection include a film type and a glass type. The film type is lightweight, hard to break, inexpensive to manufacture, and flexible, so it has the merit that it is easy to remove bubbles when bonding with other display devices and cover glass, but the light transmission of the film The rate is low compared to glass, and the position accuracy of the wiring pattern formed on the film is inferior to glass, so the frame area covering the wiring becomes large and the display area becomes narrow, the surface smoothness Due to the difference, there is a problem that it looks worse than the glass type. Therefore, many glass types are used in small products such as mobile terminals such as smartphones and tablet computers that require high definition and low power consumption. (See Patent Document 1)

  Touch panel sensors used in cellular phones, etc. are generally a frame portion, metal wiring, two layers of transparent electrodes for X and Y directions, and an interlayer insulation layer between two layers of transparent electrodes on a large glass substrate. After the protective layer on the surface is formed by multiple imposition, it is cut into individual substrates for each piece. Note that the touch panel sensor is formed with a frame portion made of a highly light-shielding material for hiding surrounding wiring and the like. Various colors and patterns can be applied to the frame portion according to the design of the device. It is common to form a frame with a color or pattern such as white or black.

  However, even if the frame portion is formed by these methods, the outer peripheral portion of the frame portion is cut at the time of cutting, or the frame portion is peeled off by cutting, and light leakage from the backlight occurs. Therefore, the light shielding layer is formed again on the individual substrates after cutting with ink having light shielding properties. The touch panel sensor cut into individual pieces is generally used by being bonded through a cover glass for preventing breakage, a transparent adhesive sheet (OCA), or the like. In addition, the frame part 6 which consists of material with high light-shielding property can be formed in a cover glass, in order to hide design property, the wiring of a peripheral part, etc.

The cover glass is a front plate disposed on the outermost surface of the touch panel sensor, and an aluminosilicate containing at least one alkali metal oxide selected from SiO ₂ , Al ₂ O ₃ , Li ₂ O and Na ₂ O. Glass that is tempered is generally used.

  The glass strengthening treatment includes physical strengthening (air cooling strengthening) that rapidly cools after heating the glass surface to near the softening point and chemical strengthening that replaces alkali ions inside the glass with alkali ions having a larger particle size. A thin plate of 1 mm or less used for a cellular phone is not suitable for physical strengthening because the temperature difference between the surface and the inside is difficult to be applied, and chemical strengthening is generally used.

  The chemical strengthening of glass involves immersing the glass in a molten salt below the glass transition point, and replacing the alkali ions inside the glass with alkali ions having a larger ionic radius, thereby reducing the compressive stress due to the difference in ionic radius. It is a method to generate. By generating compressive stress on the glass surface, the strength of the glass is improved in order to prevent tensile stress from concentrating on the scratches generated on the glass surface.

  However, chemically tempered glass has problems that it is difficult to cut due to strength during cutting, and that it is difficult to cut because it breaks irregularly due to a large compressive stress. For this reason, a method has been proposed in which a large glass substrate before the tempering treatment is cut into a small glass substrate, followed by a tempering treatment, and after firing, a small tempered glass substrate is obtained (Patent Document 2).

  In recent years, so-called cover glass integrated touch panels in which a touch panel sensor is formed on the cover glass itself to reduce the thickness and weight have been spreading. However, in the cover glass integrated touch panel, there is a problem in that the yield decreases because it is necessary to cut the cover glass using tempered glass.

  Further, even if the method described in Patent Document 2 is used, the frame portion and the wiring material and the like need to have chemical resistance against the tempering treatment liquid (molten salt) and heat resistance of about 300 ° C. or more. It is difficult to apply to a touch panel. For this reason, a method of cutting the cover glass and forming the frame part and wiring material after chemical strengthening has also been proposed. However, it is necessary to invest in new equipment to form a touch panel sensor on an individual substrate and productivity. There is a problem that decreases.

  As another countermeasure, it has been proposed to cut large tempered glass by etching with one or more mixed liquids containing hydrofluoric acid. Cutting by etching does not cause breakage or cullet at the time of cutting. However, since only the front and back surfaces of the glass are chemically strengthened, the end surfaces of the individual substrates after cutting are not chemically strengthened. Therefore, the end face of the individual substrate after cutting has a low glass strength, and thus glass breakage occurs with the end face as a base point. (See Patent Documents 3 and 4)

  In Patent Document 6, a proposal is made to improve the glass strength by forming a dense silica layer by forming a protective film containing polysilazane on the glass end face. However, if the glass edge is damaged, it does not change to a situation that causes a decrease in strength, and is insufficient as a protective film against impact and damage to the glass edge.

