CN100498386C - Transparent substrate with optical compensation function and its LCD device - Google Patents

Transparent substrate with optical compensation function and its LCD device Download PDF

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CN100498386C
CN100498386C CNB2006101452482A CN200610145248A CN100498386C CN 100498386 C CN100498386 C CN 100498386C CN B2006101452482 A CNB2006101452482 A CN B2006101452482A CN 200610145248 A CN200610145248 A CN 200610145248A CN 100498386 C CN100498386 C CN 100498386C
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transparency carrier
optical compensation
compensation function
described transparency
thickness
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CN101191859A (en
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田宏隆
吕奇明
张含章
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Industrial Technology Research Institute ITRI
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Abstract

The invention relates to a transparent substrate having optical compensation function, comprising polyimide with the formula on the right, wherein the A and A' are cyclo-aliphatic compounds or aromatic compounds; B and B' are cyclo-aliphatic compounds or aromatic compounds; and nx is equal to ny and more than nz, which means provides the invention with controlled negative c-plate compensation function, wherein the nx represents the transverse refractive index of the transparent substrate, ny represents the longitudinal refractive index of the transparent substrate, nz represents the refractive index along the thickness of the transparent substrate, and m and n is between 10 and 10000.

Description

Transparency carrier and LCD thereof with optical compensation function
Technical field
The invention relates to a kind of transparency carrier and LCD thereof, particularly about a kind of transparency carrier and LCD thereof with regulatable type minus c-plate phasic difference compensate function with optical compensation function.
Background technology
But flexible display is light, thin, shock-resistant because of having, be difficult for excellent characteristics such as broken, easy to carry curved surface demonstration, coiling and wearing property, and volume to volume (roll-to-roll) mode is produced continuously, so can reduce production costs greatly, therefore become the new trend of new generation display development.In order to meet active thin film transistor (TFT) (thin filmtransistor, TFT) harsh process conditions, the tool height is heat-resisting, the flexible base plate developing material of low thermal coefficient of expansion and high resistance to chemicals medicine, will be the important key factor of the new flexible display from generation to generation of influence development.
Present existing optical-grade plastic baseplate material comprises that tygon terephthalic acid (TPA) fat (PET), poly-dioctyl phthalate glycol ester (PEN), polycarbonate (PC), m-COC (Arton or Zeonor) are though be commercial product, but because of its glass transition temperature (Tg) less than 200 ℃, therefore operating temperature is limited, can't be applicable to the process conditions that active thin film transistor (TFT) is harsh.Polyethersulfone (PES) though the glass transition temperature can reach 225 ℃, its poor solvent resistance, and after high temperature (200 ℃) operation a period of time, have the phenomenon of embrittlement to take place.
Though existing high temperature resistant and solvent-proof pi plastic base can meet existing process conditions,, use so only be suitable for the reflective liquid-crystal display panel, and be not suitable for being used in the penetrating LCD panel because of its baseplate material is a dark brown.In addition; LCD is to utilize liquid crystal molecule that light is had optical activity; cooperate up and down two Polarizers to reach the display effect of light and shade; but the character that also has birefraction because of liquid crystal molecule itself; produce so apply to the problem that display panel has light leak often, cause the visual angle limited with problem such as contrast differences.In addition, reaching wide viewing angle is the outer optical compensation films that pastes with the straightforward procedure that promote to show contrast.Yet pasting optical compensation films outward not only increases manufacturing cost, makes that also the processing procedure of bendable LCD is complicated.
Summary of the invention
The invention provides a kind of transparency carrier with regulatable type minus c-plate phasic difference compensate function, it can be applicable to bendable liquid crystal flat panel display and reduces outer cost of manufacture of pasting view film.
