WO2014203325A1 - 液晶表示装置 - Google Patents
液晶表示装置 Download PDFInfo
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- WO2014203325A1 WO2014203325A1 PCT/JP2013/066686 JP2013066686W WO2014203325A1 WO 2014203325 A1 WO2014203325 A1 WO 2014203325A1 JP 2013066686 W JP2013066686 W JP 2013066686W WO 2014203325 A1 WO2014203325 A1 WO 2014203325A1
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- 0 *c1c([C+](c(cc2)c(*)cc2N(*)*)c(c2c3cccc2)ccc3N(*)*)ccc(N(*)*)c1 Chemical compound *c1c([C+](c(cc2)c(*)cc2N(*)*)c(c2c3cccc2)ccc3N(*)*)ccc(N(*)*)c1 0.000 description 1
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Definitions
- the present invention relates to a liquid crystal display device.
- Liquid crystal display devices are used in various electric appliances for home use, measuring instruments, automotive panels, word processors, electronic notebooks, printers, computers, televisions, etc., including clocks and calculators.
- Typical liquid crystal display methods include TN (twisted nematic), STN (super twisted nematic), DS (dynamic light scattering), GH (guest / host), and IPS (in-plane switching).
- Type OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, FLC (ferroelectric liquid crystal), etc.
- As a driving method multiplex driving is generally used instead of conventional static driving, and the active matrix (AM) method driven by a TFT (thin film transistor), TFD (thin film diode) or the like has become mainstream recently. ing.
- TFT thin film transistor
- TFD thin film diode
- a general color liquid crystal display device has a transparent electrode layer (a common electrode) between one alignment film of two substrates (1) each having an alignment film (4) and the substrate. 3a) and a color filter layer (2), a pixel electrode layer (3b) is provided between the other alignment film and the substrate, these substrates are arranged so that the alignment films face each other, and a liquid crystal layer ( 5) is sandwiched.
- the color filter layer is composed of a color filter composed of a black matrix, a red colored layer (R), a green colored layer (G), a blue colored layer (B), and, if necessary, a yellow colored layer (Y).
- the liquid crystal material constituting the liquid crystal layer has been subjected to a high degree of management because impurities have a great influence on the electrical characteristics of the display device if the impurities remain in the material.
- the alignment film directly affects the liquid crystal layer and the impurities remaining in the alignment film move to the liquid crystal layer, thereby affecting the electrical characteristics of the liquid crystal layer. The characteristics of the liquid crystal display device due to the impurities in the alignment film material are being studied.
- the material such as the organic pigment used for the color filter layer is also assumed to have an influence on the liquid crystal layer due to impurities contained in the same manner as the alignment film material.
- an alignment film and a transparent electrode are interposed between the color filter layer and the liquid crystal layer, it has been considered that the direct influence on the liquid crystal layer is significantly less than that of the alignment film material.
- the alignment film is usually only 0.1 ⁇ m or less in thickness, and the common electrode used on the color filter layer side for the transparent electrode is usually 0.5 ⁇ m or less even if the film thickness is increased to increase the conductivity. .
- the color filter layer and the liquid crystal layer are placed in a completely isolated environment, and the color filter layer is formed by impurities contained in the color filter layer through the alignment film and the transparent electrode.
- display defects such as white spots due to a decrease in voltage holding ratio (VHR), an increase in ion density (ID), uneven alignment, and burn-in may occur.
- VHR voltage holding ratio
- ID ion density
- burn-in may occur.
- the elution of impurities into the liquid crystal is controlled by using pigments whose ratio of the extract of ethyl formate is not more than a specific value.
- Patent Document 1 A method (Patent Document 1) and a method (Patent Document 2) for controlling the elution of impurities into a liquid crystal by specifying a pigment in a blue colored layer have been studied. However, these methods are not significantly different from simply reducing impurities in the pigment, and are insufficient as an improvement to solve display defects even in the current state of progress in pigment purification technology. Met.
- the difficulty of dissolving the organic impurities in the liquid crystal layer is expressed by the hydrophobic parameter of the liquid crystal molecules contained in the liquid crystal layer. Because of the correlation between the parameter value and the hydrophobic parameter and the —OCF 3 group at the end of the liquid crystal molecule, a liquid crystal compound having —OCF 3 group at the end of the liquid crystal molecule is contained in a certain proportion or more.
- Patent Document 3 A method for producing a liquid crystal composition
- the black matrix is formed by forming a metal chromium such as chromium (Cr) or chromium oxide (CrOX) or a metal chromium compound by sputtering or the like, and using a positive photoresist on the formed thin film, an etching resist pattern. Next, etching the exposed portion of the formed metal chromium film and stripping the etching resist pattern, or using a photosensitive colored resin composition in which a black pigment such as carbon black is dispersed There is a method of forming by photolithography. As for the black matrix, it has been disclosed that high-resistance carbon black or titanium black is used to prevent color unevenness and afterimage (Patent Document 4). The display failure could not be solved.
- a metal chromium such as chromium (Cr) or chromium oxide (CrOX) or a metal chromium compound by sputtering or the like
- a positive photoresist on the formed thin film, an
- Patent Document 5 a black matrix photosensitive composition containing blue, yellow, and red organic pigments has high insulation, low dielectric constant, and high optical density.
- the present invention uses a color filter having a black matrix using a specific liquid crystal composition and a specific pigment to prevent a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer,
- VHR voltage holding ratio
- ID increase in ion density
- An object of the present invention is to provide a liquid crystal display device that solves the problem of display defects such as white spots, uneven alignment, and baking.
- a color material such as a pigment constituting a black matrix of a color filter and a structure of a liquid crystal material constituting a liquid crystal layer.
- a liquid crystal display device using a color filter having a black matrix using a specific pigment prevents a decrease in voltage holding ratio (VHR) and an increase in ion density (ID) of the liquid crystal layer, white spots, uneven alignment, It has been found that the problem of display defects such as burn-in can be solved, and the present invention has been completed.
- VHR voltage holding ratio
- ID ion density
- the present invention A color filter composed of a first substrate, a second substrate, a liquid crystal composition layer sandwiched between the first substrate and the second substrate, a black matrix and at least an RGB three-color pixel portion, A pixel electrode and a common electrode;
- the liquid crystal composition layer has the general formula (I)
- R 31 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group
- M 31 to M 33 are each independently trans-1
- X 31 and X 32 each independently represent a hydrogen atom or a fluorine atom
- Z 31 represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group
- n 31 and n 32 each independently represent 0, 1 or 2
- n 31 + n 32 represents 0, 1 or 2
- M 1 and M 33 may be in the case of plurality of different be the same.
- the compounds represented by) contain one or two or more, the general formulas formulas (II-a) (II- f)
- the liquid crystal display device of the present invention uses a color filter having a black matrix using a specific liquid crystal composition and a specific pigment, thereby reducing the voltage holding ratio (VHR) of the liquid crystal layer and increasing the ion density (ID). Thus, it is possible to prevent display defects such as white spots, uneven alignment, and baking.
- VHR voltage holding ratio
- ID ion density
- FIG. 1 An example of the liquid crystal display device of the present invention is shown in FIG.
- a transparent electrode layer (3a) serving as a common electrode and a specific pigment are provided between one alignment film of the first substrate and the second substrate (1) having the alignment film (4) and the second substrate (1).
- a color filter layer (2a) having a black matrix to be contained, and a pixel electrode layer (3b) between the other alignment film and the substrate, and the substrates are arranged so that the alignment films face each other.
- a liquid crystal layer (5a) containing a specific liquid crystal composition is sandwiched.
- the two substrates in the display device are bonded together by a sealing material and a sealing material disposed in the peripheral region, and in many cases, formed by a granular spacer or a photolithography method in order to maintain a distance between the substrates.
- Spacer pillars made of the prepared resin are arranged.
- liquid crystal composition layer in the liquid crystal display device of the present invention has the general formula (I)
- R 31 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms
- M 31 to M 33 each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group, and one or two —CH in the trans-1,4-cyclohexylene group 2 — may be substituted with —O— so that the oxygen atom is not directly adjacent, and one or two hydrogen atoms in the phenylene group may be substituted with a fluorine atom
- X 31 and X 32 independently represents a hydrogen atom or a fluorine atom
- Z 31 represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group
- n 31 and n 32 represent 0, 1 or 2 independently of each other.
- R 19 to R 30 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms
- X 21 represents hydrogen
- R 31 when the ring structure to which R 31 is bonded is a phenyl group (aromatic), R 31 is a linear alkyl group having 1 to 5 carbon atoms or a linear number of carbon atoms. 1 to 4 (or more) alkoxy groups and alkenyl groups having 4 to 5 carbon atoms are preferred, and when the ring structure to which they are bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, linear Are preferably an alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms (or more) and a linear alkenyl group having 2 to 5 carbon atoms.
- R 31 is preferably an alkyl group. Further, if it is important to make a liquid crystal display device having a low viscosity and a high response speed, R 31 is preferably an alkenyl group. Furthermore, for the purpose of further shortening the response speed with a low viscosity and a high nematic-isotropic phase transition temperature (Tni), it is preferable to use an alkenyl group whose terminal is not an unsaturated bond. It is particularly preferred that the methyl group is adjacent to the end. Further, if importance is attached to good solubility at low temperatures, as one solution, R 31 is preferably an alkoxy group. As another solution, it is preferable to use many types of R 31 in combination.
- R 31 a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms is preferably used in combination, and a compound having 3 or 5 carbon atoms is preferably used in combination. It is preferable to use compounds 4 and 5 in combination.
- M 31 to M 33 are
- M 31 is,
- M 32 is,
- M 33 is
- At least one of X 31 and X 32 is preferably a fluorine atom, more preferably both are fluorine atoms.
- Z 31 is preferably a fluorine atom or a trifluoromethoxy group.
- X 31 , X 32 and Z 31 F.
- n 31 is preferably 1 or 2
- n 32 is preferably 0 or 1, more preferably 0, and n 31 + n 32 is preferably 1 or 2, and more preferably 2.
- the compound represented by the general formula (I) is preferably a compound represented by the following general formula (Ia) to general formula (If).
- R 32 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms
- X 31 to X 38 each independently represent a hydrogen atom or a fluorine atom
- Z 31 represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.
- R 32 is a straight-chain alkyl group having 1 to 5 carbon atoms and a straight chain when the ring structure to which R 32 is bonded is a phenyl group (aromatic).
- a chain-like alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms are preferred, and the ring structure to which they are bonded is a saturated ring structure such as cyclohexane, pyran and dioxane Includes a straight-chain alkyl group having 1 to 5 carbon atoms, a straight-chain alkoxy group having 1 to 4 (or more) carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms. preferable.
- R 31 is preferably an alkyl group. Further, if it is important to make a liquid crystal display device having a low viscosity and a high response speed, R 31 is preferably an alkenyl group. Furthermore, for the purpose of further shortening the response speed with a low viscosity and a high nematic-isotropic phase transition temperature (Tni), it is preferable to use an alkenyl group whose terminal is not an unsaturated bond. It is particularly preferred that the methyl group is adjacent to the end. Further, if importance is attached to good solubility at low temperatures, as one solution, R 31 is preferably an alkoxy group. As another solution, it is preferable to use many types of R 31 in combination.
- R 31 a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms is preferably used in combination, and a compound having 3 or 5 carbon atoms is preferably used in combination. It is preferable to use compounds 4 and 5 in combination.
- At least one of X 31 and X 32 is preferably a fluorine atom, more preferably both are fluorine atoms.
- Z 31 is preferably a fluorine atom or a trifluoromethoxy group.
- X 31 , X 32 and Z 31 F.
- n 31 is preferably 1 or 2
- n 32 is preferably 0 or 1
- n 31 + n 32 is preferably 1 or 2, and more preferably 2.
- At least one of X 33 and X 34 is preferably a fluorine atom, and more preferably both are fluorine atoms.
- At least one of X 35 and X 36 is preferably a fluorine atom, and the fact that both are fluorine atoms is effective in increasing ⁇ , but it is effective for Tni, solubility at low temperatures and liquid crystal display elements. From the viewpoint of chemical stability. At least one of X 37 and X 38 is preferably a hydrogen atom, and preferably both of them are hydrogen atoms. When at least one of X 37 and X 38 is a fluorine atom, it is not preferable from the viewpoint of Tni, solubility at low temperature, and chemical stability when a liquid crystal display device is formed.
- the compound group represented by the general formula (I) preferably contains 1 to 8 types, particularly preferably 1 to 5 types, and the content thereof is preferably 3 to 50% by mass, More preferably, it is 5 to 40% by mass.
- R 19 to R 30 are linear alkyl groups having 1 to 5 carbon atoms when the ring structure to which they are bonded is a phenyl group (aromatic).
- Alkenyl groups are preferred.
- R 19 to R 30 are preferably alkyl groups.
- R 19 to R 30 are preferably alkenyl groups.
- R 19 to R 30 it is preferable to use many types of R 19 to R 30 in combination.
- R 19 to R 30 a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms is preferably used in combination, and a compound having 3 or 5 carbon atoms is preferably used in combination. It is preferable to use the compounds of formulas 3, 4 and 5 in combination.
- R 19 to R 20 are preferably an alkyl group or an alkoxy group, and at least one of them is preferably an alkoxy group. More preferably, R 19 is an alkyl group and R 20 is an alkoxy group. More preferably, R 19 is an alkyl group having 3 to 5 carbon atoms, and R 20 is an alkoxy group having 1 to 2 carbon atoms.
- R 21 to R 22 are preferably an alkyl group or an alkenyl group, and at least one of them is preferably an alkenyl group. In the case where both are alkenyl groups, they are preferably used to increase the response speed, but are not preferable when it is desired to improve the chemical stability of the liquid crystal display element.
- At least one of R 23 to R 24 is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 4 to 5 carbon atoms. If a good balance between the response speed and Tni is required, at least one of R 23 to R 24 is preferably an alkenyl group. If a good balance between the response speed and solubility at low temperature is required, R 23 to At least one of R 24 is preferably an alkoxy group.
