WO2014054181A1 - 液晶組成物及びそれを用いた液晶表示素子 - Google Patents
液晶組成物及びそれを用いた液晶表示素子 Download PDFInfo
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- WO2014054181A1 WO2014054181A1 PCT/JP2012/076027 JP2012076027W WO2014054181A1 WO 2014054181 A1 WO2014054181 A1 WO 2014054181A1 JP 2012076027 W JP2012076027 W JP 2012076027W WO 2014054181 A1 WO2014054181 A1 WO 2014054181A1
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- TXHFUCYJBLLNIG-UHFFFAOYSA-N CCCCCC(CC1)CCC1C(CC1)CCC1c(cc1F)cc(F)c1F Chemical compound CCCCCC(CC1)CCC1C(CC1)CCC1c(cc1F)cc(F)c1F TXHFUCYJBLLNIG-UHFFFAOYSA-N 0.000 description 1
- 0 CCc1c(*C)cc(C)cc1*(C)C Chemical compound CCc1c(*C)cc(C)cc1*(C)C 0.000 description 1
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- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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- C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
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- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
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- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
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- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
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- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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- C09K2019/3078—Cy-Cy-COO-Ph-Cy
Definitions
- the present invention relates to a nematic liquid crystal composition having a positive dielectric anisotropy ( ⁇ ) useful as a liquid crystal display material, and a liquid crystal display device using the same.
- Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators.
- Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type.
- the liquid crystal composition used in these liquid crystal display elements is stable against external stimuli such as moisture, air, heat, light, etc., and exhibits a liquid crystal phase in the widest possible temperature range centering on room temperature. And a low driving voltage is required.
- the liquid crystal composition is composed of several to several tens of kinds of compounds in order to optimize the dielectric anisotropy ( ⁇ ) or the refractive index anisotropy ( ⁇ n) for each display element. .
- a liquid crystal composition having a negative ⁇ is used, and in a horizontal alignment type display such as a TN type, STN type, or IPS (in-plane switching) type, a liquid crystal composition having a positive ⁇ . Is used.
- a driving method has been reported in which a liquid crystal composition having a positive ⁇ is vertically aligned when no voltage is applied and a lateral electric field is applied to display the liquid crystal composition. Yes.
- low voltage driving, high-speed response, and a wide operating temperature range are required in all driving systems.
- ⁇ is positive, the absolute value is large, the viscosity ( ⁇ ) is small, and a high nematic phase-isotropic liquid phase transition temperature (Tni) is required.
- Tni nematic phase-isotropic liquid phase transition temperature
- Examples of the structure of the liquid crystal composition aimed at high-speed response include, for example, a compound represented by the formula (A-1) or (A-2) in which ⁇ is a positive liquid crystal compound, and a liquid crystal compound in which ⁇ is neutral.
- a liquid crystal composition using a combination of (B) is disclosed.
- the characteristics of these liquid crystal compositions are widely known in the field of liquid crystal compositions that a liquid crystal compound having a positive ⁇ has a —CF 2 O— structure and that a liquid crystal compound having a negative ⁇ has an alkenyl group. It has been. (Patent Documents 1 to 4)
- liquid crystal display elements using a liquid crystal composition are widely used, such as VA type and IPS type, and super large size display elements having a size of 50 type or more are practically used. Became.
- the injection method of liquid crystal composition into the substrate became the main method of injection from the conventional vacuum injection method (ODF: One Drop Fill), but the liquid crystal composition was applied to the substrate. The problem that the drop marks when dropped causes the display quality to deteriorate is brought to the surface.
- the problem to be solved by the present invention is a liquid crystal composition having a positive ⁇ , a liquid crystal phase in a wide temperature range, low viscosity, good solubility at low temperature, specific resistance and voltage holding ratio.
- IPS type and TN type liquid crystal displays that provide high liquid crystal composition that is stable against heat and light, and that are superior in display quality and are less susceptible to display defects such as image sticking and dripping marks.
- the object is to provide elements with high yield.
- liquid crystal composition having positive dielectric anisotropy which has the formula (1)
- a component (A) which is a dielectrically positive component containing a compound represented by formula (40)
- the liquid crystal composition having positive dielectric anisotropy of the present invention can obtain a significantly low viscosity, has good solubility at low temperatures, and changes in specific resistance and voltage holding ratio due to heat and light. Since it is extremely small, the practicality of the product is high, and an IPS type or FFS type liquid crystal display element using the product can achieve a high-speed response. In addition, since the performance can be stably exhibited in the liquid crystal display element manufacturing process, display defects due to the process can be suppressed and manufacturing can be performed with a high yield, which is very useful.
- a board having 100 to 105 is called a “back plane”, and a board having 200 to 205 is called a “front plane”. It is a figure of the exposure process using the pattern for columnar spacer formation formed on a black matrix as a photomask pattern.
- the liquid crystal composition having positive dielectric anisotropy of the present invention contains a component (A) which is a dielectrically positive component.
- Component (A) is composed of a compound having a dielectric anisotropy of 2 or more.
- the dielectric anisotropy of the compound is a value extrapolated from the measured value of the dielectric anisotropy of a composition prepared by adding to a liquid crystal composition having a dielectric anisotropy of about 0 at 25 ° C. is there.
- the component (A) of the liquid crystal composition of the present invention has formula (1)
- the content of the compound represented by the formula (1) constituting the component (A) is preferably 2% by mass or more based on the total amount of the liquid crystal composition of the present invention. 4 mass% or more is more preferable, 6 mass% or more is more preferable, 8 mass% or more is more preferable, 10 mass% or more is more preferable, 12 mass% or more is further preferable, 16 mass% or more is further preferable, 21 mass% % Or more is particularly preferable.
- the maximum ratio is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. 25 mass% or less is particularly preferable.
- the liquid crystal composition of the present invention has a general formula (2) in the dielectrically positive component (A).
- R 2 represents an alkyl group having 2 to 5 carbon atoms
- a 2 represents a 1,4-phenylene group or a 1,4-cyclohexylene group
- X 21 to X 24 are each independently hydrogen.
- Y 2 represents a fluorine atom or —OCF 3
- U 2 represents a single bond or —CF 2 O—).
- the compound that can be combined with the compound represented by the general formula (2) but 1 to 3 in consideration of solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. It is preferable to combine types, and it is more preferable to combine one to four or more types.
- the compound represented by the general formula (2) is preferably a compound represented by the formula (2.1) to the formula (2.5).
- the content of the compound represented by the formula (2.1) constituting the component (A) includes solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. In consideration, it is preferably 2% by mass or more, preferably 4% by mass or more, more preferably 6% by mass, and further preferably 8% by mass or more. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 15 mass% or less is more preferable, and 12 mass% or less is further more preferable.
- the content of the compound represented by the formula (2.2) constituting the component (A) includes solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. In consideration, it is preferably 2% by mass or more, preferably 4% by mass or more, more preferably 6% by mass, and further preferably 8% by mass or more. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 15 mass% or less is more preferable, and 12 mass% or less is further more preferable.
- the content of the compound represented by the formula (2.3) constituting the component (A) is such that the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, etc. In consideration, it is preferably 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass, and further preferably 7% by mass or more. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 15 mass% or less is more preferable, and 12 mass% or less is further more preferable.
- the content of the compound represented by the formula (2.4) constituting the component (A) is such that the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, etc. In consideration, it is preferably 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass, further preferably 7% by mass or more, and 9% by mass or more. More preferably, it is more preferably 10% by mass or more, and further preferably 12% by mass or more. Moreover, as a ratio which can be contained to the maximum, 22 mass% or less is preferable, 18 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the content of the compound represented by the formula (2.5) constituting the component (A) includes solubility at low temperature, transition temperature, electrical reliability, birefringence and the like. In consideration, it is preferably 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass, and further preferably 8% by mass or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- liquid crystal composition of the present invention includes the general formula (5) in the dielectrically positive component (A).
- R 5 represents an alkyl group having 2 to 5 carbon atoms
- X 51 to X 55 each independently represents a hydrogen atom or a fluorine atom
- Y 5 represents a fluorine atom or —OCF 3
- 1 type, or 2 or more types of compounds represented by these can be contained.
- the compound represented by the general formula (5) is represented by the formula (5.1) or (5.2).
- Component (A) may contain only one or two of these compounds, but the required transition temperature (Tni), dielectric anisotropy, dissolution at low temperature It is preferable to combine appropriately according to performance, such as property, electrical reliability, and birefringence.
- the content of the compound represented by formula (5.1) or formula (5.2) is preferably 2% by mass or more with respect to the total amount of the liquid crystal composition of the present invention, and is 4% by mass. Is more preferably 6% by mass, further preferably 8% by mass, further preferably 10% by mass, further preferably 12% by mass, and 15% by mass. Is more preferable, and it is especially preferable that it is 17 mass%. Moreover, as a ratio which can be contained to the maximum, 25 mass% or less is preferable, and 20 mass% or less is more preferable.
- the liquid crystal composition of the present invention has a general formula (6) in the dielectrically positive component (A).
- R 6 represents an alkyl group having 2 to 5 carbon atoms
- X 65 and X 66 each independently represent a hydrogen atom or a fluorine atom
- Y 6 represents a fluorine atom or —OCF 3
- 6 represents a single bond or —CF 2 O—
- R 6 represents an alkyl group having 2 to 5 carbon atoms
- X 65 and X 66 each independently represent a hydrogen atom or a fluorine atom
- Y 6 represents a fluorine atom or —OCF 3
- 6 represents a single bond or —CF 2 O—
- R 6 represents an alkyl group having 2 to 5 carbon atoms
- X 65 and X 66 each independently represent a hydrogen atom or a fluorine atom
- Y 6 represents a fluorine atom or —OCF 3
- 6 represents a single bond or —CF 2 O—
- R 6 represents an alkyl group having 2 to 5 carbon atoms
- it is a compound chosen from the group represented by these.
- the compounds that can be combined from the compounds represented by formula (6.1) to formula (6.6) but solubility at low temperatures, transition temperature, electrical reliability, birefringence
- the content of the compound represented by the formula (6.1) constituting the component (A) is such that the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, etc. Considering it, it is preferably 2.5% by mass or more, preferably 6% by mass or more, more preferably 8% by mass, and further preferably 10% by mass or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the content of the compound represented by the formula (6.2) constituting the component (A) is such that the solubility at low temperatures, the transition temperature, the electrical reliability, the birefringence, etc. In consideration, it is preferably 5.5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass, and further preferably 12% by mass or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 21 mass% or less is more preferable, and 16 mass% or less is further more preferable.