JP 2009-69321 A JP 2011-164508 A JP 2012-236664 A JP 2006-282492 A JP 2012-148957 A JP-A-11-322367

  An object of the present invention is to provide a glass substrate excellent in impact resistance without lowering productivity, a cover glass integrated touch panel sensor substrate using the same, and an image display device with a coordinate detection function mounted thereon. That is.

  This invention is made | formed in view of the said situation, and the invention which concerns on Claim 1 has a chemical strengthening process layer in the transparent front and back, and a DLC film is formed in the edge part cross section. It is the glass substrate characterized by these.

The invention according to claim 2 is a display area having transparent electrodes in at least the X-axis direction and the Y-axis direction on one surface of the glass substrate according to claim 1, and a decorative frame that shields the outer periphery of the display area. An area is formed on the touch panel sensor substrate.

  The invention which concerns on Claim 3 forms the display area | region which has a transparent electrode of an X-axis direction and a Y-axis direction at least on one surface of a transparent substrate, and the decoration frame area which light-shields the outer periphery of the said display area | region, Furthermore, the glass substrate of Claim 1 was laminated | stacked on it, It is a touchscreen sensor board | substrate characterized by the above-mentioned.

  The invention according to claim 4 is a display device with a coordinate detection function, characterized in that the touch panel sensor substrate according to claim 2 or 3 is mounted.

  According to the first aspect of the present invention, the impact strength of the front and back surfaces of the glass substrate is supplemented by the chemical strengthening treatment layer, and the DLC film is formed on the end cross section of the glass substrate, so that the chemical strengthening treatment is performed. It is possible to improve the impact resistance of the cross section that is not present. In particular, small touch panel sensor substrates, etc. are generally cut from the front and back to form multiple unit touch panel sensors on a large glass substrate and then cut into individual unit touch panel sensor substrates in terms of production efficiency. There was a problem that the strength of the surface was inferior. With respect to such a problem, the present invention can satisfy both the improvement of the impact strength of the cross section and the cost reduction by forming the DLC film on the cut surface.

  According to the invention of claim 2, the display area having at least the X-axis and Y-axis transparent electrodes on one surface of the glass substrate of claim 1 and the outer periphery of the display area are shielded from light. By forming the decorative frame region to be performed, it is possible to provide a touch panel sensor substrate having excellent impact strength in which the end cross section is reinforced with a DLC film in addition to the front and back strength.

  Moreover, according to the invention which concerns on Claim 3, on one side of a transparent substrate, the display area which has a transparent electrode of an X-axis direction and a Y-axis direction at least, The decoration frame area which light-shields the outer periphery of the said display area, A glass substrate according to claim 1 is laminated thereon, and in addition to the strength of the front and back, an end cross section is reinforced with a DLC film to provide a touch panel sensor substrate excellent in impact strength. Can do.

  Moreover, according to the invention which concerns on Claim 4, the display apparatus with a coordinate detection function which has an operation part excellent in impact strength strength can be provided by mounting the touch-panel sensor board | substrate of Claim 2 or 3.

The cross-sectional schematic of the glass substrate of this invention is shown. The cross-sectional schematic of the touch-panel sensor board | substrate using the glass substrate of FIG. 1 is shown. The cross-sectional schematic of the touch-panel sensor board | substrate using the glass substrate of FIG. 1 is shown. (A) The cross-sectional schematic of a touch-panel sensor board | substrate is shown. (B) A schematic plan view of a touch panel sensor substrate is shown.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

The present invention is a transparent glass substrate having a chemically strengthened treatment layer on the front and back and having a DLC film formed on the end cross section thereof, and at least the X-axis direction and Y It is preferably used as a touch panel sensor substrate formed by forming a display region having an axial transparent electrode and a decorative frame region that shields the outer periphery of the display region, and a cover glass laminated thereon.

  In addition, the touch panel sensor substrate according to the present invention is provided in a flat display such as an LCD, PDP, inorganic and organic electroluminescence display, FED, etc., and is provided as a display device with a coordinate detection function, such as a small mobile phone. be able to.

  As shown in FIG. 1, the glass substrate 1 of the present invention is characterized in that the front and back have a chemically strengthened layer 2 and a DLC film 3 is formed in a cross section. Hereinafter, the glass substrate 1 which concerns on this invention is demonstrated.

  The chemical strengthening treatment layer 2 of the glass substrate 1 is subjected to an ion exchange treatment process in which a glass substrate containing one or more kinds of alkali metals is brought into contact with a molten salt containing one or more kinds of alkali metals to perform an ion exchange treatment. can get.

  The glass substrate that can be used to apply the chemical strengthening treatment layer 2 is an alkali metal oxide that can be produced by a float method, a slit down draw method, a fusion down draw method, a redraw method, etc., and that can be subjected to an ion exchange treatment. Any glass material can be used as long as it contains glass.