- At least one of R 25 to R 26 is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.
- R 25 ⁇ R 26 is an alkenyl group
- R 25 ⁇ At least one of R 26 is preferably an alkoxy group. More preferably, R 25 is an alkenyl group and R 26 is an alkyl group. It is also preferred that R 25 is an alkyl group and R 26 is an alkoxy group.
- At least one of R 27 to R 28 is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.
- R 27 ⁇ R 28 is an alkenyl group
- R 27 ⁇ At least one of R 28 is preferably an alkoxy group. More preferably, R 27 is an alkyl group or an alkenyl group, and R 28 is an alkyl group. It is also preferred that R 27 is an alkyl group and R 28 is an alkoxy group. Furthermore, it is particularly preferred that R 27 is an alkyl group and R 28 is an alkyl group.
- X 21 is preferably a fluorine atom.
- At least one of R 29 to R 30 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms. If a good balance between the response speed and Tni is required, at least one of R 29 to R 30 is preferably an alkenyl group, and if high reliability is required, at least one of R 29 to R 30 is an alkyl group. It is preferable that More preferably, R 29 is an alkyl group or an alkenyl group, and R 30 is an alkyl group or an alkenyl group. It is also preferred that R 29 is an alkyl group and R 30 is an alkenyl group. Furthermore, it is also preferred that R 29 is an alkyl group and R 30 is an alkyl group.
- the compound group represented by the general formula (II-a) to the general formula (II-f) preferably contains 1 to 10 types, particularly preferably 1 to 8 types, and its content is 5 It is preferably ⁇ 80 mass%, more preferably 10 to 70 mass%, and particularly preferably 20 to 60 mass%.
- the liquid crystal composition layer in the liquid crystal display device of the present invention may further have the general formula (III-a) to the general formula (III-f)
- R 41 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms
- X 41 to X 48 each independently represent a hydrogen atom or a fluorine atom
- Z 41 represents a fluorine atom, a trifluoromethoxy group or a trifluoromethyl group.
- R 41 is a straight-chain alkyl group having 1 to 5 carbon atoms and a straight chain when the ring structure to which R 41 is bonded is a phenyl group (aromatic).
- a chain-like alkoxy group having 1 to 4 (or more) carbon atoms and an alkenyl group having 4 to 5 carbon atoms are preferred, and the ring structure to which they are bonded is a saturated ring structure such as cyclohexane, pyran and dioxane Includes a straight-chain alkyl group having 1 to 5 carbon atoms, a straight-chain alkoxy group having 1 to 4 (or more) carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms. preferable.
- R 41 is preferably an alkyl group. Further, if it is important to make a liquid crystal display device having a low viscosity and a high response speed, R 41 is preferably an alkenyl group. Furthermore, for the purpose of further shortening the response speed with a low viscosity and a high nematic-isotropic phase transition temperature (Tni), it is preferable to use an alkenyl group whose terminal is not an unsaturated bond. It is particularly preferred that the methyl group is adjacent to the end. Moreover, if importance is attached to good solubility at low temperature, as one solution, R 41 is preferably an alkoxy group.
- R 41 it is preferable to use many types of R 41 in combination.
- R 41 it is preferable to use a compound having an alkyl group or an alkenyl group having 2, 3 and 4 carbon atoms, preferably a compound having 3 and 5 carbon atoms is preferably used in combination, It is preferable to use compounds 4 and 5 in combination.
- At least one of X 41 and X 42 is preferably a fluorine atom, more preferably both are fluorine atoms.
- Z 41 is preferably a fluorine atom or a trifluoromethoxy group.
- X 41 , X 42 and Z 41 F.
- X 43 and X 44 at least one of them is preferably a fluorine atom, and both of them are preferably a fluorine atom in order to obtain a large ⁇ .
- both of them are preferably a fluorine atom in order to obtain a large ⁇ .
- At least one of X 45 and X 46 is preferably a hydrogen atom, and preferably both of them are hydrogen atoms.
- the heavy use of fluorine atoms is not preferable from the viewpoints of Tni, solubility at low temperatures, and chemical stability when a liquid crystal display device is formed.
- At least one of X 47 and X 48 is preferably a hydrogen atom, and preferably both are hydrogen atoms.
- the compound selected from the group of compounds represented by general formula (III-a) to general formula (III-f) preferably contains 1 to 10 types, more preferably 1 to 8 types, The content is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.
- the liquid crystal composition of the liquid crystal composition layer in the liquid crystal display device of the present invention preferably has ⁇ at 25 ° C. of +1.5 or more.
- it is preferably +1.5 to +4.0, more preferably +1.5 to +3.0.
- +8.0 to +18.0 is preferable, and +10.0 to +15.0 is more preferable.
- ⁇ n at 25 ° C. is preferably 0.08 to 0.14, and more preferably 0.09 to 0.13. More specifically, when it corresponds to a thin cell gap, it is preferably 0.10 to 0.13, and when it corresponds to a thick cell gap, it is preferably 0.08 to 0.10.
- T ni is preferably 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C.
- the liquid crystal composition in the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal and the like in addition to the above-described compounds.
- the liquid crystal composition in the present invention may contain one or more polymerizable compounds in order to produce a liquid crystal display element such as a PS mode, a transverse electric field type PSA mode, or a transverse electric field type PSVA mode.
- the polymerizable compound that can be used include a photopolymerizable monomer that undergoes polymerization by energy rays such as light.
- the structure has, for example, a liquid crystal skeleton in which a plurality of six-membered rings such as biphenyl derivatives and terphenyl derivatives are connected. Examples thereof include a polymerizable compound. More specifically, the general formula (V)
- X 51 and X 52 each independently represent a hydrogen atom or a methyl group
- Sp 1 and Sp 2 are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH 2 ) s —
- Z 51 represents —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, —CH 2 CH.
- M 51 represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and all 1,4-phenylene groups in the formula have an arbitrary hydrogen atom substituted by a fluorine atom. Also good. ) Is preferred.
- X 51 and X 52 are each preferably a diacrylate derivative that represents a hydrogen atom, or a dimethacrylate derivative that has a methyl group, and a compound in which one represents a hydrogen atom and the other represents a methyl group.
- diacrylate derivatives are the fastest, dimethacrylate derivatives are slow, asymmetric compounds are in the middle, and a preferred embodiment can be used depending on the application.
- a dimethacrylate derivative is particularly preferable.
- Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or —O— (CH 2 ) s —, but at least one of them is a single bond in a PSA display element.
- a compound in which both represent a single bond or one in which one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or —O— (CH 2 ) s — is preferable.
- 1 to 4 alkyl groups are preferable, and s is preferably 1 to 4.
- Z 51 is —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 — or a single bond
- M 51 represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted by a fluorine atom.
- C represents a ring structure other than a single bond
- Z 51 is preferably a linking group other than a single bond.
- Z 51 is preferably a single bond.
- the ring structure between Sp 1 and Sp 2 is specifically preferably the structure described below.
- the following formulas (Va-1) to (Va-5) are preferable. It is more preferable to represent (Va-1) to formula (Va-3), and it is particularly preferable to represent formula (Va-1).
- both ends shall be bonded to Sp 1 or Sp 2.
- the polymerizable compounds containing these skeletons are optimal for PSA-type liquid crystal display elements because of the alignment regulating power after polymerization, and a good alignment state can be obtained, so that display unevenness is suppressed or does not occur at all.
- the general formula (V-1) to the general formula (V-4) are particularly preferable, and the general formula (V-2) is most preferable.
- the polymerization proceeds even in the absence of a polymerization initiator, but may contain a polymerization initiator in order to accelerate the polymerization.
- the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.
- the liquid crystal composition containing the polymerizable compound in the present invention is provided with liquid crystal alignment ability by polymerization of the polymerizable compound contained therein by ultraviolet irradiation, and transmits light through the birefringence of the liquid crystal composition. It is used in a liquid crystal display element that controls As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (in-plane switching liquid crystal display element) However, it is particularly useful for AM-LCDs and can be used for transmissive or reflective liquid crystal display elements.
- the color filter in the present invention includes a black matrix and at least an RGB three-color pixel portion.
- the black matrix contains one or more pigments selected from carbon black, titanium black, and organic pigments as a color material.
- carbon black include C.I. I. Pigment Black 6, 7, 7, and 10 can be mentioned, and C.I. I. Pigment Black 7 is preferred.
- resin-coated carbon black disclosed in JP-A-2002-249678 can be used.
- titanium black include C.I. I. Pigment Black 35, and water repellent titanium black treated with a water repellent material such as a fluorine resin and a silicon resin disclosed in JP-A-2007-302836 can also be used.
- examples of yellow organic pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 9, 9, 10, 12, 13, 14, 16, 17, 24, 31 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 116, 117, 119, 120, 126, 127, 127: 1, 128, the same 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 51, 153, 154, 155, 157, 158, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 174
- Orange organic pigments include C.I. I. Pigment Orange 1, 2, 3, 4, 5, 13, 13, 15, 16, 17, 19, 21, 24, 31, 31, 34, 36, 38, 40, 43, 46, 48, 49, 51, 60, 61, 64, 65, 66, 67, 68, 69, 271 and 72 73, 81, etc.
- red organic pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 9, 12, 14, 15, 16, 17, 17, 21, 22 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57:57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113 114, 122 123, 144, 146, 147, 149, 151, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178 179, 181, 184, 185, 187, 188, 190, 19
- Examples of purple organic pigments include C.I. I. Pigment Violet 1, 2, 3, 3, 5: 1, 13, 15, 16, 17, 17, 19, 23, 25, 29, 31, 31, 32, 34, 35 36, 37, 38, 41, 44, 50, and the like.
- Examples of the blue organic pigment include C.I. I. Pigment Blue 1, 1: 2, 9,9, 14,15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like.
- Examples of the green organic pigment include C.I. I.
- brown organic pigments include C.I. I. Pigment Brown 5, 6, 23, 24, 25, 32, 38, 41, 42, and the like.
- black organic pigments include C.I. I. Pigment Black 1, 9, 11, 11, 20, 31, 32, 34 and the like.
- the organic pigments may be used alone or in combination of two or more, but preferably 1 to 6 types, and more preferably 1 to 4 types.
- a black organic pigment can be used.
- I. Pigment Black 31, 32 and 34 are preferably used.
- a mixture of a blue organic pigment, a purple organic pigment, a green organic pigment, and a red organic pigment, and a mixture of a blue organic pigment, a red organic pigment, and a yellow organic pigment are preferable.
- the black matrix in the present invention contains one or more pigments selected from carbon black, titanium black and organic pigments as a colorant, preferably 1 to 6 types, preferably 1 to 5 types. 1 to 4 are preferable. These may be selected from only carbon black, may be selected from only titanium black, or may be selected from only organic pigments. Further, carbon black and titanium black, carbon black and organic pigment, titanium black and organic pigment, or a mixture of carbon black, titanium black and organic pigment may be used. Among these, it is preferable to select only from carbon black, select from titanium black only, select from organic pigment only, or select from carbon black and organic pigment. When selecting from carbon black and organic pigment, C.I. I. Pigment Black 7 and C.I. I. Pigment Blue 15: 3, 15: 4, and 15: 6 are preferably used.
- the carbon black, titanium black, and organic pigment have a volume resistivity of preferably 10 5 ⁇ ⁇ cm or more, and more preferably 10 6 ⁇ ⁇ cm or more.
- the RGB three-color pixel part has a diketopyrrolopyrrole pigment and / or an anionic red organic dye in the R pixel part, and a metal halide phthalocyanine pigment, phthalocyanine green dye, phthalocyanine blue in the G pixel part.
- At least one selected from the group consisting of a mixture of a dye and an azo yellow organic dye contains an ⁇ -type copper phthalocyanine pigment, a triarylmethane pigment and / or a cationic blue organic dye in the B pixel portion.
- the RGB three-color pixel portion is a color material that contains C.I. I. Solvent Red 124 with C.I. I. Solvent Blue 67 and C.I. I.
- the mixture with Solvent Yellow 162 was added to C.I. I.
- the RGB three-color pixel portion includes C.I. I. Pigment Red 254 in the G pixel portion. I. Pigment Green 7, 36 and / or 58 in the B pixel portion. I. It is also preferred to contain Pigment Blue 15: 6 and / or triarylmethane pigments.
- the RGB three-color pixel portion is further provided with C.I. I. Pigment Red 177, 242, 166, 167, 179, C.I. I. Pigment Orange 38, 71, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Solvent Red 89, C.I. I. Solvent Orange 56, C.I. I.
- the RGB three-color pixel portion is further provided with C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, and 33.
- the RGB three-color pixel portion is further provided with C.I. I. Pigment Blue 1, C.I. I. Pigment Violet 23, C.I. I. Basic Blue 7, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I.
- the color filter includes a black matrix, an RGB three-color pixel portion, and a Y pixel portion.
- the diketopyrrolopyrrole red pigment contained in the R pixel is C.I. I.
- One or more selected from Pigment Red 254, 255, 264, 272, Orange 71 and 73 are preferred, and one or more selected from Red 254, 255, 264 and 272 Is more preferred, and C.I. I. Pigment Red 254 is particularly preferable.
- halogenated metal phthalocyanine pigment contained in the G pixel portion examples include Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, A halogenated metal phthalocyanine pigment having a metal selected from the group consisting of Sn and Pb as a central metal, and when the central metal is trivalent, the central metal has one halogen atom, hydroxyl group or sulfonic acid group.
- the central metal When either is bonded or oxo or thio bridged and the central metal is a tetravalent metal, the central metal has one oxygen atom or two halogen atoms which may be the same or different
- a halogenated metal phthalocyanine pigment to which either a hydroxyl group or a sulfonic acid group is bonded is preferable.
- the metal halide phthalocyanine pigment include the following two groups of metal halide phthalocyanine pigments.