- the content of the compound represented by the formula (6.3) constituting the component (A) includes solubility at low temperatures, transition temperature, electrical reliability, birefringence, and the like. In consideration, it is preferably 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass, and further preferably 5% by mass or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the content of the compound represented by the formula (6.4) constituting the component (A) is such that the solubility at low temperature, the transition temperature, the electrical reliability, the birefringence, etc. Considering it, it is preferably 2.5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass, and further preferably 12% by mass or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the content of the compound represented by the formula (6.5) constituting the component (A) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, and the like. In consideration, it is preferably 8.5% by mass or more, preferably 10% by mass or more, more preferably 12% by mass, further preferably 14% by mass or more, and 16% by mass. More preferably, it is the above. Moreover, as a ratio which can be contained at the maximum, 30 mass% or less is preferable, 25 mass% or less is more preferable, and 20 mass% or less is further more preferable.
- the content of the compound represented by the formula (6.6) constituting the component (A) includes solubility at low temperatures, transition temperature, electrical reliability, birefringence, and the like. In consideration, it is preferably 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass, further preferably 8% by mass or more, and 12% by mass or more. More preferably it is. Moreover, as a ratio which can be contained to the maximum, 35 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further comprises a compound represented by the formula (7.1) or the formula (7.3) among the compounds represented by the general formula (6) in the dielectrically positive component (A). And formula (7.4)
- the compound chosen from the compound group represented by these can also be contained.
- the content of these compounds is preferably 2% by mass or more, more preferably 4% by mass or more, and further preferably 9% by mass or more based on the total amount of the liquid crystal composition of the present invention.
- the liquid crystal composition of the present invention further includes compounds (11.1) and (11.2) among the compounds represented by the general formula (6) in the dielectrically positive component (A).
- the compound chosen from the compound group represented by these can also be contained. There are no particular restrictions on the types of compounds that can be combined, but considering the solubility at low temperatures, transition temperatures, electrical reliability, birefringence, etc., one or two of these compounds are included. It is preferable to do. Since these compounds are useful for obtaining a liquid crystal composition having a relatively large dielectric anisotropy ( ⁇ ) and a low viscosity, they should be used in appropriate combinations in consideration of the required dielectric anisotropy. good.
- the content of the compounds represented by formulas (11.1) and (11.2) is preferably 1% by mass or more with respect to the total amount of the liquid crystal composition of the present invention, and is 5% by mass or more.
- % Or more is more preferable, and 20% by mass or more is particularly preferable.
- 45 mass% or less is preferable, 35 mass% or less is more preferable, and 30 mass% or less is further more preferable.
- the liquid crystal composition of the present invention has a general formula (8) in the dielectrically positive component (A).
- R 8 represents an alkyl group having 2 to 5 carbon atoms
- a 8 represents a 1,4-phenylene group or a 1,4-cyclohexylene group
- X 86 to X 89 are each independently hydrogen.
- 1 or 2 or more types of compounds represented by this can be contained. There are no particular restrictions on the types of compounds that can be combined, but one to three of these compounds are preferably contained, more preferably one to four or more.
- the liquid crystal composition of the present invention includes a compound represented by the formula (8.1) or (8.2) among the compounds represented by the general formula (8) in the dielectrically positive component (A).
- Component (A) may contain only one or two of these compounds, but it is required to find solubility at low temperatures, transition temperature, electrical reliability, birefringence, etc. It is preferable to combine appropriately according to the performance to be performed.
- the content of the compound represented by the formula (8.1) is preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 7% by mass with respect to the total amount of the liquid crystal composition of the present invention. % Or more is more preferable, and it is further more preferable that it is 10 mass% or more.
- the content of the compound represented by the formula (8.2) is preferably 5% by mass or more, more preferably 7% by mass or more, and 9% by mass with respect to the total amount of the liquid crystal composition of the present invention. % Or more is more preferable and 12 mass% or more is further preferable. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes a general formula (12) in the dielectrically positive component (A).
- R 12 represents an alkyl group having 2 to 5 carbon atoms
- X 1201 to X 1212 each independently represents a fluorine atom or a hydrogen atom
- Y 12 represents a fluorine atom or —OCF 3
- U 12 represents a single atom. It represents a bond or —CF 2 O—
- n 12 is 0 or 1.
- It may contain one or more compounds selected from the group represented by: There are no particular restrictions on the types of compounds that can be combined, but it is preferable to contain 1 to 3 types of these compounds, more preferably 1 to 4 types, and more preferably 1 to 5 types. It is particularly preferred to have
- liquid crystal composition of the present invention among the compounds represented by the general formula (12) in the dielectrically positive component (A), from the formulas (12.1) to (12.4)
- Component (A) may contain only one or two of these compounds, but it is required to find solubility at low temperatures, transition temperature, electrical reliability, birefringence, etc. It is preferable to combine appropriately according to the performance to be performed. There are no particular restrictions on the types of compounds that can be combined, but one to two of these compounds are preferably contained, more preferably one to three, and more preferably one to four. More preferably. Since these compounds are useful for obtaining a liquid crystal composition having a relatively large dielectric anisotropy ( ⁇ ) and low viscosity, it is necessary to use them in appropriate combinations in consideration of the required transition temperature (Tni). good.
- the component (A) preferably contains 1% by mass or more, preferably 3% by mass or more of the compound represented by the formula (12.1) with respect to the total amount of the liquid crystal composition of the present invention.
- 5% by mass or more is more preferable, and 10% by mass or more is particularly preferable.
- 40 mass% or less is preferable, 30 mass% or less is more preferable, and 20 mass% or less is further more preferable.
- the liquid-crystal composition of this invention it is preferable to contain 1 mass% or more of the compound represented by Formula (12.2) with respect to the total amount of the liquid-crystal composition of this invention, It is more preferable to contain 3 mass% or more, 5 mass% or more It is more preferable to contain it, and it is especially preferable to contain 10 mass% or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the compound represented by the formula (12.3) is preferably contained in an amount of 2% by mass or more, more preferably 4% by mass or more, more preferably 6% by mass or more, based on the total amount of the liquid crystal composition of the present invention. It is more preferable to contain, it is more preferable to contain 8 mass% or more, and it is especially preferable to contain 10 mass% or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the liquid-crystal composition of this invention if it is a compound represented by Formula (12.4), it is preferable to contain 1 mass% or more with respect to the total amount of the liquid-crystal composition of this invention, and it is more preferable to contain 5 mass% or more, 7 More preferably, it is contained in an amount of 9% by mass or more, more preferably 12% by mass or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes compounds of the formula (14.1) and the formula (14.3) from the compound group represented by the general formula (12) in the dielectrically positive component (A). ) To formula (14.5)
- the compound chosen from the compound group represented by these can also be contained.
- As a ratio which can be contained at the maximum 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- Component (A) preferably contains 3% by mass or more, more preferably 5% by mass or more of the compound represented by formula (14.1) with respect to the total amount of the liquid crystal composition of the present invention. 7 mass% or more is more preferable, and 10 mass% or more is particularly preferable. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- Component (A) preferably contains 5% by mass or more, more preferably 7% by mass or more of the compound represented by formula (14.3) based on the total amount of the liquid crystal composition of the present invention. More preferably, the content is 9% by mass or more, and particularly preferably 11% by mass or more. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 17 mass% or less is more preferable, and 14 mass% or less is further more preferable.
- Component (A) preferably contains 2% by mass or more of a compound selected from the group consisting of compounds represented by formula (14.4) or (14.5) based on the total amount of the liquid crystal composition of the present invention. More preferably, the content is 6% by mass or more, and particularly preferably 10% by mass or more. Moreover, as a ratio which can be contained to the maximum, 20 mass% or less is preferable, 16 mass% or less is more preferable, and 12 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes a general formula (19) in the dielectrically positive component (A).
- R 19 represents an alkyl or alkenyl group having 2 to 5 carbon atoms
- X 191 and X 192 each independently represent a fluorine atom or a hydrogen atom
- Y 19 represents a fluorine atom, a chlorine atom or —OCF 3
- a 19 and M 19 are each independently 1,4-cyclohexylene group, 1,4-phenylene group, 2,5-difluoro-1,4-phenylene group, 2-fluoro-1,4-phenylene group
- m 19 and n 19 represent 0 or 1).
- the component (A) may contain only one kind of these compounds or two or more kinds, but the solubility at low temperature, transition temperature, electrical reliability, birefringence, etc.
- the liquid crystal composition of the present invention further includes compounds represented by formulas (19.1) to (19.6) among the compounds represented by the general formula (19) in the dielectrically positive component (A).
- One type or two or more types of compounds selected from the group of compounds represented by There are no particular restrictions on the types of compounds that can be combined, but depending on the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence, one of these compounds can be used. It is preferable to contain 3 types, more preferably 1 to 4 types, further preferably 1 to 5 types, and particularly preferably 1 to 6 types.
- the component (A) preferably contains 7% by mass or more, more preferably 9% by mass or more of the compound represented by the formula (19.2) with respect to the total amount of the liquid crystal composition of the present invention. 11% by mass or more is particularly preferable. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 16 mass% or less is more preferable, and 13 mass% or less is further more preferable.
- the component (A) preferably contains 2% by mass or more, more preferably 4% by mass or more of the compound represented by the formula (19.5) with respect to the total amount of the liquid crystal composition of the present invention. It is particularly preferable to contain 6% by mass or more. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 16 mass% or less is more preferable, and 13 mass% or less is further more preferable.
- the component (A) preferably contains 3% by mass or more, more preferably 5% by mass or more of the compound represented by the formula (19.6) with respect to the total amount of the liquid crystal composition of the present invention. 7% by mass or more is particularly preferable. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 16 mass% or less is more preferable, and 13 mass% or less is further more preferable.
- the compound represented by the formula (19.1), the formula (19.3) and (19.4) is preferably contained in an amount of 4.5% by mass or more based on the total amount of the liquid crystal composition of the present invention.
- the content is more preferably 5.5% by mass or more, and particularly preferably 8% by mass or more.
- the maximum content ratio is preferably 20% by mass or less, and more preferably 16% by mass or less.
- the liquid crystal composition of the present invention further comprises a compound represented by the formula (20.1) or (20.3) among the compounds represented by the general formula (19) in the dielectrically positive component (A). And formula (20.6) to formula (20.8)
- 1 type or 2 or more types of compounds chosen from the compound group represented by these can also be contained.
