CN101074379A - Liquid-crystal composition - Google Patents

Liquid-crystal composition Download PDF

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CN101074379A
CN101074379A CN 200710024320 CN200710024320A CN101074379A CN 101074379 A CN101074379 A CN 101074379A CN 200710024320 CN200710024320 CN 200710024320 CN 200710024320 A CN200710024320 A CN 200710024320A CN 101074379 A CN101074379 A CN 101074379A
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liquid crystal
crystal composition
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CN101074379B (en
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张宏伟
谭玉东
李奕飞
朱霞
吴凤
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Jiangsu Hecheng Display Technology Co Ltd
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JIANGSU HECHENG CHEMICAL MATERIALS CO Ltd
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Abstract

A liquid-crystal composite with ultra-high clear luminous point, excellent refractive index, anisotropy and temperature reliability and its use in first polarized small TN light valve product are disclosed. It obtains liquid-crystal composition from four kinds liquid-crystal compounds by optimized combination and proportion, clear luminous point reaches to 125-150 degree, refractive index anisotropy decreased below 10% with temperature reliability. It has better chemical stability. Additive 0.05-10% is added into liquid-crystal composite. It can be used as liquid-crystal material of first polarized small liquid-crystal display device or light valve parts.

Description

Liquid crystal composition
Technical Field
The invention relates to a liquid crystal composition with extremely high clearing point and good temperature dependence of refractive index anisotropy, and application thereof in first extremely-small TN and light valve products.
Background
The liquid crystal material is a mixture of some organic rodlike small molecular compounds which have liquid fluidity and crystal anisotropy at a certain temperature, the liquid crystal material is filled between liquid crystals of two substrates plated with transparent electrodes, liquid crystal molecules can be arranged in a certain direction under the induction of an orientation layer, a twist angle of 22.5-720 degrees is formed between the two substrates, and under a certain voltage, the light transmission is changed due to the change of the orientation of the liquid crystal molecules, and various products such as liquid crystal displays or light valves and the like can be manufactured by utilizing the special light modulation function of the liquid crystal material. In recent years, liquid crystal materials have been widely used in the technical fields of microelectronics, optoelectronic information, display, communication, and the like.
TN (i.e. Twisted Nematic) -LCDs are collectively known as Twisted Liquid Crystal displays, with twist angles of 45-150 deg.. Twisted Nematic (TN) displays are known from m.helfrich, appl.phys.lett., 18, 127 (1971). In the TN display mode, light transmission can be selected at two extreme points such as a first minimum (Δ n · d ═ 0.48 to 0.60) and a second minimum (Δ n · d ═ 1.00 to 1.20) (selection of the third minimum or more is not highly required for the extreme conditions). The second extremely small TN display is relatively simple in process manufacturing flow, relatively easy in process control, large in liquid crystal material selection range and common, but has the defects of poor contrast, incapability of performing black-and-white display, slow response, large bottom color change along with temperature change and the like; the first minimum TN display can overcome the above disadvantages to a great extent, and not only has good contrast and faster response, but also can display black and white.
Heretofore, the clearing point of the first extremely small mixed liquid crystal material was generally 120 ℃ or less, and the dependence of the refractive index anisotropy (-d.DELTA.n/.DELTA.n) on temperature20℃: a refractive index anisotropy change rate of 20 to 60 degrees) is higher than 12%. With the further expansion of the requirements of people on the performance of the display, the requirements on the working temperature range, the contrast ratio and the response speed are wider, and the requirements are more severe particularly in the applications of vehicle-mounted displays, outdoor working displays (electric meters), aerospace displays, light valves and the like. In order to satisfy such a severe condition, the mixed liquid crystal material is required to have a higher clearing point (temperature at which a nematic phase changes to isotropy) and a smaller temperature dependence of refractive index anisotropy. According to the TN display principle and the requirement of the first minimum extreme value condition, the first minimum mixed liquid crystal material must also meet the following basic performance requirements:
1. a refractive index anisotropy of 0.1200 or less so as to satisfy a condition that Δ n · d is 0.48 to 0.60;
2. the threshold voltage is lower so as to meet the energy-saving requirement and reduce the cost of a driving chip;
3. the threshold voltage has less dependence on temperature to meet wider operating temperature;
4. higher resistance and longer chemical stability to meet the requirement of longer life;
5. at least, no crystallization occurs when the film is stored (poured into a liquid crystal display) for more than 48 hours under a low-temperature environment of-10 ℃.