For example, for producing an aluminosilicate glass containing at least one alkali metal oxide selected from SiO ₂ , Al ₂ O ₃ , Li ₂ O and Na ₂ O, or a glass substrate using a float method or the like. It is preferable to use a known glass material such as soda lime glass.

  The compressive stress layer formed in the ion exchange treatment step was formed by bringing a part of an alkali metal originally contained in a glass material constituting a glass substrate into contact with a molten salt containing an alkali metal having a larger ion radius. Is a layer. For example, if the alkali metal originally contained in the glass material constituting the glass substrate is Li, it is replaced with Na, K, etc., and if the alkali metal originally contained in the glass material constituting the glass substrate is Na, K etc. Is replaced by The composition and temperature of the molten salt, and the immersion time can be appropriately selected according to the glass composition of the sheet glass, the thickness of the compression stress layer formed on the surface layer portion of the sheet glass, and the like.

  For example, if the glass composition of the plate glass is the above-mentioned aluminosilicate glass or soda lime glass, the composition and temperature of the molten salt and the immersion time are generally selected from the ranges exemplified below. It is preferable. The composition of the molten salt is preferably potassium nitrate or a mixed salt of potassium nitrate and sodium nitrate, and the temperature of the molten salt is immersed at 300 to 500 ° C. for 3 to 600 minutes to form a reinforcing layer.

  Next, a method for forming a touch panel sensor on the glass substrate 1 of the present invention will be specifically described.

  2 and 3 are schematic cross-sectional views of a touch panel sensor substrate manufactured using the glass substrate 1. FIG. 2 shows an embodiment of a cover glass integrated touch panel sensor substrate, and FIG. 3 shows an embodiment of a touch panel sensor substrate incorporated as a cover glass.

  The bar glass integrated touch panel sensor substrate 4 shown in FIG. 2 includes a display area having transparent electrodes in at least the X-axis direction and the Y-axis direction on one surface of the glass substrate 1 and a shield that shields the outer periphery of the display area. It is divided into a decorative frame area.

More specifically, as shown in FIG. 4, the transparent electrode 11 in the X-axis direction and the transparent electrode 12 in the Y-axis direction on the glass substrate 1, the jumper wiring and the insulating layer 15 at the respective intersections 13 and 14, the transparent The lead-out wiring 16 from the electrode is formed, and the display region 5 made of the transparent electrode and the decorative frame region 6 that shields the outer periphery (particularly the lead-out wiring portion) are divided.

  The touch panel sensor substrate 1 is used in combination with a display device 8 such as a liquid crystal panel or an organic EL panel, and is one member constituting a display device with a coordinate detection function. The touch panel sensor substrate 1 has a plurality of electrodes extending in the X direction and a plurality of electrodes extending in the Y direction, and detects the change in the capacitance of the electrode in contact with or close to the finger, thereby determining the coordinates of the finger contact position. Identify.

  FIG. 3 shows a schematic cross-sectional view of the touch panel sensor substrate 4 when the glass substrate 1 is used as a cover glass. Specifically, on one surface of a transparent substrate 1 ′ made of glass or resin, a display area having at least X-axis direction and Y-axis direction transparent electrodes, and a decorative frame area that shields the outer periphery of the display area Further, the glass substrate 1 can be further laminated on the touch panel sensor substrate 4 on which is formed and used as a cover glass. In this case, the decorative frame region can be formed on the cover glass.

  The decorative frame region is formed of one or more layers, and imparts design to the touch panel sensor substrate 1 and plays a role of hiding the lead-out wiring 16 provided on the peripheral edge of the touch panel sensor substrate 1. In order to avoid disconnection of the sensor, the shape is preferably a forward taper. The forward taper indicates that the angle of the tapered portion is in the range of 0 ° to 90 °. The forming method can be selected from photolithography, screen printing, and the like.

  Note that the planar shape of the decorative frame region is not limited to the rectangular frame shape as in the present embodiment, and may be any shape such as a heart shape, an egg shape, or a round shape. Also, the outer peripheral shape (outer shape) and inner peripheral shape (display area shape) of the frame portion may be similar or dissimilar.

  As a material for forming the decorative frame region, a photosensitive resin composition containing a colorant having a concealing property (light shielding property) is preferable. As the colorant, dyes, organic pigments, and inorganic pigments can be preferably used. Hereinafter, the photosensitive resin composition will be described in more detail.

  Examples of the colorant include carbon black, titanium black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment black 1, 6, 7, 12, 20, 31, 32, etc. can be used, but carbon black is preferred from the viewpoint of price and light shielding properties. Carbon black may be surface-treated with a resin or the like. Here, the black pigment resist refers to a resin in which a black pigment such as carbon black or titanium black is dispersed in a resin dissolved in a solvent. The photocured product of the black pigment resist refers to the black pigment resist. The resist is hardened by performing exposure processing by a photolithography method.

