GB2300641A - Transparent electro-conductive coating composition - Google Patents
Transparent electro-conductive coating composition Download PDFInfo
- Publication number
- GB2300641A GB2300641A GB9600822A GB9600822A GB2300641A GB 2300641 A GB2300641 A GB 2300641A GB 9600822 A GB9600822 A GB 9600822A GB 9600822 A GB9600822 A GB 9600822A GB 2300641 A GB2300641 A GB 2300641A
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- GB
- United Kingdom
- Prior art keywords
- coating composition
- acid
- conductive coating
- transparent electric
- composition according
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/86—Vessels; Containers; Vacuum locks
- H01J29/867—Means associated with the outside of the vessel for shielding, e.g. magnetic shields
- H01J29/868—Screens covering the input or output face of the vessel, e.g. transparent anti-static coatings, X-ray absorbing layers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05F—STATIC ELECTRICITY; NATURALLY-OCCURRING ELECTRICITY
- H05F1/00—Preventing the formation of electrostatic charges
- H05F1/02—Preventing the formation of electrostatic charges by surface treatment
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Glass (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
2300641 1 A TRANSPARENT ELECTRIC-CONDUCTIVE COATING COMPOSITION
Field of the Invention
The present invention relates to a transparent electric-conductive coating composition and, more particularly, to a transparent electric- conductive coating composition containing an indium compound, a polybasic carboxylic acid and a tin compound as solid components, ethylene glycol and terpineol as main solvents, and ethyl alcohol, n-butyl alcohol and ethylcellosolve as diluent solvents, which composition exhibits improved properties of optical transmittancy, friction resistance and adhesion for substrates such as glasses and ceramics. The above properties of the invention render electric-conductivity to glass substrates of display tubes such as CRT, LCD, VFD and electro luminescence so that electric failure due to static electricity in the transparent electric-conductive circuits and dust pollution of the displayer are effectively prevented.
Description of the Related Art
A large amount of static electricity is charged on the surface of the glass substrates of display tubes such as CRT, LCD, VFD and electro luminescence when they are operated. Accordingly, many charged dusts are easily attached on the surface to decrease the visual image, having a bad effect on the user. Therefore, various methods have been developed to prevent static electricity on the surface of the display tubes. Nowadays, a method has been developed by forming a transparent electric-conductive layer having metal components to give conductivity on the surface of the display tubes.
Vapour deposition methods such as chemical vapour deposition and physical vapour deposition have been performed to form a transparent electricconductive layer on glass or ceramic display tubes. A gas phase deposition, according to these 1= Z:1 vapour deposition methods, however, requires an expensive and large vacuum Z:1 deposition equipment, and limits the surface area and the form of the substrates.
To solve the above problems, Japanese Patent Publication Nos. 83-478, 83 2597 and 83-1424 disclose a method of coating a solution of an indium compound 2 and a tin compound dissolved in an organic solvent on the substrate and then baking at a temperature of 300 to 70WC. The layer formed by the above method, however, has a poor adhesive property with the substrate and problems of stripping and scratching because of low layer strength.
Description of the Invention
To solve the above problems, the present invention provides a transparent electric-conductive coating composition containing an indium compound, a polybasic carboxylic acid and a tin compound as solid components, ethylene glycol and terpineol as main solvents, and ethyl alcohol, ri-butyl alcohol and ethylcellosolve as subsidiary solvents.
The present invention also provides a process for forming a transparent electric-conductive coating composition. An indium compound and a polybasic carboxylic acid are dissolved in a solution in which water and ethyl alcohol are mixed to form a complex salt of the indium compound. Ethylene glycol as a main solvent and terpineol as a subsidiary solvent are added to the compound. A diluent solution composed of ethyl alcohol, n-butyl alcohol and ethylcellosolve is added and the resulting solution is stirred at ambient temperature for 4 hours. Tin octanoate is added to the solution and then a transparent electric-conductive coating composition of the present invention is formed by aging the solution for 24 hours.
Indium nitrate trihydrate (In(N03)33H,0) is particularly preferable for the indium compound which may form a complex salt with a polybasic carboxylic acid.
The amount of indium compound is from 1 to 10 wt % of the total composition.