- the component (A) preferably contains 1% by mass or more, more preferably 3% by mass or more of the compound represented by the formula (20.1) with respect to the total amount of the liquid crystal composition of the present invention. It is more preferable to contain 5% by mass or more. Moreover, as a ratio which can be contained to the maximum, 20 mass% or less is preferable, 16 mass% or less is more preferable, and 12 mass% or less is further more preferable.
- the compound represented by the formula (20.3), the formula (2.7) and the formula (2.8) may be contained in an amount of 0.5% by mass or more based on the total amount of the liquid crystal composition of the present invention.
- 3% by mass or more is more preferable, 5% by mass or more is more preferable, and 8% by mass or more is preferable.
- 20 mass% or less is preferable, 16 mass% or less is more preferable, and 12 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes a compound represented by the formula (18.1) or (18.2) among the compounds represented by the general formula (19) in the dielectrically positive component (A).
- the component (A) preferably contains 5% by mass or more, and 7% by mass or more of the compound of formula (18.1) or formula (18.2) based on the total amount of the liquid crystal composition of the present invention. More preferably, it is more preferably 9% by mass or more, and particularly preferably 12% by mass or more. Moreover, as a ratio which can be contained at the maximum, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the liquid crystal composition of the present invention contains a component (B) that is a dielectrically neutral component.
- Component (B) is composed of a compound having a dielectric anisotropy of greater than ⁇ 2 and less than +2.
- the component (B) of the liquid crystal composition of the present invention includes formula (40)
- the content of the compound represented by the formula (40) constituting the component (B) is preferably 15% by mass or more based on the total amount of the liquid crystal composition of the present invention, It is more preferably 18% by mass, more preferably 27% by mass or more, more preferably 29% by mass or more, more preferably 31% by mass or more, and 35% by mass or more. Is more preferably 39 mass% or more, more preferably 41 mass% or more, more preferably 45 mass% or more, more preferably 48 mass% or more, and 50 mass% or more. It is particularly preferred that Moreover, as a ratio which can be contained at the maximum, 75 mass% or less is preferable, 65 mass% or less is more preferable, 60 mass% or less is further more preferable, 55 mass% or less is especially preferable.
- the liquid crystal composition of the present invention has a general formula (16) in the component (B) which is a dielectrically neutral component.
- R 164 represents an alkyl group having 2 to 5 carbon atoms
- R 165 represents an alkyl group or alkoxy group having 1 to 5 carbon atoms
- X 161 and X 162 each independently represent a hydrogen atom or A fluorine atom
- a 16 represents a 1,4-phenylene group or a 1,4-cyclohexylene group
- m 16 represents 0 or 1.
- the content is preferably adjusted according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., preferably 1% by mass or more, and preferably 3% by mass or more. More preferably, it is more preferably 5% by mass or more. Moreover, as a ratio which can be contained at the maximum, 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes a compound represented by the formula (16.1) or (16.3) among the compounds represented by the general formula (16) in the dielectrically neutral component (B).
- the content is preferably 3% by mass or more, more preferably 6% by mass or more, and more preferably 10% by mass or more based on the total amount of the liquid crystal composition of the present invention. More preferably.
- As a ratio which can be contained at the maximum 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes a compound represented by the formula (13.1) among the compounds represented by the general formula (16) in the dielectrically neutral component (B).
- the compound represented by these can be contained.
- the content is preferably adjusted according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like, preferably 4% by mass or more, and preferably 6% by mass or more. More preferably, it is more preferably 10% by mass or more.
- a ratio which can be contained at the maximum 23 mass% or less is preferable, 18 mass% or less is more preferable, and 13 mass% or less is further more preferable.
- the liquid crystal composition of the present invention includes a general formula (3) in a dielectrically neutral component (B).
- R 36 represents an alkenyl group having 2 to 5 carbon atoms
- R 37 represents an alkyl group having 1 to 5 carbon atoms
- a 3 represents a 1,4-cyclohexylene group or a 1,4-phenylene group.
- M 3 represents 0 or 1.
- M 3 represents 0 or 1.
- the component (B) may contain a compound represented by the formula (3.2) according to required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. Even if it contains the compound represented by the formula (3.3), it contains both the compound represented by the formula (3.2) and the compound represented by the formula (3.3). Alternatively, all of the compounds represented by formulas (3.1) to (3.3) may be included.
- the content of the compound represented by the formula (3.1) or the formula (3.2) constituting the component (B) is preferably 3% by mass with respect to the total amount of the liquid crystal composition of the present invention, It is more preferably 5% by mass or more, more preferably 7% by mass or more, more preferably 9% by mass or more, more preferably 11% by mass or more, and 14% by mass or more. More preferably, it is more preferably 16% by mass or more, further preferably 18% by mass or more, and particularly preferably 21% by mass or more. Moreover, as a ratio which can be contained to the maximum, 40 mass% or less is preferable, 30 mass% or less is more preferable, and 25 mass% or less is further more preferable.
- the content of the compound represented by the formula (3.3) constituting the component (B) is preferably 3% by mass with respect to the total amount of the liquid crystal composition of the present invention, and is 5% by mass or more. More preferably, it is more preferably 8% by mass or more, further preferably 10% by mass or more, further preferably 12% by mass or more, further preferably 15% by mass or more, More preferably, it is 17 mass% or more, and it is especially preferable that it is 19 mass% or more. Moreover, as a ratio which can be contained to the maximum, 40 mass% or less is preferable, 30 mass% or less is more preferable, and 25 mass% or less is further more preferable.
- the total of both compounds is the liquid crystal composition of the present invention.
- the total amount is preferably 15% by mass or more, more preferably 19% by mass or more, further preferably 26% by mass or more, and particularly preferably 30% by mass or more.
- 45 mass% or less is preferable, 40 mass% or less is more preferable, and 35 mass% or less is further more preferable.
- the dielectric neutral component (B) the compound represented by the general formula (3), the compounds of the formulas (4.2) to (4.4)
- Component (B) may contain only one type of these compounds or two or more types, but it is preferable to combine them appropriately according to the required performance. There are no particular restrictions on the types of compounds that can be combined, but depending on the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence, one of these compounds can be used. It is preferable to contain two types, particularly preferably one to three types, and the content is preferably 2% by mass or more, and preferably 4% by mass or more, based on the total amount of the liquid crystal composition of the present invention.
- the content is more preferably 14% by mass or more, further preferably 16% by mass or more, and particularly preferably 20% by mass or more.
- 45 mass% or less is preferable, 35 mass% or less is more preferable, and 25 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes a compound represented by the formula (21.1) or (21.2) among the compounds represented by the general formula (3) in the dielectrically neutral component (B).
- the compound chosen from the compound group represented by these can also be contained.
- the liquid crystal composition of the present invention further includes a general formula (11) in the dielectrically neutral component (B).
- R 11 and R 12 each independently represents a straight-chain alkyl group or straight-chain alkenyl group having 1 to 10 carbon atoms
- the types of compounds that can be combined but depending on the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence, one of these compounds can be used. It is preferable to contain three types, more preferably one to four types, and particularly preferably one to five or more types.
- a ratio which can be contained at the maximum 35 mass% or less is preferable, 25 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the following compounds can be suitably used as the compound represented by the formula (11).
- the liquid crystal composition of the present invention further includes a general formula (9) in a dielectrically neutral component (B).
- R 91 and R 92 each independently represents an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms
- X 91 and X 92 each independently represent a hydrogen atom or fluorine.
- It can contain one or more compounds selected from the group represented by: There are no particular restrictions on the types of compounds that can be combined, but depending on the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence, one of these compounds can be used. It is preferable to contain 3 types, more preferably 1 to 4 types, further preferably 1 to 5 types, and particularly preferably 1 to 6 types or more.
- Component (B) may contain only one kind of these compounds or two or more kinds, but it has low temperature solubility, transition temperature, electrical reliability, birefringence, etc. It is preferable to combine appropriately according to the required performance. There are no particular restrictions on the types of compounds that can be combined, but one to three types are preferably contained, and one to four or more types are more preferred.
- the content of the compound represented by formula (9.1) or formula (9.2) is preferably 11% by mass or more, and 13% by mass or more with respect to the total amount of the liquid crystal composition of the present invention. It is more preferable that the content is 15% by mass or more.
- the content of the compound represented by the formula (10.7) or the formula (10.8) is preferably 0.5% by mass or more, and more preferably 2% by mass or more.
- 25 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.
- the content of the compound represented by the formula (9.3) is preferably 5% by mass or more, more preferably 7% by mass or more based on the total amount of the liquid crystal composition of the present invention, More preferably, it is 9 mass% or more. Moreover, as a ratio which can be contained to the maximum, 30 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.
- the liquid crystal composition of the present invention is further divided into compounds (10.1) to (10.6) among the compounds represented by the general formula (9) in the dielectrically neutral component (B).
- Component (B) may contain only one of these compounds or two or more thereof, but may be combined as appropriate depending on the required refractive index anisotropy and solubility at room temperature and below freezing point. It is preferable. Care must be taken because the solubility is affected by the structure of the alkyl groups at both ends of the compound.
- the neutral component (B) is a compound represented by the formula (10.1) or (10.2) in an amount of 0.5% by mass or more and 14% by mass with respect to the total amount of the liquid crystal composition of the present invention.
- the neutral component (B) contains the compound represented by the formula (10.3) or (10.4) with respect to the total amount of the liquid crystal composition of the present invention.
- the compound represented by the formula (10.5) or (10.6) is preferably contained in an amount of 5.5% by mass or more and less than 15% by mass with respect to the total amount of the liquid crystal composition of the present invention, and 9% by mass or more. And it is more preferable to contain less than 14 mass%.
- the liquid crystal composition of the present invention further includes a general formula (15) in a dielectrically neutral component (B).
- each R 15 independently represents an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms).
- the types of compounds that can be combined but depending on the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence, one of these compounds can be used. It is preferable to contain three types, and more preferably one to four or more types.
- the formulas (15.2) to (15.4) are examples of the compounds represented by the general formula (15).
- Component (B) may contain 5% by weight or more of a compound selected from the group consisting of compounds represented by formulas (15.1) to (15.3) with respect to the total amount of the liquid crystal composition of the present invention. Preferably, it is more preferably 7% by weight or more, more preferably 10% by weight or more, still more preferably 13% by weight or more, and particularly preferably 16% by weight or more. Moreover, as a ratio which can be contained at the maximum, 30 mass% or less is preferable, 25 mass% or less is more preferable, and 20 mass% or less is further more preferable.