  Examples of carbon black contained in the black pigment-based resist include, for example, Mitsubishi Chemical Corporation # 260, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 45L, # 47, # 50, # 52, MA7, MA8, MA11, MA100, MA100R, MA100S, MA220, MA230, manufactured by DEGUSSA, Printex A, Printex L, Printex P, Printex 30, Printex 35, Printex 40, Printex 45, Printex 45, Printex 45, Printr 45 , Printex 300, Printex 350, Special Black 4, Special Black 350, Special Black 550, and the like. Carbon black whose surface is modified with a resin or the like by a known method may be used. Carbon black may be used individually by 1 type, or 2 or more types may be mixed and used for it. The carbon black preferably has an oil absorption of dibutyl phthalate (hereinafter referred to as “DBP”) of 120 ml / 100 g or less from the viewpoint of sensitivity, and the smaller the DBP oil absorption, the more preferable.

  Furthermore, it is preferable that the average primary particle diameter of carbon black is 20-300 nm. Carbon black having an average primary particle size of less than 20 nm is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black color material having good stability over time. This is because the shape of the matrix may be deteriorated.

  The carbon black content in the black color material is preferably 0.5 to 60% by weight, more preferably 10 to 50% by weight, based on the solid content of the composition. When the carbon black content is more than 60% by weight, the alignment light source does not transmit and alignment at the time of exposure becomes impossible, and dispersion stability is difficult to obtain, resulting in a decrease in sensitivity and formation of a black matrix. Can be difficult. When the content of carbon black is less than 0.5% by weight, the concealability of visible light is low, and when used as the black frame part of the front plate, the light shielding property of the wiring part etc. is low, and it can be seen through. End up. A well-known thing can be used as a titanium oxide, In addition to a titanium oxide, titanium nitride and titanium oxynitride are also used suitably.

  Moreover, the pigment used for the light-shielding material of the present embodiment may be a mixture of two or more types of pigments other than black pigments. As an example, a pigment used in forming a colored transparent layer of a color filter, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 97, 122, 123, 146, 149, 166, 168, 169, 176, 177, 178, 179, 180, 184, 185, 187, 192,200,202,208,210,215,216,217,220,223,224,226,227,228,240,242,246,254,255,264,270,272,273,274,276, Red (RED) pigments typified by 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, and the like; I. At least a blue (BLUE) pigment typified by CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, etc. Therefore, a pseudo black color can be used. Further, basic dyes exhibiting red and purple, acidic dyes, and salt-forming compounds of these dyes can also be used.

  In this embodiment, in addition to the red pigment and the blue pigment, a yellow (YELLOW) pigment may be added. It is known that yellow pigments absorb light in the low wavelength region of visible light, that is, light having a wavelength of 500 nm or less (for example, “Shoji Shiji (1965)“ Printing Ink Class ”(Nihon Printing Shimbun) P170. 173). By adding a yellow pigment to a red pigment and a blue pigment, the yellow pigment absorbs low-wavelength visible light and can be made closer to black.

  Examples of yellow (YELLOW) pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , It includes the 175,176,177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220,221. Further, basic dyes exhibiting yellow, acidic dyes and salt-forming compounds of these dyes can be used in combination.

  In addition, a violet pigment may be added, and by adding a violet pigment, it is easy to absorb light in the vicinity of a wavelength of 550 nm, and black having a higher optical density (OD value) can be obtained.

  Examples of violet pigments include C.I. I. Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50.

  Further, a pigment such as an orange pigment or a green pigment may be added. Examples of the orange pigment include C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, 71, 73, and the like. Examples of the green pigment include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, 37, and 58.

  In addition to the black picture frame, any color such as white, pink or blue may be used. For example, titanium oxide, zinc oxide, petal, quinacridone, pyranthrone, perylene, ultramarine blue, Prussian blue, cobalt blue, smalto blue, cerulean blue, cobalt chrome blue, azurite, indigo blue, indanthrene blue, etc. It is done.

  In order to produce the photosensitive resin composition, a dispersant or a surfactant for dispersing the pigment may be used. Surfactants, pigment intermediates, dye intermediates, Solsperse, and the like are used as the dispersant, and have a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier. It functions to adsorb to the pigment and stabilize dispersion in the pigment carrier.

  Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long Oil-based dispersants such as chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) and polyesters having free carboxyl groups, and salts thereof , (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, and other water-soluble resins Molecular compound, polyester, modified polyacrylate , Ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Although the addition amount of a dispersing agent is not specifically limited, It is preferable to set it as 1 to 10 weight% with respect to 100 weight% of compounding quantities of a pigment. In addition, the coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine laurylsulfate, Anionic surfactants such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxye Nonionic surfactants such as lenalkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethyl Examples include alkylbetaines such as aminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, and these can be used alone or in admixture of two or more.