- (First group) It has a metal selected from the group consisting of Al, Si, Sc, Ti, V, Mg, Fe, Co, Ni, Zn, Cu, Ga, Ge, Y, Zr, Nb, In, Sn, and Pb as a central metal.
- the central metal When a hydroxyl group or a sulfonic acid group (—SO 3 H) is bonded and the central metal is a tetravalent metal, the central metal may be one oxygen atom or the same or different 2
- Halogen having molecules as structural units and each central metal of these structural units bonded through a divalent atomic group selected from the group consisting of oxygen atom, sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO 2 —)
- a pigment comprising a metal halide phthalocyanine dimer.
- all the halogen atoms bonded to the benzene ring may be the same or different. Different halogen atoms may be bonded to one benzene ring.
- the halogenated metal phthalocyanine pigment in which 9 to 15 bromine atoms out of 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule exhibits a yellowish bright green color, It is most suitable for use in the green pixel portion of the color filter.
- the metal halide phthalocyanine pigment is insoluble or hardly soluble in water or an organic solvent.
- the halogenated metal phthalocyanine pigment includes both a pigment that has not been subjected to a finishing treatment described later (also referred to as a crude pigment) and a pigment that has been subjected to a finishing treatment.
- the halogenated metal phthalocyanine pigments belonging to the first group and the second group can be represented by the following general formula (PIG-1).
- the metal halide phthalocyanine pigments belonging to the first group are as follows.
- X 1i to X 16i each represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom.
- the four X atoms bonded to one benzene ring may be the same or different.
- 8 to 16 are chlorine atoms, bromine atoms or iodine atoms.
- M represents a central metal.
- a pigment having a total of less than 8 chlorine atoms, bromine atoms and iodine atoms is blue.
- the yellow color becomes stronger as the total value of the pigments having a total of 8 or more chlorine atoms, bromine atoms and iodine atoms is increased.
- Y bonded to the central metal M is a monovalent atomic group selected from the group consisting of a halogen atom of any one of fluorine, chlorine, bromine or iodine, an oxygen atom, a hydroxyl group and a sulfonic acid group, and m is bonded to the central metal M.
- a halogen atom of any one of fluorine, chlorine, bromine or iodine an oxygen atom
- a hydroxyl group and a sulfonic acid group bonded to the central metal M.
- m The value of m is determined by the valence of the central metal M.
- One of the groups is attached to the central metal.
- the halogenated metal phthalocyanine pigment belonging to the second group is as follows in the general formula (PIG-1).
- X 1i to X 16i are as defined above, and the central metal M represents a trivalent metal selected from the group consisting of Al, Sc, Ga, Y and In, m represents 1. Y represents the following atomic group.
- the central metal M has the same definition as described above, and X 17i to X 32i have the same definition as X 1i to X 16i described above in the general formula (PIG-1).
- A represents a divalent atomic group selected from the group consisting of an oxygen atom, a sulfur atom, sulfinyl (—SO—) and sulfonyl (—SO 2 —).
- M in the general formula (PIG-1) and M in the atomic group Y are bonded via the divalent atomic group A. That is, the metal halide phthalocyanine pigment belonging to the second group is a metal halide phthalocyanine dimer in which two molecules of metal halide phthalocyanine are constituent units and these are bonded via the divalent atomic group.
- halogenated metal phthalocyanine pigment represented by the general formula (PIG-1) include the following (1) to (4).
- chlorinated brominated zinc phthalocyanine pigments include C.I. I. Pigment Green 58, particularly preferred.
- a halogenated metal phthalocyanine pigment having any of the groups and having 8 to 16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule.
- the center metal has a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as halogenated oxytitanium phthalocyanine and halogenated oxyvanadium phthalocyanine. 8 to 16 halogen atoms bonded to four benzene rings per one phthalocyanine molecule, having one oxygen atom or two halogen atoms which may be the same or different, a hydroxyl group or a sulfonic acid group Halogenated metal phthalocyanine pigment.
- a tetravalent metal selected from the group consisting of Si, Ti, V, Ge, Zr and Sn, such as halogenated oxytitanium phthalocyanine and halogenated oxyvanadium phthalocyanine. 8 to 16 halogen atoms bonded to four benzene rings per one phthalocyanine molecule, having one oxygen atom or two halogen atoms which may be the same or different
- a halogenated ⁇ -oxo-aluminum phthalocyanine dimer and a halogenated ⁇ -thio-aluminum phthalocyanine dimer.
- the valence metal is the central metal
- the halogenated metal phthalocyanine is composed of two molecules of 8-16 halogen atoms bonded to 4 benzene rings per phthalocyanine molecule. Each central metal of these structural units is an oxygen atom.
- a pigment comprising a metal halide phthalocyanine dimer bonded through a divalent atomic group selected from the group consisting of sulfur atom, sulfinyl and sulfonyl.
- halogenated metal phthalocyanine pigment in the G pixel portion examples include C.I. I. One or more selected from Pigment Green 7, 36 and 58 are preferred, and one or two selected from Green 36 and 58 are more preferred.
- Examples of the ⁇ -type phthalocyanine pigment contained in the B pixel portion include C.I. I. Pigment Blue 15: 6, and triarylmethane pigments include C.I. I. Pigment Blue 1 and / or the following general formula (1)
- R 11j to R 16j each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aryl group.
- the triarylmethane pigments represented are preferred.
- R 11j to R 16j may be the same or different. Accordingly, the —NRR (RR represents any combination of R 11j R 12j , R 13j R 14j , and R 15j R 16j ) group may be symmetric or asymmetric. When adjacent Rs (R represents any one of R 11j to R 16j ) are bonded to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.
- R 11j to R 16j are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, from the viewpoint of chemical stability.
- R 11j to R 16j are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group
- an alkyl group such as a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group and a 2-ethylhexyl group; and an aryl group such as a phenyl group and a naphthyl group.
- R 11j to R 16j represent an alkyl group or an aryl group
- the alkyl group or aryl group may further have an arbitrary substituent.
- the optional substituent that the alkyl group or aryl group may further have include the following [Substituent group Y].
- R 11j to R 16j are more preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group.
- X 11j and X 12j are the above alkyl groups, they may further have an arbitrary substituent.
- substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and propoxy group.
- Specific examples of X 11j and X 12j include haloalkyl groups such as a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, and a 2,2,2-trifluoroethyl group; an alkoxyalkyl group such as a methoxymethyl group, and the like Is mentioned.
- X 11j and X 12j are preferably a substituent having an appropriate steric hindrance that does not affect the twist, such as a hydrogen atom, a methyl group, a chlorine atom, or a trifluoromethyl group.
- X 11j and X 12j are most preferably a hydrogen atom, a methyl group or a chlorine atom from the viewpoint of color tone and heat resistance.
- the deficient Dawson-type phosphotungstic acid is preferably a 1-deficient Dawson-type phosphotungstic acid heteropolyoxometalate anion (P 2 W 17 O 61 ) 10 ⁇ / 10 from the viewpoint of durability.
- Specific examples of the triarylmethane pigment represented by the general formula (1) include, for example, the compounds described in the following Tables 1 to 7. However, the present invention is not limited to these unless the gist thereof is exceeded. Is not to be done.
- the RGB three-color pixel portion is a color material that contains C.I. I. Solvent Red 124 with C.I. I. Solvent Blue 67 and C.I. I.
- the mixture with Solvent Yellow 162 was added to C.I. I.
- it contains Solvent Blue 7.
- the RGB three-color pixel portion includes C.I. I. Pigment Red 254 in the G pixel portion. I. Pigment Green 7, 36 and / or 58 in the B pixel portion. I. It is also preferred to contain Pigment Blue 15: 6 and / or triarylmethane pigments.
- the RGB three-color pixel portion is further provided with C.I. I. Pigment Red 177, 242, 166, 167, 179, C.I. I. Pigment Orange 38, 71, C.I. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. Solvent Red 89, C.I. I. Solvent Orange 56, C.I. I. It is preferable to contain at least one organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, 162.
- the RGB three-color pixel portion is further provided with C.I. I. Pigment Yellow 150, 215, 185, 138, C.I. I.
- the RGB three-color pixel portion is further provided with C.I. I. Pigment Blue 1, C.I. I. Pigment Violet 23, C.I. I. Basic Blue 7, C.I. I. Basic Violet 10, C.I. I. Acid Blue 1, 90, 83, C.I. I. It is preferable to contain at least one organic dye or pigment selected from the group consisting of Direct Blue 86.
- the color filter includes a black matrix, an RGB three-color pixel portion, and a Y pixel portion. I. Pigment Yellow 150, 215, 185, 138, 139, C.I. I. It is also preferable to contain at least one yellow organic dye / pigment selected from the group consisting of Solvent Yellow 21, 82, 83: 1, 33, 162.
- the black matrix of the color filter can be formed by a conventionally known method.
- a typical method for forming a black matrix is a photolithography method, in which pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure a photocurable compound at a location corresponding to the black matrix. Thereafter, the unexposed portion is developed with a developer, and the black matrix is fixed to the transparent substrate. Further, a metal is formed by sputtering or the like, an etching resist pattern is formed on the formed thin film using a positive photoresist, and then etching of the exposed portion of the formed metal film is performed. There is a method of forming a black matrix by stripping an etching resist pattern.
- Each pixel portion of the color filter can also be formed by a conventionally known method.
- a typical method for forming the pixel portion is a photolithography method, which applies and heats a photocurable composition to be described later on the surface of the transparent substrate for the color filter provided with the black matrix. After drying (pre-baking), pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photo-curable compound at the location corresponding to the pixel portion, and then developing the unexposed portion with a developer. In this method, the non-pixel portion is removed and the pixel portion is fixed to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.
- a photocurable composition to be described later is prepared for each pixel of other colors such as an R pixel, a G pixel, a B pixel, and a Y pixel as necessary.
- a color filter having colored pixel portions of pixels, G pixels, B pixels, and Y pixels can be manufactured.
- Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coat method, a roll coat method, and an ink jet method.
- the drying conditions for the coating film of the photocurable composition applied to the transparent substrate are usually about 50 to 150 ° C. for about 1 to 15 minutes, although it varies depending on the type of each component, the blending ratio, and the like.
- the light used for photocuring the photocurable composition it is preferable to use ultraviolet rays or visible light in the wavelength range of 200 to 500 nm.
- Various light sources that emit light in this wavelength range can be used.
- the developing method include a liquid piling method, a dipping method, and a spray method.
- the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried.
- the color filter thus obtained is subjected to a heat treatment (post-baking) at 90 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven, thereby removing volatile components in the colored coating film and simultaneously applying light.
- the unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
- the liquid crystal layer can be prevented from decreasing the voltage holding ratio (VHR) and increasing the ion density (ID), white spots, uneven alignment, It is possible to provide a liquid crystal display device that solves the problem of display defects such as baking.
- VHR voltage holding ratio
- ID ion density
- the black matrix, the R pixel, the G pixel, the B pixel, and the Y pixel photocurable composition can be produced by using the black matrix pigment, the color filter pixel portion dye and / or the pigment composition of the present invention, and organic Using a solvent and a dispersant as essential components, mixing them and stirring and dispersing so as to be uniform, first prepare a black matrix, a pigment dispersion for forming the color filter pixel part, There is a general method in which a photocurable compound and, if necessary, a thermoplastic resin or a photopolymerization initiator are added to obtain the photocurable composition.
- organic solvent used here examples include aromatic solvents such as toluene, xylene, methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate.
- aromatic solvents such as toluene, xylene, methoxybenzene, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol methyl ether acetate.
- Acetate solvents such as diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl Ether, diethylene glycol dimethyl ether Ether solvents such as tellurium, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, ⁇ -butyrolactam, N-methyl-2-pyrrolidone, aniline And nitrogen compound solvents such as pyridine, lactone solvents such as ⁇ -butyrolactone, and carbamate esters such as a 48:52 mixture of
- Dispersants used here include, for example, Big Chemie's Dispersic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170, Dispersic 171, Dispersic 174, Dispersic 180, Dispersic 182, Dispersic 183, Dispersic 184, Dispersic 185, Dispersic 2000, Dispersic 2001, Dispersic 2020, Dispersic 2050, Dispersic 2070, Dispersic 2096, Dispersic 2150, Dispersic LPN21116, Dispersic LPN6919 Efka EFKA46, EFKA47, EFKA452, EFKALP4008, EFKA4 09, EFKA LP4010, EFKA LP4050, LP4055, EFKA400, EFKA401, EFKA402, EFKA403, EFKA450, EFKA451, EFKA453, EFKA4540, EFKA4550, EFKALP4560, EFKA120, EFKA150, EFKA1501,
- rosin such as acrylic resin, urethane resin, alkyd resin, wood rosin, gum rosin, tall oil rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, oxidized rosin, modified rosin such as maleated rosin, Rosin derivatives such as rosinamine, lime rosin, rosin alkylene oxide adduct, rosin alkyd adduct, rosin modified phenol, etc.
- a synthetic resin that is liquid and water-insoluble at room temperature can be contained. Addition of these dispersants and resins also contributes to reduction of flocculation, improvement of pigment dispersion stability, and improvement of viscosity characteristics of the dispersion.
- organic pigment derivatives such as phthalimidomethyl derivatives, sulfonic acid derivatives, N- (dialkylamino) methyl derivatives, N- (dialkylaminoalkyl) sulfonic acid amide derivatives, etc. You can also. Of course, two or more of these derivatives can be used in combination.
- thermoplastic resin used for the preparation of the photocurable composition examples include urethane resins, acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like.
- thermocurable compound examples include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, and 3-methylpentanediol diacrylate.
- Bifunctional monomers such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris [2- (meth) acryloyloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc.
- Relatively high molecular weight such as low molecular weight polyfunctional monomer, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. Functional monomer.
- photopolymerization initiator examples include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 ′ -Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid, and the like.