- the liquid crystal composition of the present invention further includes a general formula (30) in a dielectrically neutral component (B).
- R 301 and R 302 each independently represents a straight-chain alkyl group or a straight-chain alkenyl group having 1 to 10 carbon atoms
- R 301 and R 302 each independently represents a straight-chain alkyl group or a straight-chain alkenyl group having 1 to 10 carbon atoms
- R 301 and R 302 each independently represents a straight-chain alkyl group or a straight-chain alkenyl group having 1 to 10 carbon atoms
- R 301 and R 302 each independently represents a straight-chain alkyl group or a straight-chain alkenyl group having 1 to 10 carbon atoms
- the compounds represented by the general formula (30) specifically, the following compounds can be preferably used.
- the liquid crystal composition of the present invention is further divided into compounds (17.1) to (17.3) among the compounds represented by the general formula (13) in the dielectrically neutral component (B).
- the compound chosen from the compound group represented by these can also be contained. Although there is no restriction
- the content of the liquid crystal composition of the present invention is preferably 0.5% by weight or more and less than 16% by weight, more preferably 1% by weight or more and less than 12% by weight, and more preferably 11% by weight or more and 6% by weight. More preferably, it is contained in an amount of less than 1% by weight, more preferably 1% by weight and less than 4% by weight.
- the liquid crystal composition of the present invention is also suitably used when it contains 73% by mass or more of component (A) or 81% by mass or more of component (B).
- the liquid crystal composition of the present invention further has the formula (10)
- Component (B) preferably adjusts the content of the compound represented by formula (10) according to the required performance such as solubility at low temperatures, transition temperature, electrical reliability, birefringence,
- This compound is preferably contained in an amount of 11% by mass or more, more preferably 15% by mass, further preferably 23% by mass, and more preferably 26% by mass or more based on the total amount of the liquid crystal composition of the present invention. More preferably, it is particularly preferably 28% by mass or more.
- ⁇ at 25 ° C. is +3.5 or more, more preferably +3.5 to +20.0, and still more preferably +3.5 to +15.0.
- ⁇ n at 25 ° C. is 0.08 to 0.14, more preferably 0.09 to 0.13. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.10 when dealing with a thick cell gap.
- the ⁇ at 20 ° C. is 10 to 45 mPa ⁇ s, more preferably 10 to 25 mPa ⁇ s, and particularly preferably 10 to 20 mPa ⁇ s.
- Tni is 60 ° C to 120 ° C, more preferably 70 ° C to 110 ° C, and particularly preferably 75 ° C to 90 ° C.
- the liquid crystal composition of the present invention may contain normal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like in addition to the above-mentioned compounds.
- the liquid crystal composition of the present invention may contain a polymerizable compound 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.
- a polymerizable compound 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 — (wherein s represents an integer of 2 to 7, Represents an aromatic ring).
- Z 51 represents —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 CF 2 —, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, —OCO—CH 2 —, —CH 2 —COO—, —CH 2 —OCO—, —CY 1 ⁇ CY 2 — (Wherein Y 1 and Y 2 each independently represents a fluorine atom or a hydrogen atom), —C ⁇ C— or a single bond; M 51 represents a 1,4-phenylene group,
- 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
- —COO—, —OCO— or a single bond is more preferred, and a single bond is particularly preferred.
- 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. preferable.
- C represents a ring structure other than a single bond
- Z 51 is preferably a linking group other than a single bond.
- M 51 is a single bond
- Z 51 is preferably a single bond.
- the ring structure between Sp1 and Sp2 is specifically preferably the structure described below.
- 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.
- general formula (V-1) to general formula (V-4) are particularly preferable, and general formula (V-2) is most preferable.
- the polymerization proceeds even when no polymerization initiator is present, 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 of the present invention is provided with liquid crystal alignment ability by polymerizing 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 two substrates of the liquid crystal cell used in the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon.
- a transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
- the color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method.
- a method for producing a color filter by a pigment dispersion method will be described as an example.
- a curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created.
- a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.
- the substrate is opposed so that the transparent electrode layer is on the inside.
- the thickness of the obtained light control layer is 1 to 100 ⁇ m. More preferably, the thickness is 1.5 to 10 ⁇ m.
- the polarizing plate it is preferable to adjust the product of the refractive index anisotropy ⁇ n of the liquid crystal and the cell thickness d so that the contrast is maximized.
- the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good.
- a retardation film for widening the viewing angle can also be used.
- the spacer examples include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.
- a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.
- a normal vacuum injection method or an ODF method can be used as a method of sandwiching the polymerizable compound-containing liquid crystal composition between the two substrates. Although it has a problem that leaves traces, in the present invention, it can be suitably used for a display element manufactured by using the ODF method.
- a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed.
- a liquid crystal display element can be manufactured by bonding a front plane and a back plane after dropping a predetermined amount of the liquid crystal composition in the air.
- the liquid crystal composition of the present invention can be preferably used because the liquid crystal composition can be stably dropped in the ODF process.
- an appropriate polymerization rate is desirable in order to obtain good alignment performance of liquid crystals. Therefore, active energy rays such as ultraviolet rays or electron beams are irradiated singly or in combination or sequentially.
- the method of polymerizing by is preferred.
- ultraviolet rays When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used.
- the polymerization is performed in a state where the polymerizable compound-containing liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. I must.
- the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization.
- a means for polymerization In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the polymerizable compound-containing liquid crystal composition.
- the alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element.
- the pretilt angle of the liquid crystal display element can be controlled by the applied voltage.
- the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
- the temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C.
- a lamp for generating ultraviolet rays a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used.
- a wavelength of the ultraviolet-rays to irradiate it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed.
- the intensity of the irradiated ultraviolet light is preferably 0.1 mW / cm 2 to 100 W / cm 2, more preferably 2 mW / cm 2 to 50 W / cm 2.
- the amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm 2 to 500 J / cm 2, and more preferably 100 mJ / cm 2 to 200 J / cm 2.
- the intensity may be changed.
- the time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiated ultraviolet rays, but is preferably from 10 seconds to 3600 seconds, and more preferably from 10 seconds to 600 seconds.
- the liquid crystal display device using the liquid crystal composition of the present invention is useful for achieving both high-speed response and suppression of display failure, and is particularly useful for a liquid crystal display device for active matrix driving, including VA mode, PSVA mode, It can be applied to PSA mode, IPS mode or ECB mode liquid crystal display elements.
- FIG. 1 is a cross-sectional view showing a liquid crystal display element including two substrates facing each other, a sealing material provided between the substrates, and liquid crystal sealed in a sealing region surrounded by the sealing material. It is.
- the TFT layer 102 and the pixel electrode 103 are provided on the substrate a100, the backplane on which the passivation film 104 and the alignment film a105 are provided, and the black matrix 202, the color filter 203, A planarizing film (overcoat layer) 201 and a transparent electrode 204 are provided, an alignment film b205 is provided thereon, a front plane facing the back plane, a sealing material 301 provided between the substrates, and the seal A specific mode of a liquid crystal display element including a liquid crystal layer 303 sealed in a sealing region surrounded by a material and provided with a protrusion 304 on a substrate surface in contact with the sealing material 301 is shown.
- the substrate a or the substrate b is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastics, or the like can be used.
- Plastic substrates include cellulose derivatives such as cellulose, triacetyl cellulose, diacetyl cellulose, polycycloolefin derivatives, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polyethylene, etc.
- Inorganic-organic composite materials such as glass fiber-acrylic resin can be used.
- the function of the barrier film is to reduce the moisture permeability of the plastic substrate and to improve the reliability of the electrical characteristics of the liquid crystal display element.
- the barrier film is not particularly limited as long as it has high transparency and low water vapor permeability. Generally, vapor deposition, sputtering, chemical vapor deposition method (CVD method) using an inorganic material such as silicon oxide is used. ) Is used.
- the same material or different materials may be used as the substrate a or the substrate b, and there is no particular limitation.
- a glass substrate is preferable because a liquid crystal display element having excellent heat resistance and dimensional stability can be produced.
- a plastic substrate is preferable because it is suitable for a manufacturing method using a roll-to-roll method and is suitable for weight reduction or flexibility. For the purpose of imparting flatness and heat resistance, good results can be obtained by combining a plastic substrate and a glass substrate.
- a substrate is used as the material of the substrate a100 or the substrate b200.
- a TFT layer 102 and a pixel electrode 103 are provided on a substrate a100. These are manufactured by a normal array process.
- a backplane is obtained by providing a passivation film 104 and an alignment film a105 thereon.
- a passivation film 104 (also referred to as an inorganic protective film) is a film for protecting the TFT layer.
- a nitride film (SiNx), an oxide film (SiOx), or the like is formed by a chemical vapor deposition (CVD) technique or the like.
- the alignment film a105 is a film having a function of aligning liquid crystals, and a polymer material such as polyimide is usually used in many cases.
- a coating solution an alignment agent solution composed of a polymer material and a solvent is used. Since the alignment film may hinder the adhesive force with the sealing material, a pattern is applied in the sealing region.
- a printing method such as a flexographic printing method or a droplet discharge method such as an ink jet is used.
- the applied alignment agent solution is crosslinked and cured by baking after the solvent is evaporated by temporary drying. Thereafter, an alignment process is performed to provide an alignment function.
- Alignment treatment is usually performed by a rubbing method.
- the polymer film formed as described above is rubbed in one direction using a rubbing cloth made of fibers such as rayon, thereby producing liquid crystal alignment ability.
- a photo-alignment method is a method of generating alignment ability by irradiating polarized light on an alignment film containing an organic material having photosensitivity, and does not cause the generation of scratches or dust on the substrate due to the rubbing method.
- the organic material in the photo-alignment method include a material containing a dichroic dye.
- Dichroic dyes include molecular orientation induction or isomerization reaction (eg, azobenzene group), dimerization reaction (eg, cinnamoyl group), photocrosslinking reaction (eg, benzophenone group) due to Weigert effect resulting from photodichroism.
- a photo-alignment group that causes a photoreaction that causes liquid crystal alignment ability
- a photolysis reaction eg, polyimide group
- the applied alignment agent solution is irradiated with light having an arbitrary deflection (polarized light), whereby an alignment film having alignment ability in an arbitrary direction can be obtained.
