WO2010038669A1 - カラーフィルター用インクジェットインク組成物、カラーフィルター、カラーフィルターの製造方法、及び液晶表示装置 - Google Patents
カラーフィルター用インクジェットインク組成物、カラーフィルター、カラーフィルターの製造方法、及び液晶表示装置 Download PDFInfo
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- WO2010038669A1 WO2010038669A1 PCT/JP2009/066619 JP2009066619W WO2010038669A1 WO 2010038669 A1 WO2010038669 A1 WO 2010038669A1 JP 2009066619 W JP2009066619 W JP 2009066619W WO 2010038669 A1 WO2010038669 A1 WO 2010038669A1
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- pigment
- color filter
- ink
- pixel
- ink composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/003—Printing processes to produce particular kinds of printed work, e.g. patterns on optical devices, e.g. lens elements; for the production of optical devices
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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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
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
Definitions
- the present invention relates to an inkjet ink composition for a color filter used to form a cured layer having a predetermined pattern such as a pixel portion, a color filter, a method for producing a color filter using the inkjet ink composition, and the color filter Alternatively, the present invention relates to a liquid crystal display device using the manufactured color filter.
- a color liquid crystal display device (101) is provided with a gap portion 3 of about 1 to 10 ⁇ m with a color filter 1 and an electrode substrate 2 such as a TFT substrate facing each other. 3 is filled with a liquid crystal compound L, and the periphery thereof is sealed with a sealing material 4.
- the color filter 1 includes a light shielding portion 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between pixels, and a plurality of colors (usually R (red)) to form each pixel. , G (green), B (blue) three primary colors) arranged in a predetermined order, a protective film 8 and a transparent electrode film 9 are stacked in this order from the side close to the transparent substrate. I'm taking it.
- An alignment film 10 is provided on the inner surface side of the color filter 1 and the electrode substrate 2 facing the color filter 1. Furthermore, a spacer is provided in the gap portion 3 in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. As the spacer, pearls 11 having a constant particle diameter are dispersed, or columnar spacers 12 having a height corresponding to the cell gap as shown in FIG. 6 is formed in a region overlapping with the position where 6 is formed. A color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color filter.
- a pigment dispersion method As a conventional method for producing a color filter, there is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers. However, in this method, in order to color the three colors of R, G, and B, it is necessary to repeat the same process three times, which increases the cost, and the yield decreases because the same process is repeated. There is a problem.
- Patent Document 1 discloses that a colored layer (pixel portion) is formed by spraying colored ink containing a thermosetting resin onto a substrate by an inkjet method and heating. It is described to do.
- the inkjet ink is required to have a discharge property for discharging from a discharge head, and a straightness and stability during discharge. Also, when the colored layer (pixel portion) is formed by spraying on the substrate and heating by the inkjet method, the film thickness becomes non-uniform, unlike the case of patterning the uniformly formed photosensitive resin layer. There is a need to improve the shape of a pixel so as to have high brightness and high contrast while realizing a specific color.
- the viscosity of the ink increases as compared with the conventional case.
- the viscosity of the ink increases, ejection failure of the ink-jet ink occurs, so it is necessary to reduce the solid content in the ink.
- the solid content in the ink is lowered, it is necessary to increase the amount of ink per unit area (ink deposition amount) in order to color the desired color.
- the amount of ink is increased, the ink is provided on the substrate. There is a possibility that the ink film deposited on the ink layer forming site breaks down, protrudes to the surroundings, and mixes colors.
- the present invention has been accomplished in view of the above circumstances, and the first object thereof is excellent in straightness and stability when ejected from the head, can reduce the amount of ink, and can be reduced from the ink layer formation site.
- An object of the present invention is to provide an ink-jet ink composition for a color filter capable of providing a cured layer having a good shape and good film physical properties by suppressing breakage and spraying onto a substrate by an ink-jet method.
- a second object of the present invention is to provide a highly productive color filter including pixels having a specific color and good brightness and contrast.
- a third object of the present invention is to provide a highly productive color filter manufacturing method using an ink composition that achieves the above object.
- a fourth object of the present invention is to provide a highly reliable liquid crystal display device using a color filter that achieves the above object.
- An ink-jet ink composition for a color filter according to the present invention includes (A) a pigment containing CI Pigment Blue 15: 6 and CI Pigment Violet 23, (B) a pigment dispersant containing a polyallylamine derivative, and (C) thermosetting. It contains a binder and (D) an organic solvent, and the CI pigment violet 23 is contained in an amount of 8 to 30% by weight based on the whole pigment.
- the content of the pigment dispersant is preferably 5 to 20% by weight from the viewpoint of improving the film properties such as heat resistance of the cured layer.
- the pigment and the solid content other than the pigment A blending weight ratio (pigment / solid content other than pigment) of 0.1 to 0.4 is excellent in straightness and stability when ejected from the head, and can reduce the amount of ink and form an ink layer. It is preferable from the point which suppresses the breakdown from a site
- the viscosity is 5 to 11 mPa ⁇ s at 23 ° C., It is preferable from the viewpoint of excellent stability.
- the average dispersed particle diameter of (A) the pigment is 10 to 100 nm from the viewpoint of improving the contrast.
- the color filter according to the present invention is a color filter comprising at least a transparent substrate and pixels provided on the transparent substrate, and the thickness of the pixels is not uniform in the region of the pixels, and At least one of the pixels includes (A) a pigment containing CI pigment blue 15: 6 and CI pigment violet 23, (B) a pigment dispersant containing a polyallylamine derivative, and (C ′) a blue pixel containing a cured resin.
- the CI pixel violet 23 is contained in the blue pixel in an amount of 8 to 30% by weight based on the total amount of the pigment (A).
- the pixel thickness is non-uniform in the region of the pixel, and at least one of the pixels includes (A) CI pigment blue 15: 6 and CI pigment violet 23.
- the content of the (B) pigment dispersant is 5 to 20 wt. It is preferable from the viewpoint that film properties such as heat resistance of the blue pixel are improved.
- the blending weight ratio of the (A) pigment and the solid content other than the pigment when the film thickness is 2.0 ⁇ m and the y value of the C light source is 0.105
- the pigment / solid content other than the pigment is preferably 0.1 to 0.4 from the viewpoint of preventing color breakage by preventing breakage from the ink layer forming site.
- the average dispersed particle diameter of the pigment (A) in the blue pixel is preferably 10 to 100 nm from the viewpoint of improving the contrast.
- the present invention includes a step of selectively depositing the ink-jet ink composition for a color filter according to the present invention by an inkjet method to form an ink layer, and a step of curing the ink layer to form a pixel.
- a method for producing a color filter characterized by the above is also provided.
- the present invention is a liquid crystal display device in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed between the two, and the display side substrate includes the color filter according to the present invention, Alternatively, a liquid crystal display device that is a color filter manufactured by the method for manufacturing a color filter according to the present invention is also provided.
- the straightness and stability when ejected from the head are excellent, the amount of ink can be reduced, the breakage from the ink layer formation site is suppressed, and the cured layer has film properties such as heat resistance.
- An ink-jet ink composition for a color filter that is excellent in quality can be obtained.
- the shape of the pixel formed by the inkjet system can be made favorable.
- the color filter according to the present invention is a highly productive color filter that includes a pixel having a specific color and good luminance and contrast and can realize cost reduction and yield improvement.
- the ejection direction and ejection amount of the ink composition are excellent, and fine pixels can be accurately formed.
- the obtained pixel is excellent in film physical properties such as heat resistance, adhesion, and solvent resistance while realizing desired chromaticity.
- the manufacturing method uses an inkjet method, cost reduction and yield improvement can be realized.
- the color filter manufactured by the color filter or the color filter manufacturing method is used, a high-quality and highly productive liquid crystal display device can be provided.
- FIGS. 5A to 5C are photographs showing an example in which pixels are formed in a pixel formation portion partitioned using inkjet ink.
- the horizontal axis X is the film thickness
- the vertical axis Y is the blending weight ratio (P / V) of the solid content other than the pigment and the pigment
- Y aX It is a graph which shows the example of the relationship of ⁇ b.
- the present invention is described in detail below.
- the ink-jet ink for color filter according to the present invention comprises (A) a pigment containing CI Pigment Blue 15: 6 and CI Pigment Violet 23, and (B) a pigment dispersant containing a polyallylamine derivative.
- C) contains a thermosetting binder, and (D) an organic solvent, and the CI pigment violet 23 is contained in an amount of 8 to 30% by weight based on the entire pigment.
- the present invention relates to (A) CI Pigment Blue 15: 6 and CI Pigment Violet 23, and CI Pigment Violet 23 is contained so that the CI Pigment Violet 23 is contained in an amount of 8 to 30% by weight based on the whole pigment. Is included in comparison with the prior art.
- the total amount of pigment can be reduced, the solid content in the ink can be increased while lowering the viscosity of the ink composition.
- the amount of ink deposited per unit area can be reduced in order to color the desired color, so that the ink film deposited on the ink layer formation site provided on the substrate breaks down to the periphery. Suppresses the protrusion and eliminates the risk of color mixing.
- a pigment dispersant containing a polyallylamine derivative is used in combination with a pigment containing (A) CI Pigment Blue 15: 6 and C.I. Pigment Violet 23.
- a pigment containing (A) CI Pigment Blue 15: 6 and C.I. Pigment Violet 23 is used in combination with a pigment containing (A) CI Pigment Blue 15: 6 and C.I. Pigment Violet 23.
- the stability of the viscosity of the inkjet ink composition is improved, and a sudden increase in viscosity or clogging is difficult to occur at the nozzle tip of the inkjet head.
- the range of the film thickness distribution of the pixel adhered and cured by the ink jet method is easily narrowed, and the shape of the pixel is improved. If the range of the pixel thickness distribution is narrow and the shape of the pixel is good, it is possible to increase the luminance and contrast when realizing a specific color.
- the inkjet ink composition according to the present invention includes at least CI pigment blue 15: 6 and CI pigment violet 23 as pigments, and the CI pigment violet 23 is contained in an amount of 8 to 30% by weight based on the whole pigment. It is characterized by.
- Required color characteristics specifically, in the CIE XYZ color system when the coating film is measured with a C light source, the x coordinate is 0.133 ⁇ x ⁇ 0.145, and the y coordinate is 0.075 ⁇ .
- the CI pigment violet 23 is preferably 30% by weight or less based on the whole pigment, Furthermore, it is preferable that it is 13 weight% or less with respect to the said whole pigment.
- the pigment in the inkjet ink according to the present invention may be configured to include only the above two pigments, but other pigments may be appropriately used as long as the effects of the present invention are not impaired.
- any one of organic colorants and inorganic colorants can be selected and used.
- the organic colorant for example, dyes, organic pigments, natural pigments, and the like can be used.
- an inorganic coloring agent an inorganic pigment, an extender pigment, etc. can be used, for example.
- organic pigments are preferably used because they have high color developability and high heat resistance.
- organic pigments include compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), and specifically those having a Color Index (CI) number. be able to.
- CI Color Index
- Blue pigments such as CI Pigment Blue 17: 1; Violet pigments such as CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 37, CI Pigment Violet 38 A yellow pigment; a red pigment; a green pigment, and the like.
- the inorganic pigment or extender pigment examples include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, amber, etc. Can be mentioned.
- other pigments can be used alone or in admixture of two or more.
- the pigment is usually blended in an amount of 1 to 60% by weight with respect to the total solid content of the inkjet ink. In the present invention, it is preferably blended at a ratio of 1 to 35% by weight.
- the average particle diameter of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a pixel portion of a color filter, and is within a range of 10 to 100 nm. Preferably, it is in the range of 30 to 60 nm.
- a liquid crystal display device manufactured using the ink-jet ink composition for a color filter of the present invention can have high contrast and high quality.
- the average particle diameter of the pigment is measured by a dynamic light scattering method, and can be measured at 23 ° C. using a laser light scattering particle size distribution meter (for example, MICROTRAC UPA MODEL 9230 manufactured by Nikkiso Co., Ltd.). it can. Further, the average particle diameter here is a volume-based median diameter.
- the above pigment is formed when a uniform film thickness of 1.9 ⁇ m is formed using a method such as spin coating and the y value with a C light source is 0.105.
