CN101108968A - Liquid crystal mixture used for polymerization alignment manufacture process and method for manufacturing liquid crystal display board - Google Patents
Liquid crystal mixture used for polymerization alignment manufacture process and method for manufacturing liquid crystal display board Download PDFInfo
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- CN101108968A CN101108968A CNA2007101489814A CN200710148981A CN101108968A CN 101108968 A CN101108968 A CN 101108968A CN A2007101489814 A CNA2007101489814 A CN A2007101489814A CN 200710148981 A CN200710148981 A CN 200710148981A CN 101108968 A CN101108968 A CN 101108968A
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Abstract
A liquid core crystal compound for polymerizing the distribution process is provided, which comprises at least a liquid crystal molecule, at least a reactive monomer and an inhibitor with weight concentration range 0.01wt per cent to 1wt per cent of the reactive monomer content. The inhibitor quenches free radicals and polyreaction produced by the reactive monomer due to lighting or heat effect before polymerizing the distribution process, therefore reducing the reaction of the reactive monomer before polymerizing the distribution process and greatly improving the stability of the liquid core crystal compound.
Description
[technical field]
The present invention relates to a kind of making method that is used for the liquid crystal compound and the display panels of polymerization alignment manufacture process, relate in particular to a kind of making method with liquid crystal compound and display panels of inhibitor.
[background technology]
Along with the fast development of large scale liquid crystal display panel, display panels must possess the wide viewing angle characteristic, can satisfy the demand in the use.(multi-domain verticalalignment, MVA) display panels is because of having wide viewing angle and low answering time characteristics such as (response time), thereby becomes the main product of present large size two-d display panel for multiregional vertical align.
The MVA display panels system of prior art makes liquid crystal molecule produce tilt angle (pre-tilt angle) by a plurality of raised structures, therefore must utilize thin film deposition process, gold-tinted processing procedure and etch process etc. to form raised structures, improve the complexity of processing procedure and increased cost.And raised structures usually can shaded portions light, reduce picture element porosity (aperture ratio), reduce the brightness of display panels.
Therefore, industry is developed a kind of high molecular polymerization orientation (polymer stability alignment in addition, PSA) processing procedure, or be called the orientation that is separated (phase separation alignment, PSA) processing procedure, utilize high molecular polymer to replace raised structures in the MVA display panels, so that liquid crystal molecule has tilt angle in display panel.
Yet, owing to the response type monomer that uses in the polymerization alignment manufacture process is to be produced polyreaction by light or heat triggering, therefore in the sclerosis of the frame glue before the above-mentioned polymerization alignment manufacture process processing procedure, utilize energy rayed and heating fluid LCD panel with in the processing procedure that solidifies frame glue, can cause the response type monomer to aggregate into high molecular polymer in advance, so response type monomer polymerization and being separated in polymerization alignment manufacture process, the function that makes liquid crystal molecule produce tilt angle is satisfied announcement and was lost efficacy, and composition that influences liquid crystal compound and stability, more make display panels produce the defective of image inequality (mura), even cause problems such as the ghost (image sticking) of display panels 10 or optical anomaly.In addition, not only irradiation energy light in frame glue sclerosis processing procedure and heating supervisor can cause the polymerization in advance of response type monomer, during buffer zone before display panels enters polymerization alignment manufacture process, the irradiation that is subjected to environment light source in buffer zone also might influence the response type monomer, makes its polymerization in advance and causes the defective of above-mentioned display panels.
For avoiding the problems referred to above, when industry has been proposed in frame glue sclerosis processing procedure, set up light shield with blocking-up energy light direct irradiation liquid crystal compound, yet the cost of light shield is quite expensive, can significantly increase the processing procedure cost.In addition, it is more more responsive than general traditional liquid crystal compound to comprise the monomeric liquid crystal compound of response type, and the light source that therefore all must carefully carefully control environment in whole section processing procedure of display panels is affected with composition and the stability of avoiding liquid crystal compound.Hence one can see that, no matter be to use the control of light shield or reinforcement display panels processing procedure, all in the face of problems such as cost increase and the raisings of processing procedure degree of difficulty.
[summary of the invention]
Main purpose of the present invention is to provide a kind of making method that is used for the liquid crystal compound and the display panels of polymerization alignment manufacture process, with the stability of increase liquid crystal compound before polymerization alignment manufacture process, and the defective of minimizing display panels.
