Liquid crystal composition and display using composition

Abstract

Provided are a polymerizable composition of a polymerizable compound represented by formula I and a polymerizable compound represented by formula II, a liquid crystal composition formed by combining this polymerizable composition with a specific liquid crystal component, particularly a PSVA liquid crystal composition suitable for display or TV applications, and a PSA-IPS liquid crystal composition for an IPS mode; in particular, the polymerizable liquid crystal composition has a good solubility, and an adjustable rate of polymerization and morphology after polymerization; furthermore, a “material system” formed from the selected polymerizable component and liquid crystal component has a low rotary viscosity and good photoelectric properties, and has a high VHR after (UV) photoradiation, this avoiding the problems of the occurrence of afterimages in final displays, etc.

Claims

1. A polymerizable liquid crystal composition, comprising one or more polymerizable liquid crystal compounds represented by formula I-1, I-2, I-4, I-5, I-7 to I-15, I-19 to I-20 and one or more polymerizable liquid crystal compounds represented by formula II-1 to II-3: ##STR00116## ##STR00117## ##STR00118## ##STR00119## wherein each P independently represents a polymerizable group ##STR00120## each Sp independently represents a single bond, a C1-C5 alkyl group, a C2-C5 alkenyl group, or a group formed by replacing any one CH.sub.2 or several CH.sub.2 that are not adjacent in a C1-C5 alkyl group or a C2-C5 alkenyl group by —O—, —S—, —CO—, —CH.sub.2O—, —OCH.sub.2—, —COO—, —OOC— or an acrylate group; each S independently represents H, a C1-C5 alkyl group, a C1-C5 alkoxy group, a fluorine-substituted C1-C5 alkyl group, a fluorine-substituted C1-C5 alkoxy group, F or Cl, wherein any one or more unconnected CH.sub.2 in the groups represented by S may be independently replaced by —O—, —S—, —CO—, —CH.sub.2O—, —OCH.sub.2—, —COO—, —OOC— or an acrylate group or a methacrylate group; each o independently represents 0, 1, 2 or 3.

2. The polymerizable liquid crystal composition according to claim 1, wherein the compound represented by formula I-1, I-2, I-4, I-5, I-7 to I-15, I-19 to I-20 is selected from compounds represented by formulas I-1-1 to I-2-9, I-4-1 to I-5-10, I-7-1 to I-15-19, I-19-1 to I-20-19, ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173##

3. The liquid crystal composition according to claim 1, comprising one or more polymerizable liquid crystal compounds represented by formula IV and one or more polymerizable liquid crystal compounds represented by formula V: ##STR00174## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluorine-substituted alkenoxy group having a carbon atom number of 3-8, wherein any one CH.sub.2 or several CH.sub.2 that are not adjacent in the groups represented by R.sub.3 and R.sub.4 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl; Z.sub.1 and Z.sub.2 each independently represent a single bond, —CH.sub.2CH.sub.2— or —CH.sub.2O—; ##STR00175## each independently represent ##STR00176## each independently represent one or more of ##STR00177## m represents 1 or 2; and p represents 0, 1 or 2.

4. The liquid crystal composition according to claim 3, wherein in said liquid crystal composition, the total mass content of the polymerizable liquid crystal composition is 0.01%-1%, the total mass content of said one or more compounds represented by formula IV is 20%-80%, and the total mass content of said one or more compounds represented by formula V is 20%-60%.

5. The liquid crystal composition according to claim 3, wherein said one or more compounds represented by formula IV are one or more compounds represented by formulas IV-1 to IV-15; and said one or more compounds represented by formula V are one or more compounds represented by formulas V-1 to V-12 ##STR00178## ##STR00179## ##STR00180## wherein R.sub.3 and R.sub.4 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluorine-substituted alkenoxy group having a carbon atom number of 3-8, wherein any one CH.sub.2 or several CH.sub.2 that are not adjacent in the groups represented by R.sub.3 and R.sub.4 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl.

