CN1915951A - Monomer, and method for using it to fabricate LCD faceplate - Google Patents
Monomer, and method for using it to fabricate LCD faceplate Download PDFInfo
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- CN1915951A CN1915951A CN 200610110762 CN200610110762A CN1915951A CN 1915951 A CN1915951 A CN 1915951A CN 200610110762 CN200610110762 CN 200610110762 CN 200610110762 A CN200610110762 A CN 200610110762A CN 1915951 A CN1915951 A CN 1915951A
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Abstract
This invention discloses a monomer shown in formula 1, wherein A is selected from formulae 2-4 or their combination; at least one of B and R is selected from alkyl, alkoxyl, ester group, formulae 5-8 or their combination; T is selected from O, N or their combination; X is selected from H, alkyl, halogen, cyano or their combination; n s a positive integer.
Description
Technical field
The present invention relates to a kind of monomer and use the method that it makes display panels, and particularly relate to and a kind ofly can and use the method that it makes display panels with the easier monomer that dissolves each other of liquid crystal molecule.
Background technology
In the epoch now that development in science and technology is maked rapid progress, display panels has been widely used in electronics and has shown on the product, as TV, computer screen, mobile computer, mobil phone or personal digital assistant etc.Especially using polymer stable alignment (polymer-stabilized alignment, PSA) many display fields orientation (multi-domain alignment) type display panels of being prepared from of technology, it has fast response time, wide viewing angle, high aperture, high to advantages such as processing procedure when are simple, is to be subjected to the technology that industry is quite paid attention to always.
In the middle of the PSA technology, in preparation display panel process, in the liquid crystal layer that inserts and puts between first, second substrate, add the reactive monomer (reactive monomer) of trace earlier, liquid crystal molecule is mixed with reactive monomer.Then, when applying voltage and UV-light (UV) rayed in first, second substrate, reactive monomer can with liquid crystal molecule generation phenomenon of phase separation, and reactive polymeric becomes polymkeric substance on the surface of first, second substrate.When polymkeric substance when liquid crystal layer is piled up at the interface of first, second substrate pile up because polymkeric substance with the interaction force of liquid crystal molecule between, makes polymerizable molecular arrange along the liquid crystal molecule direction.Therefore, liquid crystal molecule has tilt angle (pre-tile angle) on certain orientation.
Yet, because the traditional reactive monomer and the mutual solubility of liquid crystal molecule are not fine, make liquid crystal molecule and reactive monomer see through liquid crystal drop-method (one drop fill, when ODF) dropping on first, second one of them substrate, reactive monomer all only is distributed in the peripheral or surperficial of liquid crystal pearl.That is to say that reactive monomer is not to mix or be distributed in the liquid crystal layer with liquid crystal molecule very equably.Therefore, when the corresponding assembling of first, second substrate (assemble) pressing, cause reactive monomer different with the diffusion length of liquid crystal molecule.And reactive monomer is pushed to the border of liquid crystal pearl by liquid crystal molecule easily, and causing between the brilliant pearl of two dropping liquids has the reactive monomer of higher concentration to exist.So, tilt angle on the border of liquid crystal drop can increase greatly because of reactive monomer institute polymeric polymer concentration, and then cause display panels to produce white cancellate lattice imperfection (lattice mura), have a strong impact on the display quality of display panels.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of monomer and use the method that it makes display panels.The monomer whose structure Design can increase the level of disruption of monomer side chain, and avoids monomer to produce the storehouse phenomenon.Thus, monomer will dissolve each other together more equably with liquid crystal molecule, and will be solid-state to prevent that liquid crystal layer from being become by liquid crystal state easily.In addition, can avoid display panels to produce, and promote the display quality of display panels widely because of monomer and the bad lattice imperfection problem that causes of liquid crystal molecule mutual solubility.
According to purpose of the present invention, a kind of monomer is proposed, represent with chemical formula [1];
B-A-R [1]
Wherein, A is selected from chemical formula [2], [3], [4] or above-mentioned combination;
Wherein, at least one among B and the R is selected from alkyl, alkoxyl group, ester group, chemical formula [5], [6], [7], [8] or above-mentioned combination;
Wherein, T is selected from oxygen, nitrogen or above-mentioned combination, and X is selected from hydrogen, alkyl, halogens, cyano group or above-mentioned combination, and n is a positive integer.
According to purpose of the present invention, a kind of manufacture method of display panels is proposed.At first, provide first substrate with first electrode and second substrate with second electrode.Then, folder is established liquid crystal layer between first substrate and second substrate, and liquid crystal layer is between first electrode and second electrode, and liquid crystal layer has a plurality of liquid crystal molecules and a plurality of monomer, and each monomer is represented with above-mentioned chemical formula [1].
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and in conjunction with the accompanying drawings, carry out following detailed description.
Description of drawings
Fig. 1 is the schema of demonstration according to the manufacture method of the display panels of preferred embodiment of the present invention.