According to claim of the present invention, be the liquid crystal compound that a kind of polymerization alignment manufacture process is provided, this liquid crystal compound comprises at least a liquid crystal molecule, at least a response type monomer (reactive monomer) and a kind of inhibitor (inhibitor).The weight concentration of this inhibitor is this response type monomeric 0.01～1%; And comprise at least a compound as shown in the formula (1):
According to claim of the present invention, other provides a kind of making method of display panels.Upper substrate and hypocoxa at first are provided, and filling liquid crystal compound between upper substrate and hypocoxa carries out polymerization alignment manufacture process more then, and wherein this liquid crystal compound includes at least a liquid crystal molecule, at least a response type monomer and a kind of inhibitor.The weight concentration of this inhibitor is that this response type is monomeric 0.01～1%, and comprises the compound of at least a formula as described above (1).
Because liquid crystal compound provided by the present invention is added with inhibitor, the response type monomer that can reduce liquid crystal compound in aforementioned processing procedure because of the illumination or the influence of being heated and being caused, avoid the i.e. polymerization in advance before carrying out polymerization alignment manufacture process of response type monomer, so can significantly improve the stability of liquid crystal compound, and improve the monomeric polymerization effect of response type in the polymerization alignment manufacture process, and then improve the display quality of display panels.
[description of drawings]
Fig. 1 to 4 is the synoptic diagram of a preferred embodiment of display panels making method provided by the present invention.
Fig. 5 is polymerization alignment manufacture process intensity of illumination and the inhibitor concentration graph of relation to the display panels answering time.
[main description of reference numerals]
100 display panels, 102 hypocoxas
104 upper substrates, 106,108 conductive layers
110 alignment films, 120 liquid crystal compounds
122 liquid crystal molecules, 124 response type monomers
126 inhibitor, 128 high molecular polymers
130 frame glue, 150 energy light
[embodiment]
Please refer to Fig. 1 to Fig. 4, Fig. 1 to Fig. 4 makes the synoptic diagram of the method for display panels 100 for the present invention, and wherein display panels 100 can be multi-area vertical coupling liquid crystal display panel.As Fig. 1 and shown in Figure 2, hypocoxa 102 and upper substrate 104 at first are provided, hypocoxa 102 includes conductive layer 106,108 respectively with upper substrate 104 facing surfaces, wherein conductive layer 106,108 can be respectively pixel electrode and common electrode, or both are all common electrode, and the surface of conductive layer 106,108 optionally is provided with alignment film 110 respectively, for example by polymeric amide (polyamide, PI) the vertical orientation film of Gou Chenging.As shown in Figure 1, hypocoxa 102 forms frame glue 130 with respect to the non-display area on every side on the surface of upper substrate 104.In addition, upper substrate 104 also forms frame glue 130 with respect to the non-display area on every side on the surface of hypocoxa 102.Because it is identical with hypocoxa 102 that upper substrate 104 forms the relative position of frame glue 130, omit relevant indicators at this.Next, in the frame glue 130 of 104 of hypocoxa 102 and upper substrates, inject processing procedure (liquid crystal injection process) liquid crystal compound 120 is filled in upper and lower base plate 104 by liquid crystal, between 102, or by liquid crystal drip-injection (One drop fill, ODF) processing procedure, utilize the principle of injection tube or ink-jet, with air pressure, servomotor or other similar mode instil liquid crystal compound 120 in the frame glue 130 on hypocoxa 102 surfaces, by panel combination processing procedure upper substrate 104 is covered on the hypocoxa 102 more afterwards, and carries out frame glue sclerosis (curing) processing procedure.
According to preferred embodiment provided by the present invention, liquid crystal compound 120 includes at least a liquid crystal molecule 122, at least a response type monomer 124 and a kind of inhibitor 126.The weight concentration of inhibitor 126 is 0.01% to 1% of a response type monomer 124, maybe can say to be between 10,000 ten thousand/(ppm) and 1%, and inhibitor 126 preferably comprises the compound of at least a formula as described above (1).Yet the structure of inhibitor 126 is not limited to shown in the formula (1).