- One front plane is provided with a black matrix 202, a color filter 203, a planarizing film 201, a transparent electrode 204, and an alignment film b205 on a substrate b200.
- the black matrix 202 is produced by, for example, a pigment dispersion method. Specifically, a color resin solution in which a black colorant is uniformly dispersed for forming a black matrix is applied on a substrate b200 provided with a barrier film 201, thereby forming a colored layer. Subsequently, the colored layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.
- a pigment dispersion method Specifically, a color resin solution in which a black colorant is uniformly dispersed for forming a black matrix is applied on a substrate b200 provided with a barrier film 201, thereby forming a colored layer. Subsequently, the colored layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photore
- a photoresist type pigment dispersion may be used.
- a photoresist-type pigment dispersion is applied, pre-baked, exposed through a mask pattern, and then developed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.
- the color filter 203 is prepared by a pigment dispersion method, an electrodeposition method, a printing method, a dyeing method, or the like.
- a pigment dispersion method as an example, a color resin solution in which a pigment (for example, red) is uniformly dispersed is applied onto the substrate b200, and after baking and curing, a photoresist is applied thereon and prebaked. After the photoresist is exposed through a mask pattern, development is performed and patterning is performed. Thereafter, the photoresist layer is peeled off and baked again to complete the (red) color filter 203. There is no particular limitation on the color order to be created. Similarly, a green color filter 203 and a blue color filter 203 are formed.
- the transparent electrode 204 is provided on the color filter 203 (if necessary, an overcoat layer (201) is provided on the color filter 203 for surface flattening).
- the transparent electrode 204 preferably has a high transmittance, and preferably has a low electrical resistance.
- the transparent electrode 204 is formed by sputtering an oxide film such as ITO.
- a passivation film may be provided on the transparent electrode 204 for the purpose of protecting the transparent electrode 204.
- the alignment film b205 is the same as the alignment film a105 described above.
- the shape of the columnar spacer is not particularly limited, and the horizontal cross section can be various shapes such as a circle and a polygon such as a quadrangle. A polygonal shape is particularly preferable.
- the protrusion shape is preferably a truncated cone or a truncated pyramid.
- the material of the columnar spacer is not particularly limited as long as it is a sealing material, an organic solvent used for the sealing material, or a material that does not dissolve in liquid crystal, but it may be a synthetic resin (curable resin) in terms of processing and weight reduction. preferable.
- the protrusion can be provided on the surface of the first substrate in contact with the sealing material by a photolithography method or a droplet discharge method. For these reasons, it is preferable to use a photocurable resin suitable for a photolithography method or a droplet discharge method.
- a resin solution for forming columnar spacers (not containing a colorant) is applied on the transparent electrode 204 of the front plane. Subsequently, the resin layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the resin layer. Thereafter, the photoresist layer is peeled off, and the resin layer is baked to complete the columnar spacer.
- the formation position of the columnar spacer can be determined at a desired position by the mask pattern. Therefore, both the inside of the sealing region of the liquid crystal display element and the outside of the sealing region (sealing material application portion) can be created at the same time.
- the columnar spacer is preferably formed so as to be positioned on the black matrix so that the quality of the sealing region does not deteriorate.
- a columnar spacer manufactured by a photolithography method in this way is sometimes called a column spacer or a photospacer.
- a mixture of a negative water-soluble resin such as PVA-stilbazo photosensitive resin, a polyfunctional acrylic monomer, an acrylic acid copolymer, and a triazole initiator is used.
- a color resin in which a colorant is dispersed in a polyimide resin there is no particular limitation, and a spacer can be obtained from a known material in accordance with the compatibility with the liquid crystal or the sealing material to be used.
- a sealing material (301 in FIG. 1) is applied to the surface of the backplane that contacts the sealing material.
- the material of the sealing material is not particularly limited, and a curable resin composition in which a polymerization initiator is added to an epoxy or acrylic photocurable, thermosetting, or photothermal combination curable resin is used.
- a curable resin composition in which a polymerization initiator is added to an epoxy or acrylic photocurable, thermosetting, or photothermal combination curable resin is used.
- fillers made of inorganic or organic substances may be added.
- the shape of these fillers is not particularly limited, and includes a spherical shape, a fiber shape, and an amorphous shape.
- a spherical or fibrous gap material having a monodispersed diameter is mixed, or in order to further strengthen the adhesive force with the substrate, a fibrous substance that easily entangles with the protrusion on the substrate is used. You may mix.
- the diameter of the fibrous material used at this time is preferably about 1/5 to 1/10 or less of the cell gap, and the length of the fibrous material is preferably shorter than the seal coating width.
- the material of the fibrous substance is not particularly limited as long as a predetermined shape can be obtained, and synthetic fibers such as cellulose, polyamide, and polyester, and inorganic materials such as glass and carbon can be appropriately selected.
- the sealing material As a method for applying the sealing material, there are a printing method and a dispensing method, but a dispensing method with a small amount of the sealing material used is desirable.
- the application position of the sealing material is usually on the black matrix so as not to adversely affect the sealing area.
- the sealing material application shape is a closed loop shape.
- the liquid crystal is dropped on the closed loop shape (sealing region) of the front plane coated with the sealing material.
- a dispenser is used. Since the amount of liquid crystal to be dropped coincides with the volume of the liquid crystal cell, the amount is basically the same as the volume obtained by multiplying the height of the column spacer and the seal application area. However, in order to optimize liquid crystal leakage and display characteristics in the cell bonding process, the amount of liquid crystal to be dropped may be adjusted as appropriate, or the liquid crystal dropping position may be dispersed.
- the back plane is bonded to the front plane where the sealing material is applied and the liquid crystal is dropped.
- the front plane and the back plane are adsorbed on a stage having a mechanism for adsorbing a substrate such as an electrostatic chuck, and the alignment film b on the front plane and the alignment film a on the back plane face each other. It is arranged at a position (distance) where the sealing material does not contact the other substrate.
- the system is depressurized. After decompression is completed, the positions of both substrates are adjusted while confirming the bonding position between the front plane and the back plane (alignment operation).
- the substrate is brought close to a position where the sealing material on the front plane and the back plane are in contact with each other.
- the system is filled with an inert gas, and the pressure is gradually returned to normal pressure while releasing the reduced pressure.
- the front plane and the back plane are bonded together by atmospheric pressure, and a cell gap is formed at the height of the columnar spacer.
- the sealing material is irradiated with ultraviolet rays to cure the sealing material, thereby forming a liquid crystal cell.
- a heating step is added in some cases to promote curing of the sealing material. A heating process is often added to enhance the adhesive strength of the sealing material and improve the reliability of electrical characteristics.
- the measured characteristics are as follows.
- Tni Nematic phase-isotropic liquid phase transition temperature (° C) ⁇ n: refractive index anisotropy at 25 ° C. (also known as birefringence) ⁇ : dielectric anisotropy at 25 ° C. ⁇ : viscosity at 20 ° C. (mPa ⁇ s) ⁇ 1: rotational viscosity at 25 ° C. (mPa ⁇ s) VHR: Voltage holding ratio (%) at 60 ° C.
- Burn-in evaluation of the liquid crystal display element is based on the following four-level evaluation of the afterimage level of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1000 hours and then the entire screen is uniformly displayed. went.
- the process suitability is that the liquid crystal is dropped by 50 pL at a time using a constant volume metering pump 100000 times in the ODF process, and the following “0 to 100 times, 101 to 200 times, 201 to 300 times, ..., 99901 to 100,000 times ”, the change in the amount of liquid crystal dropped 100 times each was evaluated in the following four stages.
- Example 1 A liquid crystal composition LC-1 shown below was prepared.
- the initial VHR of the liquid crystal composition LC-1 was 99.2%, whereas the VHR after standing at high temperature for 1 hour at 150 ° C. was 98.8%.
- the solubility at low temperature was evaluated, it showed excellent performance as shown in the following table.
- a liquid crystal display element was manufactured by the ODF process using the liquid crystal composition LC-1, and image sticking, dripping marks and process compatibility were examined using the above-described method. As a result, the following excellent results were obtained. It was.
- the liquid crystal composition LC-2 not containing the compound represented by the formula (2.1) has Tni and ⁇ n that are higher than those of the liquid crystal composition LC-1 containing the compound represented by the formula (2.1). It was shown to decline.
- the initial VHR of the liquid crystal composition LC-2 was 99.0%, whereas the VHR after standing at high temperature for 1 hour at 150 ° C. was 97.7%.
- precipitation was observed earlier compared to LC-1.
- a liquid crystal display element was produced using the liquid crystal composition LC-2, and image sticking, dropping marks and process suitability were measured using the above-described method. As a result, the results were inferior to those of Example 1 as shown below. showed that.
- Example 2 A liquid crystal composition LC-3 shown below was prepared.
- the initial VHR of the liquid crystal composition LC-3 was 99.4%, whereas the VHR after standing at high temperature for 1 hour at 150 ° C. was 99.0%.
- the solubility at low temperature was evaluated, it showed excellent performance as shown in the following table.
- a liquid crystal display element was prepared by the ODF process using the liquid crystal composition LC-3, and the image sticking, the drop mark and the process suitability were examined by using the above-mentioned method. As a result, the following excellent results were obtained. It was.
- the liquid crystal composition LC-4 not containing the compound represented by the formula (1) was found to have substantially the same physical properties as the liquid crystal composition LC-3 containing the compound represented by the formula (1).
- the initial VHR of the liquid crystal composition LC-4 was 99.1%, whereas the VHR after standing at high temperature for 1 hour at 150 ° C. was 97.7%.
- precipitation was observed at an early stage as compared with LC-3.
- a liquid crystal display element was produced using the liquid crystal composition LC-4, and image sticking, dropping marks and process suitability were measured using the above-described method. As a result, the results were inferior to those of Example 2 as shown below. showed that.
- Example 3 Example 4
- the following liquid crystal compositions LC-5 to LC-6 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-5 to LC-6 was good, and the initial VHR and the VHR after standing at a high temperature of 150 ° C. for 1 hour hardly changed.
- examination of image sticking, dripping marks and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-5 to LC-6 showed excellent results as shown below.
- Liquid crystal compositions LC-7 to LC-8 shown below were prepared and their physical properties were measured. The results are shown in the following table.
- the low temperature solubility of the liquid crystal compositions LC-7 to LC-8 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- examination of burn-in, dripping marks and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-7 to LC-8 showed excellent results as shown below.