  The photosensitive resin composition may further contain a photopolymerization monomer, a photopolymerization initiator, a sensitizer, a polyfunctional thiol, an ultraviolet absorber, and a polymerization inhibitor as exemplified below.

  Photopolymerizable monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylol Examples thereof include various acrylic esters and methacrylic esters such as propane tri (meth) acrylate.

  As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) -butan-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Compound, benzoin, benzoin methyl ether, benzoin ethyl ether, ben Benzoin compounds such as inisopropyl ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethyl Thioxanthone compounds such as thioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2, Triazine compounds such as 4-trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O— Benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, and other oxime ester compounds, bis (2,4,6 -Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl)- Imidazole compounds such as 4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, 9,10-phenanthrene Non camphorquinone, quinone-based compounds such as ethyl anthraquinone, borate compounds, carbazole-based compounds, titanocene compounds, and the like.

  Among these, it is more preferable to include at least one photopolymerization initiator selected from the group consisting of acetophenone compounds, phosphine compounds, and oxime ester compounds.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. Content of a photoinitiator can be used in the quantity of 1.0-200 weight part with respect to 100 weight part of coloring agents, Preferably it is 1.0-150 weight part.

  Examples of the sensitizer include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphy Derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives And spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives, and the like. In the present invention, a derivative means a compound in which a part of the compound is modified with another atom or functional group, or is modified or oxidized or reduced with respect to the original compound. The derivative only needs to contain most of the skeleton of the original compound in terms of structure, and the derivative may exhibit completely different properties only by having a similar structure of the original compound.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used. The sensitizer may contain two or more sensitizers in any ratio. The content of the sensitizer can be used in an amount of 1.0 to 100 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  In addition, silane coupling agents, antifoaming agents, silica, polymerization inhibitors. Materials other than those described above, such as ultraviolet absorbers, can be added and used.

  Next, the transparent electrodes 11 and 12 in the X and Y axis directions, the jumper wiring, the lead wiring 16, and the insulating protective layer that form the display area will be described.

  The transparent electrode 11 is for detecting the X coordinate. The transparent electrode is formed in the display region 5 using a material having electrical conductivity and transparency. The transparent electrodes are intermittently arranged in a matrix in the X direction and the Y direction, and are electrically connected to jumper wirings adjacent in the X direction. The transparent electrode 11 is made of, for example, ITO (Indium Tin Oxide).

  The transparent electrode 12 is for detecting the Y coordinate, and is formed using the same material as the transparent electrode 11. The transparent electrode 12 extends in the Y direction between each column of transparent electrodes aligned in the Y direction, and three-dimensionally intersects with the jumper wiring on the eleventh insulating film 15.

  The jumper wiring is formed using a conductive material, and is arranged intermittently and in a matrix in the display area 6 in the X direction parallel to one side of the display area 6 and in the Y direction orthogonal thereto. The jumper wiring is for connecting the transparent electrodes 11 aligned in the X direction.

  The lead-out wiring 16 is formed on the decorative frame region 6 and is electrically connected to the transparent electrodes in the X-axis and Y-axis directions located at the peripheral edge of the display region 5. The lead wiring 16 is generally formed of a metal material, and is made of, for example, a laminated body of Mo / Al / Mo (molybdenum / aluminum / molybdenum) or the like, and in addition, Au (gold), Ag (silver), Ag alloy, or the like. It may be formed.

  Next, a method for individually cutting a plurality of unit touch panel sensors formed on a large glass substrate will be described.

  When cutting by etching, it is necessary to form an etching resistant film. In the etching resistant film forming step, an etching resistant film is formed on at least one surface or both surfaces where the touch panel sensor is formed. This etching resistant film is usually formed on both surfaces of the ion-exchanged plate-like glass. However, when only one surface is brought into contact with the etching solution in the cutting step, the etching resistant film is formed only on the one surface. It only has to be.

  As such an etching resistant film, it is preferable to form a protective film using photolithography which is at least insoluble or insoluble in a hydrofluoric acid aqueous solution, or to use a peelable protective sheet. The etching resistant film can be appropriately selected as long as it can be partially removed by patterning in the patterning step and has a property that is not dissolved / removed in the etching solution used in the cutting step. In this case, in the patterning step, the resist film can be subjected to patterning processing by exposure processing using a photomask and development processing using a developer, and cutting can be performed using an etching solution in the cutting step.