- photopolymerization initiators include, for example, “Irgacure (trade name) -184”, “Irgacure (trade name) -369”, “Darocur (trade name) -1173” manufactured by BASF, “Lucirin- "TPO”, Nippon Kayaku Co., Ltd. "Kayacure (trade name) DETX”, “Kayacure (trade name) OA”, Stofer “Bicure 10", “Bicure 55", Akzo "Trigonal PI”, Sand “Sandray 1000" manufactured by Upjohn, “Deep” manufactured by Upjohn, and “Biimidazole” manufactured by Kurokin Kasei.
- a well-known and usual photosensitizer can also be used together with the said photoinitiator.
- the photosensitizer include amines, ureas, compounds having a sulfur atom, compounds having a phosphorus atom, compounds having a chlorine atom, nitriles or other compounds having a nitrogen atom. These can be used alone or in combination of two or more.
- the blending ratio of the photopolymerization initiator is not particularly limited, but is preferably in the range of 0.1 to 30% with respect to the compound having a photopolymerizable or photocurable functional group on a mass basis. If it is less than 0.1%, the photosensitivity at the time of photocuring tends to decrease, and if it exceeds 30%, crystals of the photopolymerization initiator are precipitated when the pigment-dispersed resist coating film is dried. May cause deterioration of film properties.
- 20 to 1000 parts of an organic solvent and 1 to The dye / pigment dispersion can be obtained by stirring and dispersing 100 parts of the dispersant in a uniform manner.
- the pigment dispersion is then combined with 3 to 20 parts of a total of thermoplastic resin and photocurable compound per 1 part of the pigment for black matrix, dye for color filter and / or pigment composition of the present invention.
- Photo-curing property to form black matrix and color filter pixel part by adding 0.05-3 parts photopolymerization initiator per part and further organic solvent if necessary, stirring and dispersing to make uniform A composition can be obtained.
- As the developer a known and commonly used organic solvent or alkaline aqueous solution can be used.
- the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, washing with an alkaline aqueous solution is a black matrix. In addition, it is effective for forming the color filter pixel portion.
- the manufacturing method of the color filter pixel part by the photolithographic method was described in detail, the color filter pixel part prepared by using the pigment composition for the color filter of the present invention can be used in other electrodeposition methods, transfer methods, and micelle electrolysis methods.
- a color filter may be manufactured by forming each color pixel portion by a PVED (Photovoltaic Electrodeposition) method, an inkjet method, a reverse printing method, a thermosetting method, or the like.
- the manufacturing method by the photolithography method was described in detail, but the black matrix prepared using the black matrix coloring material of the present invention is a transfer method, an inkjet method, a reverse printing method, a thermosetting method, etc.
- the black matrix may be manufactured by the method described above.
- the liquid crystal composition is aligned on the first substrate and the surface in contact with the liquid crystal composition on the second substrate. Although arranged between the liquid crystal layers, even if the alignment film is thick, it is as thin as 100 nm or less, and completely blocks the interaction between the pigment such as a pigment constituting the color filter and the liquid crystal compound constituting the liquid crystal layer. It is not a thing. Further, in a liquid crystal display device that does not use an alignment film, the interaction between a pigment such as a pigment constituting a color filter and a liquid crystal compound constituting a liquid crystal layer becomes larger.
- alignment film material transparent organic materials such as polyimide, polyamide, BCB (Penzocyclobutene Polymer), polyvinyl alcohol and the like can be used. Particularly, p-phenylenediamine, 4,4′-diaminodiphenylmethane, etc.
- Aliphatic or alicyclic tetracarboxylic anhydrides such as aliphatic or alicyclic diamines, butanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, pyromellitic dianhydride
- a polyimide alignment film obtained by imidizing a polyamic acid synthesized from an aromatic tetracarboxylic anhydride such as a product is preferable.
- rubbing is generally used as a method for imparting orientation, but when used for a vertical orientation film or the like, it can be used without imparting orientation.
- the alignment film material a material containing chalcone, cinnamate, cinnamoyl or azo group in the compound can be used, and it may be used in combination with materials such as polyimide and polyamide. In this case, the alignment film is rubbed. Or a photo-alignment technique may be used.
- the alignment film is generally formed by applying the alignment film material on a substrate by a method such as spin coating to form a resin film, but a uniaxial stretching method, Langmuir-Blodgett method, or the like can also be used. .
- a conductive metal oxide can be used as a material for the transparent electrode.
- the metal oxide include indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), and zinc oxide.
- ZnO indium tin oxide
- In 2 O 3 —SnO 2 indium zinc oxide
- niobium-doped titanium dioxide Ti 1-x Nb x O 2
- fluorine-doped tin oxide graphene
- ZnO zinc oxide
- In 2 O 3 —SnO 2 indium tin oxide
- In 2 O 3 —ZnO indium zinc oxide
- a photo-etching method or a method using a mask can be used.
- the liquid crystal display device of the present invention is particularly useful for a liquid crystal display device for active matrix driving, and is used for a liquid crystal display device for TN mode, IPS mode, polymer-stabilized IPS mode, FFS mode, OCB mode, VA mode or ECB mode. Applicable.
- the liquid crystal display device is combined with a backlight and used in various applications such as liquid crystal televisions, personal computer monitors, mobile phones, smartphone displays, notebook personal computers, personal digital assistants, and digital signage.
- the backlight include a cold cathode tube type backlight, a two-wavelength peak pseudo-white backlight and a three-wavelength peak backlight using a light emitting diode or an organic EL element using an inorganic material.
- T ni Nematic phase-isotropic liquid phase transition temperature (° C.) ⁇ n: refractive index anisotropy at 25 ° C. ⁇ : dielectric anisotropy at 25 ° C. ⁇ : viscosity at 20 ° C. (mPa ⁇ s) ⁇ 1: rotational viscosity at 25 ° C. (mPa ⁇ s) VHR: Voltage holding ratio at 70 ° C.
- a carbon black dispersion liquid was obtained by dispersing 55 parts of carbon black (CI Pigment Black 7) having a volume resistivity of 10 7 ⁇ ⁇ cm and 45 parts of a dispersant solution with a paint conditioner. 67 parts of this dispersion was mixed with 2 parts of a photopolymerizable monomer for ultraviolet curing, 7 parts of an alkali-soluble resin, 1 part of a photoinitiator, and 23 parts of a solvent to prepare a photosensitive composition 1 for black matrix.
- the photosensitive composition 1 was applied to a glass substrate using a spin coater. After vacuum drying for 1 minute, it was dried by heating on a hot plate at 90 ° C. for 90 seconds to obtain a coating film having a dry film thickness of about 3 ⁇ m. Then, after image exposure from the coating film side through a pattern mask, it developed and the black matrix 1 was created.
- this dispersion 40 parts of this dispersion was mixed with 4 parts of a photopolymerizable monomer for ultraviolet curing, 2 parts of an alkali-soluble resin, 1 part of a photoinitiator, and 53 parts of a solvent to prepare a photosensitive composition 3 for a black matrix.
- the photosensitive composition 3 was applied to a glass substrate using a spin coater. After vacuum drying for 1 minute, it was dried by heating on a hot plate at 90 ° C. for 90 seconds to obtain a coating film having a dry film thickness of about 3 ⁇ m. Thereafter, image exposure was performed from the coating film side through a pattern mask, and development was performed to create a black matrix 3.
- a photosensitive composition 4 for a black matrix 40 parts of this dispersion was mixed with 4 parts of a photopolymerizable monomer for ultraviolet curing, 2 parts of an alkali-soluble resin, 1 part of a photoinitiator, and 53 parts of a solvent to prepare a photosensitive composition 4 for a black matrix.
- the photosensitive composition 4 was applied to a glass substrate using a spin coater. After vacuum drying for 1 minute, it was dried by heating on a hot plate at 90 ° C. for 90 seconds to obtain a coating film having a dry film thickness of about 3 ⁇ m. Thereafter, the image was exposed through the pattern mask from the coating film side, and development was performed to create a black matrix 4.
- Black Matrix 5 A chromium oxide film is formed on a glass substrate by a sputtering method, a photoresist pattern for forming an opening is formed by a photolithography method, and the exposed chromium oxide film is removed by etching based on the photoresist pattern. The resist pattern was peeled off to create a black matrix 5.
- Red dye coloring composition 1 10 parts of Red Pigment 1 (CI Pigment Red 254, “IRGAPHOR RED BT-CF” manufactured by BASF) is placed in a polybin, 55 parts of propylene glycol monomethyl ether acetate, Dispersic LPN21116 (manufactured by BYK Chemie) 7.0 And 0.3-0.4 mm ⁇ sepul beads were added and dispersed for 4 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.), followed by filtration with a 5 ⁇ m filter to obtain a pigment dispersion.
- a paint conditioner manufactured by Toyo Seiki Co., Ltd.
- Green pigment coloring composition 1 Instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 6 parts of green pigment 1 (FASTOGEN GREEN A110 manufactured by CI Pigment Green 58 DIC Corporation) and yellow pigment 1 (CI Pigment Yellow 150, A green pigment coloring composition 1 was obtained in the same manner as described above using 4 parts of FANCHON FAST YELLOW E4GN manufactured by LANXESS.
- Blue pigment coloring composition 1 instead of 10 parts of the red pigment 1 of the red pigment coloring composition 1, 9 parts of blue pigment 1 (CI Pigment Blue 15: 6, “FASTOGEN BLUE EP-210” manufactured by DIC Corporation) and purple pigment 1 (C Blue pigment coloring composition 1 was obtained in the same manner as described above using 1 part of I. Pigment VIOLET 23).
- the red coloring composition 1 was applied to a glass substrate on which a black matrix had been formed in advance to a thickness of 2 ⁇ m by spin coating. After drying at 70 ° C. for 20 minutes, striped pattern exposure was performed using a photomask with ultraviolet rays using an exposure machine equipped with an ultrahigh pressure mercury lamp. Spray development with an alkali developer for 90 seconds, washing with ion exchange water, and air drying. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form red pixels, which are striped colored layers, on a transparent substrate. Next, the green coloring composition 1 is similarly applied by spin coating so that the film thickness becomes 2 ⁇ m.
- the striped colored layer was exposed and developed at a place different from the above-mentioned red pixel by an exposure machine, thereby forming a green pixel adjacent to the above-mentioned red pixel.
- the blue coloring composition 1 was similarly formed by spin coating to form a blue pixel adjacent to the red pixel and the green pixel with a film thickness of 2 ⁇ m.
- a color filter having striped pixels of three colors of red, green, and blue on the transparent substrate was obtained.
- color filters 1 to 4 and comparative color filter 1 were prepared.
- Example 1 to 4 An electrode structure is formed on at least one of the first and second substrates, a horizontal alignment film is formed on each facing side, and then a weak rubbing process is performed to create an IPS cell.
- a liquid crystal composition 1 shown below was sandwiched between two substrates.
- Table 10 shows the physical property values of the liquid crystal composition 1.
- the liquid crystal composition 1 has a liquid crystal layer temperature range of 75.8 ° C. that is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, has a low viscosity, and an optimal ⁇ n. You can see that The liquid crystal display devices of Examples 1 to 4 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Example 5 to 12 As in Example 1, the liquid crystal compositions 2 to 3 shown in Table 12 were sandwiched, and the liquid crystal display devices of Examples 5 to 12 were prepared using the color filters shown in Table 9, and their VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 13-14.
- liquid crystal display devices of Examples 5 to 12 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Example 13 to 24 As in Example 1, the liquid crystal compositions 4 to 6 shown in Table 15 were sandwiched, and the liquid crystal display devices of Examples 13 to 24 were prepared using the color filters shown in Table 9, and their VHR and ID were measured. . The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 16-18.
- liquid crystal display devices of Examples 13 to 24 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- liquid crystal display devices of Examples 25 to 36 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- liquid crystal display devices of Examples 37 to 44 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Example 45 to 56 As in Example 37, the liquid crystal compositions 12 to 14 shown in Table 26 were sandwiched, and the liquid crystal display devices of Examples 45 to 56 were prepared using the color filters shown in Table 9, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 27-29.
- liquid crystal display devices of Examples 45 to 56 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- a liquid crystal composition 15 was prepared by mixing 0.3% by mass of bismethacrylic acid biphenyl-4,4′-diyl with the liquid crystal composition 10 used in Example 37.
- the liquid crystal composition 15 was sandwiched between TN cells, and a polymerization treatment was performed by irradiating with ultraviolet rays (3.0 J / cm 2 ) for 600 seconds while a driving voltage was applied between the electrodes.
- Liquid crystal display devices of Examples 57 to 60 were prepared using the filters 1 to 4, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 30.
- liquid crystal display devices of Examples 57 to 60 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- a liquid crystal composition 16 was prepared by mixing 0.3% by mass of bismethacrylic acid biphenyl-4,4′-diyl with the liquid crystal composition 8 used in Example 29.
- the liquid crystal composition 16 was sandwiched between IPS cells, and ultraviolet light was irradiated (3.0 J / cm 2 ) for 600 seconds while a driving voltage was applied between the electrodes, followed by polymerization treatment.
- Liquid crystal display devices of Examples 61 to 64 were prepared using filters 1 to 4, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 31.
- liquid crystal display devices of Examples 61 to 64 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Example 65 to 68 A liquid crystal composition 17 was prepared by mixing 0.3% by mass of bismethacrylic acid 3-fluorobiphenyl-4,4′-diyl with the liquid crystal composition 6 used in Example 21. The liquid crystal composition 17 was sandwiched between FFS cells, and a polymerization treatment was performed by irradiating with ultraviolet rays (3.0 J / cm 2 ) for 600 seconds while applying a driving voltage between the electrodes. Liquid crystal display devices of Examples 65 to 68 were prepared using filters 1 to 4, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 32.
- liquid crystal display devices of Examples 65 to 68 were able to realize high VHR and small ID. Further, even in the burn-in evaluation, there was no afterimage, or even a very slight and acceptable level.