Transparency carrier with optical compensation function of the present invention comprises the pi with following chemical formula:
Figure C200610145248D00071
Wherein A and A ' are ring-shaped fat compounds of group or aromatics, and B and B ' are ring-shaped fat compounds of group or aromatics, and its n x=n yN z, just have regulatable type minus c-plate phasic difference compensate function, wherein n xThe lateral refraction rate of representing described transparency carrier, n yThe longitudinal refractive index of representing described transparency carrier, n zThe thickness direction refractive index of representing described transparency carrier, m and n are between 10 to 10,000.
LCD of the present invention comprises a transparency carrier, with optical compensation function and is arranged at the Polarizer of first surface of described transparency carrier and the liquid crystal material that is arranged at the second surface of described transparency carrier.Described transparency carrier comprises pi, and it has following chemical formula:
Wherein A and A ' are ring-shaped fat compounds of group or aromatics, and B and B ' are ring-shaped fat compounds of group or aromatics, and its n x=n yN z, n xThe lateral refraction rate of representing described transparency carrier, n yThe longitudinal refractive index of representing described transparency carrier, n zThe thickness direction refractive index of representing described transparency carrier, m and n are between 10 to 10,000.
The present invention utilizes diamine or bisgallic acid anhydride monomer with annular aliphatic structure to cooperate aromatic series bisgallic acid acid anhydride or diamine to form water white pi constituent through condensation reaction.Owing to import the annular aliphatic structure, make pi of the present invention be different from general traditional pi, have high transparent and colourless characteristic.Particularly, water white transparency pi of the present invention has the effect of its optical compensation value of regulation and control, therefore is suitable as the baseplate material of bendable plastic displays.
Description of drawings
The synthetic method of Fig. 1 and Fig. 2 illustration pi;
The molecular structure of the pi membraneous material of Fig. 3 and Fig. 4 illustration comparative example of the present invention;
The molecular structure of the pi membraneous material of Fig. 5 to Figure 10 view similar; And
Figure 11 illustration LCD of the present invention.
Embodiment
The synthetic of pi is a typical polycondensation reaction (polycondensation), its synthetic method has two kinds: first method is to be divided into two stages to carry out, at first diamine (diamine) and bisgallic acid acid anhydride (dianhydride) monomer are reacted in polar solvent, form precursor (precursor) polyamic acid (poly (amic acid) of pi, PAA), carry out inferior amidation (imidization) reaction through high-temperature baking (300 to 400 ℃) again, make its dehydration endless loop transform into pi, as shown in Figure 1.The diamine monomer can use 4,4 '-oxygen base diphenylamine (4,4 '-oxydianiline, ODA), the bisgallic acid anhydride monomer can use two ring [2.2.2] suffering-7-alkene-2,3,5, and the two acid anhydrides of 6-tetracarboxylic acid (bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, B1317), polar solvent can use N-methyl pyrrolidone (N-methy1-2-pyrrolidone, NMP) or dimethyl acetamide (N, N-dimethylacctamide, DMAc).
The second way is a chemical method, and diamine and bisgallic acid anhydride monomer are reacted in the phenol solvent, and is warming up to reflux temperature and carries out polyamic acid reaction, carries out inferior amidation process simultaneously, makes its dehydration endless loop transform into pi, as shown in Figure 2.The diamine monomer can use 4,4 '-oxygen base diphenylamine, the bisgallic acid anhydride monomer can use 4,4 '-oxygen base diphenylamine, the phenol solvent can use metacresol (m-cresol) or phenol (phenol).
Transparency carrier of the present invention comprises pi, and it has following chemical formula:
A and A ' are ring-shaped fat compounds of group or aromatics, and B and B ' are ring-shaped fat compounds of group or aromatics, and m and n are preferably between 10 to 10, between 000, wherein the molecular weight of pi is preferably between 3,000～500, between the 000 gram/mole.Particularly, A can be same or different from A ', and B can be same or different from B '.