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, furnaric acid, phthalic acid, isophthalic acid, terephthalic acid or edetic acid (EDTA) can be used as the polybasic carboxylic acid and the amount thereof is 0. 1 to 'D wt % in the total composition. The amount of tin compound mainly composed of tin octanoate is 0.1 to 3 wt % of the total composition. It is a feature of the present invention that ethylene glycol and terpineol are used as main solvents in the composition of the present invention. The ethylene glycol increases layer strength formed from the composition of the present invention, and the terpineol improves dryness and uniformity of the dried layer. It is preferable that the amount of j ethylene glycol is 10 to 40 wt % of the total composition and the terpineol also 10 to 40 wt %. Moreover, it is preferable that the amount of ethyl alcohol, n-butyl alcohol and ethylcellosolve is 10 to 50 wt % in the total composition respectively, and the mixing ratio is 1: 1: 1 to decrease the temperature of the composition.
The coating composition of the present invention can be easily and evenly coated on substrates such as glass or ceramic by general coating methods such as roll coating methods. The coated layer has enhanced adhesive property to substrates such as glass or ceramic, is dried rapidly below a temperature of 20CC, and is easily baked below a low temperature of 50WC. Additionally, the coated layer has not only preferable optical transmittancy but preferable friction resistance because of the enhanced surface strength thereof.
Working Example 1 g parts of indium nitrate trihydrate and 15 parts of furnaric acid were added and dissolved in 100 parts of solution in which water and ethyl alcohol were mixed with a ratio of 1: 1 by weight. A mixture of 200 parts of ethylene glycol and parts of terpineol was added to the solution and then 500 parts of a mixture of ethyl alcohol, n-butyl alcohol and ethylcellosolve with a mixing ratio of 1: 1: 1 was added and stirred at ambient temperature for 4 hours. 15 parts of tin octanoate were added in the above solution, and the resulting solution was aged for 24 hours with stirring to produce a paste-type coating composition. The coating composition was coated on a glass substrate by a roll coating method and dried at 150 to 18CC in the air atmosphere to evaporate the solvent to obtain a homogeneous coating layer.
Subsequently, the coated substrate was calcined at 50CC in air atmosphere for 3) hours to obtain a transparent electric-conductive layer.
Working Example 2 a, parts indium nitrate trihydrate and 15 parts of fumaric acid were added and dissolved in 100 parts of solution in which water and ethyl alcohol were mixed with a ratio of 1: 1 by weight. A mixture of 300 parts of ethylene glycol and 200 parts of terpineol was added in the solution and then 400 parts of a mixture of ethyl alcohol, n-butyl alcohol and ethylcellosolve with a inixing, ratio of 1: 1: 1 was 4 added and stirred at the ambient temperature for 4 hours. 15 parts of tin octanoate were added in the above solution, and the resulting solution was aged for 24 hours with stirring to produce a paste-type coating composition. The coating composition was coated on a glass substrate by a roll coating method and dried at 150 to 1800C in the air atmosphere to evaporate the solvent to obtain a homogeneous coating layer. Subsequently, the coated substrate was calcined at 50CC in air atmosphere for 3 hours to obtain a transparent electric-conductive layer.
Working Example 3 g parts indium. nitrate trihydrate and 15 parts of fumaric acid were added and dissolved in 100 parts of solution in which water and ethyl alcohol were mixed with a ratio of 1: 1 by weight. A mixture of 400 parts of ethylene glycol and 300 parts of terpineol was added in the solution and then 300 parts of a mixture of ethyl alcohol, n-butyl alcohol and ethylcellosolve with a mixing ratio of 1: 1: 1 was added and stirred at the ambient temperature for 4 hours. 15 parts of tin octanoate were added in the above solution, and the resulting solution was aged for 24 hours with stirring to produce a paste-type coating composition. The coating composition was coated on a glass substrate by a roll coating method and dried at 150 to 18CC in the air atmosphere to evaporate the solvent to obtain a homogeneous coating layer. Subsequently, the coated substrate was calcined at 5000C in air atmosphere for 3 hours to obtain a transparent electric-conductive layer.
Workins! Example 4 g parts indium nitrate trihydrate and 15 parts of furnaric acid were added and dissolved in 100 parts of solution in which water and ethyl alcohol were mixed with a ratio of 1: 1 by weight. A mixture of 400 parts of ethylene glycol and 3)00 parts of terpineol was added in the solution and then 200 parts of a mixture of ethyl alcohol, n-butyl alcohol and ethylcellosolve with a mixing ratio of 1: 1: 1 was added and stirred at the ambient temperature for 4 hours. 15 parts of tin octanoate were added in the above solution. and the resulting solution was aged for 24 hours with stirring to produce a paste-type coating composition. The coating composition was coated on a glass substrate by a roll coating method and dried at 150 to 18CC in the air atmosphere to evaporate the solvent to obtain a homogeneous coating layer. Subsequently, the coated substrate was calcined at 50CC in air atmosphere for 3 hours to obtain a transparent electric-conductive layer.