  For the cutting, a break method, a laser cut method, or a water jet flow method can be employed. As a method of cutting tempered glass, more preferably, the surface of the plate glass that has been subjected to the ion exchange treatment is provided with a patterned etching-resistant film, and is etched by bringing the surface into contact with the etching solution, thereby performing the plate exchange after the ion exchange treatment. Cut the glass into small pieces.

  The etching process is usually performed by immersing plate glass in an etching solution. The etching solution is not particularly limited as long as it contains at least hydrofluoric acid, but other acids such as hydrochloric acid and various additives such as a surfactant may be added as necessary. For example, as an etchant, hydrofluoric acid, an acidic solution containing hydrofluoric acid as a main component, hydrofluoric acid containing sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, mixed acid containing at least one of silicic acid, caustic soda, caustic potash, etc. Alkalis can be used. Moreover, etching temperature is 10 to 80 degreeC normally, Preferably it is 20 to 40 degreeC. Further, the etching time is usually 30 seconds to 30 minutes, preferably 1 minute to 10 minutes. These etching conditions can be appropriately selected according to the material of the glass substrate to be used and the like so that no reactant is precipitated.

  When not cut only by etching, a stress is applied by applying a break bar to the large tempered glass substrate after etching. As a result, the large tempered glass substrate is cut into individual pieces. Before the etching resistant film is removed, the outer peripheral edge of the individual substrate is polished, and the protrusion is removed, and then etching is performed. Further, in the etching, wet etching using a hydrofluoric acid-based etching solution is performed as in the etching step.

  Next, DLC film formation on the cut surface according to the present invention will be described below.

  DLC (Diamond-Like Carbon) film is a general term for thin films made of carbon-based materials with an amorphous structure having both SP3 bonds of diamond and SP2 bonds of graphite (graphite). The film is formed by ionized vapor deposition, sputtering, and arc ion plating. Since the DLC film has both the hardness of diamond and the lubricity of graphite, it is possible to impart excellent scratch resistance and impact resistance to the glass end face.

  The film thickness of the DLC film is preferably 0.03 to 20 μm, more preferably 0.1 to 2 μm. If the film thickness is less than 0.03 μm, sufficient hardness cannot be maintained, and if it is more than 20 μm, the adhesiveness decreases. At this time, an underlayer may be formed in order to improve the adhesion of the DLC film. By peeling off the etching resistant film after the DLC film is formed, the DLC film can be formed only on the end face of the cover glass as shown in FIG.

  Furthermore, in order to improve the performance of the touch panel, the glass touch panel, which has been cut into pieces after being cut, is coated with a black pigment on the glass edge and the decorative layer. Light leakage from the backlight through the gap between layers can be prevented. Further, although there is no problem with any method as the method of individual piece printing, it is desirable to carry out by screen printing. The screen mesh is preferably 150 to 500 mesh.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
As the glass substrate, flat glass having a length of 400 mm, a width of 500 mm, and a thickness of 0.7 mm formed by a downdraw method was used. The composition of this glass substrate is expressed in terms of mol% based on oxide, SiO ₂ : 65%, Al ₂ O ₃ : 10%, MgO: 10%, Na ₂ O: 14.5%, ZrO ₂ : 0.5 %Met. Next, this glass substrate was immersed in KNO ₃ molten salt at a temperature of 400 ° C. for 4 hours (ion exchange treatment), and then cooled to near room temperature to form a chemically strengthened layer on both sides.

  Next, a touch panel sensor substrate was produced by the following method using the glass substrate having the chemically strengthened layers on the front and back sides.

<1. Formation of decorative layer>
On one surface of the glass substrate, a photosensitive decorating material, which will be described later, was applied by spin coating to a finish of 2.5 μm. Next, after removing the solvent content with a vacuum dryer, exposure was performed by a proximity exposure system (ultra-high pressure mercury lamp). Here, as the exposure photomask, quartz glass patterned with Cr (chromium) was used. Next, it developed with the alkaline developing solution. And the heat processing of 230 degreeC x 20 minutes were performed, and the decoration layer was formed.

[Synthesis of alkali-soluble resin A]
The reaction vessel was charged with 800 parts by weight of 1-methoxy-2-propyl acetate, heated while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise to carry out a polymerization reaction. Hereinafter, parts by weight are referred to as parts.
Styrene 40 parts Methacrylic acid 60 parts Methyl methacrylate 55 parts Benzyl methacrylate 45 parts Azobisisobutyronitrile 10 parts 1,4-dimethylmercaptobenzene 3 parts

  After dripping, after heating sufficiently, what melt | dissolved 2 parts of azobisisobutyronitrile with 50 parts of 1-methoxy-2-propyl acetate was added, and reaction was further continued, and the solution of the acrylic resin was obtained. An acrylic resin solution was prepared by adding 1-methoxy-2-propylacetate to the resin solution so that the solid content was 30% by weight to obtain an alkali-soluble resin solution. The weight average molecular weight of the acrylic resin was about 20,000. After filtering with a 5 μm filter, it was used as a photosensitive decorative material.