The response type monomer 124 that is comprised in the liquid crystal compound 120 is photopolymerization or heat polymerization type monomer, and it comprises the compound as shown in the formula (2) or (3):
Wherein, the P in chemical structural formula (2), (3)
1System is independent to be polymer-based group (polymerizable), for example vinylformic acid (ester) base (acrylate) or methacrylic acid (ester) base (methacrylate).SP
1System is independent to be spacer groups (spacer group) or single group (single group).X
1System is independent to be-O-,-S-,-OCH
2-,-CO-,-COO-,-OCO-,-CO-NR-,-NR-CO-,-OCH
2-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OCC-CH=CH-or singly-bound.L
mSystem is independent to be fluorine (F), chlorine (Cl), cyanogen (CN) or alkyl (alkyl), alkyl carbonyl (alkylcarbonyl), carbalkoxy (alkoxycarbonyl) or the alkane carbonyl oxygen base (alkylcarbonyloxy) with 1 to 7 carbon atom, and m is more than or equal to 1.In addition, work as L
mDuring for alkyl with 1 to 7 carbon atom, alkyl carbonyl, alkoxy carbonyl or alkane carbonyl oxygen base, wherein one or more hydrogen atom can be replaced by the fluorine or chlorine atom.R then independently is-H ,-F ,-Cl ,-CN ,-SCN ,-SF
5H ,-NO2, strand or branched-chain alkyl with 1 to 12 carbon atom or-X
2-Sp
2-P
2X wherein
2System is independent to be-O-,-S-,-OCH
2-,-CO-,-COO-,-OCO-,-CO-NR-,-NR-CO-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OOC-CH=CH-or singly-bound; And Sp
2System is independent to be spacer groups or single group.
Wherein, R
1, R
2, R
3, R
4And R
6System is independent of having the alkyl of 1 to 12 carbon atom, its 1 or 2 non-conterminous CH
2Group can be in addition by-O-,-CH=CH-,-CO-,-OCO-or-COO-replaces, and oxygen (O) atom direct bond each other not;
R
5It is thiazolinyl with 2 to 8 carbon atoms;
D is 0 or 1.In addition
Be
Or
With
System independently is
Or
And
Be
Or
In addition, liquid crystal compound 120 also can include at least a polymerization initiator (initiator) (not shown), for example is for light or the hot polymerization initiator that has high sensitive and have good stability.
In a preferred embodiment of the invention, liquid crystal compound 120 be by the ODF processing procedure filling between upper substrate 104 and hypocoxa 102.Afterwards, carry out frame glue sclerosis processing procedure immediately.Frame glue sclerosis processing procedure system utilizes heat energy or energy rayed display panels 100, to solidify the frame glue 130 (being shown in Fig. 1) of 102 of upper substrate 104 and hypocoxas.And the liquid crystal compound 120 that this preferred embodiment provided is in this frame glue sclerosis processing procedure, though can obtain heat energy or be subjected to the irradiation of energy light, but the free radical that therefore response type monomer 124 is produced can consume inhibitor 126, so but cancellation (quench) or avoid response type monomer 124 to produce polyreactions, so the influence that response type monomer 124 is subjected in frame glue sclerosis processing procedure can reduce significantly.In addition, during buffer zone before display panels 100 enters polymerization alignment manufacture process, the irradiation that is subjected to environment light source in buffer zone also reduces because of the existence of inhibitor 126 influence that response type monomer 124 produces.In brief, owing to added inhibitor 126 in the liquid crystal compound 120, therefore can avoid liquid crystal compound 120 polymerization in advance before polymerization alignment manufacture process, even also the stability of liquid crystal compound 120 greatly improves.
Please refer to Fig. 3 and Fig. 4.After making the sclerosis of frame glue, carry out polymerization alignment manufacture process, at first conductive layer 106,108 is applied voltage repeatedly, so that all liquid crystal molecules 122 deflect to predetermined angular, the voltage that is applied can be direct current (DC) voltage, or exchanges (AC) voltage.Then as shown in Figure 4, when applying voltage, by energy light 150 irradiating liquid crystal display panels 100, for example irradiating ultraviolet light (UV), or heating; Or heat illumination more earlier, make response type monomer 124 along the progressively polymerization and being separated of this predetermined angular of liquid crystal molecule 122, and on the alignment film 110 of upper and lower base plate 104,102, form high molecular polymer 128, after waiting to remove voltage, liquid crystal molecule 122 just can produce tilt angle along with the orientation of high molecular polymer 128.
