WO2014129320A1 - 樹脂ブラックマトリクス基板およびタッチパネル - Google Patents

樹脂ブラックマトリクス基板およびタッチパネル Download PDF

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Publication number
WO2014129320A1
WO2014129320A1 PCT/JP2014/052888 JP2014052888W WO2014129320A1 WO 2014129320 A1 WO2014129320 A1 WO 2014129320A1 JP 2014052888 W JP2014052888 W JP 2014052888W WO 2014129320 A1 WO2014129320 A1 WO 2014129320A1
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Prior art keywords
black matrix
resin
substrate
resin black
pigment
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PCT/JP2014/052888
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English (en)
French (fr)
Japanese (ja)
Inventor
井上欣彦
相原涼介
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東レ株式会社
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Priority to CN201480009409.8A priority Critical patent/CN105074804B/zh
Priority to KR1020157013094A priority patent/KR101926411B1/ko
Priority to JP2014508618A priority patent/JP6365298B2/ja
Publication of WO2014129320A1 publication Critical patent/WO2014129320A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/13338—Input devices, e.g. touch panels
    • 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
    • G06F3/0412—Digitisers structurally integrated in a display
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

  • the present invention relates to a resin black matrix substrate and a touch panel.
  • Resin black matrix is a photosensitive black resin composition containing a resin and a light-shielding material such as carbon black, coated on a transparent substrate such as glass and dried to form a black film, which is then formed into a lattice pattern by photolithography. It is formed by fine patterning.
  • a transparent electrode such as an ITO electrode is formed on a black matrix formed on the cover glass.
  • Patent Documents 1 to 3 As a technique for reducing the reflectance of the black matrix surface, a black matrix having two layers is known (Patent Documents 1 to 3). In addition, a technique of laminating a resin layer containing a black pigment on a resin layer containing a black dye is also known (Patent Document 4).
  • JP 2006-011180 A JP-A-7-134208 Japanese Patent Laid-Open No. 7-248412 JP 7-073211
  • the conventional two-layer black matrix requires the presence of a metal thin film layer or a light reflecting layer containing metal fine particles, and is used for touch panel applications that require high insulation. It was extremely difficult. Furthermore, it was insufficient in terms of color matching with the black display portion of the display.
  • the present invention provides a resin black matrix substrate comprising a resin black matrix that has a low reflectance and can match the color of the black display portion of the display despite its thin film thickness and high light shielding properties. With the goal.
  • (3) The resin black matrix substrate according to claim 1 or 2 wherein the first resin black matrix contains a blue pigment and a red pigment, or contains a purple pigment.
  • a liquid crystal display device in which the color filter substrate according to (8) above and a counter substrate are bonded together, and a liquid crystal compound is filled in a gap between the two.
  • a display device in which the color filter substrate according to (8) above and a light emitting element are bonded together.
  • the resin black matrix substrate of the present invention although the resin black matrix is thin and has a high light shielding property, the reflectance is low, and the color of the resin black matrix and the black display portion of the display are easily matched. It becomes possible.
  • the resin black matrix substrate of the present invention is suitable for a touch panel because the thickness of the resin black matrix can be reduced.
  • the resin black matrix (hereinafter “resin BM”) substrate of the present invention includes a transparent substrate, a first resin BM (hereinafter “resin BM (A)”) formed on the transparent substrate, A second resin BM (hereinafter referred to as “resin BM (B)”) formed on the resin BM (A), and the film thickness of the resin BM (A) is 0.7 ⁇ m or more.
  • the transmission chromaticity coordinates are in the range of 0.001 ⁇ x ⁇ 0.300 and 0.001 ⁇ y ⁇ 0.250, and the two layers of the resin BM (A) and the resin BM (B)
  • the optical density (hereinafter referred to as “OD value”) is 3.5 or more.
  • the film thickness of the resin BM (A) needs to be 0.7 ⁇ m or more, preferably 0.7 to 2.0 ⁇ m, more preferably 0.7 to 1.5 ⁇ m.
  • the film thickness of the resin BM (A) is less than 0.7 ⁇ m, the light reflected at the interface between the resin BM (A) and the transparent substrate is reflected at the interface between the resin BM (A) and the resin BM (B).
  • the visibility of the resin BM from the transparent substrate side deteriorates due to the interference with the light.
  • the film thickness of resin BM (A) exceeds 2.0 micrometers, the transparent electrode for touchscreens, etc. on resin BM may break.