- Example 7 The following liquid crystal compositions LC-9 to LC-10 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-9 to LC-10 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- examination of image sticking, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-9 to LC-10 showed excellent results as shown below.
- Example 9 Example 10
- the following liquid crystal compositions LC-11 to LC-12 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-11 to LC-12 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- measurement of image sticking, dropping marks and process suitability of the liquid crystal display devices produced using the liquid crystal compositions LC-11 to LC-12 showed excellent results as shown below.
- Example 11 to Example 12 The following liquid crystal compositions LC-13 to LC-14 were prepared and their physical properties were measured. The results are shown in the following table.
- the low temperature solubility of the liquid crystal compositions LC-13 to LC-14 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- examination of burn-in, dripping marks and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-13 to LC-14 showed excellent results as shown below.
- Example 14 to Example 15 The following liquid crystal compositions LC-15 to LC-16 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-15 to LC-16 was good, and the initial VHR and the VHR after leaving at high temperature for 1 hour at 150 ° C. were hardly changed.
- examination of burn-in, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-15 to LC-16 showed excellent results as shown below.
- Example 16 to Example 17 The following liquid crystal compositions LC-17 to LC-18 were prepared and their physical properties were measured. The results are shown in the following table.
- the low temperature solubility of the liquid crystal compositions LC-17 to LC-18 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- examination of burn-in, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-17 to LC-18 showed excellent results as shown below.
- Example 18 The following liquid crystal compositions LC-19 to LC-20 were prepared and their physical properties were measured. The results are shown in the following table.
- the low temperature solubility of the liquid crystal compositions LC-19 to LC-20 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- examination of burn-in, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-19 to LC-20 showed excellent results as shown below.
- Example 20 to Example 21 The following liquid crystal compositions LC-21 to LC-22 were prepared and their physical properties were measured. The results are shown in the following table.
- the liquid crystal compositions LC-21 to LC-22 have good low-temperature solubility, and a slight change was observed between the initial VHR and the VHR after high temperature standing at 150 ° C. for 1 hour. It is a change.
- examination of image sticking, dropping marks, and process suitability of liquid crystal display devices manufactured using the liquid crystal compositions LC-21 to LC-22 showed excellent results as shown below.
- Example 22 to Example 23 The following liquid crystal compositions LC-23 to LC-24 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-23 to LC-24 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- examination of image sticking, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-23 to LC-24 showed excellent results as shown below.
- Example 24 to Example 25 The following liquid crystal compositions LC-25 to LC-26 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-25 to LC-26 was good, and the initial VHR and the VHR after standing at 150 ° C. for 1 hour were almost unchanged.
- examination of image sticking, dripping marks and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-25 to LC-26 showed excellent results as shown below.
- Example 26 to Example 27 The following liquid crystal compositions LC-27 to LC-28 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-27 to LC-28 was good, and the initial VHR and the VHR after standing at high temperature for 1 hour at 150 ° C. were hardly changed.
- examination of image sticking, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-27 to LC-28 showed excellent results as shown below.
- Example 28 The following liquid crystal compositions LC-29 to LC-30 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-29 to LC-30 was good, and the initial VHR and the VHR after leaving at high temperature for 1 hour at 150 ° C. were hardly changed.
- examination of image sticking, dropping marks, and process suitability of liquid crystal display devices manufactured using the liquid crystal compositions LC-29 to LC-30 showed excellent results as shown below.
- Example 30 to Example 31 The following liquid crystal compositions LC-31 to LC-32 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-31 to LC-32 was good, and the initial VHR and the VHR after leaving at high temperature for 1 hour at 150 ° C. were almost unchanged.
- examination of burn-in, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-31 to LC-32 showed excellent results as shown below.
- Example 32 to Example 33 The following liquid crystal compositions LC-33 to LC-34 were prepared and their physical properties were measured. The results are shown in the following table.
- the low-temperature solubility of the liquid crystal compositions LC-33 to LC-34 is good, and although there is a slight difference between the initial VH and the VHR after high temperature standing at 150 ° C. for 1 hour, the change is within an allowable range. .
- examination of image sticking, dropping traces and process suitability of liquid crystal display devices produced using the liquid crystal compositions LC-33 to LC-34 showed excellent results as shown below.
- Example 35 For the nematic liquid crystal composition LC-1 99.7% shown in Example 1, the formula (V-2)
- a polymerizable liquid crystal composition CLC-1 was prepared by adding 0.3% of the polymerizable compound represented by formula (II) and uniformly dissolving.
- the physical properties of CLC-1 were hardly different from those of the nematic liquid crystal composition shown in Example 1.
- CLC-1 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homogeneous alignment with a cell gap of 3.5 ⁇ m. While applying a rectangular wave having a frequency of 1 kHz to the cell, the liquid crystal cell was irradiated with ultraviolet light by a high-pressure mercury lamp through a filter that cuts ultraviolet light of 320 nm or less.
- the cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a horizontal alignment liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized. It was confirmed that the alignment regulating force for the liquid crystal compound was generated by the polymerization of the polymerizable compound.
- Example 36 Manufacture of liquid crystal display element for driving active matrix (preparation of front plane) (Formation of black matrix)
- a black matrix forming composition having the following composition was applied to a borosilicate glass substrate for liquid crystal display elements (OA-10 manufactured by Nippon Electric Glass Co., Ltd.) using a die coater so as to have a thickness of 10 ⁇ m in a wet state. After drying, prebaking was performed for 2 minutes at a temperature of 90 ° C. to form a black matrix layer having a thickness of 2 ⁇ m.
- the temperature of the main body of the exposure apparatus was adjusted to 23 ° C. ⁇ 0.1 ° C., and the relative humidity was adjusted to 60% ⁇ 1%.
- the glass substrate with the black matrix layer was adsorbed and fixed on the exposure table, and then automatically adjusted so that the gap (gap) between the coating surface of the glass substrate and the photomask pattern was 100 ⁇ m.
- the exposure position of the glass substrate was automatically detected after detecting the distance from the end face of the glass substrate, and exposure was performed after automatic adjustment so that the distance from the glass substrate to the photomask pattern position was a constant distance.
- a high-pressure mercury lamp was used as the light source, the exposure area was 200 mm ⁇ 200 mm, I-line (wavelength: 365 nm) was used, and exposure was performed at an illuminance of 15 mW / cm 2 for 20 seconds to obtain an exposure amount of 300 mJ / cm 2.
- Development processing was performed by installing a developing device downstream of the exposure machine.
- the glass substrate after the exposure processing was conveyed at a constant speed of 400 mm / min to obtain a substrate (1) with a black matrix layer on which a black matrix having a predetermined pattern was laminated.
- Alignment marks made of the same material as the black matrix are measured using a dimension measuring machine (NEXIV VMR-6555 manufactured by Nikon) at a temperature of 23 ° C. ⁇ 0.1 ° C. and a relative humidity of 60% ⁇ 1%.
- a dimension measuring machine NEXIV VMR-6555 manufactured by Nikon
- the dimension value of the pattern actually formed on the glass substrate with respect to the photomask dimension transport direction 100.000 mm and the vertical direction: 100.000 mm
- Conveying method 99.998 mm
- vertical direction 100.001 mm.
- the black matrix was thermally cured by post-baking at 220 ° C. for 30 minutes in a baking furnace.
- the dimensions of the pattern formed on the substrate (1) were Direction: 99.998 mm, vertical direction: 100.001 mm.
- a colored pattern forming composition having the following composition was applied in a wet state using a die coater so as to have a thickness of 10 ⁇ m, and after drying, the temperature was 90 ° C.
- the substrate (1) with a black matrix layer / colored pattern forming composition having a thickness of 2 ⁇ m was obtained by pre-baking for 2 minutes under the above conditions.
- the composition of the red colored pattern forming composition is shown below.
- a green colored pattern forming composition is obtained.
- a blue colored pattern forming composition is obtained. Is obtained.
- Each of the red, green, and blue color pigments may contain a resin composition for the purpose of color development and brightness improvement.
- a resin composition for such purpose a block copolymer with methacrylic acid having a primary, secondary or tertiary amino group is often used. Specifically, for example, BYK6919 manufactured by BYK is used. Or the like.
- a green pigment for example, CI Pigment Green 58
- the substrate (1) with the black matrix layer / colored pattern forming composition obtained above was introduced into an exposure apparatus provided with a transport apparatus from the upstream side to the downstream side and transported to the exposure section.
- the temperature of the main body of the exposure apparatus was adjusted to 23 ° C. ⁇ 0.1 ° C., and the relative humidity was adjusted to 60% ⁇ 1%.
- the coating film surface and photomask pattern of the substrate (1) with the black matrix layer / colored pattern forming composition was automatically adjusted so that the gap (gap) was 100 ⁇ m.
- the exposure position of the substrate (1) with the black matrix layer / colored pattern forming composition is automatically detected by detecting the distance from the end surface of the substrate (1) with the black matrix layer / colored pattern forming composition.
- alignment is performed with the RED photomask using the alignment marks formed simultaneously with the formation of the black matrix. After the exposure, exposure was performed.
- a high-pressure mercury lamp was used, the exposure area was 200 mm ⁇ 200 mm, I-line (wavelength: 365 nm) was used, and exposure was performed at an illuminance of 15 mW / cm 2 for 20 seconds to obtain an exposure amount of 100 mJ / cm 2.
- the substrate (1) with the black matrix layer / colored pattern forming composition after the exposure process is conveyed at a constant speed of 400 mm / min, and a RED colored layer is laminated at a predetermined position of the opening of the black matrix on the glass substrate. A substrate (1) was obtained. Thereafter, post-baking was performed at 220 ° C.
- GREEN and BLUE colored layers were repeatedly formed in the same manner as RED, and a color filter having a black matrix and RGB colored layers formed on the substrate (1) was obtained.
- the black matrix was measured under the same conditions as described above (temperature: 23 ° C. ⁇ 0.1 ° C., relative humidity: 60% ⁇ 1%) after the post-baking treatment of the BLUE colored layer, it was formed on the glass substrate.
- the dimension of the pattern was 99.999 mm in the transport direction and 100.002 mm in the vertical direction.
- the dimensional change of the black matrix is 10 ppm in the manufacturing process from the development of the first layer (black matrix layer) to the post-baking of the fourth layer (BLUE layer), whereby the resolution is 4 inches on the glass substrate.
- a color filter could be formed without causing pixel shift.