Comparative Example 1 g parts indium nitrate trihydrate and 15 parts of furnaric acid were added and dissolved in 100 parts of solution in which water and ethyl alcohol were mixed with a ratio of 1: 1 by weight. 500 parts of terpineol were added in the solution and then 400 parts of a mixture of ethyl alcohol, n-butyl alcohol and ethylcellosolve with the mixing ratio of 1: 1: 1 was added and stirred at the ambient temperature for 4 hours. 15 parts of tin octanoate were added in the above solution, and the resulting solution was aged for 24 hours with stirring to produce a paste-type coating composition. The coating composition was coated on a glass substrate by a roll coating method and dried at 150 to 18CC in the air atmosphere to evaporate the solvent to obtain a homogeneous coating layer. Subsequently, the coated substrate was calcined at 500 C in air atmosphere for 3 hours to obtain a transparent electric conductive layer.
Comparative Fxaml2le 2 g parts indium nitrate trihydrate and 15 parts of furnaric acid were added and dissolved in 100 parts of solution in which water and ethyl alcohol were mixed with a ratio of 1: 1 by weight. A mixture of 100 parts of ethylene glycol and 200 parts of terpineol was added in the solution and then 600 parts of a mixture of ethyl alcohol, n-butyl alcohol and ethylcellosolve with the mixing ratio of 1: 1: 1 was added and stirred at the ambient temperature for 4 hours. 15 parts of tin octanoate were added in the above solution, and the resulting solution was aged for 24 hours with stirring to produce a paste-type coating composition. The coating composition was coated on a glass substrate by a roll coating method and dried at 150 to 18CC in the air atmosphere to evaporate the solvent to obtain a homogeneous coating layer. Subsequently, the coated substrate was calcined at 50CC in air atmosphere for 3 hours to obtain a transparent electric-conductive layer.
Sheet resistance, optical transmittancy and layer strength of the electric- 6 conductive layers produced in the working examples and the comparative examples are listed in the following Table.
TABLE
Sheet Optical Layer Resistance Transmittancy Strength (kQ/cm') (%T) Work. Exam. 1 2.54 91.2 100 Work. Exam. 2 3.12 91.4 500 Work. Exam. 3 2.15 91.3 500 Work. Exam. 4 2.68 91.2 500 xam. 1 2.81 91.5 30 CF. Exam. 2 2.38_ 91.3 so The layer strength was measured by the number of times of abrasion until the coated layer was about to strip.
As shown in the above Table, the coated layers which are made from the coating compositions of the present invention show improved sheet resistance of below 3. 12 kQ/cm2, optical transmittancy of above 9 1 % and layer strength of above 100.
7
Claims (12)
1. A transparent electric-conductive coating composition comprising a main solvent, a subsidiary solvent, and solid components, wherein the said main solvent comprises ethylene glycol and terpineol, the said subsidiary solvent comprises ethyl alcohol, n-butyl alcohol and ethylcellosolvyand the solid components comprise an indium compound, a polybasic carboxylic acid and a tin compound.
2. A transparent electric-conductive coating composition according to claim 1, wherein the amount of the indium compound is 1 to 10 wt % of the total composition.
3. A transparent electric-conductive coating composition according to claim 1 or claim 2, wherein the polybasic carboxylic acid is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, furnaric acid, phthalic acid, isophthalic acid, terephthalic acid and edetic acid.
4. A transparent electric-conductive coating composition according to any one of claims 1 to 3, wherein the amount of the polybasic carboxylic acid is 1 to 3 wt % of the total composition.
5. A transparent electric-conductiv.e coating composition according to any one of claims 1 to 4, wherein the tin compound is mainly composed of tin octanoate and the amount thereof is 1 to 3 wt % of the total composition.
6. A transparent electric-conductive coating composition according to any one of claims 1 to 5, wherein the amount of the ethylene glycol is 10 to 40 wt % of the total composition.
7. A transparent electric-conductive coating composition according to any one of claims 1 to 6, wherein the amount of the terpineol is 10 to 40 wt % of the total composition.