  • transmission chromaticity coordinates of the resin BM (A) must be in the range of 0.001 ⁇ x ⁇ 0.300 and 0.001 ⁇ y ⁇ 0.250, and 0.150 ⁇ x ⁇ 0.300 and 0 It is preferable to be in the range of .010 ⁇ y ⁇ 0.250.
  • transmission chromaticity coordinates refers to coordinates of transmission chromaticity in the CIE 1931 color system measured with a C light source and a two-degree field of view.
  • the measurement of the transmission chromaticity coordinates of the resin BM (A) is performed using a microspectroscope in a state where only the coating film of the photosensitive colored resin composition for forming the resin BM (A) is formed on the glass substrate. This can be done by measuring the coating film. Since the transmission chromaticity coordinates of the resin BM (A) are in the above range, the transmission chromaticity can be changed from blue to violet, and the resin BM visually recognized on the transparent substrate side can be made deeper black. .
  • two-layer BM the transmission chromaticity coordinates of the resin BM (A) on the resin BM substrate of the present invention on which a BM composed of two layers of the resin BM (A) and the resin BM (B) (hereinafter “two-layer BM”) is formed.
  • the portion where the first-layer resin BM (resin BM (A)) is exposed the portion where the resin BM (B) is not laminated. This can be done by measuring using a vessel.
  • the composition of the resin BM (A) is analyzed to reproduce the photosensitive colored resin composition used to form the resin BM (A), and glass Measure the coating film using a microspectroscope in a state where only the coating film of the photosensitive colored resin composition is formed on the substrate so as to have the same film thickness as the resin BM (A) to be measured.
  • the transmission chromaticity coordinates can be obtained.
  • the OD value of the two-layer BM needs to be 3.5 or more, and is preferably 4.0 or more.
  • the OD value of the two-layer BM is less than 3.5, the light shielding property is insufficient, and stray light from the metal wiring on the BM and the display on the back surface of the touch panel substrate is visually recognized.
  • the OD value of the two-layer BM can be obtained by a known measurement method. Specifically, the intensity of each of the incident light and transmitted light of the two-layer BM formed on the transparent substrate using a microspectroscope can be measured and calculated from the following equation (1).
  • the OD value per 1 ⁇ m of film thickness of the resin BM (A) is preferably 0.5 to 2.0, and preferably 0.5 to 1.5. More preferred. If the OD value per 1 ⁇ m film thickness of the resin BM (A) is less than 0.2, the film thickness must be increased to obtain the desired transmission chromaticity and light shielding property, and the touch panel on the resin BM. There is a possibility that the transparent electrode for use will be disconnected. On the other hand, if the OD value per 1 ⁇ m film thickness of the resin BM (A) exceeds 2.0, it is necessary to increase the concentration of the pigment contained in the resin BM, and the reflectance of the resin BM becomes high.
  • the OD value per 1 ⁇ m thickness of the resin BM (B) is preferably 2.5 or more, and more preferably 3.0 to 6.0. If the OD value per 1 ⁇ m film thickness of the resin BM (B) is less than 2.5, it is necessary to increase the film thickness in order to obtain a desired light shielding property. May break.
  • both of the resin BM (A) and the resin BM (B) are formed by a photolithography method using a photosensitive colored resin composition. Is mentioned.
  • the photosensitive colored resin composition used for forming the resin BM contains a colorant, an alkali-soluble resin, a photopolymerization initiator, and a solvent.
  • Examples of the colorant contained in the photosensitive colored resin composition used for forming the resin BM (A), that is, the colorant contained in the resin BM (A) include organic pigments, inorganic pigments, and dyes. It is done. Organic pigments or inorganic pigments excellent in chemical resistance, heat resistance and light resistance are preferred, and blue pigments or purple pigments are more preferred. In particular, it is more preferable that it contains both a blue pigment and a red pigment, or is a violet pigment.
  • the ratio of the blue pigment / red pigment is preferably 80/20 to 30/70, more preferably 80/20 to 40/60 in terms of mass ratio. When the proportion of the blue pigment is too high, the reflection color tone becomes black with a strong bluish color, which is not preferable. On the other hand, when the ratio of the red pigment is too high, the reflection color tone is not preferable because it is a grayish black with strong redness.
  • blue pigments examples include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 or 79.
  • I. CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 or 60 are preferred.
  • I. Pigment Blue 15: 6 is more preferable.
  • Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 or 50.