B and B ' can be aromatics, for example:
Figure C200610145248D00082
Or
B and B ' also can be the ring-shaped fat compounds of group, for example:
Figure C200610145248D00084
Or
Figure C200610145248D00085
A and A ' can be the ring-shaped fat compounds of group, for example:
Figure C200610145248D00091
Or
Figure C200610145248D00092
A and A ' can be aromatics, for example:
Figure C200610145248D00094
Or
Figure C200610145248D00095
X and Y are hydrogen, methyl, trifluoromethyl, hydroxyl, C 1-18Alkyl, bromine, chlorine or iodine, Z is-O ,-CH 2-,-S-,-SO 2-,-C (CH 3) 2-,-Ar-O-Ar-,-Ar-CH 2-Ar-,-O-Ar-C (CH 3) 2-Ar-O-,-O-Ar-Ar-O-,-O-Ar-C (CF 3) 2-Ar-O-or-Ar-C (CH 3) 2-Ar-, wherein Ar is a phenyl ring.
Comparative example one: 6FDA-TFMB (PI-FT)
At room temperature, use three-necked bottle and pass to nitrogen, with 2 of 4.5 grams (g), 2 '-two (trifluoromethyl) biphenylamine (2,2 '-bis (trifluoromethyl) benzidine, TFMB) dianiline dissolves among the DMAc of 28g, treat TFMB dissolve fully after again with 2 of 3.18g, 2 '-two-(3,4-dicarboxyl phenyl) hexafluoropropane dianhydride (2,2 '-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6FDA) add, after 6FDA dissolves fully, continue to stir 3 hours. and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structure as shown in Figure 3.
Comparative example two: B1317-BAPB-co-B1317-BAPPm (PI-BAB)
At room temperature, use three-necked bottle and pass to nitrogen, with 4 of 3.05g, two (the 4-amido phenoxy group) biphenyl (4 of 4-, 4-Bis (4-aminophenoxy) biphenyl, BAPB) and 1.46g 4, two (the 4-amido phenoxy group) propane (4 of 4-, 4-Bis (4-aminophenoxy) propane, BAPPm) diamine dissolves among the DMAc of 30g, treat that BAPB and BAPPm dissolve fully after, B1317 bisgallic acid acid anhydride with 3g adds then, after B1317 dissolves fully, continue to stir 3 hours, and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structural formula as shown in Figure 4.
Embodiment one: 6FDA-m-TB-HG-co-6FDA-DACH (PI-FTD)
At room temperature, use three-necked bottle and pass to nitrogen, with 2.2 of 1.64g '-dimethyl-4-4 '-diamines biphenyl (2,2 '-Dimethyl-4,4 '-diamino biphenyl, m-TB-HG) and 0.70g 4,4-dimethylene-two-cyclohexylamine (4,4-methylene bis (cyclohexylamine), DACH) dissolve among the DMAc of 30g, treat again the 6FDA bisgallic acid acid anhydride of 5g to be added after m-TB-HG and DACH dissolve fully, after 6FDA dissolves fully, continue to stir 3 hours, and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structure as shown in Figure 5.
Embodiment two: 6FDA-ODA-co-6FDA-DACH (PI-FOD)
At room temperature, use three-necked bottle and pass to nitrogen, the ODA of 1.10g and the DACH dianiline of 1.16g are dissolved among the DMAc of 30g, treat again the 6FDA bisgallic acid acid anhydride of 5g to be added after ODA and DACH dissolve fully, after 6FDA dissolves fully, continue to stir 3 hours, and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structure as shown in Figure 6.
Embodiment three: 6FDA-DACH-co-DSDA-DACH (PI-FSD-I)
At room temperature, use three-necked bottle also to pass to nitrogen, the DACH dianiline of 2.49g dissolved among the DMAc of 30g, treat DACH dissolve fully after again with 3 of the 6FDA of 3.5g and 1.5g, 3 ', 4,4 '-diphenyl sulfone tetracarboxylic dicarboxylic anhydride 4,4-disulfonyldiphthalic anhydride, DSDA) add, after 6FDA and DSDA dissolve fully, continue to stir 3 hours, and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structure as shown in Figure 7.