- the blending weight ratio (P / V) between (P) and the solid content (V) other than the pigment is 0.1 to 0.4, more preferably 0.15 to 0.3. This is preferable from the viewpoint of the balance of ejection performance, prevention of ink breakage, and film physical properties of the obtained film.
- the film thickness of 1.9 ⁇ m in the ink jet ink composition means that the average film thickness of a uniform film formed by, for example, spin coating or the like is 1.9 ⁇ m.
- the P / V ratio is too low, in order to obtain sufficient coloring power, it is necessary to increase the amount of ink droplets that adhere to the pixel formation region, which causes problems such as ink breaking from the pixel formation region. There is a case. On the other hand, if the P / V ratio is too high, there may be a problem that the ejection performance such as clogging or flight bending occurs in the ejection head or the film surface becomes rough.
- at least CI pigment blue 15: 6 and CI pigment violet 23 are contained as pigments, and the CI pigment violet 23 is contained in an amount of 8 to 30% by weight based on the whole pigment, whereby the pigment itself is colored.
- the solid content of the ink composition for specifying the blending ratio includes all components except the solvent, and includes a liquid binder component and the like.
- the pigment dispersant is blended in the ink to favorably disperse the pigment.
- the pigment dispersant used in the present invention contains a polyallylamine derivative.
- a polyallylamine derivative is used as a pigment dispersant, there is an advantage that the viscosity stability of the ink-jet ink composition is improved, and that a sudden increase in viscosity and clogging are difficult to occur at the nozzle tip of the ink-jet head. .
- the range of the film thickness distribution of the pixel adhered and cured by the ink jet method is easily narrowed, and the shape of the pixel is improved. If the range of the pixel thickness distribution is narrow and the shape of the pixel is good, it is possible to increase the luminance and contrast when realizing a specific color.
- the polyallylamine derivative used in the pigment dispersant of the present invention is preferably a polyallylamine derivative represented by the following general formula (I).
- polyallylamine and a polyester, polyamide, or ester having a free carboxyl group And an amide co-condensate are obtained by reacting one or more compounds selected from three types of compounds.
- R 1 is a free amino group, represented by the following general formula (II) or (III)
- n represents an integer of 2 to 1,000, provided that at least one of n R 1 represents a group represented by the general formula (III).
- R 2 represents a residue obtained by removing a carboxyl group from either a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid.
- the polyallylamine derivative used in the present invention is represented by the following general formula (IV) or (V) having, for example, a polyallylamine having a polymerization degree of 2 to 1,000 and a free carboxyl group.
- One kind of a polyester represented by general formula (VI) or (VII) below or a combination of two or more kinds can be used as a raw material.
- R 3 represents a linear or branched alkylene group having 2 to 20 carbon atoms, and a represents an integer of 2 to 100
- R 4 is a linear or branched alkylene group having 2 to 20 carbon atoms, C 6 H 4 or CH ⁇ CH
- R 5 is a linear or branched alkylene group having 2 to 20 carbon atoms.
- the chain may also have an ether bond.
- R 6 represents a linear or branched alkylene group having 2 to 20 carbon atoms, and c represents an integer of 2 to 100
- R 4 is a linear or branched alkylene group having 2 to 20 carbon atoms, C 6 H 4 or CH ⁇ CH
- R 7 is a linear or branched alkylene group having 2 to 20 carbon atoms.
- a group, and d represents an integer of 2 to 100.
- the polyallylamine derivative used in the present invention is a polyester in which the repeating components of the general formula (IV) and the general formula (V) are randomly polymerized on the polyallylamine, the repeating of the general formula (VI) and the general formula (VII).
- Manufactured by reacting a polyamide in which the components are randomly polymerized, and further a polyester amide in which the repeating components of the general formulas (IV) and / or (V) and general formulas (VI) and / or (VII) are randomly polymerized. be able to.
- the polyallylamine used for the production of the polyallylamine derivative is obtained by polymerizing allylamine in the presence of a polymerization initiator, and in some cases in the presence of a chain transfer catalyst.
- the number average molecular weight of the polyallylamine used in the present invention is not particularly limited as long as it is 150 to 100,000, but 600 to 20,000 polyallylamine is preferable from the viewpoint of pigment dispersibility.
- the molecular weight of the polyester used for the production of the polyallylamine derivative may be in the range of 300 to 20,000, but is preferably 1,000 to 10,000 from the viewpoint of pigment dispersibility.
- the molecular weight of the polyallylamine derivative used in the present invention is preferably 2000 to 100,000.
- the polyallylamine derivative of the present invention forms an acid amide at a ratio of 2 mol or more of the terminal carboxyl group of polyester, polyamide or a co-condensate of ester and amide (polyesteramide) with respect to polyallylamine having n amino groups. What reacted is preferable at the point of pigment dispersibility.
- n of R 1 s contain residues in the range of 60 to 95% bonded by an acid amide bond represented by the general formula (III). Are preferably present in a range of 65 to 90% of residues in a form linked by an acid amide bond.
- the polyallylamine derivative of the present invention has a weight ratio of 1/5 to 1/30 of polyallylamine and a polyester, polyamide or ester / amide cocondensate (polyesteramide) having a carboxyl group at one end.
- the amine value (mgKOH / g) of the polyallylamine derivative is preferably 5 to 30 from the viewpoint of pigment dispersibility.
- Azisper Pb821 manufactured by Ajinomoto Fine Techno Co., Ltd.
- Azisper Pb821 manufactured by Ajinomoto Fine Techno Co., Ltd.
- the like can be used as a commercial product.
- the pigment dispersant may contain only the polyallylamine derivative, but may further contain other pigment dispersants as long as the effects of the present invention are not impaired.
- examples of other pigment dispersants that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
- polymer surfactants having a molecular weight of 1000 or more are preferable.
- the polymer surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc.
- the content of the pigment dispersant is usually preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the pigment.
- the content of the pigment in the solid content can be reduced. Therefore, the amount of the pigment dispersant can be relatively reduced. If the amount of the pigment dispersant can be reduced, there is an advantage that the heat resistance of the colored layer (pixel) to be obtained is improved. If the heat resistance is good, for example, it is possible to prevent the pixel from being discolored and the brightness and contrast from being lowered after a post-baking process such as heating at 240 ° C. for 40 minutes in the color filter manufacturing process.
- a film having a uniform film thickness of 1.9 ⁇ m is formed using a method such as a spin coating method from the viewpoint of pigment dispersibility, pigment dispersion stability over time, and heat resistance of pixels, and a C light source is used.
- the content of the (B) pigment dispersant in the solid content of the inkjet ink composition is preferably 5 to 20% by weight, more preferably 5 to 14% by weight. It is preferable.
- the ink-jet ink composition for a color filter of the present invention contains a binder component in order to impart film formability and adhesion to a coated surface. Since the ink according to the present invention is an ink used in an ink jet system, in order to form a predetermined pattern, it can be formed by selectively adhering the ink only to a predetermined pattern formation region and solidifying it, It is not necessary to form a pattern by performing exposure and development. Therefore, as a binder component, an ink layer (coating film) pattern is formed on a substrate by an ink jet method in order to impart sufficient strength, durability, and adhesion to the coating film, and then the ink layer is polymerized by heating.
- a binder component an ink layer (coating film) pattern is formed on a substrate by an ink jet method in order to impart sufficient strength, durability, and adhesion to the coating film, and then the ink layer is polymerized by heating.
- thermosetting binder that can be cured is used.
- the film physical properties of the pixel such as solvent resistance, adhesion, and ITO resistance can be improved.
- the ITO resistance refers to resistance against defects at the time of ITO circuit formation or alignment film formation, and specifically includes heat resistance at 230 to 250 ° C. after the ITO circuit formation.
- thermosetting binder there is an advantage that a special incidental equipment such as a light irradiation device is not necessary and productivity is high.
- thermosetting binder a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction may be added.
- An epoxy group is preferably used as the thermosetting functional group.
- an epoxy compound having two or more epoxy groups in one molecule is usually used as a compound having two or more thermosetting functional groups in one molecule.
- An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included).
- the epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc.
- Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.
- binder epoxy compound which is a polymer having a relatively high molecular weight, which is usually used as a binder component.
- a polymer having at least two structural units represented by the following formula (1) and structural units represented by the following formula (2) and having two or more glycidyl groups can be used.
- R 11 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 12 is a hydrocarbon group having 1 to 12 carbon atoms.
- R 13 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- the structural unit represented by the formula (1) is derived from a monomer represented by the following formula (3).
- R 12 is a hydrocarbon group having 1 to 12 carbon atoms, which may be any of straight chain aliphatic, alicyclic, and aromatic hydrocarbon groups, and further has an additional structure, For example, it may contain a double bond, a side chain of a hydrocarbon group, a side chain of a spiro ring, an intra-ring bridged hydrocarbon group, or the like.
- the monomer represented by the above formula (3) examples include methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, n-propyl (meth) acrylate, i-butyl (meth).
- R 11 is preferably hydrogen or a methyl group
- R 12 is preferably an alkyl group having 1 to 12 carbon atoms. Among them, a methyl group and a cyclohexyl group are particularly preferable.
- the monomer represented by the above formula (3) include methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA).
- the structural unit represented by the formula (2) in the polymer is derived from a monomer represented by the following formula (4).
- the monomer represented by the formula (4) is used for introducing an epoxy group (epoxy reaction point) into the polymer.
- the ink-jet ink containing the polymer is excellent in storage stability and hardly increases in viscosity during storage and discharge operations.
- One of the reasons is the epoxy group in formula (2) or formula (4). Is presumed to be because of glycidyl group.
- an alicyclic epoxy acrylate is used instead of the monomer represented by the formula (4), the viscosity of the inkjet ink is likely to increase.
- R 13 is preferably hydrogen or a methyl group.
- Specific examples of the monomer represented by the formula (4) include glycidyl (meth) acrylate, and glycidyl methacrylate (GMA) is particularly preferable.
- the polymer may be a random copolymer or a block copolymer. Further, the polymer may contain main chain constituent units other than those of formula (1) or formula (2) as long as performance required for each detail of the color filter, such as hardness and transparency, can be ensured. Good. Specific examples of such a monomer include acrylonitrile and styrene.
- the content of the structural unit of formula (1) and the structural unit of formula (2) in the binder epoxy compound is derived from the monomer that derives the structural unit of formula (1) and the structural unit of formula (2).
- the ratio is 10:90 to 90:10 in terms of the weight ratio of the monomer to be charged (monomer that derives formula (1): monomer that derives formula (2)). preferable.
- the amount of the structural unit of the formula (1) is more than the above ratio of 10:90, there is a possibility that the reaction point of curing decreases and the crosslinking density is lowered, whereas the structural unit of the formula (2) If the amount is more than the above ratio 90:10, the bulky skeleton may be reduced and curing shrinkage may be increased.
- the weight average molecular weight of the binder epoxy compound is preferably 3,000 or more, particularly 4,000 or more when expressed in terms of polystyrene-converted weight average molecular weight. This is because if the molecular weight of the binder epoxy compound is less than 3,000, physical properties such as strength and solvent resistance required for the cured layer as the details of the color filter are likely to be insufficient. On the other hand, the weight average molecular weight of the binder epoxy compound is preferably 20,000 or less, more preferably 15,000 or less, when expressed in terms of polystyrene-converted weight average molecular weight.
- the viscosity is likely to increase, and the stability of the ejection amount and the straightness of the ejection direction when ejecting from the ejection head by the inkjet method may be deteriorated, and the stability of long-term storage It is because there is a possibility that it may become worse.
- a polystyrene-reduced weight average molecular weight (Mw) is in the above range, and a GMA / MMA copolymer polymerized using at least glycidyl methacrylate (GMA) and methyl methacrylate (MMA) is used.
- GMA glycidyl methacrylate
- MMA methyl methacrylate
- the GMA / MMA copolymer may be polymerized by containing other monomer components as long as the object of the present invention can be achieved.
- a solvent containing no hydroxyl group is charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and the temperature is raised to 120 ° C. while stirring. .
- the reason for using a solvent that does not contain a hydroxyl group is to avoid the decomposition of the epoxy group during the synthesis reaction.
- a mixture of the monomer represented by the above formula (3), the monomer represented by the above formula (4), and a composition obtained by combining other monomers as necessary with a polymerization initiator (dropping component) is 2 Drop at a constant rate from the dropping funnel over time.