  • I. Pigment Violet 19 or 23 is preferred, and C.I. I. Pigment Violet 23 is more preferable.
  • red pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 1 01, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 1 9, 181, 184, 185, 187, 188, 190, 193, 194, 200,
  • I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred, and C.I. I. Pigment Red 177, 209, 224, 242 or 254 is more preferable.
  • Resin BM (A) may contain other pigments in addition to these blue pigment, red pigment and purple pigment in order to adjust the reflection color more accurately.
  • examples of other pigments include green pigments, yellow pigments, and orange pigments.
  • green pigments examples include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. I. Pigment Green 7, 36 or 58 is preferable.
  • yellow pigments examples include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184
  • orange pigments examples include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79.
  • I. Pigment Orange 38 or 71 is preferred.
  • the colorant contained in the resin BM (B) is preferably a black pigment in order to improve the light shielding property of the resin BM (B).
  • the black pigment include carbon black, resin-coated carbon black, titanium black, chromium oxide, iron oxide, aniline black, perylene pigment, C.I. I. Solvent black 123; a composite oxide containing titanium, manganese, iron, copper, or cobalt; and a pseudo black pigment in which a colored pigment such as a red pigment, a blue pigment, or a green pigment is mixed.
  • Carbon black or titanium black is preferable, and carbon black or titanium nitride is more preferable because it has high light shielding properties. These may be used alone or in combination.
  • titanium black is titanium nitride represented by TiN, low-order titanium oxide represented by Ti n O 2n-1 (1 ⁇ n ⁇ 20), TiN x O y (0 ⁇ x ⁇ 2.0, 0. It refers to titanium oxynitride and titanium nitride expressed by 1 ⁇ y ⁇ 2.0).
  • Titanium nitride contains titanium nitride as a main component, and usually contains titanium oxide, low-order titanium oxide, and titanium oxynitride as subcomponents.
  • Examples of the alkali-soluble resin contained in the photosensitive colored resin composition used for forming the resin BM include an epoxy resin, an acrylic resin, a siloxane resin, and a polyimide resin.
  • An acrylic resin or a polyimide resin is preferred because of excellent heat resistance of the coating film and storage stability of the composition.
  • acrylic resin for example, an acrylic resin having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is more preferable.
  • unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid.
  • Examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylic acid unsaturated carboxylic acid alkyl esters such as n-pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate or benzyl methacrylate; sty
  • a quaternary copolymer of monomers selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene is preferable.
  • the weight average molecular weight (Mw) is 2,000 to 100,000 and the acid value is 70 to 150 (mgKOH / g).
  • an acrylic resin having an ethylenically unsaturated group in the side chain is preferable because sensitivity during exposure and development is improved.
  • an acryl group or a methacryl group is preferable.
  • the acrylic resin having an ethylenically unsaturated group in the side chain can be obtained, for example, by adding an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to the carboxyl group of an acrylic resin having a carboxyl group. it can.
  • acrylic resin having an ethylenically unsaturated group in the side chain examples include Cyclomer (registered trademark) P (Daicel Chemical Industries, Ltd.), which is a commercially available acrylic resin, or an alkali-soluble cardo resin.
  • Mw weight average molecular weight
  • acid value is 70 to 150 (mgKOH / g).
  • the weight average molecular weight (Mw) is a weight average molecular weight obtained by measuring a measurement sample by gel permeation chromatography using tetrahydrofuran as a carrier and converting it using a calibration curve with standard polystyrene.
  • the photosensitive colored resin composition used for forming the resin BM may further contain a monomer or an oligomer.
  • the monomer or oligomer include polyfunctional or monofunctional acrylic monomers or oligomers.
  • the polyfunctional acrylic monomer or oligomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) Acrylic ester, phthalic anhydride propylene oxide (meth) acrylic ester, trimellitic acid diethylene glycol (meth) acrylic ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, full orange acrylate oligomer, tripropylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether
  • a compound having a functional group of 3 or more is preferable, a compound having a functional group of 5 or more is more preferable, and dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate is more preferable. .
  • the photosensitive colored resin composition used for forming the resin BM contains a black pigment or the like that absorbs ultraviolet rays effective for photocrosslinking, dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate
  • a (meth) acrylate having a fluorene ring having a lot of aromatic rings and high water repellency in the molecule it is preferable to use a (meth) acrylate having a fluorene ring having a lot of aromatic rings and high water repellency in the molecule.