Fig. 2 A～2D is the processing procedure sectional view of demonstration according to the manufacture method of the display panels of the first embodiment of the present invention.
Fig. 3 A～3D is the processing procedure sectional view of demonstration according to the manufacture method of the display panels of the second embodiment of the present invention.
The primary clustering nomenclature
21: the first substrates
21a; First electrode
21b: first alignment film
22: the second substrates
22a: second electrode
22b: second alignment film
23: liquid crystal layer
23a: liquid crystal molecule
24: monomer
24a: polymkeric substance
25: UV-light
26a, 26b: display panels
V: voltage
Embodiment
Please be simultaneously with reference to Fig. 1 and Fig. 2 A～2D, Fig. 1 is the schema of demonstration according to the manufacture method of the display panels of embodiments of the invention, Fig. 2 A～2D is the processing procedure sectional view of demonstration according to the manufacture method of the display panels of the first embodiment of the present invention.
At first, in step 11, shown in Fig. 2 A, provide first substrate 21 and second substrate, 22, the first substrates 21 and second substrate 22 to have the first electrode 21a and the second electrode 22a respectively.Then, enter in the step 12, and for example shown in Fig. 2 A, folder is established liquid crystal layer 23 between first substrate 21 and second substrate 22, and liquid crystal layer 23 is between the first electrode 21a and the second electrode 22a.Wherein, liquid crystal layer 23 has a plurality of liquid crystal molecule 23a and a plurality of monomer 24.Each monomer 24 can be the sensing optical activity monomer, and its chemical structure is represented with chemical formula [1]:
B-A-R [1]
Wherein, A is intercalated nucleus (hard core), and comprises chemical formula [2], [3], [4] or above-mentioned combination;
Wherein, at least one the be selected from alkyl among R and the B, alkoxyl group, ester group, chemical formula [5], [6], [7], [8] or above-mentioned combination.That is to say that at least one among R and the B can be chemical formula [5], [6], [7] or [8].Or at least one among R and the B can be combination, chemical formula [5] and the combination of [7] or the combination of chemical formula [5] and [8] of chemical formula [5] and [6].In the present embodiment, will be that chemical formula [6], chemical formula [5] and combination, chemical formula [5] and the combination of [7] of [6] or the example that is combined as of chemical formula [5] and [8] explain with among R and the B at least one, but the technology of present embodiment be not limited thereto.
Wherein, T is selected from oxygen, nitrogen or above-mentioned combination, and X is selected from hydrogen, alkyl, halogens, cyano group or above-mentioned combination, and n is a positive integer.
In the present embodiment, R can be selected from alkyl, alkoxyl group, ester group or above-mentioned combination, and B can be selected from chemical formula [5], [6], [7], [8] or above-mentioned combination.Or B and R can be selected from chemical formula [5], [6], [7], [8] or above-mentioned combination, and B and the selected substituting group of R can be identical or different.N can be 2～5 positive integer, and X can be selected from methyl, fluorine or chlorine.In addition, when R was alkoxyl group, it can be expressed as OC
mH
2m+1, m can be 1～10 positive integer.In addition, R and B can be considered as being connected in the monomer 24 side chain at the left and right two ends of intercalated nucleus A.
Then, enter in the step 13, shown in Fig. 2 B, apply voltage V between the first electrode 21a and the second electrode 22a, these liquid crystal molecules 23a is rotated.And, also can increase the disturbance of liquid crystal molecule 23a and monomer 24, but can not cause monomer 24 to produce complete polymerization, and make monomer 24 formation polymer layers by one of them mode of thermal source heating and light source irradiation.Change bag and talk about, one of them mode of thermal source that is applied and light source irradiation can make monomer produce the prepolymerization effect or can not make monomer 24 produce complete polymerization.Certainly, need to prove this moment,, also can apply the voltage gradation if the voltage V size that is applied can't allow liquid crystal molecule 23a rotate when smooth.For example, apply voltage for the first time earlier, then, apply voltage for the second time again, and for the first time voltage and the position of voltage for the second time accurate (accurate position, potential) identical or different, but the accurate summation in voltage and the position of voltage for the second time is that the position of former voltage V when applying a time is accurate for the first time.Or, apply voltage for the first time earlier, then, apply voltage for the second time again, and voltage is accurate identical or different with the position of voltage for the second time for the first time, but the accurate summation in voltage and the position of voltage for the second time is accurate greater than the position of former voltage V when applying a time for the first time.Moreover, must it should be noted that applying one of them step of voltage or heating and irradiation can carry out or carry out in regular turn simultaneously under different time.For example, present embodiment is described carry out earlier heating and irradiation one of them, then, apply voltage again.Perhaps, apply voltage earlier, then, carry out again heating and irradiation one of them.Or, heating and irradiation one of them and apply voltage and carry out simultaneously.In addition, the second electrode 22a can divide into several zones again, and the voltage that each zone applied can be identical or different, and the voltage that is applied comprises direct current, alternating-current or above-mentioned combination.Wherein, the first electrode 21a and the second electrode 22a for example are respectively common electrode and pixel electrode.