Since the optimization of the performance parameters of the mixed liquid crystal material is contradictory, and is restricted and influenced by each other, it is difficult to obtain a liquid crystal material having a high clearing point temperature and a low temperature dependence of refractive index anisotropy, and satisfying low refractive index anisotropy, low threshold voltage, temperature dependence and high stability.
Disclosure of Invention
The invention aims to provide a liquid crystal composition with high-definition bright point, super-wide temperature and refractive index anisotropy and low temperature dependence by optimized combination and optimized proportion of various liquid crystal compounds, which can overcome the contradiction of various properties of liquid crystal materials to the greatest extent and meet the requirements of first minimum TN displays or light valve products.
The liquid crystal composition comprises four types of liquid crystal compounds with general formulas I-IV, wherein the general formulas and the weight percentages of the compounds are as follows:
5% -50% of a class I liquid crystal compound:
Figure A20071002432000111
10-70% of a class II liquid crystalline compound:
Figure A20071002432000112
10-80% of a class III liquid crystal compound:
Figure A20071002432000121
1-40% of a class IV liquid crystal compound:
Figure A20071002432000122
in the formulae:
R1、R2: are each independently selected from C1~C7Alkyl, alkoxy or oxyalkyl or C2~C7Alkenyl, alkenyloxy or oxyalkenyl of (a);
x: selected from halogen or-CN, OCF3, OCHF2Or C1~C7Alkyl, alkoxy or oxyalkyl or C2~C7Alkenyl, alkenyloxy or oxyalkenyl of (a);
y: selected from halogen or-CN;
Z、Z1: each independently selected from the group consisting of a single bond, -COO-, -C2H4-、-CH2O-、-CH=CH-、-CF2O-or-C ≡ C-:
L1、L2: each independently selected from hydrogen or halogen;each independently represents phenyl, cyclohexane, dioxane, fluoro phenylene or difluoro phenylene, cyclohexenyl;
n, m: are each independently an integer of 0 or 1.
The compounds of the above classes I, II and III can reach:
a particularly high clearing point is achieved in that,
the low temperature dependence of the refractive index anisotropy,
a small anisotropy of the refractive index of the film,
low threshold voltage, drive voltage, and low temperature dependence.
In particular, the compounds of the formula I, II lead to a marked increase in the clearing point of the mixtures and a marked decrease in the temperature dependence of the refractive index anisotropy. I. The liquid crystal composition formed by the compatibility of II, III and IV has better chemical stability, and can overcome the contradiction of various properties of the liquid crystal material to the maximum extent, thereby meeting the requirements of the first minimum TN display or light valve product.
Preferred embodiments of compounds of class I are:
z is a single bond or-COO-;
is phenyl, cyclohexane, fluorophenylene or difluorophenylene,
Figure A20071002432000132
is phenyl, cyclohexane or difluorophenylene.
Among them, at least one compound represented by the following general formulae Ia to Ij is preferable:
Figure A20071002432000133
among them, at least one compound of the formulae Ic, If, Ig, Ih, Ii, Ij is preferred;
wherein particular preference is given to a compound of the formula Ih or/and Ij, and wherein R is1Is selected from C1~C7Alkyl or C2~C7Alkenyl radical, R2Is selected from C1~C7Alkyl radical, and R1And R2The sum of carbon numbers of (a) is 10 or less, specifically at least one compound of the following formulae Iha, Ihb, Ija, Ij.
Figure A20071002432000142
Preferred embodiments of class II compounds are:
L1in the case of F, the content of the compound,
L2is a compound of the formula H or F,
y is CN or F, and Y is CN or F,
Figure A20071002432000143
is phenyl, cyclohexane, fluorophenylene or difluorophenylene;
among them, at least one compound of the following formulae IIa to IIr is preferable:
Figure A20071002432000151
Figure A20071002432000161
wherein preferably at least one compound of the formulae IIa, IId, IIg, IIi, IIm, IIn, IIp or IIr,
particular preference is given to at least one compound of the formulae IIa, IIi, IIn, IIp or IIr, particularly preferably from 1 to 4 compounds.