  • Examples of the photopolymerization initiator contained in the photosensitive colored resin composition used for forming the resin BM include benzophenone compounds, acetophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, Examples include oxime ester compounds, carbazole compounds, triazine compounds, phosphorus compounds; or inorganic photopolymerization initiators such as titanates.
  • benzophenone N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Benzoin isobutyl ether, benzyldimethyl ketal, ⁇ -hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone), 379 (2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- 4- 4-
  • photopolymerization initiator selected from the group consisting of Ptomer N-1919 and Adeka Cruz NCI-831. Two or more photopolymerization initiators may be used in combination.
  • the photosensitive colored resin composition used for forming the resin BM may contain an adhesion improving agent in order to improve adhesion to a glass plate or a silicon wafer.
  • the adhesion improving agent include a silane coupling agent or a titanium coupling agent.
  • the addition amount of the adhesion improving agent is generally about 0.2 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • the photosensitive colored resin composition used for forming the resin BM may contain a polymer dispersant in order to improve the dispersion stability of the colorant.
  • a polymer dispersant include a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, and a polyallylamine polymer dispersant.
  • the addition amount of the polymer dispersant is generally about 1 to 40 parts by mass with respect to 100 parts by mass of the colorant.
  • the composition ratio of the colorant / resin component in the photosensitive colored resin composition used for forming the resin BM is preferably in the range of 80/20 to 40/60 by mass ratio, and adhesion, pattern processability and OD In order to balance the values, the range of 75/25 to 50/50 is more preferable.
  • the resin component refers to a polymer, a monomer, an oligomer and a polymer dispersant contained in the photosensitive colored resin composition. If the resin component is too small, the adhesion between the resin BM and the substrate becomes poor. On the other hand, if the amount of the coloring material is too small, the optical density (OD value / ⁇ m) of the resin BM is lowered.
  • water or an organic solvent can be appropriately selected according to the dispersion stability of the colorant to be dispersed and the solubility of the resin component to be added.
  • organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, or lactone polar solvents.
  • Examples of the organic solvent when an acrylic resin is used as the alkali-soluble resin include diethylene glycol monobutyl ether acetate (boiling point 247 ° C.), benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), methyl benzoate (boiling point 200 ° C.).
  • solvents examples include ethylene glycol monomethyl ether (boiling point 124 ° C.), ethylene glycol monoethyl ether (boiling point 135 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), diethylene glycol monomethyl ether (boiling point 193 ° C.).
  • a solvent having a boiling point of 150 to 200 ° C. contains 30 to 75% by mass.
  • a mixed solvent is preferred.
  • the photosensitive colored resin composition used for forming the resin BM may contain a surfactant in order to prevent Benard cells while ensuring applicability and smoothness of the colored coating.
  • the addition amount of the surfactant is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the colorant.
  • the surfactant examples include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine; a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride; lauryldimethylamine oxide or lauryl.
  • Amphoteric surfactants such as carboxymethylhydroxyethyl imidazolium betaine; Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate; Silicone interfaces having polydimethylsiloxane as the main skeleton An activator; or a fluorosurfactant.
  • the concentration of the solid content excluding the solvent in the photosensitive colored resin composition used for forming the resin BM is preferably 2 to 30% by mass, more preferably 5 to 20% by mass from the viewpoint of coating property and drying property.
  • Examples of the method for producing the photosensitive colored resin composition used for forming the resin BM include a method in which a pigment is directly dispersed in a resin solution using a disperser, or a pigment in water or an organic solvent using a disperser.
  • Examples of the pigment dispersion method include a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill.
  • a bead mill is preferred from the viewpoint of dispersion efficiency and fine dispersion. Examples of the bead mill include a coball mill, a basket mill, a pin mill, and a dyno mill.
  • the bead mill for example, titania beads, zirconia beads, or zircon beads are preferable.
  • the diameter of the beads used for dispersion is preferably 0.01 to 5.0 mm, more preferably 0.03 to 1.0 mm.
  • the bead diameter used for dispersion is preferably as small as 0.03 to 0.10 mm.
  • beads having a bead diameter of 0.10 mm or more are preferable in order to obtain a sufficient crushing force.
  • a photosensitive colored resin composition is applied on a transparent substrate.
  • the method for applying the photosensitive colored resin composition on the substrate include a dipping method, a roll coater method, a spinner method, a die coating method or a wire bar method, a method of immersing a substrate in a solution, or a solution on a substrate.
  • the method of spraying is mentioned.