- Comparative Examples 1 to 4 The comparative liquid crystal composition 1 shown below was sandwiched between the IPS cells used in Example 1.
- Table 33 shows the physical properties of the comparative liquid crystal composition.
- Liquid crystal display devices of Comparative Examples 1 to 4 were prepared using the color filters 1 to 4 shown in Table 9, and their VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Table 34.
- the VHR was lower and the ID was larger than the liquid crystal display device of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.
- Comparative Examples 5 to 12 In the same manner as in Example 1, the liquid crystal display devices of Comparative Examples 5 to 12 were prepared by sandwiching the comparative liquid crystal compositions 2 and 3 shown in Table 35 and using the color filters 1 to 4 shown in Table 9, and the VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 36-37.
- the liquid crystal display devices of Comparative Examples 5 to 12 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.
- Comparative Examples 13 to 20 As in Example 1, the liquid crystal display devices of Comparative Examples 13 to 24 were prepared by sandwiching the comparative liquid crystal compositions 4 to 5 shown in Table 38 and using the color filters 1 to 4 shown in Table 9, and the VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 39-40.
- the liquid crystal display devices of Comparative Examples 13 to 20 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.
- Comparative Examples 21 to 32 In the same manner as in Example 1, the liquid crystal display devices of Comparative Examples 21 to 32 were produced by sandwiching the comparative liquid crystal compositions 6 to 8 shown in Table 41 and using the color filters 1 to 4 shown in Table 9, and the VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 42 to 44.
- the liquid crystal display devices of Comparative Examples 21 to 32 had lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.
- Comparative Examples 33 to 44 In the same manner as in Example 1, the liquid crystal display devices of Comparative Examples 33 to 44 were produced by sandwiching the comparative liquid crystal compositions 9 to 11 shown in Table 45 and using the color filters 1 to 4 shown in Table 9, and the VHR and ID was measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 46 to 48.
- the liquid crystal display devices of Comparative Examples 33 to 44 have lower VHR and larger ID than the liquid crystal display devices of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.
- Comparative Examples 45 to 52 In Examples 5, 13, 17, 25, 37, 45, 61 and 65, except that the comparative color filter 1 shown in Table 9 was used instead of the color filter 1, the liquid crystal display devices of Comparative Examples 45 to 52 were similarly used. Was prepared, and its VHR and ID were measured. The burn-in evaluation of the liquid crystal display device was performed. The results are shown in Tables 49 and 50.
- the liquid crystal display devices of Comparative Examples 45 to 52 have lower VHR and larger ID than the liquid crystal display device of the present invention. Also, in the burn-in evaluation, afterimages were observed and the level was not acceptable.
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Abstract
Description
前記カラーフィルタ層は、ブラックマトリックスと赤色着色層(R)、緑色着色層(G)、青色着色層(B)、及び必要に応じて黄色着色層(Y)から構成されるカラーフィルタにより構成される。
液晶層を構成する液晶材料は、材料中に不純物が残留すると表示装置の電気的特性に大きな影響を及ぼすことから不純物についての高度な管理がなされてきた。又、配向膜を形成する材料に関しても配向膜は液晶層が直接接触し、配向膜中に残存した不純物が液晶層に移動することにより、液晶層の電気的特性に影響を及ぼすことは既に知られており、配向膜材料中の不純物に起因する液晶表示装置の特性についての検討がなされつつある。
カラーフィルタを構成する顔料に含まれる不純物に起因した表示不良を解決する方法として、顔料の蟻酸エチルによる抽出物の割合を特定値以下とした顔料を用いて、不純物の液晶への溶出を制御する方法(特許文献1)や青色着色層中の顔料を特定することで不純物の液晶への溶出を制御する方法(特許文献2)が検討されてきた。しかしながら、これらの方法では顔料中の不純物を単純に低減することと大きな差異はなく、近年、顔料の精製技術が進歩している現状においても表示不良を解決するための改良としては不十分なものであった。
しかしながら、当該引用文献の開示においても顔料中の不純物による液晶層への影響を抑えることが発明の本質となっており、カラーフィルタに使用される染顔料等の色材の構造と液晶材料の構造との直接的な関係については検討が行われていなかった。
ブラックマトリックスについても、高抵抗カーボンブラックやチタンブラックを用いることで、色ムラや、残像が見られないようになることが開示されているが(特許文献4)、近年高度化する液晶表示素子の表示不良を解決できるものではなかった。
さらに、青色、黄色、赤色の各有機顔料を含有するブラックマトリックス用感光組成物が高絶縁、低誘電率でかつ高光学濃度であることが開示されているが(特許文献5)、液晶表示素子とした場合の表示特性についての記載はなく、近年高度化する液晶表示装置の表示不良問題の解決には至っていなかった。
即ち、本発明は、
第一の基板と、第二の基板と、前記第一の基板と第二の基板間に挟持された液晶組成物層と、ブラックマトリックス及び少なくともRGB三色画素部から構成されるカラーフィルタと、画素電極と共通電極とを備え、
前記液晶組成物層が一般式(I)
前記ブラックマトリックスが、色材として、カーボンブラック、チタンブラック及び有機顔料より選ばれる1種又は2種以上の顔料を含有することを特徴とする液晶表示装置を提供する。
2 カラーフィルタ層
2a 特定の顔料を使用したブラックマトリックスを有するカラーフィルタ層
3a 透明電極層(共通電極)
3b 画素電極層
4 配向膜
5 液晶層
5a 特定の液晶組成物を含有する液晶層
前記表示装置における2枚の基板は、周辺領域に配置されたシール材及び封止材によって貼り合わされていて、多くの場合その間には基板間距離を保持するために粒状スペーサーまたはフォトリソグラフィー法により形成された樹脂からなるスペーサー柱が配置されている。
本発明の液晶表示装置における液晶組成物層は、一般式(I)
熱や光に対する化学的安定性が良いことを重視すれば、R31はアルキル基が好ましい。また、粘度が小さく応答速度が速い液晶表示素子を作ることが重視されるならば、R31はアルケニル基が好ましい。さらに、粘度が小さくかつネマチック-等方相転移温度(Tni)が高く、応答速度の更なる短縮を目的とするならば、末端が不飽和結合ではないアルケニル基を用いることが好ましく、アルケニル基の隣にメチル基が末端としてあることが特に好ましい。また、低温での溶解度が良いことを重視するならば、一つの解決策としては、R31はアルコキシ基とすることが好ましい。また、他の解決策としては、多種類のR31を併用することが好ましい。例えば、R31として、炭素原子数2、3及び4のアルキル基またはアルケニル基を持つ化合物を併用することが好ましく、炭素原子数3及び5の化合物を併用することが好ましく、炭素原子数3、4及び5の化合物を併用することが好ましい。
M31~M33は、
Z31は、フッ素原子またはトリフルオロメトキシ基であることが好ましい。
X31、X32およびZ31の組み合わせとしては、一つの実施形態ではX31=F、X32=FおよびZ31=Fである。さらに別の実施形態では、X31=F、X32=HおよびZ31=Fである。またさらに別の実施形態では、X31=F、X32=HおよびZ31=OCF3である。またさらに別の実施形態では、X31=F、X32=FおよびZ31=OCF3である。またさらに別の実施形態では、X31=H、X32=HおよびZ31=OCF3である。
n31は1又は2が好ましく、n32は0又は1が好ましく、0が更に好ましく、n31+n32は1又は2が好ましく、2がさらに好ましい。
一般式(Ia)~一般式(If)において、R32はそれが結合する環構造がフェニル基(芳香族)である場合には、直鎖状の炭素原子数1~5のアルキル基、直鎖状の炭素原子数1~4(またはそれ以上)のアルコキシ基及び炭素原子数4~5のアルケニル基が好ましく、それが結合する環構造がシクロヘキサン、ピラン及びジオキサンなどの飽和した環構造の場合には、直鎖状の炭素原子数1~5のアルキル基、直鎖状の炭素原子数1~4(またはそれ以上)のアルコキシ基及び直鎖状の炭素原子数2~5のアルケニル基が好ましい。
Z31は、フッ素原子またはトリフルオロメトキシ基であることが好ましい。
X31、X32およびZ31の組み合わせとしては、一つの実施形態ではX31=F、X32=FおよびZ31=Fである。さらに別の実施形態では、X31=F、X32=HおよびZ31=Fである。またさらに別の実施形態では、X31=F、X32=HおよびZ31=OCF3である。またさらに別の実施形態では、X31=F、X32=FおよびZ31=OCF3である。またさらに別の実施形態では、X31=H、X32=HおよびZ31=OCF3である。
n31は1又は2が好ましく、n32は0又は1が好ましく、0が更に好ましく、n31+n32は1又は2が好ましく、2がさらに好ましい。
X33及びX34は、少なくともどちらか一つはフッ素原子が好ましく、二つともフッ素原子であることが更に好ましい。
X37及びX38は、少なくともどちらか一つは水素原子が好ましく、二つとも水素原子であることが好ましい。X37及びX38のうち少なくともどちらか一つがフッ素原子である場合、Tni、低温での溶解性や液晶表示素子にしたときの化学的安定性の観点から好ましくない。
一般式(I)で表される化合物群は1種~8種含有することが好ましく、1種~5種含有することが特に好ましく、その含有量は3~50質量%であるのが好ましく、5~40質量%であることがより好ましい。
R21~R22はアルキル基またはアルケニル基が好ましく、少なくとも一方はアルケニル基であることが好ましい。両方ともアルケニル基の場合は応答速度を早くする場合に好適に用いられるが、液晶表示素子の化学的安定性を良くしたい場合は好ましくない。
R23~R24の少なくとも一方は、炭素原子数1~5のアルキル基、炭素原子数1~5のアルコキシ基または炭素原子数4~5のアルケニル基が好ましい。応答速度とTniのバランスが良いことを求めれば、R23~R24の少なくとも一方はアルケニル基であることが好ましく、応答速度と低温での溶解性のバランスが良いことを求めれば、R23~R24の少なくとも一方はアルコキシ基であることが好ましい。
R27~R28の少なくとも一方は、炭素原子数1~5のアルキル基、炭素原子数1~5のアルコキシ基または炭素原子数2~5のアルケニル基が好ましい。応答速度とTniのバランスが良いことを求めれば、R27~R28の少なくとも一方はアルケニル基であることが好ましく、応答速度と低温での溶解性のバランスが良いことを求めれば、R27~R28の少なくとも一方はアルコキシ基であることが好ましい。R27はアルキル基またはアルケニル基でありR28はアルキル基であることがより好ましい。また、R27はアルキル基でありR28はアルコキシ基であることも好ましい。さらに、R27はアルキル基でありR28はアルキル基であることが特に好ましい。
X21はフッ素原子であることが好ましい。
一般式(II-a)から一般式(II-f)で表される化合物群は1種~10種含有することが好ましく、1種~8種含有することが特に好ましく、その含有量は5~80質量%であるのが好ましく、10~70質量%であることがより好ましく、20~60質量%であることが特に好ましい。