6. The liquid crystal composition according to claim 3, wherein said liquid crystal composition is a negative liquid crystal composition and further comprises one or more compounds represented by formula VI: ##STR00181## wherein R.sub.5 and R.sub.6 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluorine-substituted alkenoxy group having a carbon atom number of 3-8, wherein any one or more CH.sub.2 in the groups represented by R.sub.5 and R.sub.6 may be replaced by cyclopentyl, cyclobutyl or cyclopropyl; and W represents O, S or —CH.sub.2O—.

7. The liquid crystal composition according to claim 3, further comprising one or more compounds represented by formula VII ##STR00182## wherein R.sub.7 and R.sub.8 each independently represent an alkyl group having a carbon atom number of 1-10, a fluorine-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluorine-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluorine-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or an fluorine-substituted alkenoxy group having a carbon atom number of 3-8; and ##STR00183## each independently represent 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene.

8. The liquid crystal composition according to claim 3, further comprising at least one selected from compounds represented by formula VII and/or IX, as a functional additive ##STR00184## wherein R.sub.9 represents an alkyl group having a carbon atom number of 1-10 or an alkoxy group having a carbon atom number of 1-10, and one or more methylene groups in the group represented by R.sub.9 may be substituted with 1,4-cyclohexylene, 2,4-dioxane, cyclopentyl and/or cyclopropyl; each Y independently represents H or methyl; and X represents 8, 10 or 12.

9. A liquid crystal display element or liquid crystal display comprising the liquid crystal composition of claim 3, wherein said display element or display is an active matrix display element or display or a passive matrix display element or display.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) The present invention is further described in conjunction with particular examples below, but is not limited to the following examples. Said methods are all conventional methods, unless otherwise specified. Said raw materials are all commercially available, unless otherwise specified.

(2) In the present specification, the percentages are mass percentages, the temperatures are in degree Celsius (° C.), and the specific meanings of other symbols and the test conditions are as follows:

(3) Cp represents the clearing point (° C.) of a liquid crystal as measured by means of a DSC quantitative method;

(4) S—N represents the melting point (° C.) for the transformation of a liquid crystal from a crystal state to a nematic phase;

(5) Δn represents optical anisotropy, n.sub.o is the refractive index of an ordinary light, n.sub.c is the refractive index of an extraordinary light, with the test conditions being: 25±2° C., 589 nm and using an abbe refractometer for testing;

(6) Δε represents dielectric anisotropy, with Δε=ε.sub.//−ε.sub.⊥, in which ε.sub.// is a dielectric constant parallel to a molecular axis, and ε.sub.⊥ is a dielectric constant perpendicular to the molecular axis, with the test conditions being 25±0.5° C., a 20 micron parallel cell, and INSTEC: ALCT-IR1 for testing;

(7) γ1 represents a rotary viscosity (mPa.Math.s), with the test conditions being 25±0.5° C., a 20 micron parallel cell, and INSTEC: ALCT-IR1 for testing; and

(8) ρ represents electrical resistivity (Ω.Math.cm), with the test conditions being: 25±2° C., and the test instruments being a TOYO SR6517 high resistance instrument and an LE-21 liquid electrode.

(9) VHR represents a voltage holding ratio (%), with the test conditions being: 20±2° C., a voltage of ±5 V, a pulse width of 10 ms, and a voltage holding time of 16.7 ms. The test equipment is a TOYO Model 6254 liquid crystal performance comprehensive tester.

(10) τ represents response time (ms), with the test instrument being DMS-501 and the test conditions being: 25±0.5° C., a test cell that is a 3.3 micron IPS test cell, an electrode spacing and an electrode width, both of which are 10 microns, and an included angle between the frictional direction and the electrode of 10°.