The preferred scheme of the class III liquid crystal compound is as follows:
z is a single bond, -COO-, -C2H4-, -CH ═ CH-or CF2O,
Z1Is a single bond, and is a single bond,
l1 is H or halogen, when X is F, L1Also referred to as F, is a linear movement,is a phenyl group or a cyclohexane group,
among them, at least one compound of the following general formulae IIIa to IIInk is preferable:
among them, at least one compound of the formulae IIIa, IIIb, IIIc, IIIg, IIIi, IIIm, IIIn is preferable, and 1 to 4 compounds of the formulae IIIa, IIIc, IIIi, IIIm, IIIn are particularly preferable.
The preferable scheme of the IV compound is as follows:
z is a single bond or-CH ═ CH-,
n=1,
is phenyl, cyclohexane or cyclohexenyl.
Among these, at least one compound of the following formulae IVa to IVd is preferred:
Figure A20071002432000182
among these, preference is given to at least one compound selected from IVa and IVb, IVd, particular preference to at least one compound selected from IVb, IVd, and very particular preference to 1 to 2 compounds of these
Preferred contents of the various compounds are:
10-40% of I compound, 20-50% of II compound, 15-60% of III compound and 1-30% of IV compound.
Particularly preferred contents are:
10-35% of I compound, 30-50% of II compound, 20-40% of III compound and 5-20% of IV compound.
The liquid crystal composition obtained by optimally combining and proportioning a large amount of known liquid crystal compounds can reach a clearing point of 125-150 ℃, and meanwhile, the dependence of refractive index anisotropy along with temperature is reduced to below 10 percent.
The liquid crystal composition of the present invention can be used as a liquid crystal material in a first very small liquid crystal display or a light valve device. Adding an additive accounting for 0.05-10% of the weight of the liquid crystal composition, mixing and filling the mixture between two substrates of a TN liquid crystal display or a light valve device, wherein the additive is selected from the following C15-R/S2011 type compounds, and the left sides of the following chemical structural formulas are respectively the commodity models of the additives.
Figure A20071002432000191
The liquid-crystal mixtures according to the invention can be prepared in a conventional manner. In general, the smaller component present therein is dissolved in the larger main component present therein at an advantageously elevated temperature, or a solution of the components in an organic solvent, such as acetone, chloroform or methanol, is mixed and after thorough mixing the solvent is removed, for example by distillation.
In the context of the present invention, all temperatures are degrees celsius and all percentages are percentages by weight, unless otherwise indicated.
Detailed Description
It should be noted that the examples are for illustrating the present invention and do not represent a limitation.
The liquid crystal display used for testing the application of the liquid crystal composition was composed of a polarizer (polarizer), an electrode substrate and a surface-treated electrode, that is, containing: two substrates plated with transparent electrodes, the surfaces of the electrodes are coated with high polymer orientation layers, after special treatment, the surfaces of the orientation layers can enable liquid crystal molecules to be arranged according to a certain direction, 90-degree twist is formed between the two substrates, and the liquid crystal composition (namely, nematic mixed liquid crystal material) of the invention is filled between the two substrates.
In the following examples, the group structures of the liquid crystal compounds are represented by the codes listed in Table 1:
TABLE 1 radical structural code of liquid crystal compounds
Figure A20071002432000201
The formula corresponding to the code listed in Table 1 can be expressed as nAEPAm, n and m in the code are respectively expressed by the C number of alkyl, when n is 3 and m is 2, the formula represents alkyl R1is-C3H7Alkyl radical R2is-C2H3(ii) a The code for this liquid crystal compound was therefore 3AAEPA5 (as in column 1 compound of Table 3-1). The structures of the liquid crystal compounds listed in the remaining tables are analogized according to the codes in Table 1.
Figure A20071002432000211
The shorthand codes of the test items in the following examples are respectively expressed as:
TN I (. degree. C.) clearing Point (nematic-isotropic phase transition temperature)
Visc flow viscosity (mm)2/s-120 ℃ unless otherwise stated),
no ordinary refractive index (589nm, 20 ℃ C.)