- the temperature is lowered to 120 ° C., a catalyst is added, the reaction is performed for 3 hours, and the reaction is terminated when the temperature is raised to 130 ° C. and kept for 2 hours, whereby the binder epoxy compound is obtained.
- thermosetting binder according to the present invention is an epoxy compound having two or more epoxy groups in one molecule (hereinafter sometimes referred to as “polyfunctional epoxy compound”), which is more than the binder epoxy compound. Those having a small molecular weight may be used. Especially, it is preferable to use the said binder epoxy compound and the said polyfunctional epoxy compound together as mentioned above.
- the polystyrene equivalent weight average molecular weight of the polyfunctional epoxy compound is preferably 4,000 or less, and particularly preferably 3,000 or less, on condition that it is smaller than the binder epoxy compound combined therewith.
- the binder epoxy compound since an epoxy group (glycidyl group) is introduced by the structural unit represented by the formula (2), there is a limit to the amount of epoxy that can be introduced into the molecule of the copolymer.
- a polyfunctional epoxy compound having a relatively small molecular weight is added to the ink-jet ink, the epoxy group is replenished in the ink-jet ink, the reaction point concentration of the epoxy is increased, and the crosslinking density can be increased.
- polyfunctional epoxy compounds it is preferable to use an epoxy compound having four or more epoxy groups in one molecule in order to increase the crosslink density of the acid-epoxy reaction.
- the weight average molecular weight of the binder epoxy compound is set to 10,000 or less in order to improve the discharge performance from the inkjet discharge head, the strength and hardness of the cured layer are likely to decrease.
- the polyfunctional epoxy compound is not particularly limited as long as it contains two or more epoxy groups in one molecule.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, Bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy Resin, trifunctional epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Nuclear polyol type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.
- bisphenol A type epoxy resins such as trade name Epicoat 828 (Japan Epoxy Resin Co., Ltd.), bisphenol F type epoxy resins such as trade name YDF-175S (manufactured by Tohto Kasei Co., Ltd.), trade name YDB-715 ( Brominated bisphenol A type epoxy resin such as Toto Kasei Co., Ltd., bisphenol S type epoxy resin such as EPICLON EXA1514 (Dainippon Ink Chemical Co., Ltd.), hydroquinone such as YDC-1312 (Toto Kasei Co., Ltd.) Type epoxy resins, naphthalene type epoxy resins such as trade name EPICLON EXA4032 (Dainippon Ink Chemical Co., Ltd.), biphenyl type epoxy resins such as trade name Epicoat YX4000H (Japan Epoxy Resin), trade name Epicoat 157S70 (Japan) Bisphenol A type novolak epoxy resin such as Poxy Resin Co.
- bisphenol A type novolak type epoxy resins such as trade name Epicoat 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and cresol novolac type epoxy resins such as trade name YDCN-701 (manufactured by Tohto Kasei Co., Ltd.) Is particularly preferred.
- the blending ratio of the binder epoxy compound and the polyfunctional epoxy compound blended as necessary is such that the weight ratio is 10 to 80 parts by weight of the binder epoxy compound and 10 to 60 parts by weight of the polyfunctional epoxy compound. It is preferable to add 20 to 60 parts by weight of the binder epoxy compound and 20 to 50 parts by weight of the polyfunctional epoxy compound, and 30 to 40 parts by weight of the binder epoxy compound is more multifunctional. It is particularly preferable to blend the epoxy compound in a proportion of 25 to 35 parts by weight.
- thermosetting binder used in the present invention is usually combined with a curing agent.
- a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid is used.
- polyhydric carboxylic acid anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride
- Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride
- fats such as 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride
- Aromatic polycarboxylic dianhydrides aromatic polycarboxylic anhydrides such as
- polyvalent carboxylic acid used in the present invention examples include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.
- aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanete
- the amount of the curing agent used in the present invention is usually in the range of 1 to 100 parts by weight, preferably 5 to 100 parts by weight per 100 parts by weight of the epoxy group-containing component (binder epoxy compound and polyfunctional epoxy compound). 50 parts by weight. If the blending amount of the curing agent is less than 1 part by weight, curing may be insufficient and a tough coating film may not be formed. Moreover, when the compounding quantity of a hardening
- a catalyst capable of promoting an acid-epoxy thermosetting reaction may be added to the thermosetting binder of the present invention.
- a thermal latent catalyst that exhibits activity during heat curing can be used.
- the heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary.
- the thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher.
- a compound obtained by neutralizing a protonic acid with a Lewis base a compound obtained by neutralizing a Lewis acid with a Lewis base
- Lewis examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds and the like, and various compounds described in JP-A-4-218561 can be used.
- Lewis acids such as BF 3 , FeCl 3 , SnCl 4 , AlCl 3 , ZnCl 2
- Examples include primary alcohols, ester compounds with secondary alcohols, (d) primary alcohols, secondary monoalcohol phosphate monoester compounds, and phosphate diester compounds.
- Examples of the onium compound include an ammonium compound [R 3 NR ′] + X ⁇ , a sulfonium compound [R 3 SR ′] + X ⁇ , and an oxonium compound [R 3 OR ′] + X ⁇ .
- R and R ′ are alkyl, alkenyl, aryl, alkoxy and the like.
- the heat-latent catalyst is usually blended at a ratio of about 0.01 to 10.0 parts by weight with respect to a total of 100 parts by weight of the compound having two or more thermosetting functional groups in one molecule and the curing agent. .
- the ink composition of the present invention contains (D) an organic solvent in order to prepare the composition into a highly concentrated solution or an ink that can be immediately ejected from the head.
- the organic solvent is not particularly limited as long as it is a solvent that suitably dissolves and disperses solid components in order to prepare a high-concentration ink for storage or an ink that can be applied immediately.
- the ink-jet ink composition of the present invention has a boiling point of 180 ° C. to 260 ° C. in order not to cause a sudden increase in viscosity or clogging of the ink and to improve dischargeability without adversely affecting the straightness and stability of discharge.
- the main solvent is preferably blended in a proportion of preferably 80% by weight or more, particularly preferably 85% by weight or more, based on the total amount of the (D) organic solvent.
- the surface tension of the main solvent is preferably 28 mN / m or more from the viewpoint that the outflow of ink to the sparse ink portion during patterning can be reduced.
- the surface tension at 23 ° C. in the present invention can be measured by a surface tension meter (Wilhelmy method) (for example, an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.).
- the boiling point of the first solvent is 180 ° C. to 260 ° C., preferably 210 ° C. to 260 ° C. and normal temperature (especially in the range of 18 ° C. to 25 ° C.).
- a solvent component having a vapor pressure of 0.5 mmHg or less, preferably 0.1 mmHg or less is contained in an amount of 60 to 95% by weight based on the total amount of the solvent, and a solvent component having a boiling point of 130 ° C. or more and less than 180 ° C. as a second solvent.
- the content is preferably 5 to 40% by weight based on the total amount of the solvent.
- the ejectability is good and the tip of the nozzle of the inkjet head does not dry quickly, but the solute can be prevented from flowing when the ink layer is dried, and the drying speed can be adjusted appropriately. It becomes possible. Therefore, a thick film portion is hardly formed at the end of the coating film, and a highly uniform pattern with a reduced film thickness can be obtained and dried efficiently.
- the proportion of the first solvent is preferably 70 to 95% by weight of the total amount of the solvent, 75 to 95% by weight of the total amount of the solvent, and further 80 to 92% by weight of the total amount of the solvent.
- the ink-jet ink used in the present invention may further contain a small amount of a solvent component other than the first solvent and the second solvent, if necessary. This is because the ink of the present invention uses a pigment as a colorant, and therefore it may be necessary to use a dispersion solvent that easily disperses the pigment in order to prepare a pigment dispersion.
- the main solvent or the first solvent can be selected from the following solvents: glycol ethers such as ethylene glycol monohexyl ether and diethylene glycol monomethyl ether; ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate Glycol ether esters such as: Acetic acid, 2-ethylhexanoic acid, aliphatic carboxylic acids such as acetic anhydride or anhydrides thereof; Ethyl acetate, aliphatic or aromatic esters such as propyl benzoate; Diethyl carbonate Dicarboxylic acid esters such as methyl 3-methoxypropionate; alkoxy carboxylic acid esters such as ethyl acetoacetate; halo such as chloroacetic acid and dichloroacetic acid Carboxylic acids; alcohols or phenols such as ethanol, isopropanol and phenol; aliphatic or aromatic ethers such as diethyl ether and anisole
- examples include diethyl acid, dimethyl succinate, and diethyl succinate.
- These solvents not only satisfy the requirements for a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less, but also have relatively good dispersibility and dispersion stability of the pigment.
- -A pigment dispersion can be prepared by mixing with or without mixing with a solvent conventionally used for preparing a pigment dispersion such as methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA). it can.
- a solvent conventionally used for preparing a pigment dispersion such as methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA). it can.
- these solvents mentioned as specific examples were measured using the standard solution shown in the wettability test specified in JIS K6768, and the contact angle ( ⁇ ) after 30 seconds was measured by contacting the droplets.
- the contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined from the graph of the plot is 25 ° or more, and the contact with the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method.
- the requirement that the angle is 10 ° or less is satisfied. Therefore, these solvents are also used in the main solvent even in the case where the wettability variable layer is provided on the surface of the substrate for exposure and the ink is selectively attached using the difference in wettability between the exposed and unexposed areas.
- the solvent component used as a 2nd solvent is a solvent component whose boiling point is 130 to 180 degreeC. If it is the solvent which has the said boiling point, you may use it individually or in mixture of 2 or more types.
- the boiling point of each solvent component used for the second solvent is 140 ° C. to 180 ° C., particularly 140 ° C. to 175 ° C., and it is difficult to form a thick film portion at the end, and the surface This is preferable because a good coating film with reduced unevenness is easily obtained.
- the viscosity of the second solvent at 23 ° C. is preferably 0.5 to 6 mPa ⁇ s.
- the viscosity of the second solvent at 23 ° C. is preferably 0.5 to 6 mPa ⁇ s.
- the viscosity of the second solvent at 23 ° C. is preferably 0.5 to 3 mPa ⁇ s.
- the viscosity at 23 ° C. in the present invention can be measured by a falling ball viscometer, for example, an automatic micro viscometer AMVn (Nihon Sibel Hegner).
- the second solvent includes ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dipropyl ether, propylene glycol monoethyl ether, propylene glycol mono Polyhydric alcohol ethers such as propyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, glycol ethers such as dipropylene glycol dimethyl ether, and glycerin ethers such as glycerin 1,3-dimethyl ether; ethylene glycol Monomethyl ether acetate, ethylene glycol Glycol esters, including glycol ether esters, including glycol ether esters, including glycol ether esters, ethylene glycol ether esters, including glycol ether esters, including glycol ether esters, including glycol ether esters, including
- ethers including polyhydric alcohol ethers such as glycol ethers and glycerin ethers, polyhydric alcohol esters such as glycol esters and glycerin esters, aliphatic esters, alkoxycarboxylic esters, ketocarboxylic acids It is preferable to use one or more selected from the group consisting of esters including esters.
- esters and ethers as described above, even when a highly reactive resin is used for the binder component, etc., the ink will maintain good stability over time and be ejected from the inkjet head. There is an advantage that stability is improved.
- glycol ethers or glycol esters are used, the wettability with respect to the glass substrate is improved, and the ink layer formation region is easily spread to every corner, which is effective in preventing color loss of pixels. .
- ethylene glycol monoethyl ether ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, glycerin 1,3-dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monomethoxymethyl ether, pro Lenglycol monomethyl ether acetate, methyl acetoacetate, hexyl formate, cyclohexyl acetate, ethyl lactate, isoamyl propionate, butyl propionate
- the content of the second solvent is 5 to 30% by weight, more preferably 5 to 25% by weight, and particularly 8 to 20% by weight, based on the total amount of the solvent.
- it is excellent in stability when ejected from an ink jet head without impeding the effect of the first solvent, can be dried more efficiently, does not easily form a thick film portion at the end, and has surface unevenness. This is preferable from the viewpoint of easily forming a reduced good pixel or the like.
- the ink is prepared using a solvent as described above usually in a proportion of 40 to 95% by weight with respect to the total amount of the ink containing the solvent.