(11) T (%) represents transmittance, with T (%)=100%*bright state (Vop) luminance/light source luminance, with the test instrument being DMS501, and the test conditions being: 25±0.5° C., a test cell that is a 3.3 micron IPS test cell, an electrode spacing and an electrode width, both of which are 10 microns, and an included angle between the frictional direction and the electrode of 10°.

(12) The conditions for the ultraviolet photopolymerization of a polymerizable compound involve using ultraviolet light with a wavelength of 313 nm and an irradiation light intensity of 0.5 Mw/cm.sup.2

(13) In the examples of the invention of the present application, liquid crystal monomer structures are represented by codes, and the codes for ring structures, end groups and linking groups of liquid crystals are represented as in Tables (I) and (II) below

(14) TABLE-US-00001 TABLE (I) Codes corresponding to ring structures Ring structure Corresponding code 04 C 05 P 06 G 07 Gi 08 Y 09 Sa 0 Sb Sc

(15) TABLE-US-00002 TABLE (II) Codes corresponding to end groups and linking groups End group and linking group Corresponding code C.sub.nH.sub.2n+1— n- C.sub.nH.sub.2n+1O— nO— —OCF.sub.3 —OT —CF.sub.2O— —Q— —CH.sub.2O— —O— —F —F —CN —CN —CH.sub.2CH.sub.2— —E— —CH═CH— —V— —C≡C— —W— —COO— —COO— —CH═CH—C.sub.nH.sub.2n+1 Vn— C(5)— C(3)—

EXAMPLES

(16) ##STR00114## ##STR00115##

(17) TABLE-US-00003 Test parent 1: Category Liquid crystal monomer code Content (%) V CY-C(5)-O4 11 V PY-C(5)-O2 9 V COY-3-O2 12 V CCOY-3-O2 8 V CY-5-O2 10 IV CC-3-V-1 5 IV CC-3-2 22 IV CC-2-5 8 IV CC-3-4 10 VII CCP-3-O1 5

(18) TABLE-US-00004 Test parent 2: Category Liquid crystal monomer code Content (%) V CY-3-O2 11 V PY-3-O2 9 V COY-3-O1 12 V CCOY-3-O2 8 IV PP-5-1 10 IV CC-3-2 20 IV CC-3-5 5 VI Sa-C(5)1O-O2 5 VII CCP-3-1 10 VII CPP-3-2 10

(19) TABLE-US-00005 Test parent 3: Category Liquid crystal monomer code Content (%) V CCY-3-O2 11 V CPY-C(3)-O2 9 V CCY-2-O2 12 VI Sa-C(3) 1O-O4 8 IV PP-1-5 10 IV CC-3-2 24 IV CP-3-O2 11 IV CCP-3-1 10 VII CPP-3-O2 5

(20) TABLE-US-00006 Test parent 4: Category Liquid crystal monomer code Content (%) V CCY-3-O2 11 V PY-3-O2 9 V CPY-3-O2 12 V CCOY-3-O2 8 V CY-3-O4 12 IV CC-3-2 22 IV CC-3-5 10 IV CC-3-4 8 IV PP-5-O2 5 VII CCP-3-O1 3

(21) Experiment 1. Investigation of Solubility of Polymerizable Liquid Crystal Compositions

(22) Determination of low-temperature reliability of polymerizable liquid crystal compositions added to different liquid crystal parents

(23) 1% of single component polymerizable compound RM1-5 is added to test parents 1-4, respectively; and for comparison, a polymerizable liquid crystal composition is added in equal quantity to test parents 1-4, respectively, and the storage performance thereof at −30° C. in sample bottles are investigated.