一般式(IIIa)~一般式(IIIf)において、R41はそれが結合する環構造がフェニル基(芳香族)である場合には、直鎖状の炭素原子数1~5のアルキル基、直鎖状の炭素原子数1~4(またはそれ以上)のアルコキシ基及び炭素原子数4~5のアルケニル基が好ましく、それが結合する環構造がシクロヘキサン、ピラン及びジオキサンなどの飽和した環構造の場合には、直鎖状の炭素原子数1~5のアルキル基、直鎖状の炭素原子数1~4(またはそれ以上)のアルコキシ基及び直鎖状の炭素原子数2~5のアルケニル基が好ましい。
Z41は、フッ素原子またはトリフルオロメトキシ基であることが好ましい。
X41、X42およびZ41の組み合わせとしては、一つの実施形態ではX41=F、X42=FおよびZ41=Fである。さらに別の実施形態では、X41=F、X42=HおよびZ41=Fである。またさらに別の実施形態では、X41=F、X42=HおよびZ41=OCF3である。またさらに別の実施形態では、X41=F、X42=FおよびZ41=OCF3である。またさらに別の実施形態では、X41=H、X42=HおよびZ41=OCF3である。
X43及びX44は、少なくともどちらか一つはフッ素原子が好ましく、二つともフッ素原子であることは大きなΔεを得るために好ましいが、反対に、低温での溶解性を良くする場合には好ましくない。
X47及びX48は、少なくともどちらか一つは水素原子が好ましく、二つとも水素原子であることが好ましい。X47及びX48のうち少なくともどちらか一つがフッ素原子である場合、Tni、低温での溶解性や液晶表示素子にしたときの化学的安定性の観点から好ましくない。
一般式(III-a)から一般式(III-f)で表される化合物群から選ばれる化合物は、1種~10種含有することが好ましく、1種~8種含有することがより好ましく、その含有量は5~50質量%であることが好ましく、10~40質量%であることがより好ましい。
本発明における液晶組成物には、PSモード、横電界型PSAモード又は横電界型PSVAモードなどの液晶表示素子を作製するために、重合性化合物を一種又は二種以上含有することができる。使用できる重合性化合物として、光などのエネルギー線により重合が進行する光重合性モノマーなどが挙げられ、構造として、例えば、ビフェニル誘導体、ターフェニル誘導体などの六員環が複数連結した液晶骨格を有する重合性化合物などが挙げられる。更に具体的には、一般式(V)
Sp1及びSp2はそれぞれ独立して、単結合、炭素原子数1~8のアルキレン基又は-O-(CH2)s-(式中、sは2から7の整数を表し、酸素原子は芳香環に結合するものとする。)を表し、Z51は-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-(式中、Y1及びY2はそれぞれ独立して、フッ素原子又は水素原子を表す。)、-C≡C-又は単結合を表し、
M51は1,4-フェニレン基、トランス-1,4-シクロヘキシレン基又は単結合を表し、式中の全ての1,4-フェニレン基は、任意の水素原子がフッ素原子により置換されていても良い。)で表される二官能モノマーが好ましい。
Sp1及びSp2はそれぞれ独立して、単結合、炭素原子数1~8のアルキレン基又は-O-(CH2)s-を表すが、PSA表示素子においては少なくとも一方が単結合であることが好ましく、共に単結合を表す化合物又は一方が単結合でもう一方が炭素原子数1~8のアルキレン基又は-O-(CH2)s-を表す態様が好ましい。この場合1~4のアルキル基が好ましく、sは1~4が好ましい。
M51は任意の水素原子がフッ素原子により置換されていても良い1,4-フェニレン基、トランス-1,4-シクロヘキシレン基又は単結合を表すが、1,4-フェニレン基又は単結合が好ましい。Cが単結合以外の環構造を表す場合、Z51は単結合以外の連結基も好ましく、M51が単結合の場合、Z51は単結合が好ましい。
一般式(V)において、M51が単結合を表し、環構造が二つの環で形成される場合において、次の式(Va-1)~式(Va-5)を表すことが好ましく、式(Va-1)~式(Va-3)を表すことがより好ましく、式(Va-1)を表すことが特に好ましい。
これらの骨格を含む重合性化合物は重合後の配向規制力がPSA型液晶表示素子に最適であり、良好な配向状態が得られることから、表示ムラが抑制されるか、又は、全く発生しない。
以上のことから、重合性化合物としては、一般式(V-1)~一般式(V-4)が特に好ましく、中でも一般式(V-2)が最も好ましい。
本発明における液晶組成物に重合性化合物を添加する場合において、重合開始剤が存在しない場合でも重合は進行するが、重合を促進するために重合開始剤を含有していてもよい。重合開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド類等が挙げられる。
本発明におけるカラーフィルタは、ブラックマトリックス及び少なくともRGB三色画素部から構成される。
ブラックマトリックスは、色材として、カーボンブラック、チタンブラック及び有機顔料より選ばれる1種又は2種以上の顔料を含有する。
カーボンブラックとしては、C.I.Pigment Black 6、同7、同8、同10が挙げることができ、C.I.Pigment Black 7が好ましい。また、特開2002-249678に開示されている樹脂被覆カーボンブラックも用いることができる。
チタンブラックとしては、C.I.Pigment Black 35を挙げることができ、特開2007-302836に開示されているフッソ樹脂、ケイ素樹脂等の撥水性物質で処理した撥水性チタンブラックも用いることができる。
青色有機顔料としては、例えば、C.I.Pigment Blue 1、同1:2、同9、同14、同15、同15:1、同15:2、同15:3、同15:4、同15:6、同16、同17、同19、同25、同27、28、同29、同33、同35、同36、同56、同56:1、同60、同61、同61:1、同62、同63、同66、同67、同68、同71、同72、同73、同74、同75、同76、同78、同79等を挙げることができる。
緑色有機顔料としては、C.I.Pigment Green 1、同4、同7、同8、同10、同15、同17、同26、同36、同48、同50、同58等を挙げることができる。
褐色有機顔料としては、C.I.Pigment Brown 5、同6、同23、同24、同25、同32、同38、同41、同42等を挙げることができる。
黒色有機顔料としては、C.I.Pigment Black 1、同9、同11、同20、同31、同32、同34等を挙げることができる。
また、上記のカーボンブラック、チタンブラック及び有機顔料は、その体積固有抵抗が、105Ω・cm以上が好ましく、106Ω・cm以上がより好ましい。
前記RGB三色画素部は、色材として、R画素部中にC.I.Solvent Red 124を、G画素部中にC.I.Solvent Blue 67とC.I.Solvent Yellow 162との混合物を、B画素部中にC.I.Solvent Blue 7を含有するのが好ましい。
前記RGB三色画素部は、色材として、R画素部中に更に、C.I.Pigment Red 177、同242、同166、同167、同179、C.I.Pigment Orange 38、同71、C.I.Pigment Yellow 150、同215、同185、同138、同139、C.I.Solvent Red 89、C.I.Solvent Orange 56、C.I.Solvent Yellow 21、同82、同83:1、同33、同162からなる群から選ばれる少なくとも1種の有機染顔料を含有するのが好ましい。
前記RGB三色画素部は、色材として、G画素部中に更に、C.I.Pigment Yellow 150、同215、同185、同138、C.I.Solvent Yellow 21、同82、同83:1、同33からなる群から選ばれる少なくとも1種の有機染顔料を含有するのが好ましい。
前記RGB三色画素部は、色材として、B画素部中に更に、C.I.Pigment Blue 1、C.I.Pigment Violet 23、C.I.Basic Blue 7、C.I.Basic Violet 10、C.I.Acid Blue 1、同90、同83、C.I.Direct Blue 86からなる群から選ばれる少なくとも1種の有機染顔料を含有するのが好ましい。
また、カラーフィルタが、ブラックマトリックスとRGB三色画素部とY画素部とから構成され、色材として、Y画素部に、C.I.Pigment Yellow 150、同215、同185、同138、同139、C.I.Solvent Yellow 21、82、同83:1、同33、同162からなる群から選ばれる少なくとも1種の黄色有機染顔料を含有するのも好ましい。
Al、Si、Sc、Ti、V、Mg、Fe、Co、Ni、Zn、Cu、Ga、Ge、Y、Zr、Nb、In、Sn及びPbからなる群から選ばれる金属を中心金属として有し、フタロシアニン分子1個当たり8~16個のハロゲン原子がフタロシアニン分子のベンゼン環に結合したハロゲン化金属フタロシアニン顔料であり、その中心金属が三価の場合には、その中心金属には1つのハロゲン原子、水酸基又はスルホン酸基(-SO3H)のいずれかが結合しており、中心金属が四価金属の場合には、その中心金属には1つの酸素原子又は同一でも異なっていても良い2つのハロゲン原子、水酸基又はスルホン酸基のいずれかが結合しているハロゲン化金属フタロシアニン顔料。
Al、Sc、Ga、Y及びInからなる群から選ばれる三価金属を中心金属とし、フタロシアニン分子1個当たり8~16個のハロゲン原子がフタロシアニン分子のベンゼン環に結合したハロゲン化金属フタロシアニンの2分子を構成単位とし、これら構成単位の各中心金属が酸素原子、硫黄原子、スルフィニル(-SO-)及びスルホニル(-SO2-)からなる群から選ばれる二価原子団を介して結合したハロゲン化金属フタロシアニン二量体からなる顔料。
ここで、フタロシアニン分子1個当たり8~16個のハロゲン原子のうち9~15個の臭素原子がフタロシアニン分子のベンゼン環に結合したハロゲン化金属フタロシアニン顔料は、黄味を帯びた明るい緑色を呈し、カラーフィルタの緑色画素部への使用に最適である。該ハロゲン化金属フタロシアニン顔料は、水や有機溶媒に不溶または難溶である。該ハロゲン化金属フタロシアニン顔料には、後述する仕上げ処理が行われていない顔料(粗顔料とも呼ばれる)も、仕上げ処理が行われた顔料も、いずれも包含される。
前記第一群および第二群に属するハロゲン化金属フタロシアニン顔料は、下記一般式(PIG-1)で表すことが出来る。
一般式(PIG-1)において、X1i~X16iは、水素原子、塩素原子、臭素原子またはヨウ素原子を表す。ひとつのベンゼン環に結合した4個のXの原子は同一でも異なっていても良い。4個のベンゼン環に結合したX1i~X16iのうち、8~16個は塩素原子、臭素原子またはヨウ素原子である。Mは中心金属を表す。後述するY及びそれの個数mが同一であるハロゲン化金属フタロシアニン顔料の範囲において、16個のX1i~X16iのうち塩素原子、臭素原子及びヨウ素原子の合計が8未満の顔料は青色であり、同様に16個のX1i~X16iのうち塩素原子、臭素原子及びヨウ素原子の合計が8以上の顔料で前記合計値が大きいほど黄味が強くなる。中心金属Mに結合するYはフッ素、塩素、臭素またはヨウ素のいずれかのハロゲン原子、酸素原子、水酸基及びスルホン酸基からなる群から選ばれる一価原子団であり、mは中心金属Mに結合するYの数を表し、0~2の整数である。
また、第二群に属するハロゲン化金属フタロシアニン顔料は、前記一般式(PIG-1)において次の通りである。
即ち、第二群に属するハロゲン化金属フタロシアニン顔料は、ハロゲン化金属フタロシアニンの2分子を構成単位とし、これらが前記二価原子団を介して結合したハロゲン化金属フタロシアニン二量体である。
(1) ハロゲン化銅フタロシアニン顔料、ハロゲン化錫フタロシアニン顔料、ハロゲン化ニッケルフタロシアニン顔料、ハロゲン化亜鉛フタロシアニン顔料の様な、Mg、Fe、Co、Ni、Zn、Cu、Zr、Sn及びPbからなる群から選ばれる二価金属を中心金属として有し、かつフタロシアニン分子1個当たり4個のベンゼン環に8~16個のハロゲン原子が結合したハロゲン化金属フタロシアニン顔料。なお、この中で、塩素化臭素化亜鉛フタロシアニン顔料は、C.I.Pigment Green 58であり、特に好ましい。
(2) ハロゲン化クロロアルミニウムフタロシアニンの様な、Al、Sc、Ga、Y及びInからなる群から選ばれる三価金属を中心金属として有し、中心金属には1つのハロゲン原子、水酸基又はスルホン酸基のいずれかを有し、かつフタロシアニン分子1個当たり4個のベンゼン環に8~16個のハロゲン原子が結合したハロゲン化金属フタロシアニン顔料。
(3) ハロゲン化オキシチタニウムフタロシアニン、ハロゲン化オキシバナジウムフタロシアニンの様な、Si、Ti、V、Ge、Zr及びSnからなる群から選ばれる四価金属を中心金属として有し、中心金属には1つの酸素原子又は同一でも異なっていても良い2つのハロゲン原子、水酸基又はスルホン酸基のいずれかを有し、かつフタロシアニン分子1個当たり4個のベンゼン環に8~16個のハロゲン原子が結合したハロゲン化金属フタロシアニン顔料。
(4) ハロゲン化されたμ-オキソ-アルミニウムフタロシアニン二量体、ハロゲン化されたμ-チオ-アルミニウムフタロシアニン二量体の様な、Al、Sc、Ga、Y及びInからなる群から選ばれる三価金属を中心金属とし、フタロシアニン分子1個当たり4個のベンゼン環に8~16個のハロゲン原子が結合したハロゲン化金属フタロシアニンの2分子を構成単位とし、これら構成単位の各中心金属が酸素原子、硫黄原子、スルフィニル及びスルホニルからなる群から選ばれる二価原子団を介して結合したハロゲン化金属フタロシアニン二量体からなる顔料。
前記B画素部中に含有するε型フタロシニアン顔料としては、C.I.Pigment Blue 15:6、トリアリールメタン顔料としては、C.I.Pigment Blue 1及び/又は下記一般式(1)
隣接するR(RはR11j~R16jのいずれかを表す。)が結合して環を形成する場合、これらはヘテロ原子で架橋された環であってもよい。この環の具体例として、例えば以下のものが挙げられる。これらの環は置換基を有していてもよい。
中でも、R11j~R16jは、各々独立して水素原子;メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基等のアルキル基;フェニル基、ナフチル基等のアリール基のいずれかであることがより好ましい。
[置換基群Y]
メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基等のアルキル基;フェニル基、ナフチル基等のアリール基;フッ素原子、塩素原子等のハロゲン原子;シアノ基;水酸基;メトキシ基、エトキシ基、プロポキシ基、ブトキシ基など炭素原子数1~8のアルコキシ基;アミノ基、ジエチルアミノ基、ジブチルアミノ基、アセチルアミノ基など置換基を有していてもよいアミノ基;アセチル基、ベンゾイル基等のアシル基;アセチルオキシ基、ベンゾイルオキシ基等のアシルオキシ基;等が挙げられる。
R11j~R16jとしては、置換基を有していてもよい炭素原子数1~8のアルキル基が更に好ましく、より具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、ペンチル基、ヘキシル基、2‐エチルヘキシル基など無置換のアルキル基;2‐メトキシエチル基、2‐エトキシエチル基等のアルコキシアルキル基;2‐アセチルオキシエチル基等のアシルオキシ基;2‐シアノエチル基等のシアノアルキル基;2,2,2‐トリフルオロエチル基、4,4,4‐トリフルオロブチル基等のフルオロアルキル基、などが挙げられる。
X11j及びX12jとしては、水素原子、メチル基、塩素原子又はトリフルオロメチル基などねじれに影響を与えない程度の適度な立体障害を有する置換基であることが好ましい。X11j及びX12jは、色調および耐熱性の点から水素原子、メチル基又は塩素原子であることが最も好ましい。
前記一般式(1)で表されるトリアリールメタン顔料の具体例としては、例えば、以下の表1~7に記載した化合物があげられるが、本発明はその主旨を超えない限り、これらに限定されるものではない。