- the ink is appropriately adjusted so as to have a viscosity suitable for ejection from an ink jet as described later. If the amount of the solvent is too small, the viscosity of the ink is high and it becomes difficult to discharge from the inkjet head. Also, if there is too much solvent, the ink film deposited on the wettability change site will be broken before the ink deposit (ink deposition amount) for the predetermined wettability change site (ink layer formation site) is not sufficient.
- the solid content concentration relative to the total weight of the color filter ink-jet ink is preferably 15 to 25% by weight, preferably 18 to 22% by weight. If the solid content concentration is too low, it is necessary to increase the amount of ink applied to the pixels, which causes problems such as breakage during patterning. On the other hand, if the solid content concentration is too high, there may be a problem such as a decrease in discharge performance such as clogging or flight bending at the discharge head.
- the ink for ink for color filters of this invention can mix
- the following can be illustrated as such an additive.
- a) Filler For example, glass, alumina and the like.
- Adhesion promoter for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
- Leveling agents For example, acrylic surfactants, fluorine surfactants, silicone surfactants, vinyl ether surfactants and the like.
- Ultraviolet absorber For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
- Anti-aggregation agent for example, sodium polyacrylate.
- the ink-jet ink composition for a color filter of the present invention may be produced by adding and mixing each component into a solvent that is a single solvent or a mixed solvent, and dissolving or dispersing the solid component.
- a solvent having good dispersibility and dispersion stability of the pigment is prepared, and the pigment is added thereto together with the dispersant, and sufficiently stirred with a dissolver or the like to prepare a pigment dispersion.
- the obtained pigment dispersion, together with components other than the pigment, for example, is put into a solvent consisting almost of the first solvent or consisting of only the first solvent, and sufficiently stirred and mixed by a dissolver or the like.
- the inkjet solvent used in the present invention can be prepared by adding the second solvent.
- the obtained pigment dispersion is put together with components other than the pigment, for example, into a mixed solvent in which the second solvent is added to a solvent consisting essentially of the first solvent or consisting of only the first solvent, and is sufficiently removed by a dissolver or the like.
- the ink-jet ink used in the present invention can be prepared by stirring and mixing.
- an inkjet ink having a composition obtained by subtracting the amount of the solvent used for preparing the pigment dispersion from the final composition of the entire solvent is diluted to the final concentration. May be completed.
- a high-concentration inkjet ink may be prepared by introducing the pigment dispersion into a relatively small amount of the main solvent. The high-concentration ink-jet ink can be stored as it is and diluted to the final concentration just before use and used in the ink-jet method.
- the ink-jet ink composition of the present invention has a viscosity of 5 to 11 mPa ⁇ s at 23 ° C., particularly 5 to 10.5 mPa ⁇ s. It is preferable from the viewpoints of ejection properties from the head and ejection stability.
- the viscosity can be measured with a falling ball viscometer, for example, an automatic micro viscometer AMVn (Nihon Sibel Hegner Co., Ltd.).
- the inkjet ink composition according to the present invention has an average dispersion particle size of the pigment (A) measured by a laser light scattering particle size distribution meter of 10 to 100 nm, so that the pigment dispersibility and the pigment dispersion stability over time can be improved. It is preferable from the viewpoint of improving brightness and contrast when the color filter is used.
- the average dispersed particle size of the pigment (A) is preferably 30 to 60 nm.
- the concentration of the ink composition in the main solvent (first solvent) used in the ink composition can be measured by a laser light scattering particle size distribution analyzer such as 100 times.
- the average particle diameter here is a volume-based median diameter.
- the inkjet ink for a color filter according to the present invention has a horizontal axis X as a film thickness when the y value of the cured layer formed by forming the ink in a uniform film and curing is 0.105 with a C light source,
- the range of ⁇ b ⁇ 1.20 is preferable in that the ratio of pigment / solid content other than pigment (P / V) can be set low.
- the color filter according to the present invention is a color filter comprising at least a transparent substrate and pixels provided on the transparent substrate, and the thickness of the pixels is not uniform within the region of the pixels, At least one of the pixels includes (A) a pigment containing CI pigment blue 15: 6 and CI pigment violet 23, (B) a pigment dispersant containing a polyallylamine derivative, and (C ′) a cured resin. It is a blue pixel, and CI pigment violet 23 is contained in the blue pixel in an amount of 8 to 30% by weight based on the total amount of the pigment (A).
- the thickness of the pixel becomes nonuniform in the region of the pixel. That is, when a pixel is formed by an inkjet method in a region surrounded by the light-shielding part on the transparent substrate, the relationship between the ink and the surface of the light-shielding part, the height of the light-shielding part, the amount of ink to be ejected, etc.
- the shape of the pixel in the opening surrounded by the light-shielding portion has a portion with a small thickness along the outer edge portion of the pixel or in the vicinity thereof, and has a maximum thickness closer to the center of the pixel than the portion with the small thickness. Or a portion having a large thickness along the outer edge of the pixel or the vicinity thereof, and a minimum thickness portion on the center side of the pixel from the thick portion. Or have a concavo-convex shape on the surface.
- the color filter of the present invention (A) a pigment containing CI pigment blue 15: 6 and CI pigment violet 23, (B) a pigment dispersant containing a polyallylamine derivative, and (C ′) a cured resin.
- the CI pixel violet 23 is contained in the blue pixel in an amount of 8 to 30% by weight based on the total amount of the pigment (A), so that the pixel is formed by an inkjet method. Even if the film has a non-uniform thickness, heat resistance and the like are improved while realizing a specific color, and it is possible to suppress discoloration and decrease in luminance and contrast.
- the film thickness of the pixel is not uniform, but a good shape with a relatively small difference in film thickness is obtained. be able to.
- FIG. 2 is a longitudinal sectional view showing an example of the color filter (color filter 103) according to the present invention.
- the color filter 103 covers the light shielding part 6 formed in a predetermined pattern on the transparent substrate 5, the pixels 7 (7R, 7G, 7B) formed in a predetermined pattern on the light shielding part, and the pixels.
- the formed protective film 8 is provided.
- a transparent electrode film 9 for driving liquid crystal is formed on the protective film 8.
- the protective film 8 may not be provided.
- An alignment film 10 is formed on the innermost surface of the color filter 103, in this case on the transparent electrode.
- the columnar spacer 12 is a shape of a convex spacer, and is formed at predetermined multiple locations (four locations in FIG. 2) on the transparent electrode 9 in accordance with the region (non-display region) where the light shielding portion 6 is formed. Yes.
- the columnar spacer 12 is formed on the transparent electrode 9, the pixel 7, or the protective film 8.
- columnar spacers are formed in a sea-island shape on the protective film 8 via the transparent electrode film 9, but the protective film 8 and the columnar spacer 12 are integrally formed and covered thereover.
- a transparent electrode film 9 may be formed.
- a columnar spacer can be formed in a region where pixels are not formed.
- the transparent substrate 5 is not particularly limited as long as it is conventionally used for a color filter.
- the transparent substrate 5 is not transparent, such as quartz glass, Pyrex (registered trademark) glass, or synthetic quartz plate.
- a transparent material having flexibility such as a rigid material, a transparent resin film, an optical resin plate, or the like can be used.
- Corning 7059 glass is a material having a small coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the active matrix. Suitable for color filters for color liquid crystal display devices.
- a transparent substrate is usually used, but a reflective substrate or a white colored substrate can also be used.
- the pixel of the color filter according to the present invention is characterized in that the thickness is not uniform within the pixel region.
- the shape of the pixel according to the present invention is a shape having a portion with a small thickness along the outer edge portion of the pixel or the vicinity thereof, and having a maximum thickness portion on the center side of the pixel with respect to the portion with the small thickness.
- the shape has a portion with a large thickness along the outer edge portion of the pixel or in the vicinity thereof, and a portion with a minimum thickness on the center side of the pixel with respect to the thick portion.
- the surface may be uneven.
- the outer edge portion of the pixel is an edge portion that defines the planar shape of the pixel.
- the outer edge portion of the pixel or the vicinity thereof means that it is only necessary to have a portion having a small thickness along at least a part of the outer edge portion or the vicinity thereof.
- the pixel thickness refers to the height from the reference surface (surface having an average height) of the substrate.
- the thickness being non-uniform within the pixel region means a case where the difference in thickness is 0.1 ⁇ m or more.
- the thickness of the pixel can be measured using, for example, an optical interference type three-dimensional non-contact surface shape measuring device (product name Micromap 557N manufactured by US Micromap).
- Micromap 557N manufactured by US Micromap
- FIGS. 3A and 3B are cross-sectional views of an example of the pixel of the color filter according to the present invention in the direction perpendicular to the transparent substrate.
- the pixel 21 has a portion 24 having a small thickness at the outer edge portion 22 of the pixel or the vicinity 23 thereof, and is closer to the center of the pixel than the portion 24 having the small thickness.
- the shape has a maximum thickness portion 25.
- a pixel having a non-uniform thickness, such as a pixel having a cross-sectional shape in which the vicinity of the central portion is raised, can be obtained when formed using, for example, an inkjet method.
- pixels can be formed with high definition, and there is an advantage that cost reduction and yield improvement can be realized.
- a pixel with a non-uniform thickness such as a pixel having a cross-sectional shape in which the vicinity of the central portion is raised, may be formed by a method other than the inkjet method.
- a pixel having a cross-sectional shape in which the vicinity of the center as described above is raised is significantly different from the shape of a pixel formed by using a photolithography method.
- a pixel formed using the photolithography method has a substantially constant thickness, and there is a portion where the thickness is not constant, there is usually no bulge in the vicinity of the center of the pixel, and the end of the pixel. There is a swell in the part of the part that rides on the shading part.
- the pixel of the color filter according to the present invention includes a pigment in which at least one of the pixels contains (A) CI pigment blue 15: 6 and CI pigment violet 23, and (B) a pigment dispersant containing a polyallylamine derivative.
- C ′ a blue pixel containing a cured resin, and CI pigment violet 23 is contained in the blue pixel in an amount of 8 to 30% by weight based on (A) the entire pigment.
- a blue pixel including a specific amount of a specific pigment and a specific pigment dispersant is formed by an ink jet method, and has a specific cross-sectional shape, for example, raised near the center. While realizing the color, the heat resistance is good, and it is possible to suppress discoloration and decrease in luminance and contrast.
- the pixel has a non-uniform film thickness, it has a favorable shape with a relatively small difference in film thickness, so that it is possible to obtain good luminance and contrast.
- the pigment containing (A) CI Pigment Blue 15: 6 and CI Pigment Violet 23 and the pigment dispersant containing (B) a polyallylamine derivative are preferably the same as those in the inkjet ink composition described above. Is omitted.
- (C ′) curable resin refers to a resin obtained by curing a curable binder.
- the curable resin is preferably a resin obtained by thermosetting the (C) thermosetting binder as described above in the inkjet ink for a color filter.
- the thermosetting binder is preferably the same as that of the inkjet ink composition, and the description thereof is omitted here.
- the content of the pigment dispersant containing (B) polyallylamine derivative is 5 to 20% by weight, and further 5 From 14 to 14% by weight is preferable from the viewpoint of film properties such as coloring power and heat resistance.
- the film thickness of 2.0 ⁇ m in the above pixel means that the average film thickness of the non-uniform film formed by the inkjet method is 2.0 ⁇ m.
- Min is preferably from 0.1 to 0.4, more preferably from 0.15 to 0.3, from the viewpoint of film properties such as coloring power and heat resistance.
- the average dispersed particle diameter of the pigment is preferably 10 to 100 nm, more preferably 30 to 60 nm, from the viewpoint that the luminance and contrast can be increased when realizing a specific color.
- An electron microscope is used to measure the average dispersed particle diameter of the pigment in the blue pixel.
- a blue pixel is thinned in a cross-sectional direction by using a FIB (focused ion beam apparatus) (for example, FB-2000A manufactured by Hitachi), and the cross-sectional sample thereof is, for example, a transmission electron microscope (for example, JEM-200CX manufactured by JEOL, acceleration voltage 100 kV) Measured at 10,000 to 500,000 times, the minor axis diameter and the major axis diameter were measured, and the volume (weight) of each particle was obtained with respect to 100 or more particles having the average as the particle diameter. It can be obtained by approximating a rectangular parallelepiped, and a volume average particle diameter can be obtained and used as an average particle diameter.