Then, enter in the step 14, shown in Fig. 2 C, these monomers 24 of polymerization when applying this voltage V.That is to say, during applying voltage, carry out the polymerization of monomer 24.For example, based on monomer 24 is the sensing optical activity monomer, can be outside second substrate, 21 upper surfaces, can cause monomer 24 polymeric light source irradiation liquid crystal layers 23 with UV-light 25 or other, make these monomers 24 become polymer layer 24a, in order to use as the alignment film on first substrate 21 and second substrate 22 at the surface aggregate of the first electrode 21a and the second electrode 22a.Must it should be noted that, in the time can causing monomer 24 polymeric light source irradiation liquid crystal layers 23 with UV-light 25 or other, can full illumination or subregion irradiating liquid crystal layer 23.And when subregion irradiating liquid crystal layer 23, the irradiation energy in each district can be identical or inequality, and the energy summation during subregion irradiating liquid crystal layer 23 can the energy when full illumination liquid crystal layer 23 identical or inequality.Must it should be noted that the voltage V that step 13 and step 14 applied can be identical or inequality, according to arrangement situation or other requirement of liquid crystal molecule 23a.
Then, enter in the step 15, shown in Fig. 2 D, remove this voltage V, and remove UV-light 25 subsequently or be removed together simultaneously, display panels 26a finishes.At this moment, polymkeric substance 24a helps liquid crystal molecule 23a and topples over a little toward at least one specific direction in order to the tilt angle of liquid crystal molecule 23a with respect to the surface tilt of the first electrode 21a and the second electrode 22a (pre-tilt angle) to be provided.Generally speaking, tilt angle is less than 90 degree, preferably less than 60 degree.Therefore, based on foregoing, the disclosed monomer 24 of present embodiment can be applicable to that (polymer-stabilized alignment, PSA) technology prepares in the process of display panels with polymer-stabilized alignment.
Please refer to Fig. 3 A～3D, it is the processing procedure sectional view of demonstration according to the manufacture method of the display panels of the second embodiment of the present invention.Refer again to Fig. 1, at first, in step 11, as shown in Figure 3A, provide first substrate 21 and second substrate, 22, the first substrates 21 and second substrate 22 to have the first electrode 21a and the second electrode 22a respectively.Wherein, have the first alignment film 21b and the second alignment film 22b on the surface of the first electrode 21a and the second electrode 22a respectively.Then, enter in the step 12, again as shown in Figure 3A, folder is established liquid crystal layer 23 between first substrate 21 and second substrate 22, and liquid crystal layer 23 is between the first electrode 21a and the second electrode 22a.That is to say that liquid crystal layer 23 is between the first alignment film 21b and the second alignment film 22b.Wherein, liquid crystal layer 23 has a plurality of liquid crystal molecule 23a and a plurality of monomer 24, the first alignment film 21b and second alignment film 22b usefulness so that liquid crystal molecule 23a tilts or arrangement toward a specific direction.Each monomer 24 can be the sensing optical activity monomer, and its chemical structure is represented with chemical formula [1].
Then, enter in the step 13, shown in Fig. 3 B, apply voltage V between the first electrode 21a and the second electrode 22a, liquid crystal molecule 23a is rotated, and allow liquid crystal molecule 23a and monomer 24 mix more.And, also can increase the disturbance of liquid crystal molecule 23a and monomer 24, but can not cause monomer 24 to produce complete polymerization, and make monomer 24 formation polymer layers by one of them mode of thermal source heating and light source irradiation.Change bag and talk about, one of them mode of thermal source that is applied and light source irradiation can make monomer produce the prepolymerization effect or can not make monomer 24 produce any polymerization.Certainly, need to prove this moment,, also can apply the voltage gradation if the voltage V size that is applied can't allow liquid crystal molecule 23a rotate when smooth.For example, apply voltage for the first time earlier, then, apply voltage for the second time again, and voltage is accurate identical or different with the position of voltage for the second time for the first time, but the accurate summation in voltage and the position of voltage for the second time is that the position of former voltage V when applying a time is accurate for the first time.Or, apply voltage for the first time earlier, then, apply voltage for the second time again, and voltage is accurate identical or different with the position of voltage for the second time for the first time, but the accurate summation in voltage and the position of voltage for the second time is accurate greater than the position of former voltage V when applying a time for the first time.Moreover, must it should be noted that apply that one of them step of voltage or heating and irradiation can be carried out simultaneously or different time under carry out in regular turn.For example, present embodiment is described carry out earlier heating and irradiation one of them, then, apply voltage again.Perhaps, apply voltage earlier, then, carry out again heating and irradiation one of them.Or, heating and irradiation one of them and apply voltage and carry out simultaneously.In addition, the second electrode 22a can divide into several zones again, and the voltage that each zone applied can be identical or different.Wherein, the first electrode 21a and the second electrode 22a for example are respectively common electrode and pixel electrode.Must it should be noted that the voltage V that step 13 and step 14 applied can be identical or inequality, according to arrangement situation or other requirement of liquid crystal molecule 23a.