8. A transparent electrical-conductive coating composition according to any one of claims 1 to 7, wherein the amount of ethyl alcohol, n-butyl alcohol or )o ethylcellosolve respectively 10 to 50 wt % of the total composition.
9. A transparent electric-conductive coating composition according to any one of claims 1 to 8, wherein the mixing ratio of ethyl alcohol, n-butyl alcohol and r 8 ethylcellosolve is about 1: 1: 1 by weight.
10. A process for forming a transparent electric-conductive coating composition comprising the steps of. dissolving an indium compound and a polybasic carboxylic acid in a solution 5 in which water and ethyl alcohol are mixed to form a complex salt of the indium compound; adding ethylene glycol and terpinol; adding ethyl alcohol, n-butyl alcohol and ethylcellosolve; stirring the solution at ambient temperature for 4 hours; adding tin octanoate to the solution; and aging for 24 hours.
11. A transparent electric-conductive coating composition substantially as described herein with reference to working Examples 1 to 4.
12. A process for forming a transparent electric-conductive coating composition substantially as describe herein with reference to working Examples 1 to 4.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950011467A KR0149293B1 (en) | 1995-05-10 | 1995-05-10 | Transparent conductive coating composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9600822D0 GB9600822D0 (en) | 1996-03-20 |
| GB2300641A true GB2300641A (en) | 1996-11-13 |
| GB2300641B GB2300641B (en) | 1998-10-21 |
Family
ID=19414119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9600822A Expired - Fee Related GB2300641B (en) | 1995-05-10 | 1996-01-16 | A transparent electric-conductive coating composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH08302248A (en) |
| KR (1) | KR0149293B1 (en) |
| CN (1) | CN1112415C (en) |
| DE (1) | DE19603796A1 (en) |
| GB (1) | GB2300641B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4373996B2 (en) * | 2006-06-09 | 2009-11-25 | 三菱マテリアル電子化成株式会社 | Conductive anti-glare film forming composition, conductive anti-glare film and display |
| DE102007013181B4 (en) * | 2007-03-20 | 2017-11-09 | Evonik Degussa Gmbh | Transparent, electrically conductive layer |
| DE102009009337A1 (en) * | 2009-02-17 | 2010-08-19 | Evonik Degussa Gmbh | Process for the preparation of semiconductive indium oxide layers, indium oxide layers produced by the process and their use |
| CN102418407A (en) * | 2011-10-11 | 2012-04-18 | 信益陶瓷(中国)有限公司 | Anti-static ceramic tile |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4303554A (en) * | 1979-06-22 | 1981-12-01 | Hitachi, Ltd. | Composition and process for producing transparent conductive film |
| US4369208A (en) * | 1979-12-14 | 1983-01-18 | Hitachi, Ltd. | Process for producing transparent electroconductive film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63143706A (en) * | 1986-12-05 | 1988-06-16 | 触媒化成工業株式会社 | Transparent conducting coat liquid composition and base material having transparent conducting film |
| KR920001836B1 (en) * | 1989-09-08 | 1992-03-05 | 삼성전관 주식회사 | Cathode ray tube |
| JPH05166423A (en) * | 1991-12-11 | 1993-07-02 | Asahi Glass Co Ltd | Manufacture of conductive film and low reflective conductive film |
-
1995
- 1995-05-10 KR KR1019950011467A patent/KR0149293B1/en not_active IP Right Cessation
-
1996
- 1996-01-16 GB GB9600822A patent/GB2300641B/en not_active Expired - Fee Related
- 1996-02-02 DE DE19603796A patent/DE19603796A1/en not_active Withdrawn
- 1996-03-26 JP JP8068856A patent/JPH08302248A/en active Pending
- 1996-05-09 CN CN96105842A patent/CN1112415C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4303554A (en) * | 1979-06-22 | 1981-12-01 | Hitachi, Ltd. | Composition and process for producing transparent conductive film |
| US4369208A (en) * | 1979-12-14 | 1983-01-18 | Hitachi, Ltd. | Process for producing transparent electroconductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9600822D0 (en) | 1996-03-20 |
| JPH08302248A (en) | 1996-11-19 |
| KR0149293B1 (en) | 1998-10-01 |
| KR960041295A (en) | 1996-12-19 |
| CN1112415C (en) | 2003-06-25 |
| DE19603796A1 (en) | 1996-11-14 |
| CN1141322A (en) | 1997-01-29 |
| GB2300641B (en) | 1998-10-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20010116 |