- FIB focused ion beam apparatus
- a pixel is usually formed of three colors of red (R), green (G), and blue (B).
- the coloring pattern shape in the pixel can be a known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type, and the coloring area can be arbitrarily set.
- the pixel thickness is usually about 0.5 to 2.5 ⁇ m. Alternatively, the thickness of each color pixel may be changed so that the red pixel 7R is the thinnest, and the green pixel 7G and the blue pixel 7B become thicker in this order, and the optimum thickness may be set for each color.
- the light shielding portion 6 is provided so as to surround the pixels 7R, 7G, and 7B and the outside of the pixel formation region in order to improve the contrast of the display image.
- the light shielding portion 6 may be a metal thin film such as chromium by sputtering, vacuum deposition, or the like.
- the light shielding part 6 may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder.
- a resin layer containing light-shielding particles there are a method of patterning by development using a photosensitive resist and a method of patterning using an inkjet ink containing light-shielding particles.
- the thickness of the light shielding portion is about 1000 to 2000 mm in the case of a metal thin film, and about 0.5 to 2.5 ⁇ m in the case of a light shielding resin layer.
- the light shielding part may contain a liquid repellent material exhibiting liquid repellency.
- a liquid-repellent material By including such a liquid-repellent material, a substrate having a light-shielding portion with excellent liquid repellency can be obtained without performing a liquid-repellent step for making the light-shielding portion liquid-repellent before the pixel forming step. Can do. If the light-shielding part is excellent in liquid repellency, it can effectively prevent the ink jet ink discharged to the opening surrounded by the light-shielding part in the ink layer forming step described later from leaking to the adjacent opening. Color mixing can be prevented from occurring in the color filter.
- the liquid repellent material used in the present invention is not particularly limited as long as a desired liquid repellency can be exhibited when the light shielding portion is formed.
- Examples of such a liquid repellent material include a fluorine-containing compound and fine particles of a low surface energy substance.
- fluorine-containing compound examples include monomers or oligomers of compounds represented by the following formula (1) or (2).
- Rf and Rf ′ represent a fluoroalkyl group
- R and R ′ represent an alkylene group
- Rf and Rf ′ may be the same or different. good.
- X, X ′ and Y are —COO—, —OCOO—, —CONR ′′ —, —OCONR ′′ —, —SO 2 NR ′′ —, —SO 2 —, —SO 2 O—, —O—, It represents any one of —NR ′′ —, —S—, —CO—, OSO 2 O—, —OPO (OH) O—, and X, X ′ and Y may be the same or different.
- R ′′ represents an alkyl group or hydrogen.
- the fluorine-containing compound polytetrafluoroethylene, perfluoroethylenepropylene resin, perfluoroalkoxy resin, or the like can also be used.
- the fine particles of the low surface energy substance include fine particles composed of polyvinylidene fluoride, a fluoroolefin vinyl ether copolymer, a trifluoroethylene-vinylidene fluoride copolymer, and silicone fine particles. it can.
- a hydrophilic / hydrophobic pattern in which the liquid repellency of the light shielding portion is higher than that of the substrate surface in the opening may be formed by irradiating with plasma using a fluorine compound or the like as an introduction gas.
- the protective film 8, the transparent electrode film 9, the alignment film 10, the columnar spacer 12 and the like are not particularly limited, and can be appropriately formed by a known method using a known material.
- the method for producing a color filter according to the present invention comprises forming an ink layer by selectively attaching the ink-jet ink composition for a color filter according to the present invention to the ink-jet ink for a color filter by an ink-jet method. And a step of curing the ink layer to form a pixel. Since the color filter manufacturing method according to the present invention uses an ink jet method, cost reduction and yield improvement can be realized, and the manufacturing method is highly productive.
- FIGS. 4 (A) to 4 (E) An example of a method for manufacturing a color filter according to the present invention will be described with reference to FIGS. 4 (A) to 4 (E).
- a transparent substrate for a color filter is prepared as shown in FIG.
- the light shielding portion 6 is formed in a region serving as a boundary between the pixel portions on the one surface side of the transparent substrate 5.
- a metal thin film as the light shielding portion 6 it can be formed by patterning the thin film.
- the patterning method a normal patterning method such as a sputtering method or a vacuum deposition method can be used.
- a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the resin binder as the light-shielding portion 6, as a patterning method a photolithography method
- a generally used method such as a printing method can be used. Or you may form using an inkjet system similarly to the pixel 7 mentioned later.
- an ink-repellent partition wall having a narrower width than the light shielding part may be formed at the center of the light shielding part pattern in the width direction, if necessary.
- the composition of such an ink repellent partition is not particularly limited as long as it is a resin composition having ink repellent properties. Moreover, it does not need to be transparent in particular and may be colored. For example, a material that is used for the light-shielding portion and does not include a black material can be used. The liquid repellent material is preferably used. Further, the ink repellent partition wall may have a surface treated with an ink repellent treatment agent such as a silicon compound or a fluorine-containing compound.
- the patterning of the ink-repellent partition walls can be performed by printing using an ink-repellent resin composition coating liquid or photolithography using a photo-curable coating liquid.
- the height of the ink repellent partition is preferably set to a certain degree because it is provided to prevent ink from being mixed when colored by the ink jet method as described above.
- the thickness is preferably close to the thickness of the pixel. Specifically, although it varies depending on the amount of ink to be sprayed, it is usually preferably in the range of 0.1 to 2.5 ⁇ m.
- an ink-jet ink for a color filter according to the present invention and an ink-jet ink for a color filter in which green (G) and red (R) pigments are blended are prepared for blue (B).
- the pixel forming inkjet ink of the corresponding color is formed on the pixel forming regions 31 ⁇ / b> R, 31 ⁇ / b> G, 31 ⁇ / b> B of each color defined by the pattern of the light shielding portion 6 on the surface of the transparent substrate 5.
- the ink layer is formed so that a red pattern, a green pattern, and a blue pattern are arranged in a desired form such as a mosaic type, a stripe type, a triangle type, or a four-pixel arrangement type.
- a desired form such as a mosaic type, a stripe type, a triangle type, or a four-pixel arrangement type.
- the ink of the corresponding color can be adhered accurately and uniformly in a predetermined pixel formation region, and a pixel portion free from color unevenness and color loss can be formed with an accurate pattern.
- the inkjet ink for pixel formation of each color can be simultaneously sprayed on the substrate using a plurality of heads, the working efficiency is improved as compared with the case where the pixel portion is formed for each color by a method such as printing. Can do.
- the ink layers 33R, 33G, and 33B of the respective colors are dried and pre-baked as necessary, and then cured by appropriate exposure and / or heating.
- the crosslinking element of the curable resin contained in the inkjet ink causes a crosslinking reaction, and the ink layer is cured to form pixels.
- the protective film 8 is formed on the side of the transparent substrate on which the pixels 34R, 34G, and 34B are formed.
- the protective film can be formed by a method such as spin coater, roll coater, spray, printing, etc. using a transparent resin composition. For example, it is preferably formed by applying a spin coater within a range of 500 to 1500 revolutions / minute, and then curing by exposure and / or heating.
- the transparent electrode on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof, such as sputtering, vacuum deposition, CVD, etc. It is formed by a general method, and can be formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. In others, it can manufacture using the method similar to the method of forming a normal color filter.
- ITO indium tin oxide
- ZnO zinc oxide
- SnO tin oxide
- alloys thereof such as sputtering, vacuum deposition, CVD, etc. It is formed by a general method, and can be formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. In others, it can manufacture using the method similar to the method of forming a normal color filter.
- the liquid crystal display device according to the present invention is a liquid crystal display device in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed between the two, and the display side substrate is The color filter according to the present invention, or the color filter manufactured by the method for manufacturing a color filter according to the present invention. Since the liquid crystal display device according to the present invention uses the color filter having pixels with high brightness and contrast as described above, the liquid crystal display device can be a high-quality and highly productive liquid crystal display device.
- An active matrix color liquid crystal display device belonging to the liquid crystal display device according to the present invention can be obtained by filling the gap between the substrates with liquid crystal and sealing it. Since other configurations and manufacturing methods in the liquid crystal display device can use commonly used configurations and methods, description thereof is omitted here.
- the liquid crystal display device of the present invention is not particularly limited as long as it has the above-described color filter, and may be a known liquid crystal display device. Specifically, IPS (In-Plane Switching) type, STN (Super Twisted Nematic) type, TN (Twisted Nematic) type, ferroelectric type, antiferroelectric type, MVA mode type and the like can be mentioned.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.
- Examples 1-3 and Comparative Examples 1-2 Preparation of inkjet ink composition for color filter
- pigment dispersion A pigment, a pigment dispersant, and an organic solvent are mixed at the ratio shown below, 500 parts by weight of zirconia beads having a diameter of 0.3 mm are added, and a paint shaker (manufactured by Asada Steel Corporation) is used.
- PB15: 6 CI Pigment Blue 15: 6) pigment dispersion
- PV23 CI Pigment Violet 23
- Pigment 10 parts by weight Pigment dispersant (Ajisper Pb821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) (solid content 30% by weight in organic solvent)): 20 parts by weight BCA (diethylene glycol monobutyl ether acetate): 50 parts by weight
- inkjet ink PB15: 6 (C.I. Pigment Blue 15: 6) pigment dispersion obtained above and PV23 (C.I.) so as to obtain a blending ratio as shown in Table 2 Pigment Violet 23)
- the binder solution and a solvent are further added and mixed well, and a y value with a C light source of 0.105 can be achieved at a film thickness of 1.9 ⁇ m.
- Inkjet ink compositions for color filters of Examples 1 to 3 and Comparative Examples 1 to 2 were obtained.
- EPP as the second solvent is ethyl 3-ethoxypropionate.
- the first solvent (BCA) is appropriately increased or decreased so that the composition ratio of the pigment, pigment dispersant and binder remains fixed, and the second solvent is 10% by weight of the total amount of ink. Then, the solid content maximum value was determined when the ink compositions of the examples and comparative examples satisfy the appropriate viscosity at the time of inkjet discharge (viscosity of 10.5 mPa ⁇ s at 23 ° C.). The obtained results are shown in Table 3. The viscosity was measured with an automatic micro viscometer AMVn (Nihon Sibel Hegner Co., Ltd.).
- Each inkjet ink composition obtained above was adhered to the pixel forming portion partitioned by the black matrix of the substrate by an inkjet method. Then, it dried under reduced pressure at 10 Torr for 120 seconds, and also pre-baked for 10 minutes on an 80 degreeC hotplate. Thereafter, in a clean oven, post-baking was performed by heating at 200 ° C. for 30 minutes, and further, post-baking was performed by heating at 240 ° C. for 30 minutes to form a pixel pattern having an average film thickness of 2.0 ⁇ m on the substrate. .
- the fat pixel means a pixel in which the ink composition protrudes from the pixel formation portion to the black matrix portion as shown in FIG. 5B, and the broken pixel means as shown in FIG. 5C.
- a normal pixel is observed to be fat or broken as shown in FIG. This refers to a pixel in which an ink composition is patterned in a pixel forming portion partitioned without any other pattern.