Then, enter in the step 14, shown in Fig. 3 C, these monomers 24 of polymerization when applying this voltage V.That is to say, during applying voltage, carry out the polymerization of monomer 24.For example, based on monomer 24 is the sensing optical activity monomer, can be outside second substrate, 21 upper surfaces, other can cause monomer 24 polymeric light source irradiation liquid crystal layers 23 with UV-light 25, makes these monomers 24 become polymer layer 24a at the surface aggregate of the first alignment film 21b and the second alignment film 22b.Must it should be noted that, when other can cause monomer 24 polymeric light source irradiation liquid crystal layers 23 with UV-light 25, can shine all or subregion irradiating liquid crystal layer 23.And when subregion irradiating liquid crystal layer 23, the irradiation energy in each district can be identical or inequality, and the energy summation during subregion irradiating liquid crystal layer 23 can the energy when full illumination liquid crystal layer 23 identical or inequality.
Then, enter in the step 15, shown in Fig. 3 D, remove this voltage V, and remove UV-light 25 subsequently or be removed together simultaneously, display panels 26b finishes.At this moment, polymer layer 24a helps liquid crystal molecule 23a and topples over toward at least one specific direction in order to liquid crystal molecule 23a to be provided the tilt angle with respect to the surface tilt of the first electrode 21a and the second electrode 22a.Because, before forming polymer layer 24a, the specific direction of the existing first alignment film 21b and the second alignment film 22b, so, when forming polymer layer 24a, can make that the pre-dumping direction of liquid crystal molecule is more remarkable.
How to be located between first substrate 21 and second substrate 22 as for the liquid crystal layer in the foregoing description 23, to be simply described as follows at this.Establish liquid crystal layer 23 before between first substrate 21 and second substrate 22 at folder, need the non-display area (not shown) of a substrate in first substrate 21 and second substrate 22 to be coated with upper ledge glue.Then, folder is established liquid crystal layer 23 between first substrate 21 and second substrate 22 again.At this moment, press from both sides the method for establishing liquid crystal layer 23 following several mode is arranged.
In first kind of mode, at first, corresponding assembling first substrate 21 and second substrate 22.Wherein, the frame glue between first substrate 21 and second substrate 22 has liquid crystal injection opening (not shown).Then, the liquid crystal that sees through frame glue injects opening, injects between liquid crystal layer 23 to first substrates 21 and second substrate 22.This kind elder generation assembling two substrates then injects the mode of liquid crystal layer between two substrates and is referred to as liquid crystal injection method (liquid crystal injection method).
In the second way, at first, the non-display area (not shown) of a substrate in first substrate 21 and second substrate 22 is coated with upper ledge glue.Then, splash on the surface of the substrate of liquid crystal layer 23 in first substrate 21 with frame glue and second substrate 22, promptly splash into liquid crystal layer 23 in substrate upper ledge glue institute area surrounded.Then, corresponding assembling first substrate 21 and second substrate 22, establish liquid crystal layer 23 between first substrate 21 and second substrate 22 with folder, this kind splash into earlier liquid crystal layer on a substrate, then assemble the mode of two substrates be referred to as the liquid crystal drop-method (one drop fill method, ODF).
Chemical structure as for monomer 24 is described as follows for example at this, but the technology of present embodiment is not confined to this.When A comprises chemical formula [2], [3], [4] or above-mentioned combination, and R is selected from alkyl, alkoxyl group, ester group or above-mentioned combination, and B is when representing with chemical formula [6], and monomer 24 is with chemical formula [11], [12], [13], [14], [15] or [16] expression:
Wherein, the left side chain end functional group of chemical formula [11], [13] and [15] can be selected from acrylate-based (acrylate), methacrylate based (methyl acrylate), acrylate radical derivative, methacrylate based or above-mentioned combination.In addition, the left side chain end functional group of chemical formula [12], [14] and [16] can be selected from peptidyl (peptide), peptide radical derivative or above-mentioned combination.
When A comprises chemical formula [2], [3], [4] or above-mentioned combination, and R is selected from alkyl, alkoxyl group, ester group or above-mentioned combination, and when B represented with the combination of the combination of the combination of chemical formula [5] and [6], chemical formula [5] and [7] or chemical formula [5] and [8], monomer 24 was with chemical formula [17], [18], [19], [20], [21] or [22] expression:
Wherein, the left side chain end functional group of chemical formula [23]～[25] can be selected from vinyloxy group (vinyloxy), vinyloxy group derivative or above-mentioned combination, and the left side chain end functional group of chemical formula [26]～[28] can be selected from styryl (styrene), styryl derivative or above-mentioned combination.
