JP3330156B2 - Antistatic display - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display having a display surface having an antistatic property. More specifically, the present invention relates to a CRT display and a liquid crystal display used in AV products such as home televisions and computers.

[0002]

2. Description of the Related Art A conventional CRT type display is made of glass and, when used, emits light while operating an electron beam internally, so that the display surface is easily charged, and dust and dust floating in a room due to the charging are liable to be charged. There was a drawback that it was attracted and easily stained. Therefore, in order to prevent this charging, a method of applying a conductive resin to the glass surface of the display surface, attaching a conductive film, or vapor-depositing a conductive ceramic such as ITO (indium-tin oxide) has been used. . As another means, for example, a light-transmitting plate made of a plastic plate is provided on the front of a display such as a word processor or a personal computer, and a conductive layer such as ITO is formed on the surface of the plastic plate.

[0003]

However, the method of applying a conductive resin or attaching a conductive film or the method of installing a light transmitting plate made of a plastic plate is inferior in transparency and easily peeled or scratched. There were drawbacks. In addition, the method of depositing ITO has high reliability but has problems such as high cost.

[0004] In order to solve the above-mentioned problems of the prior art, the present invention forms an antistatic film having high transparency and durability and a desired weak electrical conductivity on a display surface, and is used for AV products such as home televisions and the like. It is an object of the present invention to provide an invention for effectively preventing a display for a computer from being stained.

[0005]

In order to achieve the above object, an antistatic display according to the present invention is a display having a display surface covered with a chemisorption monomolecular film, wherein the chemisorption monomolecular film has the display. Surface and a siloxane bond and contain a hydrophilic group on the monomolecular film surface .
The conductivity is in the range of 10 ⁻⁶ S / cm to 10 ⁻¹⁰ S / cm
It is characterized by being within . In the above structure, the monomolecular film has the following formula: A- (B) _r -SiCl ₃ (where A is a bromo group, an iodo group, a cyano group,
A functional group containing a thiocyano group, a chlorosilyl group, or an ester bond , B represents an organic group, and r represents a natural number of 30 or less). It is preferable that the surfaces are bonded by a siloxane bond.

In the above structure, the hydrophilic group is -OH,
—COOH, —NH ₂ , —N ⁺ R ₃ X ⁻ (R represents an alkyl group, X represents a halogen atom), —NO ₂ , or —S
It is preferably an O ₃ H group.

[0007] In addition the configuration, -COOH, or H is an alkali metal -SO ₃ H group, it is preferably substituted with an alkaline earth metal or other metals.

[0008]

According to the constitution of the present invention, the CRT is formed by a siloxane bond via a molecule having a weakly conductive functional group chemically adsorbed thereon.
Since it is fixed to a display surface such as a display, it exhibits an antistatic effect and does not peel off. Moreover, since the thickness of this monomolecular film is on the order of nanometers, there is no possibility that the image characteristics of the display screen will be reduced. Accordingly, it is possible to prevent generation of stains due to charging of a display surface of a CRT or the like, and to achieve excellent durability.

Further, when the hydrophilic group is -OH, -COOH, -N
According to the preferred structure of the present invention in which H ₂ , —N ⁺ R ₃ X ⁻ (R represents an alkyl group and X represents a halogen atom), —NO ₂ , or —SO ₃ H group, further excellent charging is achieved. It can exhibit the prevention function.

[0010] Further, H of -COOH or -SO ₃ H group
Is preferably substituted by an alkali metal, an alkaline earth metal or another metal, thereby exhibiting a particularly excellent antistatic function.

[0011]

The present invention will be described more specifically with reference to the following examples. The antistatic display of the present invention is manufactured as follows. First, a finished glass CRT
Was prepared, materials containing the molecular end a chlorosilyl group at the display surface, for example, _{A- (B) r -SiX q Cl} 3-q ( although, A is bromo group, iodo group, cyano group, thiocyano group, chlorosilyl group Or a functional group containing an ester bond, q is 0 or 1 or 2, r is a natural number of 30 or less,
B is contacted with a non-aqueous solvent mixed with an organic group),
Reacting the hydroxyl group on the T display surface with the chlorosilyl group of the substance containing the chlorosilyl group at the molecular terminal to deposit the substance on the display surface, and leaving the substance on the CRT display surface using a non-aqueous organic solvent. After washing and removing the substance containing a plurality of unreacted chlorosilyl groups, the bromo group of the substance,
Iodine group, cyano group, thiocyano group, chlorosilyl group,
Alternatively, a functional group containing an ester bond is directly or chemically reacted to form —OH, —COOH, —NH ₂ , —N ⁺ R
₃ X ^- (X represents a halogen atom), - NO _2, or by a step of converting the -SO ₃ H group to form an antistatic chemisorption monomolecular film on the CRT display surface. Or -C
OOH, or converted into -SO ₃ H group, -COOH, or to form a -SO ₃ H and alkali metal in the functional group of the H group, an alkaline earth metal or other metal and substituted monolayer. Here, the alkali metal is, for example, Li, Na,
K, Rb, Cs, Fr; or alkaline earth metal refers to, for example, Be, Mg, Ca, Sr, Ba, Ra; or other metal refers to Al, Ti, V, Cr, M
n, Fe, Co, Ni, Cu, Zn, Ga, Zr, Ln
Such as 4A, 5A, 6A, 7A,
8, 1B, 2B, 3B). In short, any metal that can form a salt (including a complex salt) with the carboxylic acid or sulfonic acid can be used.

