JPS5887536A - Liquid crystal display device - Google Patents

Abstract

PURPOSE:To prevent the doubling of electric current value and defective orientation and to elongate the life by forming an oriented film and an oxygen absorbing or radical capturing film on an electrically conductive transparent film on a flexible polymer film. CONSTITUTION:An oxygen radical capturing agent or an oxygen absorber is used by 10-100pts.wt. basing on 100pts.wt. components forming an oriented film, and when it serves also as a component of the film, the amount is adjusted to 20-100pts.wt. basing on 4pts.wt. resin. 0.5% Soln. of acetylacetonatozirconium is applied to an oriented film, dried with hot air and heated at 150 deg.C for 30min to form an oxygen absorbing or radical capturing film, and the resulting panel is rubbed with cotton cloth under 1kg/cm<2> pressure in one direction to form a TN cell contg. a dichromatic dye. Ti(OC5H7)0.7[OC2H4N(CH3)2]5.5, titanium dihydroxybis (lactate) or trihydroxyaluminum may be used as other composition.

Description

[Detailed description of the invention] The present invention relates to a novel liquid crystal display device.

The liquid crystal display device uses a liquid crystal display panel with an inorganic glass substrate as a substrate made of gold or hard synthetic wood along with other components.
It has been known for a long time to have a structure in which it is housed in a sturdy case. Since known liquid crystal display devices are equipped with liquid crystal display panels using inorganic glass as a substrate, they are heavy and are easily broken by external impact, requiring careful handling. Disadvantages include that bending and other free-form processing is difficult during manufacturing, and that a sturdy storage case is required to protect the display panel made of inorganic glass, which reduces the overall weight and makes it inconvenient to carry. was there.

Therefore, in recent years, instead of using inorganic glass as a substrate for product display panels, flexible polymer films, which have excellent bending and other processability and can withstand external impact, have been used. However, when using such a polymer film as a panel substrate for product display equipment, heat resistance problems such as doubling of the flow value and poor orientation occur in the Agenobu test at 80°C for 200 to 400 hours. There were sexual limits. The inventor of the present invention has conducted extensive research into the causes of such agglomeration, and has found that oxygen gas (02) in the air that enters through the substrate film, sealant, dirt, and their interfaces becomes radicals and is formed. It is logical that the oxygen radicals (0°) caused by cutting the 4A chains of the chemical stores that make up the liquid crystal, promoting gasification, promoting isomerization, and promoting polymerization have adverse effects. It turned out that there was a problem.

Therefore, the present invention was completed after further research on measures to eliminate such adverse effects. That is, an object of the present invention is to provide a liquid crystal display device with excellent reliability, particularly heat resistance. In a liquid crystal display device in which a liquid crystal or a liquid crystal mixed with a dichroic dye is sealed using a sealant, a combination of at least one of each of the following 181) and (b), or a mixture of llIi, is used as a panel substrate. 1. (Island) alignment film (b) Oxygen absorption/radical scavenging film A detailed description of the present invention will be given below. As the flexible polymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyether sulfone film, polycarbonate film, etc. are used, and a transparent conductive film of indium oxide, tin oxide, etc. is provided on these by known means,
The surface is further subjected to an orientation treatment. For the orientation treatment, components according to the invention of the present inventors can be used. Examples of the components include (1) saturated polyester, 3) saturated polyester, Reactive titanium compound, isocyanate compound, epoxy brain, +1
A reaction product of 1# with a water substance, a reinforcing agent such as melamine tree 1fiI, a) a mixture of a saturated polyester and a low melting point copolymerized nylon, (4) a mixture of a saturated polyester and a low melting point copolymerized nylon, and the above-mentioned reinforcement. 6) a reaction product between a low melting point copolymerized nylon and the reinforcing agent, (6) thiocol,
σ) n-compound, (8) reaction product of chelate-containing titanate ester and epoxy tree M, (9)) n-loxane, (10) konium acetylacetate 1, non-1
-1 (11) Periodic law 4th ~ including thorium and uranium
A reaction product of a compound of the 6aglL group and the following components (bl) to (b4), (bl) an alloy of a metal of group 2.3 of the periodic law (b2) an alloy of a metal of group 2.3 of the periodic law ) Metal hydrides of Groups 1 to 8 of the Periodic Table (b4) Gold w4 organic compounds of Groups 1 to 8 of the Periodic Table (12) Reaction products of titanium halides and organic aluminum, (1B) What are titanium chelate compounds? reaction product of organic aluminum, (14) reaction product of titanate ester and organic aluminum, (15)
) Compounds of metals that are 14 in periodic table Bb, 4m, and 4b,
(lfj) It is possible to use a mixture of fatigue metals of metals belonging to 8b, 4a, and 4b of the periodic law excluding titanium and synthetic S resin. An alignment film is formed by coating fBI91 in a solvent on a panel substrate and drying it, but in the present invention, an oxygen radical scavenger and/or an oxygen absorber is used in the alignment film and/or in combination with the alignment film. It is characterized by using an agent. Various types of oxygen radical scavengers and oxygen absorbers can be used, and for example, those consisting of at least one of the following compositions can be used. Compounds, complexes, and polymers (d) Reaction products of organic compounds of metals 4 to 6a of the Periodic Law, including thorium and uranium, and the following components (dl) to (d4) (dl) 2.8 of the Periodic Law Group metals (dl) Metal alloys of group 2.8 of the periodic law (di) Metal hydrides of groups 1 to 8 of the periodic law (d4) Metal compounds of groups 1 to 3 of the periodic law and their complexes and polymers <e> Periodic law @ 8b, 4m, composite reaction phase of gold m organic compounds, complexes and polymers that Jim in b. Mechanical compounds, tank bodies, and Bo! J? -(
[3] (d) As the acid component, compounds such as titanium, zirconium, hafnium, thorium, uranium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten can be used, and among these, compounds of titanium , the taste includes titanium tetrahalides (e.g. tetrachloride, titanium esters (e.g. tetrakis(2-ethylhexoxy) titanium), chelated titanium (e.g. no-bropoxy bis(acetyl ayatonato) titanium), titanium ash L. - (e.g. trihebutoxytitanium monostearate) and the corresponding zirconium,
Compounds of chromium, vanadium, (libdenum) are generally preferred.