When A with chemical formula [2], [3] or [4] expression, and R and B represent with the combination of chemical formula [5] and [7] or the combination of chemical formula [5] and [8], and R and B be when identical, monomer 24 is with chemical formula [29], [30] or [31] expression:
Wherein, the and arranged on left and right sides chain end functional group of chemical formula [29]～[31] can be selected from vinyloxy group, vinyloxy group derivative or above-mentioned combination, and the and arranged on left and right sides chain end functional group of chemical formula [32]～[34] can be selected from styryl, styryl derivative or above-mentioned combination.
How monomer 24 as for this enforcement makes acquisition, will explain with 6 synthesis examples, but the technology of present embodiment is not confined to this.
First synthesis example: a kind of enforcement aspect in the chemical formula [11]
(1-1) synthetic 4-hydroxyl-4 '-ethoxybiphenyl (4-hydroxy-4 '-ethyloxybiphenyl), shown in chemical formula [51]:
At first, in reaction flask, fill argon gas, and (dimethoxyethane puts in the reaction flask DME) with the sodium hydride of 8 mmoles (mmol), 60 weight % and 200 milliliters exsiccant glycol dimethyl ether into.Then, when reaction soln cools off by ice cube, add 4 of 2 mmoles again, (4,4 '-dihydroxybiphenyl) to reaction soln for 4 '-dihydroxybiphenyl.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into the monobromethane (bromoethane) of 1 mmole gradually to reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography (gel column chromatography) method purifying residue, and carry out obtaining 4-hydroxyl-4 '-ethoxybiphenyl, shown in chemical formula [51] in crystallization with toluene.
(1-2) synthon, shown in chemical formula [52]:
At first, in reaction flask, fill argon gas, and 4-hydroxyl-the 4 '-ethoxybiphenyl of 1 mmole, the triethylamine (triethylamine) of 3 mmoles and 20 milliliters methylene dichloride are put in the reaction flask.Then, when reaction soln cooled off by ice cube, the methacrylic chloride (methyl acryloyl chloride) that splashes into 3 mmoles more gradually was to reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 3 hours.Then, reaction soln is poured in the distilled water, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, and carry out obtaining monomer, shown in chemical formula [52] in crystallization with acetone.
Second synthesis example: a kind of enforcement aspect in the chemical formula [17]
(2-1) synthetic 4-(2-hydroxyl-oxethyl)-4 '-ethoxybiphenyl (4-(2-hydroxyethyloxy)-4 '-ethyloxybiphenyl), shown in chemical formula [53]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 4 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cools off by ice cube, add again 1 mmole 4-hydroxyl-4 '-ethoxybiphenyl (4-hydroxy-4 '-ethyloxybiphenyl) to reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into the bromoethanol (bromoethanol) of 1.5 mmoles gradually to reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, and carry out obtaining 4-(2-hydroxyl-oxethyl)-4 '-ethoxybiphenyl, shown in chemical formula [53] in crystallization with toluene.
(2-2) synthon, shown in chemical formula [54]:
At first, in reaction flask, fill argon gas, and 4-(2-hydroxyl-oxethyl)-the 4 '-ethoxybiphenyl of 1 mmole, the triethylamine of 3 mmoles and 20 milliliters methylene dichloride are put in the reaction flask.Then, when reaction soln cools off by ice cube, splash into the methacrylic chloride of 3 mmoles more gradually to reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 3 hours.Then, reaction soln is poured in the distilled water, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, and carry out obtaining monomer, shown in chemical formula [54] in crystallization with acetone.
The 3rd synthesis example: a kind of enforcement aspect in the chemical formula [23]
(3-1) and (2-1) have same steps as,, repeat no more in this omission to obtain 4-(2-hydroxyl-oxethyl)-4 '-ethoxybiphenyl.
(3-2) synthon, shown in chemical formula [55]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 4 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cooled off by ice cube, 4-(2-hydroxyl-oxethyl)-the 4 '-ethoxybiphenyl that adds 1 mmole again was in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into 3-bromo-2-fluorine third-1-alkene (3-bromo-2-fluoroprop-1-ene) of 1.5 mmoles gradually in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, and carry out obtaining monomer, shown in chemical formula [55] in crystallization with toluene.
The 4th synthesis example: a kind of enforcement aspect in the chemical formula [26]
(4-1) synthetic 4-(2-bromine oxethyl)-4 '-ethoxybiphenyl (4-(2-bromoethyloxy)-4 '-ethyloxybiphenyl), shown in chemical formula [56]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 8 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cooled off by ice cube, 4-hydroxyl-the 4 '-ethoxybiphenyl that adds 2 mmoles again was in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into gradually 2 mmoles glycol dibromide (1,2-dibromoethane) in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer through benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, via distilling to separate solvent.Then, see through gelinite column chromatography purifying residue, with acquisition 4-(2-bromine oxethyl)-4 '-ethoxybiphenyl, and for example shown in the chemical formula [56].
(4-2) synthon, shown in chemical formula [57]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 4 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cooled off by ice cube, the 4-vinylphenol (4-vinylphenol) that adds 1 mmole again was to reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into 4-(2-bromine oxethyl)-the 4 '-ethoxybiphenyl of 1.5 mmoles gradually in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, to obtain monomer, shown in chemical formula [57].