  • substrate by processing the board
  • the transparent substrate examples include quartz glass, borosilicate glass, aluminosilicate glass, or inorganic glass such as soda lime glass having a silica-coated surface; or an organic plastic film or sheet.
  • the coating film is heated and dried by air drying, heat drying, vacuum drying, or the like to form a dry film.
  • air drying heat drying, vacuum drying, or the like
  • the obtained dry film is subjected to pattern processing using a method such as photolithography after forming an oxygen barrier film as necessary. Thereafter, if necessary, after removing the oxygen blocking film, the resin BM is obtained by further drying by heating and curing.
  • the thermosetting conditions vary depending on the resin, but when an acrylic resin is used, it is preferably heated at 200 to 250 ° C. for 1 to 60 minutes.
  • the reflection chromaticity of the resin BM is calculated from the CIE L * a * b * color system using the reflection spectrum with respect to the standard C light source according to the method of JIS-Z8729. Generally, the chromaticity values (a *, b *) are used.
  • the resin BM in the resin BM substrate of the present invention is composed of multiple layers, the light reflected at the interface of each layer interferes, and the measured value may not match the visually recognized hue. Therefore, in the present invention, a sample BM formed with printing ink was used as a comparison object, and a judgment was made by visual sensory evaluation under sunlight.
  • the reflected color tone is preferably less glossy and has a bluish reflective color tone.
  • the touch panel substrate of the present invention is obtained by further forming an insulating film and a transparent electrode on the resin BM substrate of the present invention.
  • the jumper wiring 5 made of a transparent electrode such as ITO is formed on the transparent substrate 2.
  • the following method can be used.
  • an ITO film is formed on the transparent substrate 2 on which the two-layer BM is formed by a sputtering method or a vacuum evaporation method.
  • a novolac positive resist is applied on the ITO film, the positive resist is dried, exposed and developed, and then the ITO film is etched with an acid to pattern the ITO film.
  • the jumper wiring 5 is formed by peeling the positive resist with alkali.
  • a first insulating film 6 is formed on the jumper wiring 5.
  • the second insulating film 10 may be formed on the resin BM for the purpose of protecting the resin BM.
  • the insulating film both an organic film and an inorganic film are preferably used.
  • the insulating film made of an organic film is formed by applying, drying, exposing, developing, and heat-curing a general acrylic negative resist.
  • the metal wiring 7 is formed on the resin BM and / or on the second insulating film.
  • a method for forming the metal wiring for example, a metal film having a three-layer structure in which a Mo layer, an Al layer, and a Mo layer are sequentially formed is formed by sputtering, and then the metal film is patterned in the same manner as the jumper wiring. The method of performing is mentioned.
  • a transparent electrode 8 is formed on the transparent substrate 2 in the same manner as the jumper wiring 5 so as to be electrically connected to the metal wiring 7.
  • the protective film 9 is formed so as to cover each member formed as described above.
  • the protective film 9 both an organic film and an inorganic film are preferably used.
  • the color filter of the present invention is one in which red, green or blue pixels are formed in a portion (hereinafter referred to as an opening) where the two-layer resin BM is not formed on the resin BM substrate of the present invention.
  • red, green or blue pixels are formed by a known method.
  • Examples of the material of the pixel include an inorganic film whose film thickness is controlled so as to transmit only arbitrary light, or a colored resin film in which a dye or pigment is dispersed in a binder resin. Among these, a colored resin film in which a pigment is dispersed in a binder resin is preferable.
  • the binder resin include acrylic copolymer, polyvinyl alcohol, polyamide, and polyimide. From the viewpoint of heat resistance and chemical resistance, polyimide is preferable.
  • pigment those excellent in light resistance, heat resistance and chemical resistance are preferable.
  • red pigments examples include C.I. I. Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240 or 254.
  • orange pigments examples include C.I. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 or 71.
  • yellow pigments examples include C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 83, 86, 93, 94, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 173, 180 or 185.
  • purple pigments examples include C.I. I. Pigment violet 19, 23, 29, 30, 32, 36, 37, 38, 40 or 50.
  • blue pigments examples include C.I. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 22, 60, 64 or 80.
  • green pigments examples include C.I. I. Pigment green 7, 10, 36 or 58.
  • pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment or the like, and a pigment derivative may be added as a dispersant, as necessary.
  • An overcoat film may be formed on the pixel as necessary.
  • the overcoat film include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a silicon-containing polyimide film, and a polyimidesiloxane film.