Embodiment four: 6FDA-DACH-co-DSDA-DACH (PI-FSD-II)
At room temperature, use three-necked bottle and pass to nitrogen, the DACH dianiline of 2.60g is dissolved among the DMAc of 30g, treat again the 6FDA of 2.5g and the DSDA bisgallic acid acid anhydride of 2.5g to be added after DACH dissolves fully, after 6FDA and DSDA dissolve fully, continue to stir 3 hours, and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structure as shown in Figure 8.
Embodiment five: 6FDA-DACH-co-DSDA-DACH (PI-FSD-III)
At room temperature, use three-necked bottle and pass to nitrogen, the DACH dianiline of 2.71g is dissolved among the DMAc of 30g, treat again the 6FDA of 1.5g and the DSDA bisgallic acid acid anhydride of 3.5g to be added after DACH dissolves fully, after 6FDA and DSDA dissolve fully, continue to stir 3 hours, and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structure as shown in Figure 9.
Embodiment six: B1317-BAPPm-co-B1317-DACH (PI-BBD)
At room temperature, use three-necked bottle and pass to nitrogen, the DACH diamine of 1.4g is dissolved among the DMAc of 31g, after treating that DACH dissolves fully, then the BAPPm diamine of 2.84g is added, treat that BAPPm dissolves fully after, B1317 bisgallic acid acid anhydride with 3.5g adds again, after B1317 dissolves fully, continue to stir 3 hours, and form thick polyamic acid solution.Then with the scraper film forming on glass substrate, through being heated to after 100 ℃, 200 ℃ and 300 ℃ baking in each 1 hour carries out inferior amidation process, form the pi membraneous material of high clear, colorless again, its molecular structure as shown in figure 10
Table one: the characteristic of transparent pi
Figure C200610145248D00111
Tg represents the glass transition temperature; CTE represents thermal expansivity; Rth represents the light sluggishness.Rth={ (n x+ n y)/2-n z} * d, d represent the thickness of transparency carrier.n xThe lateral refraction rate of representing described transparency carrier, n yThe longitudinal refractive index of representing described transparency carrier, n zThe thickness direction refractive index of representing described transparency carrier.
Transparency carrier of the present invention has n x=n yN zOptical characteristics, just have minus c-plate phasic difference compensate function.The thickness of transparency carrier of the present invention can be between 30 to 200 microns, preferably between 50 to 150 microns.Particularly, the Rth value of the transparency carrier that the embodiment of the invention is synthesized (PI-FTD, PI-FOD, PI-FSD-I, PI-FSD-II, PI-FSD-III and PI-BBD) is between 50 to 400 nanometers, preferably between 100 to 250 nanometers.Relatively, the Rth value of embodiment and other conventional macromolecules (Kapton and Ube) is all quite big, can't be as the baseplate material of bendable plastic displays.In addition, though conventional PES material has good mist degree, penetration and yellow index, but it does not have an optical compensation function and its glass transition temperature (only having 225 ℃) is too low and elching resistant is poor, therefore can't be applied to the high temperature process of LCD, be not suitable as the baseplate material of LCD.
The compositing formula of transparency carrier of the present invention can be following combination:
1. aromatic series bisgallic acid acid anhydride and aromatic series diamine and annular aliphatic diamine are according to the co-polymer of different proportion formation;
2. aromatic series bisgallic acid acid anhydride and annular aliphatic bisgallic acid acid anhydride and annular aliphatic diamine are according to the co-polymer of different proportion formation;
3. annular aliphatic bisgallic acid acid anhydride and aromatic series diamine are according to the co-polymer of different proportion formation;
4. annular aliphatic bisgallic acid acid anhydride and aromatic series diamine and annular aliphatic diamine are according to the co-polymer of different proportion formation.