- the color filter was introduced into a sputtering apparatus, and reactive sputtering using oxygen as a reactive gas by DC sputtering was used as a target with ITO (indium tin oxide) as a target, and the film thickness was 150 nm on the black matrix and the RGB colored layer.
- ITO was formed into an ITO electrode layer.
- the sheet resistance value of the ITO electrode thus produced was 45 ⁇ / ⁇ .
- a columnar spacer forming composition made of a negative photosensitive resin is applied on a PET base film having a thickness of 25 ⁇ m using a die coater so that the thickness in a wet state is 20 ⁇ m. After drying, the temperature was prebaked for 2 minutes at a temperature of 90 ° C. to a thickness of 4.5 ⁇ m. Thereafter, a PET cover film having a thickness of 25 ⁇ m was laminated thereon to obtain a columnar spacer forming dry film.
- the pattern spacer-forming dry film having the cover film previously peeled off is used as the columnar spacer-forming composition as the ITO electrode layer.
- the columnar spacer forming composition layer was continuously transferred under the conditions of roller pressure: 5 kg / cm 2, roller surface temperature: 120 ° C., and speed: 800 mm / min. At this time, the base film was not peeled off, and proceeded to the next exposure step in a state of being attached on the columnar spacer forming composition. (Exposure process)
- the laminated substrate obtained above was introduced into an exposure apparatus provided with a transport apparatus from the upstream side to the downstream side and transported to the exposure unit.
- the temperature of the main body of the exposure apparatus was adjusted to 23 ° C. ⁇ 0.1 ° C., and the relative humidity was adjusted to 60% ⁇ 1%.
- the gap (gap) between the base film and the photomask pattern of the laminated substrate was automatically adjusted to 30 ⁇ m.
- the photomask pattern used at this time was designed to be a spacer pattern formed on the black matrix.
- the exposure position of the pattern of the multilayer substrate is automatically detected from the distance from the end surface of the multilayer substrate, and automatically adjusted so that the position of the photomask pattern from the multilayer substrate is a constant distance according to the detection result, and then the black matrix is formed. After aligning with the photomask for columnar spacers using the alignment mark formed simultaneously, exposure was performed.
- a high-pressure mercury lamp was used, the exposure area was 200 mm ⁇ 200 mm, I-line (wavelength: 365 nm) was used, exposure was performed at an illuminance of 15 mW / cm 2 for 20 seconds, and an exposure amount of 300 mJ / cm 2 was obtained.
- the developing process was performed while a developing device was installed on the downstream side of the exposure machine, and the base film was peeled off from the laminated substrate after exposure in the developing device while being conveyed at a constant speed of 400 mm / min.
- a color filter having a pattern spacer formed at a predetermined position of the lattice pattern portion of the black matrix of the substrate (1) on which the black matrix, the RGB colored layer, and the ITO electrode layer were formed was obtained.
- post-baking treatment was performed at 220 ° C. for 30 minutes in a baking furnace to thermally cure the columnar spacers.
- a front plane using the spacer pattern and having a black matrix, an RGB colored layer, an ITO electrode layer, and columnar spacers formed on the substrate (1) was obtained.
- a transparent substrate As a transparent substrate, a glass plate for liquid crystal display elements (OA-10 manufactured by Nippon Electric Glass Co., Ltd.) was used, and a TFT electrode layer was formed on the transparent substrate according to the method described in JP-A No. 2004-140381. That is, after forming an amorphous Si layer with a thickness of 100 nm on a glass substrate, an oxidized Si layer (SiOx) was formed by a vacuum film formation method. Thereafter, a TFT layer and a pixel electrode were formed on the oxidized Si layer by using a photolithography method and an etching method to obtain a glass substrate with a TFT array serving as a backplane.
- SiOx oxidized Si layer
- a liquid crystal alignment film was formed on the front plane and the back plane manufactured as described above. After washing both substrates with pure water, a liquid crystal aligning agent containing polyimide is applied using a liquid crystal alignment film coating printing machine (flexographic printing machine) and dried in an oven at 180 ° C. for 20 minutes. A coating film having a dry average film thickness of 600 mm was formed on the surface on which ITO was formed and on the surface on which the TFT electrode layer of the backplane was formed.
- the rubbing treatment was performed at a rotation speed of the roll of 400 rpm, a stage moving speed of 30 mm / second, and a hair foot pushing length of 0.4 mm, and then washed with water. Then, it dried for 10 minutes on 120 degreeC oven. It applied so that the closed loop of a sealing material might be drawn on the sealing material application part of a front plane using a dispenser.
- the sealing material a photothermal combined curable resin composition containing a bisphenol A type methacrylic acid modified epoxy resin is used, and a spherical spacer having the same size as the columnar spacer formed in the sealing material is set to 0 with respect to the resin component. .5% by mass was mixed.
- the application amount of the sealing material was adjusted to be the sealing width (0.7 mm) of the liquid crystal display element.
- the liquid crystal composition (LC-13) shown in Example 11 was once 24.times. 7 pL each was added dropwise in 90 times.
- the front plane and the back plane after dropping the liquid crystal were adsorbed to the electrostatic chuck.
- the front plane and the back plane were arranged so as to face each other, and the back plane was slowly lowered to stand still at a distance of 300 ⁇ m from the front plane.
- the pressure in the vacuum chamber was reduced to 100 Pa.
- the alignment position of the front plane and the back plane was adjusted using an alignment mark formed in advance. After the alignment was completed, the front plane and the back plane were brought closer to each other, and both base materials were held at a height where the sealing material and the TFT electrode layer were in contact with each other. In this state, an inert gas was introduced into the vacuum chamber, and the system was returned to atmospheric pressure.
- the front and back planes were pressed by atmospheric pressure, and a cell gap was formed at the height of the columnar spacer.
- the sealing material application portion was irradiated with ultraviolet rays (365 nm, 30 kJ / m 2) to cure the sealing material, and the substrates were fixed to each other.
- the substrate containing the liquid crystal composition was conveyed to a heating device, held at a surface temperature of 120 ° C. for 1 hour, and air-cooled after heating to obtain an active matrix driving liquid crystal display element.
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Abstract
Description
このように、TFT素子等で駆動するアクティブマトリックス駆動液晶表示素子に使用される液晶組成物おいては、高速応答性能等の液晶表示素子として求められている特性や性能を維持しつつ、従来から重視されてきた高い比抵抗値あるいは高い電圧保持率を有することや光や熱等の外部刺激に対して安定であるという特性に加えて、液晶表示素子の製造方法を考慮した開発が求められてきている。
すなわち、正の誘電率異方性を有する液晶組成物であって、式(1)
一般式(5)で表される化合物は、式(5.1)または(5.2)
一般式(6)で表される化合物は、式(6.1)から(6.6)