  • a transparent conductive film may be further formed on the overcoat film.
  • the transparent conductive film include an oxide thin film such as ITO having a film thickness of about 0.1 ⁇ m.
  • Examples of the method for producing the ITO film include a sputtering method and a vacuum evaporation method.
  • a liquid crystal display device can be produced by laminating the color filter substrate and the counter substrate of the present invention and filling a gap between them with a liquid crystal compound. May form a fixed spacer.
  • the fixed spacer refers to a spacer that is fixed at a specific location on the color filter substrate and contacts the counter substrate when a liquid crystal display device is manufactured. Thus, a certain gap is maintained between the counter substrate and the liquid crystal compound is filled between the gaps.
  • a display device can be manufactured by bonding the color filter substrate of the present invention and a light emitting element.
  • organic electroluminescence element As the light emitting element, an organic electroluminescence element (hereinafter referred to as “organic EL element”) is preferable.
  • the display device of the present invention effectively shields excess light from the light emitting element in black display and suppresses reflection of external light by utilizing the feature that the two-layer resin BM substrate has high OD and low reflection. A clear display with high contrast can be obtained.
  • a flexible color filter substrate can be produced.
  • a flexible display device can be obtained by bonding the flexible color filter substrate and the light emitting element. If an organic EL element is used as the light emitting element, a flexible organic EL display can be produced.
  • a resin BM having a desired film thickness is formed on a chemically tempered glass (Gorilla; manufactured by Corning) having a thickness of 0.7 mm, and measured using a microspectroscope (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a two-degree field of view.
  • MCPD2000 manufactured by Otsuka Electronics Co., Ltd.
  • the transmission chromaticity coordinates in the CIE 1931 color system were measured.
  • the OD value of the two-layer resin BM is determined by measuring the two-layer resin BM formed on the transparent substrate using a microspectroscope (manufactured by Otsuka Electronics Co., Ltd., MCPD300). It calculated from Formula (1).
  • the OD value per 1 ⁇ m thickness of the resin BM is such that a resin BM having a thickness of 1.0 ⁇ m is formed on a chemically tempered glass having a thickness of 0.7 mm, and the resin BM is obtained using a microspectroscope (manufactured by Otsuka Electronics Co., Ltd., MCPD300).
  • the intensity of each of the incident light and transmitted light from the coating surface was measured and calculated from the following formula (1).
  • OD value log 10 (I 0 / I) (1)
  • I 0 Incident light intensity
  • I Transmitted light intensity.
  • a resin BM having a desired film thickness was formed on a chemically tempered glass having a thickness of 0.7 mm, and the reflection chromaticity from the glass surface was measured using a spectroscopic clock (UV-2500PC; manufactured by Shimadzu Corporation) (measurement) Wavelength region: 300 to 780 nm, sampling pitch: 1.0 nm, scan speed: low speed, slit width: 2.0 nm).
  • a black printing ink (GLS-912; manufactured by Teikoku Ink) was printed on a chemically tempered glass having a thickness of 0.7 mm using a 230 mesh plate so that the thickness after drying was 10 ⁇ m, and then at 150 ° C. for 30 minutes. Oven drying was performed to prepare a sample BM.
  • a desired resin BM was formed on a chemically tempered glass having a thickness of 0.7 mm, and visually compared with the above sample BM under sunlight, and the reflection color tone was determined based on the following criteria.
  • Synthesis of acrylic polymer (P-1) 100 parts by mass of the copolymer obtained after synthesizing a methyl methacrylate / methacrylic acid / styrene copolymer (mass composition ratio 30/40/30) by the method described in the literature (Japanese Patent No.
  • the preliminary dispersion was supplied to an ultra apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 0.05 mm ⁇ zirconia beads (YTZ balls; manufactured by Netulen) and dispersed for 3 hours at a rotational speed of 8 m / s.
  • Colorant dispersion DR-1 was obtained in the same manner as colorant dispersion DB-1, except that red organic pigment PR254 (manufactured by BASF) was used as the colorant instead of blue organic pigment PB15: 6.
  • a colorant dispersion DV-1 was obtained in the same manner as the colorant dispersion DB-1, except that a purple organic pigment PV23 (manufactured by Clariant) was used instead of the blue organic pigment PB15: 6 as the colorant.
  • titanium nitride particles manufactured by Nissin Engineering Co., Ltd.