Δ n optical anisotropy (589nm, 20 ℃ C.)
no ordinary refractive index (589nm, 60 ℃ C.)
Δ n optical anisotropy (589nm, 60 ℃ C.)
dΔn/Δn20℃% refractive index dependence on temperature (Δ n)20℃-Δn60℃)/Δn20℃*100%
a (V10/V90-1) · 100 (%) characteristic line steepness Vsat/Vth,
v90, 0, 25(V) threshold voltage (normally white mode) which is the characteristic voltage at 90% relative contrast
V10, 0, 25(V) characteristic voltage at 10% relative contrast (normally white mode)
Wherein,
measurement of threshold voltage V (90, 0, 25) value and characteristic line steepness a value: the mixed liquid crystal material is poured into a liquid crystal display in a vacuum suction mode and is driven by square waves (100Hz), and the test temperature is 25 +/-2 ℃;
the flow viscosity Visc was measured using a cone and plate viscometer;
the refractive index and the refractive index anisotropy were measured using an Abbe refractometer under a sodium lamp (589nm) light source at 20 ℃ and 60 ℃.
Tables 2-1 and 2-2 show the components, ratios and performance test results of the liquid crystal composition of the comparative example filled between two substrates of the liquid crystal display for comparison with the liquid crystal composition of the present invention.
TABLE 2-1 COMPARATIVE EXAMPLE COMPOSITION AND MIXTURE
Liquid crystal compound (indicated by code) parts by weight
3AAEPA3 3
3AAEPA5 3
2PEBN 5
3PEBN 4
4PEBN 5
5PEBN 5
3AAEPF 5
3AAEBF 5
3AAEMF 5
4AAEMF 5
3AMN 10
3AABF 10
4AABF 10
7AABF 10
3AAP1 9
5AAV 6
Additive S8110.1
Table 2-2 comparative examples performance test data
Test item data
TN I(℃) 100.0
Δn(589nm,20℃) 0.1001
ne(589nm,20℃) 1.5868
no(589nm,20℃) 1.4857
Δn(589nm,60℃) 0.0871
ne(589nm,60℃) 1.5648
no(589nm,60℃) 1.4777
dΔn/Δn20℃% 12.99
Viscosituy(mm2s-1,20℃) 30.0
V90,0,25(V) 1.27
(V10/V90-1)·100(%) 50
Example one
The liquid crystal compounds, additives and corresponding parts by weight of the mixed liquid crystal materials listed in Table 3-1 were filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in Table 3-2.
TABLE 3-1
Liquid crystal compound (indicated by code) parts by weight
3AAEPA2 6
3AAEPA4 6
3APEMN 13
3AAEMF 8
4AAEMF 9
5AAEMF 8
3AABF 5
4AABF 5
5AABF 5
5AAV 6
V2AAP1 9
V2AABF 7
5AEMN 9
4AAEAA3 2
5AAEAA3 2
Additive S8110.1
TABLE 3-2
Test item data
TN I(℃) 149.3
Δn(589nm,20℃) 0.0964
ne(589nm,20℃) 1.5798
no(589nm,20℃) 1.4834
Δn(589nm,60℃) 0.0894
ne(589nm,60℃) 1.5644
no(589nm,60℃) 1.475
dΔn/Δn20℃% 7.26
Viscosity(mm2s-1,20℃) 35.6
V90,0,25(V) 1.297
(V10/V90-1)·100(%) 50
Example two
The components and the formulation of the mixed liquid crystal material are shown in the table 4-1, and the performance test results are shown in the table 4-2.