また、前記RGB三色画素部は、色材として、R画素部中にC.I.Pigment Red 254を、G画素部中にC.I.Pigment Green 7、36及び/又は同58を、B画素部中にC.I.Pigment Blue 15:6及び/又はトリアリールメタン顔料を含有するのも好ましい。
前記RGB三色画素部は、色材として、G画素部中に更に、C.I.Pigment Yellow 150、同215、同185、同138、C.I.Solvent Yellow 21、同82、同83:1、同33からなる群から選ばれる少なくとも1種の有機染顔料を含有するのが好ましい。
前記RGB三色画素部は、色材として、B画素部中に更に、C.I.Pigment Blue 1、C.I.Pigment Violet 23、C.I.Basic Blue 7、C.I.Basic Violet 10、C.I.Acid Blue 1、同90、同83、C.I.Direct Blue 86からなる群から選ばれる少なくとも1種の有機染顔料を含有するのが好ましい。
また、カラーフィルタが、ブラックマトリックスとRGB三色画素部とY画素部とから構成され、色材として、Y画素部に、C.I.Pigment Yellow 150、同215、同185、同138、同139、C.I.Solvent Yellow 21、82、同83:1、同33、同162からなる群から選ばれる少なくとも1種の黄色有機染顔料を含有するのも好ましい。
後記する光硬化性組成物をガラス等の透明基板上に塗布する方法としては、例えば、スピンコート法、ロールコート法、インクジェット法等が挙げられる。
透明基板に塗布した光硬化性組成物の塗膜の乾燥条件は、各成分の種類、配合割合等によっても異なるが、通常、50~150℃で、1~15分間程度である。また、光硬化性組成物の光硬化に用いる光としては、200~500nmの波長範囲の紫外線、あるいは可視光を使用するのが好ましい。この波長範囲の光を発する各種光源が使用できる。
現像方法としては、例えば、液盛り法、ディッピング法、スプレー法等が挙げられる。光硬化性組成物の露光、現像の後に、必要な色の画素部が形成された透明基板は水洗いし乾燥させる。こうして得られたカラーフィルタは、ホットプレート、オーブン等の加熱装置により、90~280℃で、所定時間加熱処理(ポストベーク)することによって、着色塗膜中の揮発性成分を除去すると同時に、光硬化性組成物の硬化着色皮膜中に残存する未反応の光硬化性化合物が熱硬化し、カラーフィルタが完成する。
前記ブラックマトリックス及びR画素、G画素、B画素、Y画素の光硬化性組成物の製造方法としては、本発明のブラックマトリックス用顔料、カラーフィルタ画素部用染料及び/又は顔料組成物と、有機溶剤と分散剤とを必須成分として使用し、これらを混合し均一となる様に攪拌分散を行って、まずブラックマトリックス、カラーフィルタの画素部を形成するための顔料分散液を調製してから、そこに、光硬化性化合物と、必要に応じて熱可塑性樹脂や光重合開始剤等を加えて前記光硬化性組成物とする方法が一般的である。
また、分散助剤として、有機顔料誘導体の、例えば、フタルイミドメチル誘導体、同スルホン酸誘導体、同N-(ジアルキルアミノ)メチル誘導体、同N-(ジアルキルアミノアルキル)スルホン酸アミド誘導体等も含有することも出来る。もちろん、これら誘導体は、異なる種類のものを二種以上併用することも出来る。
光硬化性化合物としては、例えば、1,6-ヘキサンジオールジアクリレート、エチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリエチレングリコールジアクリレート、ビス(アクリロキシエトキシ)ビスフェノールA、3-メチルペンタンジオールジアクリレート等のような2官能モノマー、トリメチルロールプロパトントリアクリレート、ペンタエリスリトールトリアクリレート、トリス〔2-(メタ)アクリロイルオキシエチル)イソシアヌレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等の比較的分子量の小さな多官能モノマー、ポリエステルアクリレート、ポリウレタンアクリレート、ポリエーテルアクリレート等の様な比較的分子量の大きな多官能モノマーが挙げられる。
光重合開始剤としては、例えばアセトフェノン、ベンゾフェノン、ベンジルジメチルケタノール、ベンゾイルパーオキサイド、2-クロロチオキサントン、1,3-ビス(4’-アジドベンザル)-2-プロパン、1,3-ビス(4’-アジドベンザル)-2-プロパン-2’-スルホン酸、4,4’-ジアジドスチルベン-2,2’-ジスルホン酸等が挙げられる。市販の光重合開始剤としては、たとえば、BASF社製「イルガキュア(商標名)-184」、「イルガキュア(商標名)-369」、「ダロキュア(商標名)-1173」、BASF社製「ルシリン-TPO」、日本化薬社製「カヤキュアー(商標名)DETX」、「カヤキュアー(商標名)OA」、ストーファー社製「バイキュアー10」、「バイキュアー55」、アクゾー社製「トリゴナールPI」、サンド社製「サンドレー1000」、アップジョン社製「デープ」、黒金化成社製「ビイミダゾール」などがある。
また上記光重合開始剤に公知慣用の光増感剤を併用することもできる。光増感剤としては、たとえば、アミン類、尿素類、硫黄原子を有する化合物、燐原子を有する化合物、塩素原子を有する化合物またはニトリル類もしくはその他の窒素原子を有する化合物等が挙げられる。これらは、単独で用いることも、2種以上を組み合わせて用いることもできる。
前記した様な各材料を使用して、質量基準で、本発明のブラックマトリックス用顔料、カラーフィルタ画素部用染料及び/又は顔料組成物100部当たり、20~1000部の有機溶剤と、1~100部の分散剤とを、均一となる様に攪拌分散して前記染顔料分散液を得ることができる。次いでこの顔料分散液に、本発明のブラックマトリックス用顔料、カラーフィルタ用染料及び/又は顔料組成物1部当たり、熱可塑性樹脂と光硬化性化合物の合計が3~20部、光硬化性化合物1部当たり0.05~3部の光重合開始剤と、必要に応じてさらに有機溶剤を添加し、均一となる様に攪拌分散してブラックマトリックス及びカラーフィルタ画素部を形成するための光硬化性組成物を得ることができる。
現像液としては、公知慣用の有機溶剤やアルカリ水溶液を使用することができる。特に前記光硬化性組成物に、熱可塑性樹脂または光硬化性化合物が含まれており、これらの少なくとも一方が酸価を有し、アルカリ可溶性を呈する場合には、アルカリ水溶液での洗浄がブラックマトリックス及びカラーフィルタ画素部の形成に効果的である。
ブラックマトリックスについても、フォトリソグラフィー法による製造方法について詳記したが、本発明のブラックマトリックス用色材を使用して調製されたブラックマトリックスは、転写法、インクジェット法、反転印刷法、熱硬化法等の方法でブラックマトリックスを製造しても良い。
本発明の液晶表示装置において、第一の基板と、第二の基板上の液晶組成物と接する面には液晶組成物を配向させるため、配向膜を必要とする液晶表示装置においてはカラーフィルタと液晶層間に配置するものであるが、配向膜の膜厚が厚いものでも100nm以下と薄く、カラーフィルタを構成する顔料等の色素と液晶層を構成する液晶化合物との相互作用を完全に遮断するものでは無い。
又、配向膜を用いない液晶表示装置においては、カラーフィルタを構成する顔料等の色素と液晶層を構成する液晶化合物との相互作用はより大きくなる。
配向膜材料としては、カルコン、シンナメート、シンナモイル又はアゾ基等を化合物中に含む、材料を使用することができ、ポリイミド、ポリアミド等の材料と組み合わせて使用してもよく、この場合配向膜はラビングを用いてもよく光配向技術を用いてもよい。
配向膜は、基板上に前記配向膜材料をスピンコート法などの方法により塗布して樹脂膜を形成することが一般的であるが、一軸延伸法、ラングミュア・ブロジェット法等を用いることもできる。
本発明の液晶表示装置において、透明電極の材料としては、導電性の金属酸化物を用いることができ、金属酸化物としては酸化インジウム(In2O3)、酸化スズ(SnO2)、酸化亜鉛(ZnO)、酸化インジウムスズ(In2O3―SnO2)、酸化インジウム亜鉛(In2O3―ZnO)、ニオブ添加二酸化チタン(Ti1-xNbxO2)、フッ素ドープ酸化スズ、グラフェンナノリボン又は金属ナノワイヤー等が使用できるが、酸化亜鉛(ZnO)、酸化インジウムスズ(In2O3―SnO2)又は酸化インジウム亜鉛(In2O3―ZnO)が好ましい。これらの透明導電膜のパターニングには、フォト・エッチング法やマスクを用いる方法などを使用することができる。
本液晶表示装置と、バックライトを組み合わせて、液晶テレビ、パソコンのモニター、携帯電話、スマートフォンのディスプレイや、ノート型パーソナルコンピューター、携帯情報端末、デジタルサイネージ等の様々な用途で使用される。バックライトとしては、冷陰極管タイプバックライト、無機材料を用いた発光ダイオードや有機EL素子を用いた、2波長ピークの擬似白色バックライトと3波長ピークのバックライト等がある。
実施例中、測定した特性は以下の通りである。
Tni :ネマチック相-等方性液体相転移温度(℃)
Δn :25℃における屈折率異方性
Δε :25℃における誘電率異方性
η :20℃における粘度(mPa・s)
γ1 :25℃における回転粘性(mPa・s)
VHR:70℃における電圧保持率(%)
(セル厚3.5μmのセルに液晶組成物を注入し、5V印加、フレームタイム200ms、パルス幅64μsの条件で測定した時の測定電圧と初期印加電圧との比を%で表した値)
ID :70℃におけるイオン密度(pC/cm2)
(セル厚3.5μmのセルに液晶組成物を注入し、MTR-1(株式会社東陽テクニカ製)で20V印加、周波数0.05Hzの条件で測定した時のイオン密度値)
焼き付き:
液晶表示素子の焼き付き評価は、表示エリア内に所定の固定パターンを1000時間表示させた後に、全画面均一な表示を行ったときの固定パターンの残像のレベルを目視にて以下の4段階評価で行った。
◎残像無し
○残像ごく僅かに有るも許容できるレベル
△残像有り許容できないレベル
×残像有りかなり劣悪
尚、実施例において化合物の記載について以下の略号を用いる。
(環構造)
[ブラックマトリックスの作成]
[ブラックマトリックス1]
体積固有抵抗107Ω・cmのカーボンブラック(C.I.Pigment Black 7)55部、分散剤溶液45部を、ペイントコンディショナーで分散して、カーボンブラックの分散液を得た。この分散液67部を、紫外線硬化用の光重合性モノマー2部、アルカリ可溶性樹脂7部、光開始剤1部、溶剤23部を混合し、ブラックマトリックス用の感光性組成物1を調整した。
前記感光組成物1をスピンコーターを用いてガラス基板に塗布した。1分間真空乾燥後、ホットプレート上で90℃にて90秒間加熱乾燥し、乾燥膜厚約3μmの塗布膜を得た。その後、塗布膜側から、パターンマスクを介して画像露光した後、現像を行い、ブラックマトリックス1を作成した。
体積固有抵抗106Ω・cmのチタンブラック(C.I.Pigment Black 35)70部、分散剤養鶏30部を、ペイントコンディショナーで分散して、チタンブラックの分散液を得た。この分散液16部を、紫外線硬化用の光重合性モノマー66部、アルカリ可溶性樹脂16部、光開始剤2部、溶剤16部を混合し、ブラックマトリックス用の感光性組成物2を調整した。
前記感光組成物2をスピンコーターを用いてガラス基板に塗布した。1分間真空乾燥後、ホットプレート上で90℃にて90秒間加熱乾燥し、乾燥膜厚約3μmの塗布膜を得た。その後、塗布膜側から、パターンマスクを介して画像露光した後、現像を行い、ブラックマトリックス2を作成した。
体積固有抵抗1010Ω・cmの青色有機顔料(C.I.Pigment Blue 60)5部、体積固有抵抗109Ω・cmの紫色有機顔料(C.I.Pigment Violet 23)2部、体積固有抵抗1013Ω・cmの緑色有機顔料(C.I.Pigment Green 7)4部、体積固有抵抗109Ω・cmの赤色有機顔料(C.I.Pigment Red 179)4部、分散剤溶液85部を、ペイントコンディショナーで分散して、有機顔料の黒色分散液を得た。この分散液40部を、紫外線硬化用の光重合性モノマー4部、アルカリ可溶性樹脂2部、光開始剤1部、溶剤53部を混合し、ブラックマトリックス用の感光性組成物3を調整した。
前記感光組成物3をスピンコーターを用いてガラス基板に塗布した。1分間真空乾燥後、ホットプレート上で90℃にて90秒間加熱乾燥し、乾燥膜厚約3μmの塗布膜を得た。その後、塗布膜側から、パターンマスクを介して画像露光した後、現像を行い、ブラックマトリックス3を作成した。
体積固有抵抗109Ω・cmの青色有機顔料(C.I.Pigment Blue 15:6)6部、体積固有抵抗1010Ω・cmの赤色有機顔料(C.I.Pigment Red 254)4部、体積固有抵抗109Ω・cmの黄色有機顔料(C.I.Pigment Yellow 150)5部、分散剤溶液85部を、ペイントコンディショナーで分散して、有機顔料の黒色分散液を得た。この分散液40部を、紫外線硬化用の光重合性モノマー4部、アルカリ可溶性樹脂2部、光開始剤1部、溶剤53部を混合し、ブラックマトリックス用の感光性組成物4を調整した。
前記感光組成物4をスピンコーターを用いてガラス基板に塗布した。1分間真空乾燥後、ホットプレート上で90℃にて90秒間加熱乾燥し、乾燥膜厚約3μmの塗布膜を得た。その後、塗布膜側から、パターンマスクを介して画像露光した後、現像を行い、ブラックマトリックス4を作成した。
ガラス基板上にスパッタリング法で酸化クロム膜を設けフォトリソグラフィー法により開口部を形成するためのフォトレジストパターンを形成し、このフォトレジストパターンに基づいて露出した酸化クロム膜をエッチング除去し、次にフォトレジストパターンを剥離して、ブラックマトリックス5を作成した。
[赤色染料着色組成物1]
赤色顔料1(C.I.Pigment Red 254、BASF社製「IRGAPHOR RED BT-CF」)10部をポリビンに入れ、プロピレングリコールモノメチルエーテルアセテート55部、ディスパービックLPN21116(ビックケミー株式会社製)7.0部、0.3-0.4mmφセプルビーズを加え、ペイントコンディショナー(東洋精機株式会社製)で4時間分散した後、5μmのフィルタで濾過し顔料分散液を得た。この顔料分散液75.00部とポリエステルアクリレート樹脂(アロニックス(商標名)M7100、東亜合成化学工業株式会社製)5.50部、ジぺンタエリストールヘキサアクリレート(KAYARAD(商標名)DPHA、日本化薬株式会社製)5.00部、ベンゾフェノン(KAYACURE(商標名)BP-100、日本化薬株式会社製)1.00部、ユーカーエステルEEP13.5部を分散撹拌機で撹拌し、孔径1.0μmのフィルタで濾過し、赤色顔料着色組成物1を得た。
上記赤色顔料着色組成物1の赤色顔料1 10部に代え、緑色顔料1(C.I.Pigment Green 58 DIC株式会社製FASTOGEN GREEN A110)6部と黄色顔料1(C.I.Pigment Yellow 150、LANXESS社製FANCHON FAST YELLOW E4GN)4部を用いて、上記と同様にして、緑色顔料着色組成物1を得た。
上記赤色顔料着色組成物1の赤色顔料1 10部に代え、青色顔料1(C.I.Pigment Blue 15:6、DIC株式会社製「FASTOGEN BLUE EP-210」)9部と紫色顔料1(C.I.Pigment VIOLET 23)1部を用いて、上記と同様にして、青色顔料着色組成物1を得た。
予めブラックマトリックスが形成されてあるガラス基板に、赤色着色組成物1をスピンコートにより膜厚2μmとなるように塗布した。70℃で20分間乾燥の後、超高圧水銀ランプを備えた露光機にて紫外線をフォトマスクを介してストライプ状のパターン露光をした。アルカリ現像液にて90秒間スプレー現像、イオン交換水で洗浄し、風乾した。さらに、クリーンオーブン中で、230℃で30分間ポストベークを行い、ストライプ状の着色層である赤色画素を透明基板上に形成した。
次に、緑色着色組成物1も同様にスピンコートにて膜厚が2μmとなるように塗布。乾燥後、露光機にてストライプ状の着色層を前述の赤色画素とはずらした場所に露光し現像することで、前述赤色画素と隣接した緑色画素を形成した。