  • the pre-dispersed liquid was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 75% 0.05 mm ⁇ zirconia beads, and dispersed at a rotational speed of 8 m / s for 3 hours to obtain a solid concentration of 25
  • a colorant dispersion DK-2 having a mass%, colorant / resin (mass ratio) 80/20 was obtained.
  • a photosensitive colored resin composition A-1 having a blue pigment / red pigment (mass ratio) of 40/60 was prepared.
  • Example 1 The prepared photosensitive colored resin composition A-1 was filtered through a 2 ⁇ m Teflon (registered trademark) filter, and then applied onto a 0.7 ⁇ m thick chemically tempered glass substrate so that the film thickness became 1.5 ⁇ m (after post-baking). The coating was applied with a spin coating apparatus 1H-DS manufactured by Mikasa Corporation. The substrate coated with the photosensitive colored resin composition A-1 was heated for 2 minutes with pin-shaped protrusions on a hot plate at 90 ° C., and further pre-baked by leaving the substrate directly on the hot plate for 2 minutes. . A mask aligner (PEM-6M; manufactured by Union Optics Co., Ltd.) was used for this coating film, and ultraviolet rays were exposed at a dose of 200 mJ / cm 2 through a resolution test mask.
  • PEM-6M manufactured by Union Optics Co., Ltd.
  • the BM (B)- has a thickness of 1.4 ⁇ m on the BM (A) -1 substrate. 1 was formed to prepare a two-layer BM-1.
  • Example 2 A BM (A) -2 substrate was obtained in the same manner as BM (A) -1, except that A-2 was used as the photosensitive colored resin composition.
  • Example 3 A BM (A) -3 substrate was obtained in the same manner as BM-1, except that A-2 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • the BM (B)- has a thickness of 1.4 ⁇ m on the BM (A) -3 substrate. 1 was formed to prepare a two-layer BM-3.
  • Example 4 A BM (A) -4 substrate was obtained in the same manner as BM-1, except that A-2 was used as the photosensitive colored resin composition and the film thickness was 0.7 ⁇ m.
  • the BM (B)- has a thickness of 1.4 ⁇ m on the BM (A) -4 substrate. 1 was formed to prepare a two-layer BM-4.
  • Example 5 A BM (A) -5 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was adjusted to 1.5 ⁇ m.
  • BM (B)- so that the film thickness is 1.4 ⁇ m on the BM (A) -5 substrate in the same manner as BM (A) -1, except that B-1 is used as the photosensitive colored resin composition. 1 was formed to prepare a two-layer BM-6.
  • Example 6 A BM (A) -6 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • the BM (B)- has a thickness of 1.4 ⁇ m on the BM (A) -6 substrate. 1 was formed to prepare a two-layer BM-6.
  • Example 7 A BM (A) -7 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was 0.7 ⁇ m.
  • Example 8 A BM (A) -8 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 1.5 ⁇ m.
  • Example 9 A BM (A) -9 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • BM (B)- so that the film thickness is 1.4 ⁇ m on the BM (A) -9 substrate, in the same manner as BM (A) -1, except that B-1 is used as the photosensitive colored resin composition. 1 was formed to prepare a two-layer BM-9.
  • a BM (A) -10 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 0.7 ⁇ m.
  • Example 11 A BM (A) -11 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was adjusted to 1.5 ⁇ m.
  • the BM (B)- has a thickness of 1.4 ⁇ m on the BM (A) -11 substrate. 1 was formed to prepare a two-layer BM-11.
  • Example 12 A BM (A) -12 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • a BM (A) -13 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was 0.7 ⁇ m.
  • BM (B)- so that the film thickness is 1.4 ⁇ m on the BM (A) -13 substrate in the same manner as BM (A) -1, except that B-1 is used as the photosensitive colored resin composition. 1 was formed to prepare a two-layer BM-13.
  • a BM (A) -14 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.5 ⁇ m.
  • a BM (A) -15 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • Example 16 A BM (A) -16 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 0.7 ⁇ m.
  • Example 17 A BM (A) -17 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was adjusted to 1.5 ⁇ m.
  • Example 18 A BM (A) -18 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • Example 19 A BM (A) -19 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 0.7 ⁇ m.
  • BM (B)- so that the film thickness is 1.4 ⁇ m on the BM (A) -19 substrate, in the same manner as BM (A) -1, except that B-1 is used as the photosensitive colored resin composition. 1 was formed to prepare a two-layer BM-19.