(24) TABLE-US-00007 Experiment −30° C. number Sample composition (5 d) Comparative Parent 1 RM-1 (1%) NG Example 1-1 Comparative RM-3 (1%) NG Example 1-2 Comparative RM-5 (1%) NG Example 1-3 Example 1-1 RM-1 (0.5%) + RM-5 (0.1%) OK Example 1-2 RM-3 (0.5%) + RM-5 (0.5%) OK Comparative Parent 2 RM-2 (1%) NG Example 1-4 Comparative RM-4 (1%) NG Example 1-5 Comparative RM-5 (1%) NG Example 1-6 Example 1-3 RM-2 (0.5%) + RM-5 (0.1%) OK Example 1-4 RM-4 (0.5%) + RM-5 (0.5%) OK Comparative Parent 3 RM-1 (1%) NG Example 1-7 Comparative RM-3 (1%) NG Example 1-8 Comparative RM-5 (1%) NG Example 1-9 Example 1-5 RM-1 (0.5%) + RM-5 (0.5%) OK Example 1-6 RM-3 (0.5%) + RM-5 (0.5%) OK Example 1-7 RM-1 (0.4%) + RM-3 (0.4%) + OK RM-5 (0.2%) Comparative Parent 4 RM-2 (1%) NG Example 1-10 Comparative RM-2 (1%) NG Example 1-11 Comparative RM-4 (1%) NG Example 1-12 Comparative RM-5 (1%) NG Example 1-13 Example 1-8 RM-2 (0.5%) + RM-5 (0.5%) OK Example 1-9 RM-3 (0.5%) + RM-5 (0.5%) OK Example 1-10 RM-4 (0.5%) + RM-5 (0.5%) OK

(25) As can be seen from the above table, comparing Comparative Examples 1-1 to 1-13 with Examples 1-1 to 1-10, none of the low-temperature reliabilities of the compositions in which the monomer of formula I or the monomer of formula II is used alone can achieve criteria, whereas the low-temperature reliabilities of the compositions in which the monomer of formula II and the monomer of formula I are used can achieve the criteria.

(26) The non-benzene ring structures in formula I and formula II can increase the solubilities of the polymerizable monomers. It is an essential component in the polymerizable liquid crystal composition.

(27) Experiment 2. Evaluation of Conversion Rate of Polymerizable Liquid Crystal Compositions

(28) Determination of rate of polymerization of polymerizable liquid crystal compositions added to different liquid crystal parents

(29) 4000 ppm of single component polymerizable compound RM1-6 is added to test parents 1-4, respectively; and for comparison, a polymerizable liquid crystal composition is added in equal quantity to test parents 1-4, respectively; liquid crystal media are prepared by the liquid crystal medium preparation method mentioned above, the liquid crystal media are filled into liquid crystal cells, a PSA panel process 1 is simulated, and the rates of polymerization thereof are determined, with the specific conditions being: UV1: 72 mW/cm.sup.2@365 nm, 100 s; furthermore, the liquid crystal cells are cut open for HPLC analysis, and the results of the rate of polymerization under UV1 conditions are compared and as shown in the following table.

(30) TABLE-US-00008 UV1 Experiment conversion number Sample composition rate (%) Comparative Parent 1 RM-1 (0.4%) 87 Example 2-1 Comparative RM-3 (0.4%) 55 Example 2-2 Comparative RM-5 (0.4%) 31 Example 2-3 Example 2-1 RM-1 (0.3%) + RM-5 (0.1%) 80 Example 2-2 RM-3 (0.3%) + RM-1 (0.1%) 49 Comparative Parent 2 RM-2 (0.4%) 85 Example 2-4 Comparative RM-4 (0.4%) 64 Example 2-5 Comparative RM-5 (0.4%) 33 Example 2-6 Example 2-3 RM-2 (0.2%) + RM-5 (0.2%) 62 Example 2-4 RM-4 (0.2%) + RM-5 (0.2%) 49 Comparative Parent 3 RM-1 (0.4%) 90 Example 2-7 Comparative RM-3 (0.4%) 59 Example 2-8 Comparative RM-5 (0.4%) 33 Example 2-9 Example 2-5 RM-1 (0.3%) + RM-5 (0.1%) 78 Example 2-6 RM-3 (0.3%) + RM-1 (0.1%) 53 Example 2-7 RM-1 (0.2%) + RM-3 (0.1%) + 74 RM-5 (0.1%) Comparative Parent 4 RM-3 (0.4%) 62 Example 2-10 Comparative RM-4 (0.4%) 68 Example 2-11 Comparative RM-5 (0.4%) 35 Example 2-12 Example 2-8 RM-3 (0.36%) + RM-5 (0.04%) 60 Example 2-9 RM-4 (0.36%) + RM-5 (0.04%) 66