TABLE 4-1
Liquid crystal compound (indicated by code) parts by weight
3AAEPA2 5
3AAEPA4 5
3APEMN 13
3AAEMF 8
4AAEMF 7
5AAEMF 8
3AABF 5
4AABF 5
5AABF 5
5AAV 6
V2AAP1 9
V2AABF 7
4AA3 9
4AAEAA3 3
5AAEAA3 3
3AMN 2
Additive S8110.1
TABLE 4-2
Test item data
TN I(℃) 149.7
Δn(589nm,20℃) 0.0906
ne(589nm,20℃) 1.5741
no(589nm,20℃) 1.4835
Δn(589nm,60℃) 0.0858
ne(589nm,60℃) 1.5592
no(589nm,60℃) 1.4734
dΔn/Δn20℃% 5.30
Viscosity(mm2s-1,20℃) 27
V90,0,25(V) 1.524
(V10/V90-1)·100(%) 50
As can be seen from the test data of the above examples one and two, the clearing point of the liquid crystal composition is more than 149 degrees, which is 49 degrees higher than that of the control example; the rate of change of the refractive index anisotropy with temperature was 7.26%, 5.30%, which was reduced by nearly 50% or more as compared with 12.99% of the comparative example. Therefore, LCD products using the two examples of liquid crystal compositions can be used at higher operating temperatures and displays can provide better contrast; the light valve products adopting the two liquid crystal compositions have more stable reflected or transmitted light wavelength at different temperatures.
EXAMPLE III
The components and the proportion of the mixed liquid crystal material are shown in the table 5-1, and the results of various performance tests are shown in the table 5-2.
TABLE 5-1
Liquid crystal compound (indicated by code) parts by weight
3AAEPA2 6
3AAEPA4 8
5AEMN 10
3AAEMF 10
4AAEMF 5
5AAEMF 10
5AAV 5
V2AAP1 9
V2AABF 10
3AABF 5
4AABF 5
5AABF 5
3MEBN 5
4MEBN 2
2PEBN 2
5APF 3
Additive S8110.1
TABLE 5-2
Test item data
TN I(℃) 123.1
Δn(589nm,20℃) 0.0912
ne(589nm,20℃) 1.5734
no(589nm,20℃) 1.4822
Δn(589nm,60℃) 0.0821
ne(589nm,60℃) 1.5562
no(589nm,60℃) 1.4741
dΔn/Δn20℃% 9.98
Viscosity(mm2s-1,20℃) 28.2
V90,0,25(V) 1.311
(V10/V90-1)·100(%) 50
Example four
The components and the proportion of the mixed liquid crystal material are shown in the table 6-1, and the results of various performance tests are shown in the table 6-2.
TABLE 6-1
Liquid crystal compound (indicated by code) parts by weight
3AAEPA2 8
3AAEPA4 8
5AEMN 10
3AAEMF 10
4AAEMF 5
5AAEMF 10
5AAV 6
V2AAP1 7
V2AABF 9
3AABF 5
4AABF 5
5AABF 5
3MEBN 5
4MEBN 2
2PEBN 2
5APF 3
Additive S8110.1
TABLE 6-2
Test items
TN I(℃) 124.9
Δn(589nm,20℃) 0.089
ne(589nm,20℃) 1.571
no(589nm,20℃) 1.482
Δn(589nm,60℃) 0.0807
ne(589nm,60℃) 1.5536
no(589nm,60℃) 1.4729
dΔn/Δn20℃% 9.33
Viscosity(mm2s-1,20℃) 29.6
V90,0,25(V) 1.311
(V10/V90-1)·100(%) 50
As can be seen from the test data of example three and example four above, the clearing point of the liquid crystal composition exceeded 123 degrees; the rate of change of refractive index anisotropy with temperature is less than 10%, which is significantly lower than 12.99% of the comparative example, therefore, LCD products using the two examples of liquid crystal compositions can be used at higher operating temperatures, and displays can provide better contrast; the light valve products adopting the two liquid crystal compositions have more stable reflected or transmitted light wavelength at different temperatures.

Claims (10)

1. A liquid crystal composition comprises four types of liquid crystal compounds with general formulas I-IV, wherein the general formulas and the weight percentages of the compounds are as follows:
5% -50% of a class I liquid crystal compound:
Figure A2007100243200002C1
10-70% of a class II liquid crystalline compound:
Figure A2007100243200002C2
10-80% of a class III liquid crystal compound:
Figure A2007100243200002C3
1-40% of a class IV liquid crystal compound:
Figure A2007100243200002C4
in the formulae:
R1、R2: are each independently selected from C1~C7Alkyl, alkoxy or oxyalkyl or C2~C7Alkenyl, alkenyloxy or oxyalkenyl of (a);
x: selected from halogen or OCF3, OCHF2Or C1~C7Alkyl, alkoxy or oxyalkyl or C2~C7Alkenyl, alkenyloxy or oxyalkenyl of (a);
y: selected from halogen or CN;
Z、Z1: each independently selected from the group consisting of a single bond, -COO-, -C2H4-、-CH2O-、-CH=CH-、-CF2O-or-C ≡ C-;
L1、L2: each independently selected from hydrogen or halogen;
Figure A2007100243200003C1
each independently represents phenyl, cyclohexane, dioxane, fluoro phenylene or difluoro phenylene, cyclohexenyl;
n, m: are each independently an integer of 0 or 1.