  • a BM (A) -20 substrate was obtained in the same manner as BM-1, except that A-1 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • a BM (A) -21 substrate was obtained in the same manner as BM-1, except that A-2 was used as the photosensitive colored resin composition and the film thickness was 0.5 ⁇ m.
  • a BM (A) -22 substrate was obtained in the same manner as BM-1, except that A-3 was used as the photosensitive colored resin composition and the film thickness was 0.5 ⁇ m.
  • a BM (A) -23 substrate was obtained in the same manner as BM-1, except that A-4 was used as the photosensitive colored resin composition and the film thickness was 0.5 ⁇ m.
  • a BM (A) -24 substrate was obtained in the same manner as BM-1, except that A-5 was used as the photosensitive colored resin composition and the film thickness was 0.5 ⁇ m.
  • BM (B)- so that the film thickness is 1.4 ⁇ m on the BM (A) -24 substrate in the same manner as BM (A) -1, except that B-1 is used as the photosensitive colored resin composition. 1 was formed to prepare a two-layer BM-24.
  • a BM (A) -25 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.5 ⁇ m.
  • BM (B)- so that the film thickness is 1.4 ⁇ m on the BM (A) -25 substrate in the same manner as BM (A) -1, except that B-1 is used as the photosensitive colored resin composition. 1 was formed to prepare a two-layer BM-25.
  • a BM (A) -26 substrate was obtained in the same manner as BM-1, except that A-6 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • a BM (A) -27 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 1.5 ⁇ m.
  • a BM (A) -28 substrate was obtained in the same manner as BM-1, except that A-7 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • BM (B)- so that the film thickness is 1.4 ⁇ m on the BM (A) -28 substrate in the same manner as BM (A) -1, except that B-1 is used as the photosensitive colored resin composition. 1 was formed to prepare a two-layer BM-28.
  • a BM (A) -29 substrate was obtained in the same manner as BM-1, except that A-8 was used as the photosensitive colored resin composition and the film thickness was 1.5 ⁇ m.
  • a BM (A) -30 substrate was obtained in the same manner as BM-1, except that A-8 was used as the photosensitive colored resin composition and the film thickness was 1.0 ⁇ m.
  • a single layer BM is formed on a glass substrate to a thickness of 1.4 ⁇ m in the same manner as BM (A) -1, except that A-1 is not used as the photosensitive colored resin composition and B-1 is used. -31 was formed.
  • Table 1 shows the composition of the colorant dispersion used in Examples 1 to 19 and Comparative Examples 1 to 12, and Table 2 shows the composition of the photosensitive colored resin composition.
  • Tables 3 and 4 show the evaluation results of BM (A), BM (B), and two-layer BM prepared using the photosensitive colored resin composition.
  • a pigment is used as the coloring material, it is excellent in chemical resistance and heat resistance as compared with BM using a dye.
  • the resin BM substrate of the present invention can be preferably used as a BM substrate and a decoration substrate of a display device such as a liquid crystal display device, an organic EL display device, an inorganic EL display device, or a plasma display display device. It can be used more preferably as a cover glass integrated touch panel resin BM substrate.

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WO2019026858A1 (ja) * 2017-07-31 2019-02-07 大日本印刷株式会社 表示パネルおよび表示装置
JP2019028308A (ja) * 2017-07-31 2019-02-21 大日本印刷株式会社 表示パネル及び表示装置
JP2019028370A (ja) * 2017-08-02 2019-02-21 大日本印刷株式会社 表示装置用前面板及び表示装置
JP2019066613A (ja) * 2017-09-29 2019-04-25 大日本印刷株式会社 表示パネルおよびタイリング表示装置
US11156918B2 (en) * 2017-03-29 2021-10-26 Toray Industries, Inc. Photosensitive composition, cured film and organic el display device

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TWI622908B (zh) * 2016-03-18 2018-05-01 財團法人工業技術研究院 觸控顯示面板
KR102109544B1 (ko) * 2019-10-16 2020-05-12 삼성에스디아이 주식회사 컬러 필터 및 이를 포함하는 액정 표시 장치

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JP2019028308A (ja) * 2017-07-31 2019-02-21 大日本印刷株式会社 表示パネル及び表示装置
JP2019028370A (ja) * 2017-08-02 2019-02-21 大日本印刷株式会社 表示装置用前面板及び表示装置
JP2019066613A (ja) * 2017-09-29 2019-04-25 大日本印刷株式会社 表示パネルおよびタイリング表示装置

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