Hereinafter, in order to prepare a chemically adsorbed film having weak conductivity for the purpose of preventing the display from being charged according to the present invention, a monomolecular film having -O as a functional group having an antistatic function is used.
_{H, -COOH, -NH 2, -N} + R 3 X - (R represents an alkyl group, X is a halogen atom), - NO _2, or there is a method of introducing a -SO ₃ H group, or less It will be described in order.

Example 1 (Introduction of -OH group) First, a glass CRT 11 was prepared (FIG. 1 (a)), washed with an organic solvent, and the display surface was ester-bonded (R-CO).
A non-aqueous solvent mixed with a functional group containing —OCH ₂ — (R is a functional group)) and a chemical adsorbent containing a chlorosilane group, for example, CH ₃ OOC (CH ₂ ) ₇ SiCl ₃ ;
80 wt% n-hexadecane (may be toluene, xylene, bicyclohexyl) dissolved at a concentration of about
When the CRT display surface is immersed for about 5 hours after preparing a wt% carbon tetrachloride and 8 wt% chloroform solution, since the CRT display surface contains a large number of hydroxyl groups 12, the chemical adsorbent contains SiCl groups and the hydroxyl groups. React to cause a dehydrochlorination reaction. Next, the unreacted chemical adsorbent is washed and removed using chloroform, which is an example of a non-aqueous solution, and then reacted with water to form the bond shown below (Chem. 1) over the entire CRT display surface, and the ester is formed. The monomolecular film 13 containing a bond is CR
A film having a thickness of about 20 Å was formed in a state of being chemically bonded to the T display surface (FIG. 1B).

[0014]

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Next, the CRT display surface is reacted at room temperature for 20 minutes in an ether solution containing a few wt% of lithium aluminum hydride (LiAlH ₄ ) to convert the terminal to a hydrophilic hydroxyl group. Was formed (FIG. 1 (c)).

[0016]

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Since the monomolecular film 14 is extremely strongly chemically bonded to the CRT display surface, it does not peel off. The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ⁻⁸ S / cm.

Further, when the CRT display surface is immersed in a hexane solution in which about 5 wt% of an organic compound of an alkali metal, for example, Li (CH ₂ ) ₃ CH ₃ (or NaOCH ₃ ) is dissolved, the following chemical formula is obtained. An extremely hydrophilic film 15 was formed (FIG. 1D).

[0019]

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The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ^-6 S / cm. In this embodiment, the adsorption is performed after the CRT is assembled. However, the chemisorption film of the present embodiment may be formed in advance on the face plate before the assembly.

Example 2 (Introduction of -COOH group) For example, a flat glass liquid crystal display 21 was prepared (FIG. 2A), washed well, and then an ester bond (R-CO-OCH _2- ( R is a non-aqueous solvent mixed with a chemical adsorbent containing a functional group having an organic group)) and a chlorosilyl group, for example, CH ₃ OOC (CH ₂ ) ₁₀ SiCl _3, and is dissolved at a concentration of about 2 wt% to 80 wt%. A solution of n-hexadecane (toluene, xylene, bicyclohexyl), 12 wt% carbon tetrachloride, 8 wt% chloroform solution is prepared, and the substrate is immersed for about 5 hours. The display surface contains a large number of hydroxyl groups 22. Therefore, the SiCl group of the chemical adsorbent reacts with the hydroxyl group to cause a dehydrochlorination reaction. Next, the unreacted chemical adsorbent is washed and removed using chloroform, which is an example of a non-aqueous solution, and then reacted with water, whereby the bond shown in the following (Formula 4) is formed over the entire surface of the substrate, and the ester is formed. Monolayer 23 containing a bond
Was formed with a thickness of about 20 Å in a state of being chemically bonded to the surface of the display surface (FIG. 2B).