[Photosensitive decoration material]
A mixture having the following composition was spread and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to obtain a dispersion of a light shielding agent.
Red pigment: C.I. I. Pigment Red 254
("ILGER FOR RED B-CF" manufactured by BASF) 50 parts Blue pigment: C.I. I. Pigment Blue 15: 6
(Toyo Ink Co., Ltd., LIONOGEN BLUE 7706) 50 parts Dispersant (Ajinomoto Fine Techno Co., Ltd. “Ajisper PB821”) 3.3 parts Alkali-soluble resin A 183 parts Thereafter, a mixture having the following composition was stirred and mixed to be uniform. Thereafter, the mixture was filtered through a 5 μm filter to obtain a photosensitive decorative material.
Dispersion 233 parts Alkali-soluble resin A 173 parts Multifunctional polymerizable monomer 50 parts ("Aronix M-400" manufactured by Toa Gosei)
Photoinitiator 25 parts ("Irgacure 369" manufactured by Ciba Specialty Chemicals)
Sensitizer 4,4'-bis (diethylamino) benzophenone 5 parts ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
186 parts cyclohexanone 333 parts propylene glycol monomethyl ether acetate

<2. Jumper wiring formation>
First, an ITO film was formed by heat sputtering, in which sputtering was performed while heating at 170 ° C. by a DC magnetron sputtering method. Next, a general novolac positive resist was spin-coated, pre-baked, exposed, and then positively developed with an alkaline developer. Here, a proximity exposure system (ultra-high pressure mercury lamp) was used for exposure, and a soda glass patterned with Cr was used as a photomask for exposure. Then, etching is performed using an etching solution containing oxalic acid ((COOH) 2) as a main component, the entire surface of the positive resist is exposed, the positive resist is stripped with an alkaline stripping solution, and a jumper wiring is formed using an ITO film. did.

<3. Formation of insulating film>
An acrylic insulating material was applied by spin coating on the glass substrate surface on which the jumper wiring was formed. Next, pre-baking was performed to remove the solvent, and exposure was performed by a proximity exposure system (super high pressure mercury lamp). Here, as a photomask for exposure, a quartz glass having a pattern made of Cr was used. Next, it developed with the alkaline developing solution and heat-processed. In this way, an insulating film was formed on the jumper wiring.

<4. Formation of lead-out wiring>
On the glass substrate, a Mo layer, an Al layer, and a Mo layer were sequentially formed in vacuum by a DC magnetron sputtering method to form a three-layered Mo / Al / Mo laminated body.

  Next, a novolac positive resist was spin-coated, pre-baked, exposed, and then positively developed with an alkaline developer. Here, a proximity exposure system (ultra-high pressure mercury lamp) was used for exposure, and a soda glass patterned with Cr was used as a photomask for exposure. Etching with a phosphoric acid, nitric acid, and acetic acid ternary etchant (etching solution), exposing the entire positive resist, and then stripping the positive resist with an alkaline stripping solution to form a lead wiring made of a metal material did.

<5. Formation of transparent electrode>
First, an ITO film was formed by heat sputtering, in which sputtering was performed while heating at 170 ° C. by a DC magnetron sputtering method. Next, a general novolac positive resist was spin-coated, pre-baked, exposed, and then positively developed with an alkaline developer. Here, a proximity exposure system (ultra-high pressure mercury lamp) was used for exposure, and a quartz glass pattern with Cr was used as an exposure photomask. And it etched using the etching liquid which has oxalic acid as a main component, and exposed the positive resist to the whole surface, Then, the positive resist was peeled with the alkaline peeling liquid. In this way, transparent electrodes in the X-axis and Y-axis directions were formed from the ITO film.

<6. Formation of insulating protective film>
First, an acrylic overcoat material was applied by spin coating. Next, pre-baking was performed to remove the solvent, and exposure was performed by a proximity exposure system (super high pressure mercury lamp). Here, as the photomask for exposure, a soda lime glass patterned with Cr was used. Next, it developed with the alkaline developing solution and heat-processed. In this way, an insulating protective film was formed, and a touch panel sensor was manufactured and completed.

<7. Cutting and polishing of glass substrates>
The etching-resistant film sheet | seat which provided weak adhesiveness to the fluorine-type sheet | seat which has etching resistance was bonded together on both surfaces of the surface in which the touch panel sensor is formed, and the glass surface facing a touch panel sensor.

  Next, the bonded substrate is immersed in an etching solution containing 6% by weight of hydrofluoric acid, 4% by weight of sulfuric acid, and 12% by weight of hydrochloric acid for 10 minutes to complete the etching, and a cutting groove is formed at the cutting position. Formed.