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Abstract
Description
また、本発明の第二の目的は、特定の色を有し輝度及びコントラストが良好な画素を備えた、生産性の高いカラーフィルターを提供することにある。
また、本発明の第三の目的は、上記目的を達するインク組成物を用いた、生産性の高いカラーフィルターの製造方法を提供することにある。
更に、本発明の第四の目的は、上記目的を達するカラーフィルターを用いて信頼性の高い液晶表示装置を提供することにある。
本発明によれば、(A)C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を含み、前記C.I.ピグメントバイオレット23が全顔料中に8~30重量%含まれる顔料、(B)ポリアリルアミン誘導体を含む顔料分散剤、(C)熱硬化性バインダー、及び(D)有機溶剤を含有することにより、ヘッドから吐出した時の直進性、安定性に優れ、インクの盛り量を低減可能でインク層形成部位からの決壊を抑制し、且つ、インクジェット方式で基板上に吹き付けて、形状が良好で膜物性が良好な硬化層を提供可能なカラーフィルター用インクジェットインク組成物を提供することができる。
本発明に係るカラーフィルターは、画素の厚みが、当該画素の領域内で不均一であり、且つ、当該画素の少なくとも1つが、(A)C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を含む顔料と、(B)ポリアリルアミン誘導体を含む顔料分散剤と、(C’)硬化樹脂を含む青色画素であって、前記青色画素中にC.I.ピグメントバイオレット23が(A)顔料全体に対して8~30重量%含まれることにより、特定の色を有し輝度およびコントラストが良好な画素を備えた、生産性の高いカラーフィルターとすることができる。
また、本発明は、表示側基板と液晶駆動側基板とを対向させ、両者の間に液晶を封入してなる液晶表示装置であって、前記表示側基板が、前記本発明に係るカラーフィルター、又は前記本発明に係るカラーフィルターの製造方法によって製造されたカラーフィルターである、液晶表示装置も提供する。
また、本発明に係るカラーフィルターは、特定の色を有し輝度及びコントラストが良好な画素を備えた、コスト低減や歩留まり向上を実現可能な生産性の高いカラーフィルターである。
また、本発明に係るカラーフィルターの製造方法によれば、インク組成物の吐出方向や吐出量の安定性が優れ、精細な画素を正確に形成できる。得られた画素は、所望の色度を実現しながら、耐熱性、密着性、耐溶剤性等の膜物性に優れている。また、インクジェット方式を用いた製造方法であるため、コストダウンや歩留まりの向上が実現可能である。
また、本発明によれば、上記カラーフィルター或いはカラーフィルターの製造方法により製造されたカラーフィルターを用いることから、高品質で生産性の高い液晶表示装置を提供することができる。
1.カラーフィルター用インクジェットインク
本発明に係るカラーフィルター用インクジェットインク組成物は、(A)C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を含む顔料、(B)ポリアリルアミン誘導体を含む顔料分散剤、(C)熱硬化性バインダー、及び(D)有機溶剤を含有し、前記C.I.ピグメントバイオレット23が前記顔料全体に対して8~30重量%含まれる。
((A)顔料)
本発明に係るインクジェットインク組成物においては、顔料として、C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を少なくとも含み、前記C.I.ピグメントバイオレット23が前記顔料全体に対して8~30重量%含まれることを特徴とする。要求される色特性、具体的には特に、塗膜をC光源で測色した時のCIEのXYZ表色系においてx座標が0.133≦x≦0.145、y座標が0.075≦y≦0.122を満足させる点から、或いは、顔料分散性及び顔料分散安定性の点から、前記C.I.ピグメントバイオレット23は、中でも、前記顔料全体に対して30重量%以下であることが好ましく、更に前記顔料全体に対して13重量%以下であることが好ましい。
他の顔料としては、有機着色剤及び無機着色剤の中から任意のものを選んで使用することができる。有機着色剤としては、例えば、染料、有機顔料、天然色素等を用いることができる。また、無機着色剤としては、例えば、無機顔料、体質顔料等を用いることができる。これらの中で有機顔料は、発色性が高く、耐熱性も高いので、好ましく用いられる。有機顔料としては、例えばカラーインデックス(C.I.;The Society of Dyers and Colourists 発行) においてピグメント(Pigment)に分類されている化合物、具体的には、カラーインデックス(C.I.)番号が付されているものを挙げることができる。例えば、C.I.ピグメントブルー15:1、C.I.ピグメントブルー15:2、C.I.ピグメントブルー15:3、C.I.ピグメントブルー15:4、C.I.ピグメントブルー15:5、C.I.ピグメントブルー16、C.I.ピグメントブルー17:1等のブルー系ピグメント;C.I.ピグメントバイオレット1、C.I.ピグメントバイオレット19、C.I.ピグメントバイオレット29、C.I.ピグメントバイオレット32、C.I.ピグメントバイオレット36、C.I.ピグメントバイオレット37、C.I.ピグメントバイオレット38等のバイオレット系ピグメント;更には、イエロー系ピグメント;レッド系ピグメント;グリーン系ピグメント等が挙げられる。
インクジェットインクにおいて、顔料は、インクジェットインクの固形分全量に対して、通常は1~60重量%で配合される。本発明においては、好ましくは1~35重量%の割合で配合される。本発明においては、顔料として、C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を少なくとも含み、前記C.I.ピグメントバイオレット23が前記顔料全体に対して8~30重量%含まれることにより、顔料自体の着色力が高いため、目的とする色度(例えば、y=0.075~0.122)を得るために固形分中の顔料の総量減少可能である。
本発明に用いられる顔料の平均粒径としては、カラーフィルターの画素部とした場合に、所望の発色が可能なものであればよく、特に限定されないが、10~100nmの範囲内であることが好ましく、30~60nmの範囲内であることがより好ましい。当該顔料の平均粒径が上記範囲であることにより、本発明のカラーフィルター用インクジェットインク組成物を用いて製造された液晶表示装置を高コントラストで、かつ高品質なものとすることができる。
なお、上記顔料の平均粒径は、動的光散乱法により測定したものであり、レーザー光散乱粒度分布計(例えば、日機装社製、MICROTRAC UPA MODEL9230)を用いて23℃にて測定することができる。また、ここでの平均粒径は、体積基準中位径である。
P/V比が低すぎると、充分な着色力を得るためには画素形成領域に付着させるインクの液滴量を多くしなければならないため、画素形成領域からインクが決壊するなどの問題が起こる場合がある。一方、P/V比が高すぎると、吐出ヘッドで目詰まりや飛行曲がりが発生する等の吐出性能が低下したり、膜の表面が荒れるなどの問題が起こる場合がある。
本発明においては、顔料として、C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を少なくとも含み、前記C.I.ピグメントバイオレット23が前記顔料全体に対して8~30重量%含まれることにより、顔料自体の着色力が高いため、インクジェットインクにおいて、前記P/V比を小さくすることが可能である。P/V比を小さくすることにより、インクジェットインクの粘度が下がるため、インクジェットインクの固形分濃度を上げることが可能になる。その結果、インクが吐出可能で吐出安定性が高い粘度を実現しながら、インクの盛り量を低減可能であるため、インク層形成部位からの決壊を抑制することが可能になる。なお、配合割合を特定するためのインク組成物の固形分とは、溶剤を除く全ての成分を含み、液状のバインダー成分等も固形分に含まれる。
顔料分散剤は、顔料を良好に分散させるためにインク中に配合される。本発明に用いられる顔料分散剤は、ポリアリルアミン誘導体を含むものである。顔料分散剤としてポリアリルアミン誘導体を用いる場合には、インクジェットインク組成物の粘度の安定性が良好になり、且つ、インクジェットヘッドのノズル先端において急激な粘度の上昇や目詰まりを起こし難いというメリットがある。更に、インクジェット方式により付着させて硬化させた画素の膜厚分布の範囲を狭くしやすく、画素の形状を良好にするというメリットがある。画素の膜厚分布の範囲が狭く画素の形状が良好であると、特定の色を実現する時に、輝度及びコントラストを高くすることが可能である。
また、ポリアリルアミン誘導体の製造に用いられるポリエステルの分子量は、300~20,000の範囲のものであればよいが、顔料分散性の点から、1,000~10,000が好ましい。
なお、本発明に用いられるポリアリルアミン誘導体の分子量は、2000~100000であることが好ましい。
本発明のカラーフィルター用インクジェットインク組成物は、成膜性や被塗工面に対する密着性を付与するために、バインダー成分を含有する。本発明に係るインクは、インクジェット方式に用いるインクであるため、所定のパターンを形成するためには、所定のパターン形成領域にのみインクを選択的に付着させて固化すれば形成することができ、露光及び現像を行なうことによりパターンを形成する必要がない。従って、バインダー成分としては、塗膜に十分な強度、耐久性、密着性を付与するために、インクジェット方式により基板上にインク層(塗膜)のパターンを形成後、当該インク層を加熱により重合硬化させることができる熱硬化性バインダーを用いる。熱硬化性バインダーを用いると、耐溶剤性、密着性、ITO耐性等の画素の膜物性をより良好にすることができる。なお、ここでITO耐性とは、ITO回路形成時又は配向膜形成時の不具合に対する耐性であり、具体的にはITO回路形成後の230~250℃での耐熱性が挙げられる。また、熱硬化性バインダーを用いる場合には、光照射装置を始めとする特別な附帯設備が不要となり、生産性が高いというメリットもある。
通常バインダー成分として用いられる比較的分子量の高い重合体であるエポキシ化合物(以下、「バインダー性エポキシ化合物」ということがある)としては、少なくとも下記式(1)で表される構成単位及び下記式(2)で表される構成単位から構成され且つグリシジル基を2個以上有する重合体を用いることができる。
重合体中の式(2)で表される構成単位は、下記式(4)で表されるモノマーから誘導される。
上記バインダー性エポキシ化合物と、必要に応じて配合される多官能エポキシ化合物の配合割合は、重量比ではバインダー性エポキシ化合物を10~80重量部と多官能エポキシ化合物を10~60重量部の割合で配合するのが好ましく、バインダー性エポキシ化合物を20~60重量部と多官能エポキシ化合物を20~50重量部の割合で配合するのが更に好ましく、バインダー性エポキシ化合物を30~40重量部と多官能エポキシ化合物を25~35重量部の割合で配合するのが特に好ましい。
本発明に用いられる熱硬化性バインダーには、通常、硬化剤が組み合わせて配合される。硬化剤としては、例えば、多価カルボン酸無水物または多価カルボン酸を用いる。
多価カルボン酸無水物の具体例としては、無水フタル酸、無水イタコン酸、無水コハク酸、無水シトラコン酸、無水ドデセニルコハク酸、無水トリカルバリル酸、無水マレイン酸、無水ヘキサヒドロフタル酸、無水ジメチルテトラヒドロフタル酸、無水ハイミック酸、無水ナジン酸などの脂肪族または脂環族ジカルボン酸無水物;1,2,3,4-ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物などの脂肪族多価カルボン酸二無水物;無水ピロメリット酸、無水トリメリット酸、無水ベンゾフェノンテトラカルボン酸などの芳香族多価カルボン酸無水物;エチレングリコールビストリメリテイト、グリセリントリストリメリテイトなどのエステル基含有酸無水物を挙げることができ、特に好ましくは、芳香族多価カルボン酸無水物を挙げることができる。また、市販のカルボン酸無水物からなるエポキシ樹脂硬化剤も好適に用いることができる。
本発明の熱硬化性バインダーには、硬化層の硬度および耐熱性を向上させるために、酸-エポキシ間の熱硬化反応を促進できる触媒を添加してもよい。そのような触媒としては、加熱硬化時に活性を示す熱潜在性触媒を用いることができる。
熱潜在性触媒は、加熱されたとき、触媒活性を発揮し、硬化反応を促進し、硬化物に良好な物性を与えるものであり、必要により加えられるものである。この熱潜在性触媒は、60℃以上の温度で酸触媒活性を示すものが好ましく、このようなものとしてプロトン酸をルイス塩基で中和した化合物、ルイス酸をルイス塩基で中和した化合物、ルイス酸とトリアルキルホスフェートの混合物、スルホン酸エステル類、オニウム化合物類等が挙げられ、前記特開平4-218561号公報に記載されているような各種の化合物を使用することができる。具体的には、(イ)ハロゲノカルボン酸類、スルホン酸類、リン酸モノ及びジエステル類などを、アンモニア、モノメチルアミン、トリエチルアミン、ピリジン、エタノールアミン類などの各種アミン若しくはトリアルキルホスフィン等で中和した化合物、(ロ)BF3、FeCl3、SnCl4、AlCl3、ZnCl2などのルイス酸を前述のルイス塩基で中和した化合物、(ハ)メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸などと第一級アルコール、第二級アルコールとのエステル化合物、(ニ)第一級アルコール類、第二級アルコール類のリン酸モノエステル化合物、リン酸ジエステル化合物等を挙げることができる。また、オニウム化合物としては、アンモニウム化合物[R3NR']+X-、スルホニウム化合物[R3SR']+X-、オキソニウム化合物[R3OR']+X-等を挙げることができる。なお、ここでR及びR'はアルキル、アルケニル、アリール、アルコキシ等である。