[0022]

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Next, this display surface is made of hydrochloric acid (HCl) 36.
After reacting at 65 ° C. for 30 minutes in a wt% solution,
A hydrophilic carboxyl group was formed at the terminal shown in FIG.

[0024]

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The monomolecular film 24 (FIG. 2 (c)) was also very strongly chemically bonded to the display surface, and thus did not peel off. The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ^-9 S / cm.

Further, when the display surface is immersed in an aqueous solution in which about 1% by weight of a compound of an alkali metal, an alkaline earth metal or another metal, for example, NaOH (Ca (OH) ₂ may be separately used) is dissolved, An extremely conductive film 25 (FIG. 2D) represented by the following (Formula 6) was formed on the display surface.

[0027]

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The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ^-6 S / cm. In this embodiment, adsorption was performed after assembling the liquid crystal cell.
A chemical adsorption film may be formed on the face plate before assembly.

Example 3 (Introduction of —NH ₂ group) First, a CRT face plate 31 was prepared (FIG. 3).
(A)) a non-aqueous solvent, such as NC, which is washed with an aqueous solution containing dichromic acid at 80 ° C. for about 30 minutes and then washed with a chemical adsorbent containing a cyano group and a chlorosilyl group;
Using (CH ₂ ) ₁₇ SiCl ₃ , a solution of 80 wt% n-hexadecane (toluene, xylene, bicyclohexyl), 12 wt% carbon tetrachloride and 8 wt% chloroform dissolved at a concentration of about 1 wt% was prepared. When the plate is immersed for about 2 hours, a large number of hydroxyl groups 32 are contained on the plate surface.
The Cl group reacts with the hydroxyl group to cause a dehydrochlorination reaction. Next, the unreacted chemical adsorbent is washed and removed using chloroform, which is an example of a non-aqueous solution, and then reacted with water.
The following bond (Formula 7) was generated over the entire surface, and a monomolecular film 33 containing a cyano group could be formed in a state chemically bonded to the surface (FIG. 3B).

[0030]

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Next, the plate is immersed in ether (10 mg / ml) in which lithium aluminum hydride is dissolved, and reacted overnight. Thereafter, the solution is taken out of the solution, and ether is added, followed by 10 wt% hydrochloric acid in the same volume as the ether. Then, further put in a triethylamine solution,
After performing the reaction for a time, the resultant was washed with a chloroform solution to obtain a highly hydrophilic monomolecular film represented by the following (Formula 8). The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ^-9 S / cm. This monomolecular film 33 (FIG. 3 (c)) was also very strongly chemically bonded to the plate surface, and thus did not peel off.

[0032]

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Examples of the introduction of other --NH ₂ groups are as follows. First, after washing well with a face plate, a non-aqueous solvent mixed with a chemical adsorbent containing a bromo group or an iodine group and a chlorosilane group, for example, Br (CH)
₂ ) 80 wt% n-hexadecane (toluene, xylene, bicyclohexyl may be used) dissolved at a concentration of about 1 wt% using ₁₇ SiCl ₃ , 12 wt% carbon tetrachloride, 8 wt%
After preparing a chloroform solution and immersing the plate for about 2 hours, since the surface contains many hydroxyl groups,
The SiCl group of the chemical adsorbent containing a bromo group reacts with the hydroxyl group to cause a dehydrochlorination reaction.
Was formed, and a monomolecular film containing a bromo group was formed in a state chemically bonded to the surface.

[0034]

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Next, N, N dissolved in sodium amide
The plate was placed in a dimethylformamide solution (8 mg / ml) and reacted overnight to obtain a monomolecular film shown in the following (Chemical Formula 10).

[0036]

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Further, the plate was immersed in ether (10 mg / ml) in which lithium aluminum hydride was dissolved, allowed to react overnight, taken out, put in an empty container, and then put ether, and then 10 wt% of the same volume as ether. Add hydrochloric acid. Then put in triethylamine solution and add 2
After reacting for hours, washing with chloroform solution,
A monomolecular film shown in the following (Formula 11) was obtained.