Figure 11 illustration LCD 10 of the present invention, it comprises two substrates 12, a plurality of gap son 13 and liquid crystal material 14, and wherein said substrate 12 comprises a transparency carrier 11 and a Polarizer 20.Described Polarizer 20 is the first surface 11A that are arranged at described transparency carrier 11, and described a plurality of gaps 13 is the second surface 11B that are arranged at described transparency carrier 11, and described liquid crystal material 14 is to be arranged between described a plurality of gaps 13.Described Polarizer 20 comprises two layer 22A and 22B and and is sandwiched in polarizing layer 24 between described two layer 22A and 22B.Described layer 22A and 22B can (Triacetyl cellulose TAC) constitutes, and described polarizing layer 24 is that (Poly vinylalcohol PVA) constitutes by polyvinyl alcohol (PVA) by triacetate fiber.Transparency carrier 11 of the present invention itself promptly has optical compensation function, thereby can save outer manufacturing cost of pasting optical compensation films.In addition, transparency carrier 11 of the present invention has high transparent, high-fire resistance and high chemical resistance, satisfies the optics of LCD and the requirement of process conditions.Particularly, transparency carrier 11 of the present invention directly film forming on existing glass substrate, must do not fixed as the conventional resin viscose glue that must see through, can take off easily behind its multiple tracks gold-tinted, the etch process (or through specific water bath processing) through Thin Film Transistor-LCD, the problem that does not have residual viscose is obviously simplified the processing procedure of Thin Film Transistor-LCD.In addition, pi baseplate material of the present invention also can be applicable to comprise among flexible displays such as soft LCD, PDP, FED, SED, E-ink or E-Paper and the OLED.
The present invention utilizes diamine or bisgallic acid anhydride monomer with annular aliphatic structure to cooperate aromatic series bisgallic acid acid anhydride or diamine to form water white pi constituent through condensation reaction.Owing to import the annular aliphatic structure, make synthetic pi be different from general traditional pi, have high transparent and colourless characteristic.Particularly, the water white transparency pi that the present invention synthesizes has the effect of its optical compensation value of regulation and control, therefore is applicable to the baseplate material of bendable plastic displays.
Technology contents of the present invention and technical characterstic disclose as above, yet one of ordinary skill in the art still may be based on teaching of the present invention and announcements and done all replacement and modifications that does not deviate from spirit of the present invention.Therefore, protection scope of the present invention should be not limited to those disclosed embodiments, and should comprise various do not deviate from replacement of the present invention and modifications, and is contained by following claim.

Claims (20)

1. transparency carrier with optical compensation function is characterized in that comprising the pi with following chemical formula:
Figure C200610145248C00021
Wherein A and A ' are ring-shaped fat compounds of group or aromatics, and B and B ' are ring-shaped fat compounds of group or aromatics, and its n x=n yN z, n xThe lateral refraction rate of representing described transparency carrier, n yThe longitudinal refractive index of representing described transparency carrier, n zThe thickness direction refractive index of representing described transparency carrier, m and n are between 10 to 10,000; And
The R of wherein said transparency carrier Th={ (n x+ n y)/2-n z} * d is that d represents the thickness of described transparency carrier between 50 to 400 nanometers.
2. the transparency carrier with optical compensation function according to claim 1, the thickness that it is characterized in that described transparency carrier is between 30 to 200 microns.
3. the transparency carrier with optical compensation function according to claim 1, the thickness that it is characterized in that described transparency carrier is between 50 to 150 microns.
4. the transparency carrier with optical compensation function according to claim 1 is characterized in that the R of described transparency carrier Th={ (n x+ n y)/2-n z} * d is that d represents the thickness of described transparency carrier between 100 to 250 nanometers.