熱潜在性触媒は、1分子中に熱硬化性官能基を2個以上有する化合物及び硬化剤の合計100重量部に対して、通常は0.01~10.0重量部程度の割合で配合する。
本発明のインク組成物には、当該組成物を高濃度溶液又は直ちにヘッドから吐出できるインキに調製するために、(D)有機溶剤を含有する。(D)有機溶剤としては、保存用の高濃度インク又は直ちに塗布可能な濃度のインクに調製するために、固形分を好適に溶解及び分散させる溶剤であれば、特に限定されない。
中でも、第二溶剤に用いられる各溶剤成分の沸点は、更に、140℃~180℃であることが、特に140℃~175℃であることが、端部に厚膜部分が生じ難く、且つ表面ムラが低減された良好な塗膜が得られ易い点から好ましい。
前記第二溶剤としては、具体的には、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジプロピルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールエーテル類や、グリセリン1,3-ジメチルエーテルのようなグリセリンエーテル類などの多価アルコールエーテル類;エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノメトキシメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートのようなグリコールエーテルエステル類を含むグリコールエステル類や、グリセリン1-モノアセタートのようなグリセリンエステル類などの多価アルコールエステル類;イソ吉草酸、イソ酪酸、プロピオン酸、酪酸のようなカルボン酸類;イソ吉草酸エチル、蟻酸ヘキシル、酢酸アミル、酢酸イソアミル、酢酸シクロヘキシル、乳酸エチル、乳酸メチル、プロピオン酸イソアミル、プロピオン酸ブチル、酪酸ブチル、クエン酸トリブチル、シュウ酸ジメチルのような脂肪族エステル類;3-エトキシプロピオン酸エチルのようなアルコキシカルボン酸エステル類;アセト酢酸メチルのようなケトカルボン酸エステル類;n-アミルアルコール、イソアミルアルコール、2-エチルブタノール、グリシドール、n-ヘキサノール、2-メチルシクロヘキサノール、4-メチル-2-ペンタノール、2-オクタノール、シクロヘキサノール、2-ヘプタノール、3-ヘプタノール、n-ヘプタノールのような1価アルコール類;ジイソアミルエーテル、及び1、8-シネオールのようなエーテル類;エチル-n-ブチルケトン、ジイソブチルケトン、ジ-n-プロピルケトン、メチルシクロヘキサノン、メチル-n-ヘキシルケトン、アセチルアセトン、ジアセトンアルコールのようなケトン類;ノナン、デカン等のアルカン類等が挙げられる。
更に、本発明のカラーフィルター用インクジェットインクには、必要に応じて、その他の添加剤を1種又は2種以上配合することができる。そのような添加剤としては、次のようなものを例示できる。
a)充填剤:例えば、ガラス、アルミナなど。
b)密着促進剤:例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシランなど。
c)レベリング剤:例えば、アクリル系界面活性剤、フッ素系界面活性剤、シリコーン系界面活性剤、ビニルエーテル系界面活性剤など。
d)紫外線吸収剤:例えば、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール、アルコキシベンゾフェノンなど。
e)凝集防止剤:例えば、ポリアクリル酸ナトリウムなど。
本発明のカラーフィルター用インクジェットインク組成物は、各成分を単独溶剤又は混合溶剤である溶剤に投入して混合し、固形成分を溶解又は分散させて製造しても良い。
しかしながら、顔料をバインダー系等の他の成分と共に溶剤全体中に直接投入し攪拌混合すると、顔料を溶剤中に十分に分散させられないことが多い。そこで通常は、顔料の分散性及び分散安定性が良好な溶剤を用意し、そこに顔料を分散剤と共に投入してディソルバーなどにより十分攪拌し、顔料分散液を調製する。そして、得られた顔料分散液を、顔料以外の成分と共に、例えばほとんど第一溶剤からなるか又は第一溶剤のみからなる溶剤に投入し、ディソルバーなどにより十分に攪拌混合し、必要に応じて最後に第二溶剤を添加することによって、本発明に用いられるインクジェットインクを調製することができる。或いは、得られた顔料分散液を、顔料以外の成分と共に、例えばほとんど第一溶剤からなるか又は第一溶剤のみからなる溶剤に第二溶剤を添加した混合溶剤に投入し、ディソルバーなどにより十分に攪拌混合し、本発明に用いられるインクジェットインクを調製することができる。
直ちにヘッドから吐出できるインクとする場合には、本発明のインクジェットインク組成物は、23℃で粘度が5~11mPa・sであることが、中でも5~10・5mPa・sであることが、インクジェットヘッドからの吐出性や吐出安定性の点から好ましい。粘度は、落球式粘度計、例えば自動マイクロ粘度計 AMVn (日本シイベルヘグナー株式会社)にて測定することができる。
本発明に係るカラーフィルター用インクジェットインクは、インクを均一な膜に成膜し、硬化して形成した硬化層のC光源でのy値が0.105の時に、横軸Xを膜厚とし、縦軸Yを顔料と、顔料以外の固形分の配合重量比(P/V)とした場合に、Y=aX^bの関係において、0.40<a<0.64、及び-1.27<b<-1.20の範囲にあることが、顔料/顔料以外の固形分の比(P/V)を低く設定できる点から好ましい。Y=aX^bの関係の例を示すグラフを図6に示す。
本発明に係るカラーフィルターは、透明基板と、当該透明基板上に設けられた画素とを少なくとも備えるカラーフィルターであって、当該画素の厚みが、該画素の領域内で不均一であり、且つ、当該画素の少なくとも1つが、(A)C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を含む顔料と、(B)ポリアリルアミン誘導体を含む顔料分散剤と、(C’)硬化樹脂を含む青色画素であって、前記青色画素中にC.I.ピグメントバイオレット23が(A)顔料全体に対して8~30重量%含まれることを特徴とする。
透明基板5としては、従来よりカラーフィルターに用いられているものであれば特に限定されるものではないが、例えば石英ガラス、パイレックス(登録商標)ガラス、合成石英板等の可とう性のない透明なリジット材、あるいは透明樹脂フィルム、光学用樹脂板等の可とう性を有する透明なフレキシブル材を用いることができる。この中で特にコーニング社製7059ガラスは、熱膨脹率の小さい素材であり寸法安定性および高温加熱処理における作業性に優れ、また、ガラス中にアルカリ成分を含まない無アルカリガラスであるため、アクティブマトリックス方式によるカラー液晶表示装置用のカラーフィルターに適している。本発明においては、通常、透明基板を用いるが、反射性の基板や白色に着色した基板でも用いることは可能である。また、基板は、必要に応じてアルカリ溶出防止やガスバリア性付与その他の目的で表面処理を施したものを用いてもよい。
本発明に係るカラーフィルターの画素は、上述のように、厚みが画素の領域内で不均一であることが特徴的である。本発明に係る画素の形状は、該画素の外縁部又はその近傍に沿って厚みの小さい部分を有し、且つ当該厚みの小さい部分よりも画素の中心側に厚みの最大部を有するような形状であったり、逆に、該画素の外縁部又はその近傍に沿って厚みの大きい部分を有し、且つ当該厚みの大きい部分よりも画素の中心側に厚みの最小部を有するような形状であったり、さらに、その表面が凹凸形状であったりする。ここで、画素の外縁部とは、画素の平面形状を規定している縁部である。また、画素の外縁部又はその近傍に沿ってとは、少なくとも外縁部又はその近傍の一部に沿って厚みの小さい部分を有していれば良い旨を言う。また、画素の厚みとは、基板の基準面(平均高さを有する面)からの高さをいう。また、厚みが画素の領域内で不均一であるとは、厚みの差が0.1μm以上の場合をいう。画素の厚みは、例えば、光干渉方式の三次元非接触表面形状計測装置(米国マイクロマップ製 製品名Micromap557N)を用いて測定することができる。以下の説明では、画素の外縁部又はその近傍に沿って厚みの小さい部分を有し、且つ当該厚みの小さい部分よりも画素の中心側に厚みの最大部を有するような形状の場合を中心に説明する。
上記中央部付近が盛り上がった断面形状を有する画素のような、厚みが不均一な画素は、例えばインクジェット方式を用いて形成する場合に得られる。インクジェット方式を用いる場合には、高精細に画素を形成することができる上、コスト低減や歩留まり向上を実現可能というメリットを有する。なお、上記中央部付近が盛り上がった断面形状を有する画素のような、厚みが不均一な画素は、インクジェット方式以外の方式で形成されても良い。
青色画素における、顔料の平均分散粒径の測定は電子顕微鏡が使用される。例えば、青色画素をFIB (集束イオンビーム装置) (例えばHitachi製FB-2000A)によって断面方向に薄膜化し、その断面サンプルを例えば透過型電子顕微鏡(例えば、日本電子製JEM-200CX、加速電圧100kV)で10000~500000倍で観察し、短軸径と長軸径を計測し、その平均をその粒子の粒径とする100個以上の粒子について、それぞれの粒子の体積(重量)を、求めた粒径の直方体と近似して求め、体積平均粒径を求めそれを平均粒径とすることができる。
画素の厚みは、通常0.5~2.5μm程度とする。また、赤色画素7Rが最も薄く、緑色画素7G、青色画素7Bの順に厚くなるというように各色の画素の厚みを変えて、各色ごとに最適な厚みに設定してもよい。
遮光部6は、表示画像のコントラストを向上させるために、画素7R,7G,7Bの間及び画素形成領域の外側を取り囲むように設けられる。遮光部6は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部6は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法と、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法がある。
遮光部の厚さは、金属薄膜の場合は1000~2000Å程度とし、遮光性樹脂層の場合は、0.5~2.5μm程度とする。
本発明に用いられる撥液性材料としては、遮光部を形成した際に所望の撥液性を発現できるものであれば特に限定されるものではない。このような撥液性材料としては、例えば、フッ素含有化合物、および、低表面エネルギー物質の微粒子等を挙げることができる。
一般式(1):Rf-X-Rf’
一般式(2):(Rf-X-R)-Y-(R’-X’-Rf’)
ここで、上記式(1)または(2)において、RfおよびRf’はフルオロアルキル基、RおよびR’はアルキレン基を表し、RfとRf’また、RとR'は同一でも異なっていても良い。また、X、X’およびYは、-COO-、-OCOO-、-CONR”-、-OCONR”-、-SO2NR”-、-SO2-、-SO2O-、-O-、-NR”-、-S-、-CO-、OSO2O-、-OPO(OH)O-のうちのいずれかを表し、X、X’およびYは同一でも異なっていても良い。R”はアルキル基または水素を表す。
一方、上記低表面エネルギー物質の微粒子としては、例えば、ポリフッ化ビニリデン、フルオロオレフィンビニルエーテル系共重合体、3フッ化エチレン-フッ化ビニリデン共重合体等からなる微粒子や、シリコーン微粒子等を挙げることができる。
通常カラーフィルターに形成されるその他の部材をさらに含んでいても良い。例えば、インクジェット方式を用いてカラーフィルターが形成される場合には、画素間の隔壁があっても良い。インクジェット方式用の隔壁については、後述するインクジェット方式による製造方法のところで説明する。
本発明に係るカラーフィルターの製造方法は、前記本発明に係るカラーフィルター用インクジェットインク組成物を、カラーフィルター用インクジェットインクを、インクジェット方式によって選択的に付着させてインク層を形成する工程と、前記インク層を硬化させて画素を形成する工程とを含むことを特徴とする。
本発明に係るカラーフィルターの製造方法は、インクジェット方式を用いるため、コスト低減や歩留まり向上を実現可能であり、生産性の高い製造方法である。
先ず、図4(A)に示すようにカラーフィルターの透明基板を準備する。
次に、図4(B)に示すように、透明基板5の一面側の画素部間の境界となる領域に遮光部6を形成する。遮光部6として、金属薄膜を形成する場合には、当該薄膜をパターニングすることにより形成することができる。このパターニングの方法としては、スパッタリング法、真空蒸着法等の通常のパターニング方法を用いることができる。