[0038]

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Note that this monomolecular film was also very strongly chemically bonded to the plate, and thus did not peel off. Example 4 (Introduction of -N ⁺ R ₃ X ^- group (X represents a halogen atom)) First, a CRT was prepared (FIG. 4 (a)), washed with an organic solvent, and then a chlorosilyl group and another were added to one end. 80 wt% n-hexadecane dissolved at a concentration of about 2 wt% using a non-aqueous solvent, for example, ClSi (CH ₃ ) ₂ (CH ₂ ) ₁₀ SiCl ₃ mixed with a chemical adsorbent containing a chlorosilyl group at one end. (Toluene, xylene, bicyclohexyl), a solution of 12 wt% carbon tetrachloride and 8 wt% chloroform are prepared, and the CRT display surface 41 is immersed for about 5 hours. The CRT display surface contains many hydroxyl groups 42. Therefore, the SiCl group of the chemical adsorbent reacts with the hydroxyl group to cause a dehydrochlorination reaction. Next, when the unreacted chemical adsorbent is washed and removed using chloroform, which is an example of a non-aqueous solution, a bond shown in the following (Formula 12) is formed over the entire CRT display surface, and a monomolecular film containing a chlorosilyl group is formed. 43 is C
It was formed in a state of being chemically bonded to the surface of the RT display surface (FIG. 4B).

[0040]

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Therefore, 10 wt% (CH ₃ ) ₂ NC ₂ H ₄ O
The CRT display surface was immersed in a chloroform solution of H to cause a dehydrochlorination reaction, and then washed with chloroform to obtain a monomolecular film 44 shown in the following (Chem. 13) (FIG. 4 (c)).

[0042]

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Then, when immersed in a chloroform solution in which CH ₃ I containing iodine as a halogen atom is dissolved and refluxed for 2 hours, a highly hydrophilic single molecule having a quaternary amino group on the surface as shown in the following (formula 14) is obtained. The film 45 was obtained (FIG. 4D).

[0044]

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This monomolecular film adsorbed water vapor in the air and had a conductivity of about 10 ^-7 S / cm. Example 5 (Introduction of -NO ₂ group) First, a CRT was prepared (FIG. 5 (a)), washed with an organic solvent, and then a chemical adsorbent containing a bromo or iodo group and a chlorosilyl group [for example, Chemical adsorbent shown in the following) was dissolved in 80 wt% n-hexadecane (toluene, xylene, bicyclohexyl), 12 wt% carbon tetrachloride, 8 wt% chloroform solution at a concentration of about 2 wt% to prepare.

[0046]

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When the CRT display surface 51 is immersed for about 5 hours, since the CRT display surface contains a large number of hydroxyl groups, the SiCl group of the chemical adsorbent containing a bromo group reacts with the hydroxyl groups 52 to cause a dehydrochlorination reaction. Occurs. Then, the unreacted chemical adsorbent is washed and removed using chloroform, which is an example of a non-aqueous solution, and then reacted with water, whereby the bond shown in the following (Formula 16) is generated over the entire CRT display surface, A monomolecular film 53 containing a bromo group was formed to a thickness of about 20 angstroms in a state chemically bonded to the CRT display surface (FIG. 5B).

[0048]

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Next, this CRT display surface is made of 5 wt% AgNO.
_When reacted at 80 ° C. for 2 hours in an alkaline aqueous solution containing ₃ , a hydrophilic monomolecular film 54 represented by the following (Formula 16) is obtained.
(FIG. 5 (c)) was obtained.

[0050]

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The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ^-10 S / cm. Since this monomolecular film was also very strongly chemically bonded to the CRT display surface, it did not peel off.

Example 6 (Introduction of -SO ₃ H group) First, a CRT was prepared (FIG. 6 (a)), washed with an organic solvent, and then a chemical adsorbent containing a thiocyano group (-SCN) and a chlorosilyl group. Mixed with a non-aqueous solvent such as N
Using CS (CH ₂ ) ₁₀ SiCl ₃ , an 80 wt% n-hexadecane (toluene, xylene, bicyclohexyl), 12 wt% carbon tetrachloride, 8 wt% chloroform solution dissolved at a concentration of about 2 wt% was prepared. When the CRT display surface 61 is immersed for about 5 hours, since the CRT display surface contains a large number of hydroxyl groups 62, the SiCl groups of the thiocyano group and the chlorosilyl group-containing chemical adsorbent react with the hydroxyl groups to cause a dehydrochlorination reaction. . Next, the unreacted chemical adsorbent is washed using chloroform, which is an example of a non-aqueous solution.
When removed and then reacted with water, a bond shown in the following (Formula 18) is generated over the entire surface of the CRT display surface, and the monomolecular film 63 containing a thiocyano group is chemically bonded to the surface of the CRT display surface. A film having a thickness of 20 Å was formed (FIG. 6B).

[0053]

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Next, the CRT display surface was put in ether (10 mg / ml) in which lithium aluminum hydride was dissolved, and reacted for 4 hours. When the reaction was carried out for 4 hours, a hydrophilic monomolecular film 64 shown in the following (Chemical Formula 19) (FIG. 6C) )was gotten.