  Thereafter, a stress was applied to the glass substrate by applying a break bar, and the glass substrate was cut into individual pieces. Further, the outer peripheral edge of the individual substrate was polished to remove the protrusions, and then the residue was etched using the same etching solution as in the etching step.

<8. Formation of DLC film>
The glass substrate cut into pieces is put into a vacuum chamber while leaving an etching resistant film, and after performing DLC coating on the glass end face by performing ionization vapor deposition while introducing hydrocarbon gas, The etching film was peeled off. The DLC film thickness at this time was 1.5 μm.

<9. Shading layer formation by individual printing>
After the DLC film was formed by the above method, a touch panel sensor was obtained by performing screen printing of a light shielding material on the frame portion and the end face of the substrate on the individual substrate cut for each piece. The light shielding material was obtained by dispersing the following composition three times with three rolls.
[Shading material for individual printing]
Carbon black 40 parts Acrylic dispersion resin (manufactured by Nippon Kayaku Co., Ltd .: ZFR-1124) 30 parts Antifoaming agent (BIC Chemie: BYK-066N) 1 part Solvent: 1-methoxy-2-propyl acetate 19 parts

(Example 2)
A touch panel sensor substrate was produced in the same manner as in Example 1 except that the DLC film thickness was 0.02 μm.

(Example 3)
A touch panel sensor substrate was produced in the same manner as in Example 1 except that the DLC film thickness was 0.03 μm.

Example 4
A touch panel sensor substrate was produced in the same manner as in Example 1 except that the DLC film thickness was 19.5 μm.

(Example 5)
A touch panel sensor substrate was produced in the same manner as in Example 1 except that the DLC film thickness was 21.3 μm.

(Comparative Example 1)
A touch panel sensor substrate was produced in the same manner as in Example 1 except that the DLC film was not formed on the edge of the glass substrate cut into pieces.

<Evaluation of touch panel sensor substrate>
For the touch panel sensor substrates obtained in Examples 1 to 5 and Comparative Example 1, the impact resistance was evaluated by the following four-point bending test and pendulum test. The results are shown in Table 1.

[4-point bending evaluation]
The glass end face of the touch panel sensor substrate is scratched with 250 g of sandpaper (# 400), and then the glass strength is measured by a four-point bending test according to “JIS R 1601 Fine Ceramic Bending Strength Test Method”. It was measured. The speed at which the pressurizer was lowered was 10 mm / min. Such strength measurement was performed on 20 glass substrates, and an average value was obtained.

[Pendulum test]
A pendulum with a steel ball having a height of 30 g and a weight of 30 g was prepared and dropped from 45 degrees and 90 degrees so as to contact the end face of the cover glass, and the appearance of the glass end face was observed. As a result, there was no appearance abnormality: ○, and there was appearance abnormality: x.

<Comparison result>
As can be seen from Table 1, the glass strength and the pendulum test strength in the 4-point bending test are improved in any of the examples. However, in Example 2, since the film thickness of the DLC film was not sufficient, the glass strength was inferior compared to other examples. On the other hand, in Example 5, floating of the DLC film was observed by the pendulum test at 90 degrees. In the comparative example, the four-point bending test was damaged starting from scratches, and the pendulum test confirmed chipping from 45 degrees.

  The present invention can be used as an image display device with a coordinate detection function for an electronic device such as a mobile phone or a portable information terminal.

DESCRIPTION OF SYMBOLS 1 ... Glass substrate 2 ... Chemical strengthening process layer 3 ... DLC film 4 ... Touch panel sensor substrate 5 ... Display area 6 ... Decorated frame area 7 ... X, Y-axis direction Transparent electrode 8 ... liquid crystal panel 9 ... casing 10 ... image display device 11 with coordinate detection function ... transparent electrode 12 in X axis direction ... transparent electrode 13 in Y axis direction ... Transparent electrode connection part 14 .. Transparent electrode connection part 15 in the Y-axis direction .. Insulating layer 16..

Claims (4)

  A glass substrate, which is transparent and has a chemically strengthened layer on both sides, and a DLC film is formed on the end cross section.   A display area having at least a transparent electrode in the X-axis direction and the Y-axis direction and a decorative frame area that shields the outer periphery of the display area are formed on one surface of the glass substrate according to claim 1. Touch panel sensor board characterized by   A display region having transparent electrodes in at least the X-axis direction and the Y-axis direction and a decorative frame region that shields the outer periphery of the display region are formed on one surface of the transparent substrate, and further on the display region. A touch panel sensor substrate, wherein the glass substrate described above is laminated.   An image display device with a coordinate detection function, wherein the touch panel sensor substrate according to claim 2 is mounted.