次に、青色着色組成物1についても同様にスピンコートにて膜厚2μmで赤色画素、緑色画素と隣接した青色画素を形成した。これで、透明基板上に赤、緑、青の3色のストライプ状の画素を持つカラーフィルタが得られた。
表9に示すブラックマトリックスを用い、カラーフィルタ1~4及び比較カラーフィルタ1を作成した。
電極構造を第一及び第二の基板の少なくとも一方に作成し、各々の対向側に水平配向性の配向膜を形成したのち弱ラビング処理を行い、IPSセルを作成し、第一の基板と第二の基板の間に以下に示す液晶組成物1を挟持した。液晶組成物1の物性値を表10に示す。次に、表9に示すカラーフィルタ1~4を用いて実施例1~4の液晶表示装置を作成した(dgap=4.0μm、配向膜AL-1051)。得られた液晶表示装置のVHR及びIDを測定した。また、得られた液晶表示装置の焼き付き評価を行った。その結果を表11に示す。
実施例1~4の液晶表示装置は、高いVHR及び小さいIDを実現できた。また、焼き付き評価においても残像がないか、又はあってもごく僅かであり許容できるレベルであった。
実施例1と同様に表12に示す液晶組成物2~3を狭持し、表9に示すカラーフィルタを用いて実施例5~12の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表13~14に示す。
実施例1と同様に表15に示す液晶組成物4~6を狭持し、表9に示すカラーフィルタを用いて実施例13~24の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表16~18に示す。
電極構造を第一及び第二の基板に作成し、各々の対向側に水平配向性の配向膜を形成したのち弱ラビング処理を行い、TNセルを作成し、第一の基板と第二の基板の間に表19に示す液晶組成物7~9を挟持した。次に、表9に示すカラーフィルタ1~4を用いて実施例25~36の液晶表示装置を作成した(dgap=3.5μm、配向膜SE-7492)。得られた液晶表示装置のVHR及びIDを測定した。また、得られた液晶表示装置の焼き付き評価を行った。その結果を表20~22に示す。
電極構造を第一及び第二の基板の少なくとも一方に作成し、各々の対向側に水平配向性の配向膜を形成したのち弱ラビング処理を行い、FFSセルを作成し、第一の基板と第二の基板の間に表23に示す液晶組成物10~11を挟持した。次に、表9に示すカラーフィルタ1~4を用いて実施例37~44の液晶表示装置を作成した(dgap=4.0μm、配向膜AL-1051)。得られた液晶表示装置のVHR及びIDを測定した。また、得られた液晶表示装置の焼き付き評価を行った。その結果を表24~25に示す。
実施例37と同様に表26に示す液晶組成物12~14を狭持し、表9に示すカラーフィルタを用いて実施例45~56の液晶表示装置作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表27~29に示す。
実施例37で用いた液晶組成物10にビスメタクリル酸ビフェニル‐4,4’‐ジイルを0.3質量%混合し液晶組成物15とした。TNセルにこの液晶組成物15を挟持し、電極間に駆動電圧を印加したまま、紫外線を600秒間照射(3.0J/cm2)し、重合処理を行い、次に、表9に示すカラーフィルタ1~4を用いて実施例57~60の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表30に示す。
実施例29で用いた液晶組成物8にビスメタクリル酸ビフェニル‐4,4’‐ジイルを0.3質量%混合し液晶組成物16とした。IPSセルにこの液晶組成物16を挟持し、電極間に駆動電圧を印加したまま、紫外線を600秒間照射(3.0J/cm2)し、重合処理を行い、次に、表9に示すカラーフィルタ1~4を用いて実施例61~64の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表31に示す。
実施例21で用いた液晶組成物6にビスメタクリル酸 3‐フルオロビフェニル‐4,4’‐ジイルを0.3質量%混合し液晶組成物17とした。FFSセルにこの液晶組成物17を挟持し、電極間に駆動電圧を印加したまま、紫外線を600秒間照射(3.0J/cm2)し、重合処理を行い、次に、表9に示すカラーフィルタ1~4を用いて実施例65~68の液晶表示装置を作成し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表32に示す。
実施例1で用いたIPSセルに以下に示す比較液晶組成物1を挟持した。比較液晶組成物の物性値を表33に示す。表9に示すカラーフィルタ1~4を用いて比較例1~4の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表34に示す。
実施例1と同様に表35に示す比較液晶組成物2及び3を狭持し、表9に示すカラーフィルタ1~4を用いて比較例5~12の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表36~37に示す。
実施例1と同様に表38に示す比較液晶組成物4~5を狭持し、表9に示すカラーフィルタ1~4を用いて比較例13~24の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表39~40に示す。
実施例1と同様に表41に示す比較液晶組成物6~8を狭持し、表9に示すカラーフィルタ1~4を用いて比較例21~32の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表42~44に示す。
実施例1と同様に表45に示す比較液晶組成物9~11を狭持し、表9に示すカラーフィルタ1~4を用いて比較例33~44の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表46~48に示す。
実施例5、13、17、25、37、45、61及び65において、カラーフィルタ1に代えて表9に示す比較カラーフィルタ1を用いた以外は同様にして比較例45~52の液晶表示装置を作製し、そのVHR及びIDを測定した。また、その液晶表示装置の焼き付き評価を行った。その結果を表49及び50に示す。
Claims (12)
- 第一の基板と、第二の基板と、前記第一の基板と第二の基板間に挟持された液晶組成物層と、ブラックマトリックス及び少なくともRGB三色画素部から構成されるカラーフィルタと、画素電極と共通電極とを備え、
前記液晶組成物層が一般式(I)
前記ブラックマトリックスが、色材として、カーボンブラック、チタンブラック及び有機顔料より選ばれる1種又は2種以上の顔料を含有することを特徴とする液晶表示装置。 - 体積固有抵抗が、106Ω・cm以上の、カーボンブラック、チタンブラック及び有機顔料より選ばれる1種又は2種以上の顔料を含有することを特徴とする請求項1記載の液晶表示装置。
- 前記RGB三色画素部が、色材として、R画素部中にC.I.Solvent Red 124を、G画素部中にC.I.Solvent Blue 67とC.I.Solvent Yellow 162との混合物を、B画素部中にC.I.Solvent Blue 7を含有することを特徴とする請求項1又は2記載の液晶表示装置。
- 前記RGB三色画素部が、色材として、R画素部中にC.I.Pigment Red 254を、G画素部中にC.I.Pigment Green 7及び/又は同36を、B画素部中にC.I.Pigment Blue 15:6を含有することを特徴とする請求項1~3のいずれか一項に記載の液晶表示装置。
- R画素部中に更に、C.I.Pigment Red 177、同242、同166、同167、同179、C.I.Pigment Orange 38、同71、C.I.Pigment Yellow 150、同215、同185、同138、同139、C.I.Solvent Red 89、C.I.Solvent Orange 56、C.I.Solvent Yellow 21、同82、同83:1、同33、同162からなる群から選ばれる少なくとも1種の有機染顔料を含有する請求項1~4のいずれか一項に記載の液晶表示装置。
- G画素部中に更に、C.I.Pigment Yellow 150、同215、同185、同138、C.I.Solvent Yellow 21、同82、同83:1、同33からなる群から選ばれる少なくとも1種の有機染顔料を含有する請求項1~5のいずれか一項に記載の液晶表示装置。
- B画素部中に更に、C.I.Pigment Blue 1、C.I.Pigment Violet 23、C.I.Basic Blue 7、C.I.Basic Violet 10、C.I.Acid Blue 1、同90、同83、C.I.Direct Blue 86からなる群から選ばれる少なくとも1種の有機染顔料を含有する請求項1~6のいずれか一項に記載の液晶表示装置。
- カラーフィルタが、ブラックマトリックスとRGB三色画素部とY画素部とから構成され、色材として、Y画素部に、C.I.Pigment Yellow 150、同215、同185、同138、同139、C.I.Solvent Yellow 21、82、同83:1、同33、同162からなる群から選ばれる少なくとも1種の黄色有機染顔料を含有する請求項1~7のいずれか一項に記載の液晶表示装置。
- 前記液晶組成物層に、重合性化合物を一種又は二種以上含有する液晶組成物を重合してなる重合体により構成される請求項1~10の何れか一項に記載の液晶表示装置。
- 前記液晶組成物層に、一般式(V)
Sp1及びSp2はそれぞれ独立して、単結合、炭素原子数1~8のアルキレン基又は-O-(CH2)s-(式中、sは2から7の整数を表し、酸素原子は芳香環に結合するものとする。)を表し、Z1は-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-(式中、Y1及びY2はそれぞれ独立して、フッ素原子又は水素原子を表す。)、-C≡C-又は単結合を表し、Cは1,4-フェニレン基、トランス-1,4-シクロヘキシレン基又は単結合を表し、式中の全ての1,4-フェニレン基は、任意の水素原子がフッ素原子により置換されていても良い。)で表されるニ官能モノマーを含有する請求項1~11の何れか一項に記載の液晶表示装置。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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KR1020157015013A KR101616775B1 (ko) | 2013-06-18 | 2013-06-18 | 액정 표시 장치 |
US14/654,308 US9593280B2 (en) | 2013-06-18 | 2013-06-18 | Liquid crystal display device |
CN201380060636.9A CN104797974B (zh) | 2013-06-18 | 2013-06-18 | 液晶显示装置 |
PCT/JP2013/066686 WO2014203325A1 (ja) | 2013-06-18 | 2013-06-18 | 液晶表示装置 |
EP13887506.7A EP2957949B1 (en) | 2013-06-18 | 2013-06-18 | Liquid crystal display device |
JP2014528769A JP5652576B1 (ja) | 2013-06-18 | 2013-06-18 | 液晶表示装置 |
TW102124465A TWI495712B (zh) | 2013-06-18 | 2013-07-09 | The liquid crystal display device |
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PCT/JP2013/066686 WO2014203325A1 (ja) | 2013-06-18 | 2013-06-18 | 液晶表示装置 |
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US (1) | US9593280B2 (ja) |
EP (1) | EP2957949B1 (ja) |
JP (1) | JP5652576B1 (ja) |
KR (1) | KR101616775B1 (ja) |
CN (1) | CN104797974B (ja) |
TW (1) | TWI495712B (ja) |
WO (1) | WO2014203325A1 (ja) |
Cited By (1)
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JP2016044311A (ja) * | 2014-08-25 | 2016-04-04 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 液晶媒体 |
Families Citing this family (3)
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EP3054343B1 (en) * | 2013-11-29 | 2018-05-30 | DIC Corporation | Lcd device |
CN104749816B (zh) * | 2015-04-14 | 2017-11-10 | 京东方科技集团股份有限公司 | 一种显示基板的制作方法、显示基板和显示装置 |
KR102633265B1 (ko) * | 2016-06-30 | 2024-02-05 | 티씨엘 차이나 스타 옵토일렉트로닉스 테크놀로지 컴퍼니 리미티드 | 표시 장치 |
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- 2013-06-18 WO PCT/JP2013/066686 patent/WO2014203325A1/ja active Application Filing
- 2013-06-18 CN CN201380060636.9A patent/CN104797974B/zh active Active
- 2013-06-18 US US14/654,308 patent/US9593280B2/en active Active
- 2013-06-18 EP EP13887506.7A patent/EP2957949B1/en not_active Not-in-force
- 2013-06-18 JP JP2014528769A patent/JP5652576B1/ja active Active
- 2013-07-09 TW TW102124465A patent/TWI495712B/zh not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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CN104797974A (zh) | 2015-07-22 |
TW201500525A (zh) | 2015-01-01 |
JPWO2014203325A1 (ja) | 2017-02-23 |
TWI495712B (zh) | 2015-08-11 |
KR101616775B1 (ko) | 2016-04-29 |
EP2957949A4 (en) | 2016-11-23 |
EP2957949B1 (en) | 2018-07-18 |
CN104797974B (zh) | 2016-08-24 |
US9593280B2 (en) | 2017-03-14 |
KR20150074198A (ko) | 2015-07-01 |
US20150344778A1 (en) | 2015-12-03 |
EP2957949A1 (en) | 2015-12-23 |
JP5652576B1 (ja) | 2015-01-14 |
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