Coating composition comprising bis-type silane compound

Abstract

The present invention relates to a coating composition comprising a bis-type silane compound, and particularly relates to a coating composition which has high storage stability and can form a highly transparent and high-strength coating film, a preparation method thereof and a coating film formed using the same.

Claims

1. A coating film comprising: a transparent substrate selected from the group consisting of a glass substrate, a polyimide (PI) substrate, a polyethylene terephthalate (PET) substrate, a polycarbonate (PC) substrate, a cycloolefin polymer (COP) substrate, and a polyethylene naphthalate (PEN) substrate, and a coating composition disposed on the transparent substrate comprising a bis-type silane compound represented by the following chemical formula 1, graphene or a conductive polymer, and a mixture solvent of an acidic or basic aqueous solution and an alcohol, wherein the ratio of SiOH of chemical formula 1 is at least 50% of the total silane residue SiR: ##STR00005## wherein, R is a divalent linking group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a combination thereof; R is each independently selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a vinyl group, an epoxy group, a thiol group and a combination thereof; and n is an integer of 1 to 20, and wherein the pH of the aqueous solution is not higher than 6.5 or not lower than 7.5, wherein the pH of the aqueous solution and the alcohol are characterized by having such a relationship that a value calculated by the following calculation formula 1 satisfies a range of 0.001 to 5:
(pH of aqueous solution 100 g/amount of alcohol (g))100.[Calculation formula 1]

2. The coating film according to claim 1, wherein the ratio of SiOH of chemical formula 1 is at least 98% of the total silane residue SiR.

3. A method of preparing a coating film comprising: preparing a coating composition by stirring a silane compound represented by the following chemical formula 2 in a mixture solvent of an acidic or basic aqueous solution and an alcohol: ##STR00006## wherein, R is a divalent linking group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a combination thereof; R is each independently selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a vinyl group, an epoxy group, a thiol group and a combination thereof, with the proviso that at least two or more are a hydroxyl group or an alkoxy group; and n is an integer of 1 to 20, and wherein the pH of the aqueous solution is not higher than 6.5 or not lower than 7.5, wherein the pH of the aqueous solution and the alcohol are characterized by having such a relationship that a value calculated by the following calculation formula 1 satisfies a range of 0.001 to 5:
(pH of aqueous solution 100 g/amount of alcohol (g))100,[Calculation formula 1] mixing a graphene or a conductive polymer with the coating composition, and coating the mixed composition on a transparent substrate selected from the group consisting of a glass substrate, a polyimide (PI) substrate, a polyethylene terephthalate (PET) substrate, a polycarbonate (PC) substrate, a cycloolefin polymer (COP) substrate, and a polyethylene naphthalate (PEN) substrate, and, curing the mixed composition.

4. The method of preparing a coating film as claimed in claim 1, wherein the value calculated by calculation formula 1 satisfies a range of 0.05 to 2.

5. The coating film according to claim 1, wherein the graphene or the conductive polymer is included in an amount of 0.005 to 90% by weight of the coating composition.

6. The coating film as claimed in claim 1, wherein a hardness of the coating film is not less than 8H when the transparent substrate is coated with the composition and cured.

7. The coating film as claimed in claim 1, wherein a transmittance of the coating film is not less than 92% when the transparent substrate is coated with the composition and cured.

8. The coating film as claimed in claim 1, wherein a sheet resistance of the coating film is not more than 8.0 ohm/sq when the transparent substrate is coated with the composition and cured.

9. An article containing the coating film described in claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph showing the TGA thermal analysis results of the coating composition of Example 1 of the present invention.

(2) FIG. 2 is a microscope picture of the surfaces obtained after curing the coating compositions prepared in Example of the present invention and Comparative Example.

DETAILED DESCRIPTION OF THE INVENTION

(3) Hereinafter, the invention will be described in detail.

(4) The coating composition of the present invention comprises a bis-type silane compound represented by the following chemical formula 1, and a mixture solvent of an acidic or basic aqueous solution and an alcohol, wherein the ratio of SiOH of chemical formula 1 is at least 50% of the total silane residue SiR:

(5) ##STR00003##

(6) wherein,

(7) R is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a vinyl group, an epoxy group, a thiol group and a combination thereof;

(8) R is each independently selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a vinyl group, an epoxy group, a thiol group and a combination thereof; and

(9) n is an integer of 1 to 20.

(10) Preferably, the ratio of SiOH of chemical formula 1 may be at least 95% of the total SiR, more preferably at least 98%. In this case, it is more advantageous for forming a coating film of high strength.

(11) The above coating composition may be prepared by reacting a bis-type silane monomer of the following chemical formula 2 with an alcohol as a solvent in an acidic or basic aqueous solution:

(12) ##STR00004##

(13) wherein,

(14) R is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a vinyl group, an epoxy group, a thiol group and a combination thereof;

(15) R is each independently selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 30 carbon atoms, an amino group, a vinyl group, an epoxy group, a thiol group and a combination thereof, with the proviso that at least two or more are a hydroxyl group or an alkoxy group; and

(16) n is an integer of 1 to 20.

(17) In the present invention, in order to obtain a stable coating composition, the pH of the acidic or basic aqueous solution (100 g) is not higher than 6.5 or not lower than 7.5 when one mole of the monomer is used, and the pH of the aqueous solution and the alcohol used as a solvent are characterized by having such a relationship that a value calculated by the following calculation formula 1 satisfies a range of 0.001 to 5.
(pH of aqueous solution 100 g/amount of alcohol (g))100[Calculation formula 1]

(18) In the present invention, the value calculated according to the above calculation formula 1 may satisfy a range of 0.001 to 5, preferably 0.05 to 2. If the pH of the aqueous solution is not within the above range, the above calculation formula is not applicable.