Pentahapto precedent: a kind of enforcement aspect in the chemical formula [29]
(5-1) synthetic 4-(2-hydroxyl-oxethyl)-4 '-(2-hydroxyl-oxethyl) biphenyl (4-(2-hydroxyethyloxy)-4 '-(2-hydroxyethyloxy) biphenyl), shown in chemical formula [58]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 4 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cools off by ice cube, add 4 of 1 mmole again, 4 '-dihydroxybiphenyl is in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into the monobromethane of 3 mmoles gradually in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, with acquisition 4-(2-hydroxyl-oxethyl)-4 '-(2-hydroxyl-oxethyl) biphenyl, and for example shown in the chemical formula [58].
(5-2) synthon, shown in chemical formula [59]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 4 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cooled off by ice cube, the 4-vinyl benzene that adds 1 mmole again was in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into 4-(2-hydroxyl-oxethyl)-4 '-(2-hydroxyl-oxethyl) biphenyl of 2 mmoles gradually in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, to obtain monomer, shown in chemical formula [59].
Six directions precedent: a kind of enforcement aspect in the chemical formula [32]
(6-1) synthetic 4-(2-bromine oxethyl)-4 '-(2-bromine oxethyl) biphenyl (4-(2-bromoethyloxy)-4 '-(2-bromoethyloxy) biphenyl), shown in chemical formula [60]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 4 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cools off by ice cube, add 4 of 1 mmole again, 4 '-dihydroxybiphenyl is in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into the glycol dibromide of 3 mmoles gradually in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, with acquisition 4-(2-bromine oxethyl)-4 '-(2-bromine oxethyl) biphenyl, and for example shown in the chemical formula [60].
(6-2) synthon, shown in chemical formula [61]:
At first, in reaction flask, fill argon gas, and the sodium hydride of 4 mmoles, 60 weight % and 200 milliliters exsiccant glycol dimethyl ether are put in the reaction flask.Then, when reaction soln cooled off by ice cube, 4-(2-hydroxyl-oxethyl)-4 '-(2-hydroxyl-oxethyl) biphenyl that adds 1 mmole again was in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution 2 hours.Then, cooled reaction solution is to subzero 60 ℃.Then, splash into 3-bromo-2-fluorine third-1-alkene of 3 mmoles gradually in reaction soln.Then, reacting by heating solution is to room temperature, and lasting stirring reaction solution is to every other day.Then, reaction soln is poured in the dilute hydrochloric acid, and from reaction soln, extracted organic layer by benzene.Then, clean the organic layer that is extracted, and carry out drying with anhydrous sodium sulphate with distilled water.Then, by distilling to separate solvent.Then, by gelinite column chromatography purifying residue, with the acquisition monomer, and for example shown in the chemical formula [61].
The moment of dipole of monomer 24 on its molecule minor axis, and for the size of the moment of dipole of monomer 24 need be controlled at 0～5 debye (Debye, D) between, preferably between 0～3.Wherein, 1 debye equals 3.33564 * 10
-30Coulomb * rice (C*m).The reason of moment of dipole between 0～3 of control monomer 24 is because the moment of dipole of liquid crystal molecule 23a probably also is about about 3, therefore can increase the mutual solubility of liquid crystal molecule 23a and monomer 24.In addition, the moment of dipole of monomer 24 should not be too big or too small, in order to avoid influence the orientation to liquid crystal molecule 23a of the electric field that produced when applying voltage V between the first electrode 21a and the second electrode 22a.
When R was alkoxyl group, it can be expressed as OC
mH
2m+1, the m value can be controlled between 1～10.The adjustment of the carbochain length of R can be regulated and control the mutual solubility of monomer 24 and liquid crystal molecule 23a, but the carbochain of R is unsuitable oversize, in order to avoid impact polymer 24a is for the orientation power of liquid crystal molecule 23a.And, monomer 24 can absorb luminous energy or heat energy and aggregate into polymkeric substance 24a apace by acrylate-based, methacrylate based, peptidyl, vinyloxy group, styryl, acrylate radical derivative, methacrylate based derivative, peptide radical derivative, vinyloxy group derivative, styryl derivative or above-mentioned these type of functional groups such as combination, makes liquid crystal molecule 23a have tilt angle.In order to increase the stability of free radical, present embodiment imports vinyloxy group, styryl, vinyloxy group derivative, styryl derivative or above-mentioned combination in the structure of monomer 24, to keep the ability that monomer 24 aggregates into polymkeric substance 24a.
Moreover, must it should be noted that, to aggregate into the monomer of polymer layer 24a sometimes, still need other polymerization stabilizer or promotor, then comprise these materials and just be called precursor (precursor).Certainly, precursor can only comprise more than one the described monomer of the foregoing description or monomer more than two kinds, so that the polymeric polymer layer 24a of institute can provide preferred tilt angle.