また、例えば式(12.4)で表される化合物であれば本発明の液晶組成物の総量に対して1質量%以上含有することが好ましく、5質量%以上含有することがさらに好ましく、7質量%以上含有することがさらに好ましく、9質量%以上含有することがさらに好ましく、12質量%以上含有することが特に好ましい。また、最大に含有できる比率としては、25質量%以下が好ましく、20質量%以下がより好ましく、15質量%以下がさらに好ましい。
本発明の液晶組成物は、更に、誘電的に中性な成分(B)の中に、一般式(11)
式(11)で表される化合物は、具体的には次に挙げる化合物が好適に使用できる。
一般式(30)で表される化合物は、具体的には次に挙げる化合物が好適に使用できる。
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、トランスー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。
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。
本発明の液晶組成物にモノマー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。
前記基板a又は前記基板bは、実質的に透明であれば材質に特に限定はなく、ガラス、セラミックス、プラスチック等を使用することができる。プラスチック基板としてはセルロ-ス、トリアセチルセルロ-ス、ジアセチルセルロ-ス等のセルロ-ス誘導体、ポリシクロオレフィン誘導体、ポリエチレンテレフタレ-ト、ポリエチレンナフタレ-ト等のポリエステル、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリカーボネート、ポリビニルアルコ-ル、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアミド、ポリイミド、ポリイミドアミド、ポリスチレン、ポリアクリレート、ポリメチルメタクリレ-ト、ポリエーテルサルホン、ポリアリレート、さらにガラス繊維-エポキシ樹脂、ガラス繊維-アクリル樹脂などの無機-有機複合材料などを用いることができる。
Δn :25℃における屈折率異方性(別名:複屈折率)
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:周波数60Hz,印加電圧1Vの条件下で60℃における電圧保持率(%)
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
滴下痕 :
液晶表示装置の滴下痕の評価は、全面黒表示した場合における白く浮かび上がる滴下痕を目視にて以下の4段階評価で行った。
○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
プロセス適合性 :
プロセス適合性は、ODFプロセスにおいて、定積計量ポンプを用いて1回に50pLずつ液晶を滴下することを100000回行い、次の「0~100回、101~200回、201~300回、・・・・99901~100000回」の各100回ずつ滴下された液晶量の変化を以下の4段階で評価した。
○変化が僅かに有るも許容できるレベル
△変化が有り許容できないレベル(斑発生により歩留まりが悪化)
×変化が有りかなり劣悪(液晶漏れや真空気泡が発生)
低温での溶解性:
低温での溶解性評価は、液晶組成物を調製後、2mLのサンプル瓶に液晶組成物を1g秤量し、これに温度制御式試験槽の中で、次を1サイクル「-20℃(1時間保持)→昇温(0.1℃/毎分)→0℃(1時間保持)→昇温(0.1℃/毎分)→20℃(1時間保持)→降温(-0.1℃/毎分)→0℃(1時間保持)→降温(-0.1℃/毎分)→-20℃」として温度変化を与え続け、目視にて液晶組成物からの析出物の発生を観察し、以下の4段階評価を行った。
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)
以下に示す液晶組成物LC-1を調製した。
式(2.1)で表される化合物を含有しない、以下に示される液晶組成物LC-2を調製した。
また、液晶組成物LC-2を用いて液晶表示素子を作製し、前述の方法を用いて焼き付き、滴下痕及びプロセス適合性の測定したところ、以下に示すように実施例1に比べて劣る結果を示した。
以下に示す液晶組成物LC-3を調製した。
式(1)で表される化合物を含有しない、以下に示される液晶組成物LC-4を調製した。
また、液晶組成物LC-4を用いて液晶表示素子を作製し、前述の方法を用いて焼き付き、滴下痕及びプロセス適合性の測定したところ、以下に示すように実施例2に比べて劣る結果を示した。
(実施例3から実施例4)
次に示す液晶組成物LC-5~LC-6を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-9~LC-10を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-11~LC-12を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-13~LC-14を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-15~LC-16を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-17~LC-18を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-19~LC-20を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-21~LC-22を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-23~LC-24を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-25~LC-26を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-27~LC-28を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-29~LC-30を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-31~LC-32を調製し、その物性値を測定した。この結果を次の表に示す。
次に示す液晶組成物LC-33~LC-34を調製し、その物性値を測定した。この結果を次の表に示す。
液晶組成物LC-33~LC-34の低温溶解性は良好であり、初期のVHと150℃で1時間の高温放置後のVHRとの差は多少見られるものの、許容範囲内の変化である。また、液晶組成物LC-33~LC-34を用いて作製した液晶表示素子の焼き付き、滴下痕及びプロセス適合性の検討をしたところ、以下に示すように優れた結果を示した。
実施例1に示すネマチック液晶組成物LC-1 99.7%に対して、式(V-2)
(実施例36)アクティブマトリックス駆動用液晶表示素子の製造
(フロントプレーンの作成)
(ブラックマトリックスの形成)
液晶表示素子用のホウ珪酸ガラス基板(日本電気硝子社製OA-10)に、下記の組成のブラックマトリックス形成用組成物を、ウェット状態で厚みが10μmになるようダイコーターを用いて塗布し、乾燥後、温度が90℃の条件で2分間プリベークして2μmの厚みのブラックマトリックス層を形成した。
(ブラックマトリックス形成用塗料組成物)
・ベンジルメタクリレート/メタクリル酸共重合体(モル比=73/27) 300部
・ジペンタエリスリトールヘキサアクリレート 160部
・カーボンブラック分散液 300部
・光重合開始剤(2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)ブタノン-1) 5部
・プロピレングリコールモノメチルエーテルアセテート 1200部
※部数はいずれも質量基準
その後、上流側から下流側に基板を搬送する装置を備えた露光装置に、上記で得られたブラックマトリックス層付きのガラス基板を導入し露光部まで搬送した。
(RGB着色層の形成)
前記ブラックマトリックス層付きの基板(1)の上に、下記の組成の着色パターン形成用組成物を、ウェット状態で厚み;10μmになるようダイコーターを用いて塗布し、乾燥後、温度が90℃の条件で2分間プリベークして2μmの厚みのブラックマトリックス層・着色パターン形成用組成物付きの基板(1)を得た。
(赤色着色パターン形成用組成物)
・ベンジルメタクリレート/メタクリル酸共重合体(モル比=73/27) 50部
・トリメチロールプロパントリアクリレート 40部
・赤色顔料(C.I.Pigment Red 254) 90部
・光重合開始剤(2-メチル-1-〔4-(メチルチオ)フェニル〕-2-モルフォリノプロパノン-1) 1.5部
・プロピレングリコールモノメチルエーテルアセテート 600部
※部数はいずれも質量基準
(緑色着色パターンの場合)
赤色着色パターン形成用組成物において、赤色顔料に変えて緑顔料(例えば、C.I.Pigment Green 58)を使用する以外は赤色着色パターン形成用組成物と同様にして製造。
赤色着色パターン形成用組成物において、赤色顔料に変えて青顔料(例えば、C.I.Pigment Blue 15.6)を使用する以外は赤色着色パターン形成用組成物と同様にして製造。
続いて、このカラーフィルタをスパッタリング装置に導入し、DCスパッタにより酸素を反応ガスに用いた反応性スパッタでITO(indium tin oxide)をターゲットとして用い、ブラックマトリックスおよびRGBの着色層上に膜厚150nmのITOの成膜を行い、これをITO電極層とした。このようにして作製したITO電極のシート抵抗値は45Ω/□であった。
(柱状スペーサーの形成)
(ドライフィルムの準備)
柱状スペーサー形成用のドライフィルムとして、厚みが25μmのPETベースフィルム上に、ネガ型感光性樹脂からなる柱状スペーサー形成用組成物を、ウェット状態で厚み;20μmになるようダイコーターを用いて塗布し、乾燥後、温度;90℃の条件で2分間プリベークして4.5μmの厚みとした。その後、その上に、厚み25μmのPETカバーフィルムをラミネートし、柱状スペーサー形成用ドライフィルムとした。(積層基板の作成)
上記で得られたブラックマトリックス、RGB着色層、およびITO電極層が形成された基板(1)上に、カバーフィルムを予め剥離したパターンスペーサ形成用ドライフィルムを柱状スペーサー形成用組成物がITO電極層と向かい合うように積層して、柱状スペーサー形成用組成物層を、ローラ圧;5kg/cm2、ローラ表面温度;120℃、および速度;800mm/minの条件にて、連続的に転写した。この際、ベースフィルムは剥離せず、柱状スペーサー形成用組成物上に付いた状態で次の露光工程へと進めた。(露光処理工程)
上流側から下流側に搬送装置を備えた露光装置に、上記で得られた積層基板を導入し露光部まで搬送した。
また積層基板のパターンの露光位置は、積層基板の端面からの距離を自動検出して、この検出結果にしたがって積層基板からフォトマスクパターン位置が一定距離になるよう自動調整後、前記ブラックマトリックス形成時に同時形成したアライメントマークを用いて柱状スペーサー用フォトマスクとアライメントを行った後、露光を行った。光源としては、高圧水銀ランプを用いて、露光エリアを200mm×200mmとして、I線(波長;365nm)を用い、15mW/cm2の照度で20秒間露光し、300mJ/cm2の露光量とした。(現像処理・ポストベーク処理工程)
現像処理は、露光機の下流側に現像装置を設置し、この現像装置内で露光後の積層基板からベースフィルムを剥離しながら、400mm/minの一定速度で搬送しながら行った。このようにして、前記ブラックマトリックス、RGB着色層、およびITO電極層が形成された基板(1)のブラックマトリックスの格子パターン部の所定位置にパターンスペーサが形成されたカラーフィルタを得た。その後、ベーク炉にて220℃、30分のポストベーク処理を行って、柱状スペーサーを熱硬化した。 このようにして、前記スペーサーパターンを使用した、基板(1)上にブラックマトリックス、RGB着色層、ITO電極層、柱状スペーサーが形成されたフロントプレーンを得た。
(バックプレーンの作成)
(TFT電極層の形成)
透明基板として、液晶表示素子用のガラス板(日本電気硝子社製OA-10)を用い、特開2004-140381号公報に記載された方法にしたがって、透明基板上にTFT電極層を形成した。
すなわち、ガラス基板上にアモルファスSi層を100nm厚で形成した後、酸化Si層(SiOx)を真空成膜法により形成した。その後、上記酸化Si層上に、フォトリソグラフィ法およびエッチング法を用いてTFT層および画素電極を形成しバックプレーンとなるTFTアレイ付ガラス基板を得た。
(液晶表示素子の製造)
(配向膜形成)
上記のように作製されたフロントプレーン及びバックプレーンに液晶配向膜を形成した。両基板ともに純水にて洗浄後、ポリイミドを含む液晶配向剤を、液晶配向膜塗布用印刷機(フレキソ印刷機)を用いて塗布し、180℃のオーブン内で20分間乾燥し、フロントプレーンのITOを形成した面及びバックプレーンのTFT電極層を形成した面上に乾燥平均膜厚600Åの塗膜を形成した。この塗膜にレーヨン製の布を巻き付けたロールを有するラビング装置により、ロールの回転数400rpm、ステージの移動速度30mm/秒、毛足押し込み長さ0.4mmでラビング処理を行い、水洗を行った後、120℃のオーブン上で10分間乾燥した。 フロントプレーンのシール材塗布部分に、ディスペンサーを用いてシール材の閉ループを描くように塗布した。
シール材として、ビスフェノールA型メタクリル酸変性エポキシ樹脂を含む光熱併用硬化型樹脂組成物を使用し、シール材の中に前述で形成した柱状スペーサとほぼ同じサイズの球状スペーサを樹脂成分に対して0.5質量%混合した。シール材の塗布量は、液晶表示素子のシール幅(0.7mm)となるように調製した。 続いて、シール材閉ループ内の所定の位置に定積計量ポンプ式のディスペンサーを用いて、実施例11に示した液晶組成物(LC-13)を、1枚のフロントプレーンにつき、1回24.7pLずつを90回に分けて滴下した。(合計2230pL)
液晶滴下後のフロントプレーンとバックプレーンとを静電チャックに吸着させた。フロントプレーンとバックプレーンとが互いに向き合うように配置し、バックプレーンをゆっくり降下させてフロントプレーンとの距離が300μmとなる距離で静止させた。この状態で真空チャンバー内を100Paまで減圧した。あらかじめ形成しておいたアライメントマークを用いて、フロントプレーンとバックプレーンとの貼り合せ位置を調整した。アライメント完了後、フロントプレーンとバックプレーンとをさらに接近させ、シール材とTFT電極層とが接する高さに両基材を保持した。この状態で真空チャンバー内に不活性ガスを導入し、系内を大気圧までもどした。大気圧によりフロントプレーンとバックプレーンが圧迫され、柱状スペーサーの高さでセルギャップが形成された。続いてシール材塗布部分に紫外線を照射して(365nm、30kJ/m2)シール材を硬化させ、お互いの基板を固定した。この状態で液晶組成物入りの基板を加熱装置に搬送し、表面温度が120℃の状態で1時間保持し、加熱終了後に空冷することによってアクティブマトリックス駆動用液晶表示素子を得た。
102:TFT層
103:画素電極
104:パッシベーション膜
105:配向膜a
200:基板b
201:平坦化膜(オーバーコート層)
202:ブラックマトリックス
203:カラーフィルタ
204:透明電極
205:配向膜b
301:シール材
302:柱状スペーサ
303:液晶層
304:突起
401:柱状スペーサーパターンフォトマスク
402:柱状スペーサ形成用組成物
Claims (8)
- 請求項1から7のいずれか一項に記載の液晶組成物を用いたアクティブマトリックス駆動用液晶表示素子。
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JP2016204479A (ja) * | 2015-04-20 | 2016-12-08 | Dic株式会社 | 組成物及びそれを使用した液晶表示素子 |
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CN105295957B (zh) * | 2015-10-16 | 2017-12-19 | 石家庄诚志永华显示材料有限公司 | 液晶组合物及使用该液晶组合物的显示元件或显示器 |
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US9695361B2 (en) | 2017-07-04 |
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