2. The liquid crystal composition according to claim 1, wherein the group I liquid crystal compound has the formula:
z is a single bond or-COO-;
Figure A2007100243200003C2
is phenyl, cyclohexane, fluorophenylene or difluorophenylene,
Figure A2007100243200003C3
is phenyl, cyclohexane or difluorophenylene.
3. The liquid crystal composition according to claim 1, wherein the group II compound has the following general formula:
L1in the case of F, the content of the compound,
L2is a compound of the formula H or F,
y is CN or F, and Y is CN or F,
Figure A2007100243200003C4
is phenyl, cyclohexane, fluorophenylene or difluorophenylene.
4. The liquid crystal composition according to claim 1, wherein the group III compound has the formula:
x is selected from F or C1~C7Alkyl, alkoxy or oxyalkyl or C2~C7Alkenyl, alkenyloxy or oxyalkenyl of (1).
Z is a single bond, -COO-, -C2H4-, -CH ═ CH-or CF2O,
Z1Is a single bond, and is a single bond,
l1 is H or halogen, when X is F, L1Also referred to as F, is a linear movement,
Figure A2007100243200003C5
is a phenyl group or a cyclohexane group,
n is 0 or 1.
5. The liquid crystal composition according to claim 1, wherein the group IV compound has the following general formula:
z is a single bond or-CH ═ CH-,
n=1,
Figure A2007100243200003C6
is phenyl, cyclohexane or cyclohexenyl.
6. The liquid crystal composition of claim 2, 3, 4 or 5, wherein the compounds I to IV are each:
the I compound is at least one compound in the following formulas Ia to Ij:
Figure A2007100243200005C1
the II compound is at least one compound in the following formulas IIa to IIr:
Figure A2007100243200005C2
Figure A2007100243200006C1
the III compound is at least one compound in the following formulas IIIa to IIIi:
Figure A2007100243200007C1
the IV compound is at least one compound in the following formulas Iva to IVd:
wherein, the content of the I compound is 10-40%, the content of the II compound is 20-50%, the content of the III compound is 15-60%, and the content of the IV compound is 1-30%.
7. The liquid crystal composition according to claim 6, wherein said group I compound is at least one compound selected from the group consisting of Ia to Ij.
8. The liquid crystal composition according to claim 7, wherein:
the I compound is a compound in a formula Ih or/and Ij, and R in the I compound1Is selected from C1~C7Alkyl or C2~C7Alkenyl radical, R2Is selected from C1~C7Alkyl radical, and R1And R2The sum of carbon numbers of (a) is 10 or less;
the II compound is at least one compound in IIa, IId, IIg, IIi, IIm, IIn, IIp and IIr formulas;
the III-type compound is at least one compound in IIIa, IIIb, IIIc, IIIg, IIIi, IIIm or IIIn.
The IV compound is at least one compound in IVa and IVb formula IVd formula.
9. The liquid crystal composition according to claim 8, wherein; wherein the II compound is 1-4 compounds selected from IIa, IIi, IIn, IIp and IIr; wherein the III compounds are 1-4 compounds in IIIa, IIIc, IIIi, IIIm and IIIn, and the IV compounds are 1-2 compounds in IVb and IVd; 10-35% of I compound, 30-50% of II compound, 20-40% of III compound and 5-20% of IV compound.
10. Use of a liquid crystal composition according to any one of claims 1 to 9 in a first very small TN display or light valve, the liquid crystal composition being filled between two substrates of a TN product after mixing with 0.05 to 1% of an additive selected from the group consisting of:
Figure A2007100243200009C1
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