In addition, must it should be noted that, in the above embodiment of the present invention, one of them of the disclosed second electrode 22a and the first electrode 21a for the pre-dumping direction that helps liquid crystal molecule 23a or orientation can be more variation, arrange (multi-domain alignment) to form many display fields, so one of them of the second electrode 22a and the first electrode 21a can have a plurality of opening (not shown), so that one of them of the second electrode 22a and the first electrode 21a forms polygonal shape.And shape that these openings form, for example: pectination, branch-like, X-shaped, W shape, V-arrangement or similarly shape or above-mentioned combination.Moreover when if the employed material of the second electrode 22a is transparent material, display panels is called the penetrating type display panels.If when the employed material of the second electrode 22a was the reflection material, display panels was called the reflective liquid crystal display panel.If when the employed material of the second electrode 22a was transparent material and mixing use of reflection material or subregion use, display panels was called semi-penetrate through and semi-reflection-type liquid crystal display board.And transparent material comprises indium-zinc oxide, aluminium tin-oxide, indium tin oxide or similarly material or above-mentioned combination.The reflection material comprises the alloy of the nitride of gold and silver, copper, aluminium, titanium, tantalum, molybdenum, neodymium, tungsten, above-mentioned metal, above-mentioned metal or above-mentioned combination.
The disclosed monomer of the above embodiment of the present invention and use the method that it makes display panels, the monomer whose structure Design can increase the level of disruption of monomer side chain, and avoids monomer to produce the storehouse phenomenon.Thus, monomer will dissolve each other together more equably with liquid crystal molecule, and will be solid-state to prevent that liquid crystal layer from being become by liquid crystal state easily.In addition, can avoid display panels to produce, and promote the display quality of display panels widely because of monomer and the bad lattice imperfection problem that causes of liquid crystal molecule mutual solubility.
In sum, though the present invention with preferred embodiment openly as above, it is not in order to limit the present invention.The technician of the technical field of the invention without departing from the spirit and scope of the present invention, can carry out various changes and retouching.Therefore, protection scope of the present invention is with being as the criterion that claims were limited.
Claims (23)
1. a monomer is represented with chemical formula [1];
B-A-R [1]
Wherein, A is selected from chemical formula [2], [3], [4] or above-mentioned combination;
Wherein, at least one among B and the R is selected from alkyl, alkoxyl group, ester group, chemical formula [5], [6], [7], [8] or above-mentioned combination;
Wherein, T is selected from oxygen, nitrogen or above-mentioned combination, and X is selected from hydrogen, alkyl, halogens, cyano group or above-mentioned combination, and n is a positive integer.
2. the described monomer of claim 1, wherein R is selected from alkyl, alkoxyl group, ester group or above-mentioned combination, and B is selected from chemical formula [5], [6], [7], [8] or above-mentioned combination.
3. the described monomer of claim 1, wherein B and R are selected from chemical formula [5], [6], [7], [8] or above-mentioned combination, and the selected substituting group of B and R is identical.
4. the described monomer of claim 1, wherein n is 2～5 positive integer.
5. the described monomer of claim 1, wherein X is selected from methyl, fluorine, chlorine or above-mentioned combination.
6. the described monomer of claim 1, wherein R is OC
mH
2m+1, m is 1～10 positive integer.
7. the described monomer of claim 1 has the moment of dipole that is essentially 0～3 debye (D).
8. the described monomer of claim 1, with chemical formula [11], [12], [13], [14], [15] or [16] expression:
9. the described monomer of claim 1, with chemical formula [17], [18], [19], [20], [21] or [22] expression:
10. the described monomer of claim 1, with chemical formula [23], [24] or [25] expression:
11. the described monomer of claim 1 is represented with chemical formula [26], [27] or [28]:
12. the described monomer of claim 1 is represented with chemical formula [29], [30] or [31]:
13. the described monomer of claim 1 is represented with chemical formula [32], [33] or [34]:
14. the manufacture method of a display panels comprises:
First substrate with first electrode and second substrate with second electrode are provided; And
Folder is established liquid crystal layer between this first substrate and this second substrate, and this liquid crystal layer is between this first electrode and this second electrode, and this liquid crystal layer has a plurality of liquid crystal molecules and a plurality of monomer, and respectively this monomer is represented with chemical formula [1]:
B-A-R [1]
Wherein, A is selected from chemical formula [2], [3], [4] or above-mentioned combination;
Wherein, at least one among B and the R is selected from alkyl, alkoxyl group, ester group, chemical formula [5], [6], [7], [8] or above-mentioned combination;
Wherein, T is selected from oxygen, nitrogen or above-mentioned combination, and X is selected from hydrogen, alkyl, halogens, cyano group or above-mentioned combination, and n is a positive integer.
15. the described method of claim 14 also comprises:
Apply a voltage between this first electrode and this second electrode.
16. the described method of claim 15 also comprises:
These monomers of polymerization when applying this voltage.
17. the described method of claim 16 also comprises:
Remove this voltage.