Examples of the metals in Group 2.3 of the Periodic Law for the (dl) component include aluminum, magnesium, +i, carralum, etc.; , alloys of the above-mentioned positions.

(As the diluent component, aluminum hydride, hydrogen hydride, etc. can be mentioned.

In addition, (d and (d4) components are general formula (1)%
Formula % () (In the formula, human is alkali gold J14, M is aluminum or 61IIl, 8' and 2' are hydrocarbon residues, the younger sister is an alkyl group, X and 1, and y are hydrocarbon residues or hydrogen. ) can also be used. Furthermore, (as a component, general formula (1) % formula % () (in the formula, 8 and t are hydrocarbon residues, especially alkyl groups, and t is a hydrocarbon residue, hydrogen, halogen atom, or alkoxy group) Compounds represented by the following formulas are also preferably used.Organic compounds of magnesium and zinc can also be used.

These oxygen radical scavengers and/or oxygen absorbers are usually used for 100 parts of the components constituting the alignment treatment film, but if they also serve as alignment film components, the resin content should be increased to 4 parts of the power source. On the other hand, 迩太 falls in the range of 20 to 100 Jyu Toshibu. Further, it may be coated on a layer other than the alignment film. The degree of hemorrhoids and a at this time is u, t
-1.0% is desirable.

Since the above components (e), (d), and (6) can also serve as alignment film components, the present invention excludes the case where the alignment film is a (CbadHe) component. Also, the above-mentioned iaJ layer and fb1 layer can be effective with only one crystal layer each, or with a mixture of both ryJ 114 layers, but? ! It is effective even if more than the r1 layer is combined.

Note that the oxygen radical scavenger/and oxygen absorbent used with the alignment film as described above should: l) have no adverse effect on the liquid crystal; 2) have no adverse effect on the alignment film;
8) Preferably, it is stable against heat of 80 to 150°C.

Two pieces of the oriented plate are knitted together and liquid crystal is sealed using a sealant. Liquid crystals include azomethine compounds, azo compounds, azoxy compounds, ester compounds, biphenylated compounds, stilbene compounds, terphenylation, trans-cyclohexanation, pyrimidine compounds, nematic liquid crystals and smectifuku liquid crystals, and cholesterol derivatives. , cholesteric liquid crystals such as chiral mesogen substances, etc. are used. As a sealing agent for bonding two panel substrates together and sealing a liquid crystal, a compound according to the invention of the present inventors can be used. For example, α) the following ta) (b) (C)
(Ili) Nylon and/or linear saturated polyester (b) Epoxy mah and/or isocyanate compound (C) Dissolves (a) and (b) above and seals the panel substrate. These include soluble solvents (for example, haloalcohols), (2) ultraviolet curable adhesives, and (8) silicone adhesives.

Further, depending on the liquid crystal display method, it is natural that a polarizing plate, a reflecting plate, etc. may be further attached to the outside of the panel substrate.