また、遮光部6として、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた層を形成する場合には、パターニングの方法としては、フォトリソグラフィー法、印刷法等一般的に用いられている方法を用いることができる。或いは、後述する画素7と同様にインクジェット方式を用いて形成しても良い。
次に、図4(E)に示すように、透明基板の画素34R、34G、34Bを形成した側に、保護膜8を形成する。保護膜は、透明な樹脂組成物を用いて、スピンコーター、ロールコーター、スプレイ、印刷等の方法により形成できる。例えば、スピンコーターにより500~1500回転/分の範囲内で塗工後、露光及び/又は加熱することにより硬化させて形成することが好ましい。
その他においては、通常のカラーフィルターを形成する方法と同様の方法を用いて製造することができる。
更に、本発明に係る液晶表示装置は、表示側基板と液晶駆動側基板とを対向させ、両者の間に液晶を封入してなる液晶表示装置であって、前記表示側基板が前記本発明に係るカラーフィルター或いは、前記本発明に係るカラーフィルターの製造方法によって製造されたカラーフィルターであることを特徴とする。
本発明に係る液晶表示装置は、上述のように輝度とコントラストが高い画素を有するカラーフィルターを用いることから、高品質で且つ生産性の高い液晶表示装置とすることができる。
液晶表示装置におけるその他の構成及び製造方法は、通常用いられる構成及び方法を用いることができるので、ここでは説明を省略する。
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
(製造例1:バインダー性エポキシ化合物の合成)
温度計、還流冷却器、攪拌機、滴下ロートを備えた4つ口フラスコに、表1に示す配合割合に従って、水酸基を含有しない溶剤ジエチレングリコールモノブチルエーテルアセテート(別名ブチルカルビトールアセテート、以下、BCAと示すことがある。)を40.7重量部仕込み、攪拌しながら加熱して140℃に昇温した。次いで、140℃の温度で第1表に記載した組成の単量体、及び、重合開始剤の混合物(滴下成分)54.7重量部を、2時間かけて滴下ロートより等速滴下した。滴下終了後、110℃に降温し重合開始剤及び水酸基を含有しない溶剤ジエチレングリコールモノブチルエーテルアセテート(BCA)の混合物(追加触媒成分)4.6重量部を添加し、110℃の温度を2時間保ったところで反応を終了することにより、表1に記載の特性を有するバインダー性エポキシ化合物が得られた。
GMA:グリシジルメタクリレート
MMA:メチルメタクリレート
パーブチルO:t-ブチルパーオキシ2-エチルヘキサノエート(日本油脂(株)製商品名)
*2)重量平均分子量:ゲル浸透クロマトグラフィーによるポリスチレン換算の値である。
(1)顔料分散液の調製
顔料、顔料分散剤、及び有機溶剤を下記に示す割合で混合し、直径0.3mmのジルコニアビーズを500重量部加え、ペイントシェーカー(浅田鉄鋼社製)を用いて4時間分散し、PB15:6(C.I.ピグメントブルー15:6)顔料分散液、及びPV23(C.I.ピグメントバイオレット23)顔料分散液をそれぞれ調製した。
[顔料分散液の組成]
・顔料:10重量部
・顔料分散剤(アジスパーPb821(味の素ファインテクノ株式会社製)(有機溶剤中に固形分30重量%)):20重量部
・BCA(ジエチレングリコールモノブチルエーテルアセテート):50重量部
サンプル瓶にテフロン(登録商標)被覆した回転子を入れ、マグネチックスターラーに設置した。このサンプル瓶の中に、下記の割合に従って前記製造例1に記載のバインダー性エポキシ化合物、多官能エポキシ樹脂等を加え、室温で十分に攪拌溶解し、次いで、粘度調整のために希釈溶剤BCAを加えて攪拌溶解した後、これを濾過してバインダー組成物を得た。
・製造例1のバインダー性エポキシ化合物(溶剤BCA中に固形分30重量%):10重量部
・多官能エポキシ樹脂(商品名エピコート154、ジャパンエポキシレジン(株)製):2重量部
・ネオペンチルグリコールグリシジルエーテル:1重量部
・トリメリット酸:2重量部
・BCA(ジエチレングリコールモノブチルエーテルアセテート):1重量部
表2に示されるような配合割合となるように、上記で得られたPB15:6(C.I.ピグメントブルー15:6)顔料分散液、及びPV23(C.I.ピグメントバイオレット23)顔料分散液を用いて、上記バインダー溶液と、更に溶剤を加えて、充分に混合し、膜厚1.9μmにてC光源でのy値が0.105を達成できるような実施例1~3及び比較例1~2のカラーフィルター用インクジェットインク組成物を得た。なお、表2中の第二溶剤のEPPとは、3-エトキシプロピオン酸エチルである。
各実施例及び比較例について、膜厚1.9μmにてC光源でのy値が0.105の時の、顔料中のバイオレット23(V23)添加量、顔料以外の固形分の配合重量比(顔料/顔料以外の固形分:P/V)、及び固形分中の顔料分散剤量を表3に示す。
顔料、顔料分散剤、バインダーの組成比は固定したままで、第二溶剤はインク全体量の10重量%となるようにして、第一溶剤(BCA)を適宜増減して、各実施例及び比較例のインク組成物がインクジェット吐出時の適正粘度(23℃で粘度10.5mPa・s)を満たす場合の、固形分最大値を求めた。得られた結果を表3に示す。なお、粘度は、自動マイクロ粘度計 AMVn (日本シイベルヘグナー株式会社)にて測定した。
(a)塗膜の形成
厚み0.7mmで10cm×10cmのガラス基板(NA35、NHテクノガラス製)上の全面に、スピンコート法により上記で得られた各インクジェットインク組成物を塗布し、C光源でのy値が0.105を達成するように膜厚1.9μmの塗膜を形成した。得られたスピンコート法による塗膜の乾燥後の膜厚は、接触式膜厚測定装置(日本真空技術(株)製、商品名「Dectak-3030ST」)により行った。
塗膜を作製後、加熱試験(240℃、200分)の前後で輝度を測定し、加熱試験前の測定結果をY1、加熱試験後の測定結果をY2とした時に下記式により輝度低下率ΔYを求めた。なお、輝度の測定は、顕微分光光度計(商品名「OSP200」、オリンパス社製)を用いて行った。結果を表3に示す。
ΔY(%)=(Y2-Y1)/Y2×100
また、下記評価基準で塗膜の耐熱性(輝度低下抑制効果)を評価した。合わせて表3に示す。
[評価基準]
○:輝度低下率8%未満
×:輝度低下率8%以上
厚み0.7mmで10cm×10cmのガラス基板(NA35、NHテクノガラス製)上に、ブラックマトリックス用硬化性樹脂組成物を用いてフォトリソグラフィー法により線幅20μm、膜厚2.2μmのブラックマトリックスパターンを形成した。当該ブラックマトリックスパターンにフッ素ガスを導入ガスとしたプラズマ処理を行うことにより、ブラックマトリックスの撥液性を開口内の基板表面のそれよりも高くした親疎水性パターンを形成した。
上記基板のブラックマトリックスにより区画された画素形成部に、上記で得られた各インクジェットインク組成物をインクジェット方式によって付着させた。その後、120秒間10Torrで減圧乾燥を行い、更に、80℃のホットプレート上で10分間プリベークを行った。その後、クリーンオーブン内で、200℃で30分加熱してポストベークを行い、更に240℃で30分加熱してポストベークを行って、基板上に平均膜厚2.0μmの画素パターンを形成した。
[評価基準]
◎:100画素観察の結果、決壊及び太りなく、全て正常画素
○:100画素観察の結果、決壊画素なし、太り画素あり
×:100画素観察の結果、決壊画素あり
2 電極基板
3 間隙部
4 シール材
5 透明基板
6 遮光部
7(7R、7G、7B) 画素
8 保護膜
9 透明電極膜
10 配向膜
11 パール
12 柱状スペーサー
21 画素
22 外縁部
23 外縁部の近傍
24 厚みが小さい部分
25 厚みの最大部
26 遮光部
31 画素形成領域
32 インクジェットヘッド
33 インク層
34 画素部
101、102 カラー液晶表示装置
103 カラーフィルター
Claims (12)
- (A)C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を含む顔料、(B)ポリアリルアミン誘導体を含む顔料分散剤、(C)熱硬化性バインダー、及び(D)有機溶剤を含有し、前記C.I.ピグメントバイオレット23が前記顔料全体に対して8~30重量%含まれる、カラーフィルター用インクジェットインク組成物。
- 膜厚1.9μmに成膜し、C光源でのy値が0.105の時の、インク組成物の固形分中における(B)顔料分散剤の含有量が、5~20重量%である、請求の範囲第1項に記載のカラーフィルター用インクジェットインク組成物。
- 膜厚1.9μmに成膜し、C光源でのy値が0.105の時の、(A)顔料と、顔料以外の固形分の配合重量比(顔料/顔料以外の固形分)が0.1~0.4である、請求の範囲第1項又は第2項に記載のカラーフィルター用インクジェットインク組成物。
- 粘度が23℃で5~11mPa・sである、請求の範囲第1項~第3項のいずれかに記載のカラーフィルター用インクジェットインク組成物。
- (A)顔料の平均分散粒径が10~100nmである、請求の範囲第1項~第4項のいずれかに記載のカラーフィルター用インクジェットインク組成物。
- インクを均一な膜に成膜し、C光源でのy値が0.105の時の、横軸Xを膜厚とし、縦軸Yを顔料と、顔料以外の固形分の配合重量比とした場合にY=aX^bの関係において、0.40<a<0.64、及び-1.27<b<-1.20の範囲にある、請求の範囲第1項~第5項のいずれかに記載のカラーフィルター用インクジェットインク組成物。
- 透明基板と、当該透明基板上に設けられた画素とを少なくとも備えるカラーフィルターであって、当該画素の厚みが、該画素の領域内で不均一であり、且つ、当該画素の少なくとも1つが、(A)C.I.ピグメントブルー15:6、及びC.I.ピグメントバイオレット23を含む顔料と、(B)ポリアリルアミン誘導体を含む顔料分散剤と、(C’)硬化樹脂を含む青色画素であって、前記青色画素中にC.I.ピグメントバイオレット23が(A)顔料全体に対して8~30重量%含まれることを特徴とする、カラーフィルター。
- 前記青色画素において、膜厚2.0μmで、C光源でのy値が0.105の時の(B)顔料分散剤の含有量が、5~20重量%である、請求の範囲第7項に記載のカラーフィルター。
- 前記青色画素における、膜厚2.0μmで、C光源でのy値が0.105の時の(A)顔料と、顔料以外の固形分の配合重量比(顔料/顔料以外の固形分)が0.1~0.4である、請求の範囲第7項又は第8項に記載のカラーフィルター。
- 前記青色画素における、顔料の平均分散粒径が10~100nmである、請求の範囲第7項~第9項のいずれかに記載のカラーフィルター。
- 前記請求の範囲第1項~第6項のいずれかに記載のカラーフィルター用インクジェットインク組成物を、インクジェット方式によって選択的に付着させてインク層を形成する工程と、
前記インク層を硬化させて画素を形成する工程とを含むことを特徴とするカラーフィルターの製造方法。 - 表示側基板と液晶駆動側基板とを対向させ、両者の間に液晶を封入してなる液晶表示装置であって、前記表示側基板が、前記請求の範囲第7項~第10項のいずれかに記載のカラーフィルター、又は前記請求の範囲第11項に記載のカラーフィルターの製造方法によって製造されたカラーフィルターであることを特徴とする、液晶表示装置。
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JP2013164457A (ja) * | 2012-02-09 | 2013-08-22 | Dainippon Printing Co Ltd | 遮光層形成用樹脂組成物、遮光層形成用樹脂組成物から構成される遮光層を備えたカラーフィルタおよびカラーフィルタを備えた表示装置 |
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CN112959836A (zh) * | 2021-02-04 | 2021-06-15 | 东莞市天迪印刷有限公司 | 一种多功能发光体的印刷制作工艺 |
Also Published As
Publication number | Publication date |
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JP2014056248A (ja) | 2014-03-27 |
TW201022377A (en) | 2010-06-16 |
JP5582034B2 (ja) | 2014-09-03 |
JP5708749B2 (ja) | 2015-04-30 |
JP5708748B2 (ja) | 2015-04-30 |
US8553180B2 (en) | 2013-10-08 |
JP2014056249A (ja) | 2014-03-27 |
CN102165338B (zh) | 2014-03-26 |
JPWO2010038669A1 (ja) | 2012-03-01 |
TWI432535B (zh) | 2014-04-01 |
CN102165338A (zh) | 2011-08-24 |
US20110176095A1 (en) | 2011-07-21 |
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