[0055]

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Next, 10 wt% of hydrogen peroxide solution and 10 wt%
Acetic acid in a 1: 5 mixed solution by volume and reacted at 40 ° C. to 50 ° C. for 30 minutes to obtain a highly hydrophilic monomolecular film 65 (see FIG. 6 (d)). ))was gotten.

[0057]

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The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ^-8 S / cm. Furthermore, here compounds of alkali metals, alkaline earth metals or other metals, such as NaOH (Alternatively, Ca (OH)
₂ ) was dissolved in an aqueous solution in which about 2 wt% was dissolved, whereby a very hydrophilic film 66 shown in the following (Chem. 21) could be formed (FIG. 6 (e)).

[0059]

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The monomolecular film adsorbed water vapor in the air, and had a conductivity of about 10 ⁻⁷ S / cm.

[0061]

As described above, according to the method of the present invention, the surface of the CRT display surface is formed by a chemical bond through a molecule in which a hydrophilic functional group for the purpose of preventing static electricity is chemically adsorbed on the display surface. Therefore, an antistatic chemisorption monomolecular film having any conductivity can be relatively freely formed on the display surface. That is, since the weakly conductive functional group is fixed to the CRT display surface by a chemical bond via the chemically adsorbed molecule, the CRT surface can be prevented from being charged. Further, since this monomolecular film is fixed by a chemical bond, it does not peel off. Moreover, since the thickness of the monomolecular film is on the order of nanometers, there is no possibility of deteriorating the image on the display screen. Accordingly, there is an effect that it is possible to eliminate the generation of dirt due to charging of the CRT display surface.

[Brief description of the drawings]

FIG. 1 is a view for explaining a step of forming an antistatic monomolecular thin film on a CRT display surface according to a first embodiment of the present invention;
It is a process sectional view which expanded a CRT display surface to the molecular level.

FIG. 2 is a process sectional view in which a display surface is enlarged to a molecular level in order to explain a step of forming an antistatic monomolecular thin film on a liquid crystal display surface according to a second embodiment of the present invention.

FIG. 3 is a view for explaining a step of forming an antistatic monomolecular thin film on a CRT display surface according to a third embodiment of the present invention;
It is a process sectional view which expanded a CRT display surface to the molecular level.

FIG. 4 is a view for explaining a step of forming an antistatic monomolecular thin film on a CRT display surface according to a fourth embodiment of the present invention;
It is a process sectional view which expanded a CRT display surface to the molecular level.

FIG. 5 is a view for explaining a step of forming an antistatic monomolecular thin film on a CRT display surface according to a fifth embodiment of the present invention;
It is a process sectional view which expanded a CRT display surface to the molecular level.

FIG. 6 is a view for explaining a step of forming an antistatic monomolecular thin film on a CRT display surface according to a sixth embodiment of the present invention;
It is a process sectional view which expanded a CRT display surface to the molecular level.

[Explanation of symbols]

11, 31, 41, 51, 61 CRT display surface 21 Liquid crystal display surface 12, 22, 32, 42, 52, 62 Hydroxyl groups 13, 14, 15, 23, 24, 25, 33, 34, 4
3, 44, 45, 53, 54, 63, 64, 65, 66
Monolayer

 ──────────────────────────────────────────────────続 き Continuing on the front page Judge Chief of the Panel Mitsuaki Hara Judge Keiichi Hashimoto Judge Akihiro Yamamoto (56) References JP-A-63-160131 (JP, A) JP-A-63-6792 (JP, A) JP 63-96655 (JP, A)

Claims (4)

(57) [Claims] 1. A display having a display surface covered with a chemisorption monolayer, wherein the chemisorption monolayer is bonded to the display surface by a siloxane bond, and a hydrophilic group is formed on the surface of the monolayer. And a conductivity of 10 ^-6 S / c
An antistatic display characterized by being in the range of m to ^{10 -10} S / cm . 2. The monomolecular film has the following formula: A- (B) _r -SiCl ₃ (where A is a bromo group, an iodo group, a cyano group,
A functional group containing a thiocyano group, a chlorosilyl group, or an ester bond , B represents an organic group, and r represents a natural number of 30 or less). The antistatic display according to claim 1, wherein the surface and the surface are bonded by a siloxane bond. 3. The compound according to claim 2, wherein the hydrophilic group is —OH, —COOH, or —NH.
_{^{2, -N + R 3 X -}} (R is an alkyl group, X represents a halogen atom), - NO ₂ antistatic display according to claim 1 or -SO ₃ H group,. 4. The antistatic display according to claim _{3, wherein} H of the —COOH or —SO ₃ H group is substituted with an alkali metal, an alkaline earth metal or another metal.