It should be noted that, according to method provided by the present invention, because the polyreaction of the existence meeting cancellation response type monomer 124 of inhibitor 126, inhibitor 126 can make response type monomer 124 too stable when polymerization alignment manufacture process in other words, might make the display panels 100 that completes have long answering time.Therefore, in the time of according to a preferred embodiment of the invention, can when polymerization alignment manufacture process, increase the illumination energy of energy light 150, for example increase about time to three minute of display panels 100 irradiation energy light 150, perhaps improve the energy intensity of energy light 150, to consume the inhibitor 126 in the liquid crystal compound 120.Please refer to Fig. 5, Fig. 5 is the graph of relation that includes the liquid crystal compound 120 of different inhibitor concentration and shine the display panels answering time of different-energy light intensity gained in polymerization alignment manufacture process.As shown in Figure 5, when 126 concentration of the inhibitor in the liquid crystal compound 120 were 1500ppm, (Joule J) can significantly shorten the answering time of display panels 100 to increase the intensity to 5 joule of energy light 150.Hence one can see that, though the inhibitor 126 in liquid crystal compound 120 can increase the stability of liquid crystal compound 120, response type monomer 124 is reduced before polymerization alignment manufacture process or in the reaction at polymerization alignment manufacture process initial stage, but can be by time that increases energy light 150 irradiating liquid crystal display panels 100 or the means that improve the fine setting polymerization alignment manufacture process parameters such as energy intensity of energy light 150, consume the inhibitor 126 in the liquid crystal compound 120, improve the polyreaction of response type monomer 124, to obtain to conform with even surmount the display panels 100 that general answering time requires.
Than prior art, because the liquid crystal compound that is used for polymerization alignment manufacture process provided by the present invention has added inhibitor, can effectively avoid the response type monomer in the liquid crystal compound was polymerization reaction take place before polymerization alignment manufacture process, therefore can significantly improve the stability of liquid crystal compound.In addition, method according to making display panels provided by the present invention, can consume inhibitor by the process parameter of fine setting polymerization alignment manufacture process, so the inhibitor that is added in the liquid crystal compound can't change the optical appearance that is used for the liquid crystal compound of polymerization alignment manufacture process originally, even can obtain to surmount the display panels that general answering time requires by the fine setting of polymerization alignment manufacture process.From the above, the present invention is an economy effective means again, in liquid crystal compound, add an amount of inhibitor, promptly can effectively improve response type monomer polymeric situation in advance, and can not have influence on the optical appearance and the reliability test of display panels, can reach the purpose of improving quality product.
The above only is the preferred embodiments of the present invention, and all equivalent variations and modifications of doing according to claim of the present invention all should belong to the scope that the present invention is contained.
Claims (25)
1. liquid crystal compound that is used for polymerization alignment manufacture process includes:
At least a liquid crystal molecule;
At least a response type monomer; And
A kind of inhibitor, its weight concentration are that this response type is monomeric 0.01～1%, and this inhibitor comprises at least a compound as shown in the formula (1):
2. liquid crystal compound as claimed in claim 1, wherein this response type monomer is photopolymerization or heat polymerization type monomer.
3. liquid crystal compound as claimed in claim 2, wherein this response type monomer comprises the compound as shown in the formula (2) or (3):
4. liquid crystal compound as claimed in claim 3, wherein P
1System is independent to be polymer-based group.
5. liquid crystal compound as claimed in claim 4, wherein P
1System includes vinylformic acid (ester) base or methacrylic acid (ester) base independently.
6. liquid crystal compound as claimed in claim 3, wherein SP
1System is independent to be spacer groups or single group.
7. liquid crystal compound as claimed in claim 3, wherein X
1System is independent to be-O-,-S-,-OCH
2-,-CO-,-COO-,-OCO-,-CO-NR-,-NR-CO-,-OCH
2-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OCC-CH=CH-or singly-bound.
8. liquid crystal compound as claimed in claim 3, wherein L
mSystem is independent to be fluorine, chlorine, cyanogen or alkyl, alkyl carbonyl, carbalkoxy or the alkane carbonyl oxygen base with 1 to 7 carbon atom, and m is more than or equal to 1.
9. liquid crystal compound as claimed in claim 8 is wherein worked as L
mDuring for alkyl with 1 to 7 carbon atom, alkyl carbonyl, alkoxy carbonyl or alkane carbonyl oxygen base, its one or more hydrogen atoms can be replaced by the fluorine or chlorine atom.
10. liquid crystal compound as claimed in claim 3, wherein R system is independent is-H ,-F ,-Cl ,-CN ,-SCN ,-SF
5H ,-NO
2, have the strand of 1 to 12 carbon atom or branched-chain alkyl or-X
2-Sp
2-P
2, wherein:
X
2System is independent to be-O-,-S-,-OCH
2-,-CO-,-COO-,-OCO-,-CO-NR-,-NR-CO-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OOC-CH=CH-or singly-bound; And
Sp
2System is independent to be spacer groups or single group.