5. the transparency carrier with optical compensation function according to claim 1 is characterized in that A and A ' are selected from:
Figure C200610145248C00022
Or
Figure C200610145248C00023
6. the transparency carrier with optical compensation function according to claim 1 is characterized in that A and A ' are selected from:
Figure C200610145248C00024
Figure C200610145248C00031
Figure C200610145248C00032
Or X and Y are hydrogen, methyl, trifluoromethyl, hydroxyl, C1-18 alkyl, bromine, chlorine or iodine, Z is-O-,-CH2-,-S-,-SO2-,-C (CH3) 2-,-Ar-O-Ar-,-Ar-CH2-Ar-,-O-Ar-C (CH3) 2-Ar-O-,-O-Ar-Ar-O-,-O-Ar-C (CF3) 2-Ar-O-or-Ar-C (CH3) 2-Ar-, wherein Ar is a phenyl ring.
7. the transparency carrier with optical compensation function according to claim 1 is characterized in that B and B ' are selected from:
Or
Figure C200610145248C00035
8. the transparency carrier with optical compensation function according to claim 1 is characterized in that B and B ' are selected from:
Or
Figure C200610145248C00037
9. the transparency carrier with optical compensation function according to claim 1, the molecular weight that it is characterized in that pi is between 3,000～500, between the 000 gram/mole.
10. LCD is characterized in that comprising:
One has the transparency carrier of optical compensation function, comprises the pi with following chemical formula:
Figure C200610145248C00038
Wherein A and A ' are ring-shaped fat compounds of group or aromatics, and B and B ' are ring-shaped fat compounds of group or aromatics, and its n x=n yN z, n xThe lateral refraction rate of representing described transparency carrier, n yThe longitudinal refractive index of representing described transparency carrier, n zThe thickness direction refractive index of representing described transparency carrier, m and n are between 10 to 10,000:
One Polarizer is arranged at the first surface of described transparency carrier; And
Liquid crystal material is arranged at the second surface of described transparency carrier;
And the R of wherein said transparency carrier Th={ (n x+ n y)/2-n z} * d is that d represents the thickness of described transparency carrier between 50 to 400 nanometers.
11. LCD according to claim 10, the thickness that it is characterized in that described transparency carrier is between 30 to 200 microns.
12. LCD according to claim 10, the thickness that it is characterized in that described transparency carrier is between 50 to 150 microns.
13. LCD according to claim 10 is characterized in that the R of described transparency carrier Th={ (n x+ n y)/2-n z} * d is that d represents the thickness of described transparency carrier between 100 to 250 nanometers.
14. LCD according to claim 10 is characterized in that A and A ' are selected from:
Or
Figure C200610145248C00042
15. LCD according to claim 10 is characterized in that A and A ' are selected from:
Figure C200610145248C00044
Or
Figure C200610145248C00045
X and Y are hydrogen, methyl, trifluoromethyl, hydroxyl, C1-18 alkyl, bromine, chlorine or iodine, Z is-O-,-CH 2-,-S-,-SO 2-,-C (CH 3) 2-,-Ar-O-Ar-,-Ar-CH 2-Ar-,-O-Ar-C (CH 3) 2-Ar-O-,-O-Ar-Ar-O-,-O-Ar-C (CF 3) 2-Ar-O-or-Ar-C (CH 3) 2-Ar-, wherein Ar is a phenyl ring.
16. LCD according to claim 10 is characterized in that B and B ' are selected from:
Figure C200610145248C00046
Or
17. LCD according to claim 10 is characterized in that B and B ' are selected from:
Or
Figure C200610145248C00052
18. LCD according to claim 10 is characterized in that described Polarizer comprises two supporting layers and and is sandwiched in polarizing layer between described two supporting layers.
19. LCD according to claim 18 it is characterized in that described supporting layer is to be made of triacetate fiber, and described polarizing layer is to be made of polyvinyl alcohol (PVA).
20. LCD according to claim 10, the molecular weight that it is characterized in that pi is between 3,000～500, between the 000 gram/mole.
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