18. the described method of claim 14, wherein R is selected from alkyl, alkoxyl group, ester group or above-mentioned combination, and B is selected from chemical formula [5], [6], [7], [8] or above-mentioned combination.
19. the described method of claim 14, wherein B and R are selected from chemical formula [5], [6], [7], [8] or above-mentioned combination, and the selected substituting group of B and R is identical.
20. the described method of claim 14, wherein this monomer has the moment of dipole that is essentially 0～3 debye (D).
21. the described method of claim 14, wherein n is 2～5 positive integer.
22. the described method of claim 14, wherein X is selected from methyl, fluorine, chlorine or above-mentioned combination.
23. the described method of claim 14, wherein R is OC
mH
2m+1, m is 1～10 positive integer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178412.5A CN102701983B (en) | 2006-08-11 | 2006-08-11 | Monomer and apply it and manufacture the method for display panels |
| CNB2006101107622A CN100572351C (en) | 2006-08-11 | 2006-08-11 | Monomer and use the method that it makes display panels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101107622A CN100572351C (en) | 2006-08-11 | 2006-08-11 | Monomer and use the method that it makes display panels |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210178412.5A Division CN102701983B (en) | 2006-08-11 | 2006-08-11 | Monomer and apply it and manufacture the method for display panels |
| CN200910178650A Division CN101659614A (en) | 2006-08-11 | 2006-08-11 | Monomer and method for manufacturing liquid crystal display (LCD) panel applying same |
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| Publication Number | Publication Date |
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| CN1915951A true CN1915951A (en) | 2007-02-21 |
| CN100572351C CN100572351C (en) | 2009-12-23 |
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| CN201210178412.5A Expired - Fee Related CN102701983B (en) | 2006-08-11 | 2006-08-11 | Monomer and apply it and manufacture the method for display panels |
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| CN201210178412.5A Expired - Fee Related CN102701983B (en) | 2006-08-11 | 2006-08-11 | Monomer and apply it and manufacture the method for display panels |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101556404B (en) * | 2008-04-07 | 2011-04-27 | 财团法人工业技术研究院 | Bistable liquid crystal display and forming method thereof |
| CN102472922A (en) * | 2009-07-08 | 2012-05-23 | 夏普株式会社 | Liquid crystal display panel and process for production thereof |
| CN102936504A (en) * | 2012-10-29 | 2013-02-20 | 深圳市华星光电技术有限公司 | Liquid crystal composition and liquid crystal panel |
| US20170051206A1 (en) * | 2015-08-20 | 2017-02-23 | Jnc Corporation | Liquid crystal compound having alkenyl on both ends, liquid crystal composition and liquid crystal display device |
| WO2017217311A1 (en) * | 2016-06-17 | 2017-12-21 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4175826B2 (en) * | 2002-04-16 | 2008-11-05 | シャープ株式会社 | Liquid crystal display |
| CN1688916A (en) * | 2002-09-03 | 2005-10-26 | 奥博特瑞克斯株式会社 | Image display system |
| CN101052613B (en) * | 2004-11-04 | 2011-04-13 | 株式会社艾迪科 | Polymerizable compound and composition containing the polymerizable compound |
| KR101447290B1 (en) * | 2004-12-17 | 2014-10-06 | 메르크 파텐트 게엠베하 | Liquid crystal system and liquid crystal display |
-
2006
- 2006-08-11 CN CNB2006101107622A patent/CN100572351C/en not_active Expired - Fee Related
- 2006-08-11 CN CN201210178412.5A patent/CN102701983B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101556404B (en) * | 2008-04-07 | 2011-04-27 | 财团法人工业技术研究院 | Bistable liquid crystal display and forming method thereof |
| CN102472922A (en) * | 2009-07-08 | 2012-05-23 | 夏普株式会社 | Liquid crystal display panel and process for production thereof |
| CN102472922B (en) * | 2009-07-08 | 2014-07-30 | 夏普株式会社 | Liquid crystal display panel and process for production thereof |
| CN102936504A (en) * | 2012-10-29 | 2013-02-20 | 深圳市华星光电技术有限公司 | Liquid crystal composition and liquid crystal panel |
| US20170051206A1 (en) * | 2015-08-20 | 2017-02-23 | Jnc Corporation | Liquid crystal compound having alkenyl on both ends, liquid crystal composition and liquid crystal display device |
| JP2017039710A (en) * | 2015-08-20 | 2017-02-23 | Jnc株式会社 | Compound having alkenyl group at both terminals, liquid crystal composition and liquid crystal display element |
| WO2017217311A1 (en) * | 2016-06-17 | 2017-12-21 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| JPWO2017217311A1 (en) * | 2016-06-17 | 2018-06-28 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| CN108884392A (en) * | 2016-06-17 | 2018-11-23 | Dic株式会社 | Liquid-crystal composition and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102701983B (en) | 2015-10-28 |
| CN100572351C (en) | 2009-12-23 |
| CN102701983A (en) | 2012-10-03 |
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