As described above, the liquid crystal display device of the present invention has f! An isthmus containing an I4 radical scavenger and/or an oxygen absorber is provided. Therefore, even if oxygen gas in the air penetrates into the liquid crystal from the sealant layer, the oxygen absorbing and/or radical scavenger used with the alignment film will absorb the oxygen gas.
It stabilizes it. In the unlikely event that unabsorbed oxygen gas decomposes into radicals (0°) and causes liquid crystal deterioration reactions such as side chain scission, isomerization, and polymerization, an oxygen radical scavenger will capture the radicals and This prevents such liquid crystal deterioration reactions from occurring.

Therefore, the liquid crystal display device of the present invention can exhibit good performance for a long time even in aging tests.

EXAMPLES The present invention will be explained in detail below with reference to examples, but the present invention is not limited to the above examples unless the gist of the invention is missed.

Example 1 0.2% of the above composition (weighted percentage,
(Same below) Apply an alignment agent solution and dry with hot air to form an alignment film.

Ingredients Heavy j1s isocyanate compound (trade name "Desmodurou") 1. Zirconium acetylacetonate) 0.
After applying the 6*#l solution and drying with hot air, it is heated at 160° C. for 80 minutes to form an oxygen absorption and/or radical scavenging film, and the panel is rubbed in one direction with a cotton cloth under pressure of 1 kl/cd. A liquid crystal display device was created by stacking panel substrates so that the rubbing directions were perpendicular to each other and sealing a mixture of (product name: r1lDf[-1-46'') and dichroic dye (product name: rD-16J) between the substrates. . In air at a temperature of 80°C and a humidity of 40%, we measured the passage of time and the alignment layer of the liquid crystal using a luminance needle, and also measured the panel current consumption when driving gV and B2flz.The results are shown in Table 1. Shown below.

As is clear from Table 1, the oriented layer was good and the current consumption value did not increase.

Ratio Example 1 A liquid crystal display device was prepared in exactly the same manner as in Example 1 except that zirconium acetylacetonate was applied, and the elapse of time, the alignment state of the liquid crystal, and the current consumption value of the panel were measured in the same manner. The results are shown in Table 2.7 Table 2 The current consumption value increased with the passage of time, and the oriented layer became defective after 144 hours had passed.

Example 2 A 1% hexane solution of oxygen absorbing and/or radical scavenging membrane components having the following composition is applied onto the same film substrate as in Example 1.

Ingredients Part by weight Ti((X3iH7)e,y(OCzMaN((Jig
) t) i, i l Dihydroxybis(lactato)titanium 1 Trihydroxyaluminum 5 Next, dry with hot air, apply a 1% solution of bis(8-aminopropyl)tetramethyldisiloxane on the membrane and dry with hot air, then 150 ℃ for 80 minutes to form an alignment film, rubbed in the same manner as in Example 1, stacked the substrates, and sealed with PCH-based liquid crystal (Merok 11! trade name "ZLI/665") to form a liquid crystal display device. Created. When the orientation state and current consumption value were measured in the same manner as in Example 1, good results were obtained as in Example 1.

A liquid crystal display device was prepared and tested in exactly the same manner as in Example 2 except that an oxygen absorption and/or radical scavenging film was formed, and the results shown in Table 8 were obtained.

Table 3 The current consumption value increased with the passage of time, and the orientation state became poor after 192 hours.

Agent Patent Attorney Tsutomu Ashitachi

Claims (1)

[Scope of Claims] 1. A flexible polymer film provided with a transparent conductive film is used as a panel substrate, and a combination of at least one or more layers of each of the following e) and (b), or a mixed layer of both, is provided on the cough substrate. A liquid crystal display device characterized in that: is formed. (a) Alignment film (b) Oxygen absorption and/or radical IIa capture, except when the alignment film consists of at least one of the following compositions. (C) Organic compounds, monoliths, and polymers of Periodic Law 6a gold; (d) Reaction products of organic compounds of Periodic Law 44 to 6a metals, including thorium and uranium, and dl to (dl) components; (d) Periodic law i @ Group 2.8 gold - (dl) Periodic law group 2.8 metal alloy (di) Period ni metal hydride of groups 1 to 8 (d4)
Composite reaction products of organic compounds, complexes and polymers of metals belonging to Groups 1 to 3 of the Periodic Law, complexes and polymers <e> of metals belonging to Groups 1 to 3 of the Periodic Law, patent claim 2 (C) An organic compound with a periodic law of 61 mm , complexes, and polymers (d) Reaction products of organic compounds of metals from Group 4 to 6a of the Periodic Law, including thorium and uranium, and the following components (dl) to (d4) (dl) Group 2.8 of the Periodic Law Metals (dl) Metal alloys of group 2.8 of the periodic law (ds) Metal hydrides of groups 1 to 3 of the periodic law (d4)
Organometallic compounds of Groups 1 to 3 of the Periodic Law and their complexes and polymers (6) Complex reaction product oxides of organic compounds, metals and polymers of metals belonging to Groups 3b, 4a and 4b of the Periodic Law