11. liquid crystal compound as claimed in claim 1, wherein this liquid crystal molecule system comprises the compound as shown in the formula one of (4), (5) and (6) and (7):
R wherein
1, R
2, R
3, R
4And R
6System is independent of having the alkyl of 1 to 12 carbon atom, its 1 or 2 non-conterminous CH
2Group can be in addition by-O-,-CH=CH-,-CO-,-OCO-or-COO-replaces, and Sauerstoffatom direct bond each other not;
R
5It is thiazolinyl with 2 to 8 carbon atoms;
D is 0 or 1;
12. liquid crystal compound as claimed in claim 1 further includes at least a polymerization initiator.
13. the making method of a display panels includes:
Upper substrate and hypocoxa are provided;
Around this upper substrate and this hypocoxa facing surfaces, form frame glue respectively, and filling liquid crystal compound in this frame glue between this upper substrate and this hypocoxa; And
Carry out polymerization alignment manufacture process;
Wherein this liquid crystal compound system includes:
At least a liquid crystal molecule;
At least a response type monomer; And
A kind of inhibitor, its weight concentration are that this response type is monomeric 0.01～1%, and this inhibitor system comprises at least a compound as shown in the formula (1):
14. method as claimed in claim 13, wherein this liquid crystal compound system inject processing procedure or liquid crystal drip-injection processing procedure by liquid crystal and filling between this upper substrate and this hypocoxa.
15. method as claimed in claim 14 further is included between this upper substrate and this hypocoxa after this liquid crystal compound of filling, carries out frame glue sclerosis processing procedure.
16. method as claimed in claim 15 wherein when carrying out this frame glue sclerosis processing procedure, can consume this inhibitor to avoid this response type monomer polymerization reaction take place.
17. method as claimed in claim 13, wherein this polymerization alignment manufacture process system utilizes voltage to make this liquid crystal deflecting element to predetermined angular.
18. method as claimed in claim 17, wherein this polymerization alignment manufacture process system utilizes this display panels of energy rayed, makes the predetermined angular polymerization of this response type monomer along liquid crystal molecule, and makes this liquid crystal molecule produce tilt angle.
19. method as claimed in claim 18, wherein this polymerization alignment manufacture process comprises the illumination energy that increases this energy light, to consume the inhibitor in this liquid crystal compound.
20. method as claimed in claim 19 wherein increases the method for the illumination energy of this energy light, comprises the energy intensity that improves this energy light or increases time of this this display panels of energy rayed.
21. method as claimed in claim 13, wherein this response type monomer is photopolymerization or heat polymerization type monomer.
22. method as claimed in claim 21, wherein this response type monomer comprises the compound as shown in the formula (2) or (3):
P wherein
1System is independent to be polymer-based group, includes vinylformic acid (ester) base or methacrylic acid (ester) base independently, SP
1System is independent to be spacer groups or single group, X
1System is independent to be-O-,-S-,-OCH
2-,-CO-,-COO-,-OCO-,-CO-NR-,-NR-CO-,-OCH
2-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OCC-CH=CH-or singly-bound, L
mSystem is independent to be fluorine, chlorine, cyanogen or alkyl, alkyl carbonyl, carbalkoxy or the alkane carbonyl oxygen base with 1 to 7 carbon atom, and m works as L more than or equal to 1
mDuring for alkyl with 1 to 7 carbon atom, alkyl carbonyl, alkoxy carbonyl or alkane carbonyl oxygen base, its one or more hydrogen atoms can be replaced by the fluorine or chlorine atom.
23. liquid crystal compound as claimed in claim 22, wherein R system is independent is-H ,-F ,-Cl ,-CN ,-SCN ,-SF
5H ,-NO
2, have the strand of 1 to 12 carbon atom or branched-chain alkyl or-X
2-Sp
2-P
2, wherein:
X
2System is independent to be-O-,-S-,-OCH
2-,-CO-,-COO-,-OCO-,-CO-NR-,-NR-CO-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OOC-CH=CH-or singly-bound; And
Sp
2System is independent to be spacer groups or single group.
24. method as claimed in claim 13, wherein this liquid crystal molecule system comprises the compound as shown in the formula (4), (5) or (6) and (7):
R wherein
1, R
2, R
3, R
4And R
6System is independent of having the alkyl of 1 to 12 carbon atom, its 1 or 2 non-conterminous CH
2Group can be in addition by-O-,-CH=CH-,-CO-,-OCO-or-COO-replaces, and oxygen (O) atom direct bond each other not;
R
5It is thiazolinyl with 2 to 8 carbon atoms;
D is 0 or 1;
25. method as claimed in claim 13, wherein this liquid crystal compound also includes at least a polymerization initiator.
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