(31) As can be seen from the above table, comparing Comparative Examples 2-1 to 2-12 with Examples 2-1 to 2-9, the rates of polymerization of those having the same RM in different parents are different, which is in line with general industry knowledge, and also brings challenges in terms of the types and quantities of polymers added to the LCDs to different LCD manufacturers when carrying out liquid crystal formulation. Overall, the conversion rate of the polymerizable compound of formula I is higher than that of the polymerizable compound of formula II, and the conversion rate of the polymerizable compound of formula I is too fast, resulting in a risk of forming broken bright spots, so that it is not suitable for use alone. By means of the polymerizable composition provided by the present invention formed by the adjustment of the polymerizable compounds of formula I and formula II, the effects of different rates of polymerization can be achieved.

(32) Furthermore, it can be found that after the polymerization and mixing of different components, the rate of polymerization thereof does not lie in a simple weighted average relationship, wherein among the components, some tend towards the fast components after being promoted by each other, some have no effect, some tend towards the slow components, and some may tend to be slower than the slowest component due to being diluted with each other; therefore, it is very important to carry out the adjustment of the polymerizable liquid crystal composition.

(33) Experiment 3. Evaluation of Reliability and Pretilt Angle of Polymerizable Liquid Crystal Compositions

(34) The same liquid crystal compositions as in Experiment 2 are used, wherein the small number liquid crystal components in the samples of Example 3 are the same as the small number liquid crystal components in Example 2, e.g., the liquid crystal component in Example 3-2 is equivalent to that in Example 2-2.

(35) PSA panel process 2 is completed on the basis of Experiment 2, with the specific conditions being: UV2: 5 mW/cm.sup.2@365 nm, and 100 min, and the final conversion rate, voltage holding ratio (VHR), and pretilt angle thereof are tested, wherein due to the PSVA mode, the pretilt angle is actually evaluated by using a 90-measured value during the evaluation.

(36) TABLE-US-00009 UV1 UV2 Experiment conversion conversion Pretilt angle number rate (%) rate (%) (°) VHR Comparative 87 99 87.8 99.1 Example 3-1 Comparative 55 90 88.9 99.0 Example 3-2 Comparative 31 76 89.0 99.3 Example 3-3 Example 3-1 80 98 88.8 99.5 Example 3-2 49 87 88.9 99.7 Comparative 85 99 87.6 99.0 Example 3-4 Comparative 64 93 88.1 99.3 Example 3-5 Comparative 33 77 89.3 99.1 Example 3-6 Example 3-3 62 92 88.7 99.4 Example 3-4 49 87 88.3 99.5 Comparative 90 99 87.3 99.1 Example 3-7 Comparative 59 90 88.1 99.3 Example 3-8 Comparative 33 77 88.9 99.2 Example 3-9 Example 3-5 78 96 88.4 99.5 Example 3-6 53 88 88.6 99.6 Example 3-7 74 94 88.6 99.5 Comparative 62 97 87.8 99.1 Example 3-10 Comparative 68 94 87.9 99.4 Example 3-11 Comparative 35 76 88.3 99.2 Example 3-12 Example 3-8 60 97 88.6 99.5 Example 3-9 66 82 88.6 99.6

(37) As can be seen from Comparative Examples 3-1 to 3-12 and Examples 3-1 to 3-9, although the difference in conversion rate after UV1 is relatively large, the difference in conversion rate after UV2 is decreased; furthermore, the final pretilt angles of samples with similar conversion rates are also different; the conversion rates of some of the single component samples of formula I are too fast, and uneven sample particles may cause the pretilt angle thereof to be too large, thereby forming a large Bump, easily causing light leakage; however, the mixed samples to which formula II is added have a relatively stable pretilt angle, can suppress the generation of larger particles, contributing to the stability of the pretilt angle. Therefore, under the premise of satisfying the processes of LCD manufacturers, the polymer particles are uniform, and the pretilt angle is appropriate, which are the characteristics of the adjustment of the polymerizable liquid crystal mixture. The voltage holding ratio (VHR) data obtained by the tested samples are all excellent, and the data of the examples in which polymerizable liquid crystal compositions of components of formula I and formula II are added to the same parent for comparison (for different parents, direct comparison is impossible) are significantly preferred.

(38) Experiment 4. Evaluation of Reliability of Functional Additives on Polymerizable Liquid Crystal Compositions

(39) On the basis of Experiment 3, the same liquid crystal compositions as those in Comparative Example 3-12, Example 3-5 and Example 3-7 are selected for an aging test; polymerizable compounds are polymerized by means of ultraviolet irradiation, and tested under the conditions of ultraviolet light, a high temperature, etc. for the voltage holding ratios (VHR) thereof; in addition, by adding functional additives to Example 3-5 and Example 3-7, the voltage holding ratios (VHR) of Examples 4-1 to 4-6 are further investigated under the conditions of ultraviolet light, a high temperature, etc.

(40) TABLE-US-00010 VHR VHR (high Experiment VHR (ultra- temper- number Composition (initial) violet) ature) Comparative Comparative 99.2 95.2 93.7 Example 4-1 Example 3-12 Comparative Example 3-5 99.5 97.2 97.1 Example 4-2 Example 4-1 Example 3-5 + 200 99.2 97.6 99.0 ppm of Additive-1 Example 4-2 Example 3-5 + 100 99.3 99.0 97.8 ppm of Additive-2 Example 4-3 Example 3-5 + 100 99.1 98.5 98.7 ppm of Additive-1 + 100 ppm of Additive-2 Comparative Example 3-7 99.5 97.4 97.6 Example 4-3 Example 4-4 Example 3-7 + 200 99.2 97.7 98.9 ppm of Additive-1 Example 4-5 Example 3-7 + 100 99.2 99.1 98.1 ppm of Additive-2 Example 4-6 Example 3-7 + 200 99.1 98.7 99.0 ppm of Additive-1 + 100 ppm of Additive-2

(41) As can be seen from Comparative Examples 4-1 to 4-3, the VHR after ultraviolet irradiation and the VHR after high temperature of the samples are significantly reduced as compared with the initial VHR thereof; and the reductions in the VHRs after ultraviolet irradiation and high temperature of Comparative Example 4-2 and Comparative Example 4-3 manufactured from Example 3-5 and Example 3-7 are smaller than those of Comparative Example 4-1, indicating that the VHRs after ultraviolet irradiation and high temperature thereof can be improved after being mixed with RM;

(42) in addition, as can be seen from Examples 4-1 to 4-6, the VHR after high temperature and the VHR after ultraviolet irradiation are both improved after the addition of additive-1 and additive-2 in the liquid crystal composition, and the effects of improvement of additive-1 and additive-2 are not the same, wherein additive-1 focuses on improving the VHR after high temperature, and improves the VHR after ultraviolet irradiation, but the amplitude of the improvement is not as good as the effect after high temperature; and additive-2 focuses on improving the VHR after ultraviolet irradiation, and improves the VHR after high temperature, but the amplitude of the improvement is not as good as the effect after ultraviolet irradiation; however, using additive-1 and additive-2 in combination can achieve more ideal results; of course, the addition of the additives will cause the initial value to decrease, and the addition amount and type thereof should be used according to specific circumstances.