(19) Furthermore, there is no restriction on the kinds of the acids, bases and alcohols, and any kinds of them may be used as long as they are commonly used in the pertinent art.

(20) The monomer in the coating composition of the present invention is in an organic-inorganic hybrid form, the alkoxy group or hydroxyl group represented by R participates in precursor reaction, and the R serves to improve the surface properties by acting as an organic bridge in the curing process of the prepared precursor to minimize the shrinkage. In addition, even after prepared into a coating film after the curing process, the electronic environment of the organic bridge and silicon becomes greatly stable in comparison with conventional TEOS or silazane and therefore, it is a structure that can assure a high stability even after the process.

(21) Accordingly, the precursor in the accordance with the present invention where the residual rate of SiOH in the coating composition is high exists in a stable state while SiOH of the bis-type silane is not being condensed, and in the subsequent condensation curing process by heat, it is simultaneously condensed at a fast speed, thereby to be able to prepare a high-density and high-strength film.

(22) Further, the present invention provides a functional coating composition further comprising an organic functional material in addition to the above coating composition. More particularly, since the coating composition in accordance with the present invention exhibits excellent compatibility with various organic functional materials, the functional coating composition of the present invention may be a composition that comprises the bis-type silane monomer as a matrix binder and further comprises an organic functional material as a functional material.

(23) In the present invention, the organic functional material may be functional materials that are commonly used in the pertinent art, preferably hydrophilic materials, and more preferably graphene, a conductive polymer or an organic dye. In the present invention, the organic functional material may be mixed in an amount of 0.005 to 90% by weight, preferably in an amount of 0.05 to 60% by weight.

(24) The present invention provides a coating film prepared by coating and curing the above coating composition or functional coating composition on a base material.

(25) In the present invention, the coating film may be prepared by methods that are commonly used in the pertinent art, and for example it can be prepared by coating the coating composition or functional coating composition on a base material which is selected for the intended purpose, and drying and heat-curing it.

(26) In the present invention, a variety of coating methods that are commonly used in the pertinent art may be used, in particular a method using a solution process can be used, and preferably, by using a spin coating method, dipping method, bar coating method, roll coating method, spraying method, etc., the coating film can be printed on a commonly used transparent substrate, for example, a glass substrate, a polyimide (PI) substrate, a polyethylene terephthalate (PET) substrate, a polycarbonate (PC) substrate, a cycloolefin polymer (COP) substrate, a polyethylene naphthalate (PEN) substrate and so on. In addition, the coating thickness is preferably adjusted properly depending on its purpose.

(27) The coating film may be cured by a conventional curing method, preferably a thermal curing method, and preferably it can be carried out at a temperature of 80 to 500 C.

(28) The coating film prepared in accordance with the invention has excellent surface properties such as density and strength by using the precursor coating solution with a high SiOH residual rate whereby the remaining SiOH is simultaneously condensed at a fast speed during the curing process, and preferably it may have a hardness of not less than 8H, a transmittance of not less than 92%, and a sheet resistance of not more than 8.0 ohm/sq.

(29) In addition, the functional coating film prepared from the functional coating composition further comprising the organic functional material shows not only a high transmittance, high strength and excellent sheet resistance, but also a stable performance with little change in the physical properties even when combined with organic functional materials and thus, it can be applied without limits in a variety of fields such as a heat resistant light-sensitive material, a high refraction property based flexible substrate material, and a material for manufacturing special film.

(30) For a better understanding of the present invention, preferred examples follow. The following examples are intended to merely illustrate the invention without limiting the scope of the invention.

EXAMPLES

Example 1: Preparation of Stable Coating Composition Using Bis-Type Silane Monomer

(31) 100 G of 0.01 M aqueous hydrochloric acid solution was dropwise added to a dry flask equipped with a cooling tube and a stirrer, stirred for 10 min, and followed by the addition of 1000 g of ethanol so that a value of the following calculation formula (1) was adjusted to 0.2. One mole (354.59 g) of 1,2-bis(triethoxysilyl)ethane (BTSE) was dropwise added to the thus prepared mixture solvent, and stirred at a room temperature for 24 hours to prepare a coating composition.
(pH of aqueous solution 100 g/amount of alcohol (g))100[Calculation formula 1]

Comparative Example 1

Preparation of Coating Composition Using TEOS as Monomer

(32) 100 G of 0.01 M aqueous hydrochloric acid solution was dropwise added to a dry flask equipped with a cooling tube and a stirrer, stirred for 10 min, and after the addition of one mole of TEOS and 1000 g of ethanol, stirred at a room temperature for 24 hours to prepare a coating composition.

Test Example 1: Stability Test of Coating Composition

(33) In order to examine a degree of hydrolysis and an amount of SiOH that stably remains without being condensed in the coating compositions prepared in the above Example 1 and Comparative Example 1, .sup.1H-NMR and .sup.29Si-NMR were measured every 10 days for 60 days, and the results are shown in Table 1 below.

(34) TABLE-US-00001 TABLE 1 Hydrolysis Rate (%).sup.a SiOH Residual Rate (%).sup.b 10 20 40 60 10 20 40 60 days days days days days days days days Beginning after after after after Beginning after after after after Ex. 1 100 100 100 100 100 98.4 98.2 98.2 98.0 97.9 Com. 100 100 Gelation 80.4 71.2 gelation Ex. 1 .sup.aresidual amount of alkoxy groups calculated using .sup.1H-NMR .sup.bsiloxane production amount calculated using .sup.29Si-NMR

(35) As shown in Table 1 above, in the case of the coating composition of Comparative Example 1, gelation occurred within 20 days and reaction stability was remarkably deteriorated, whereas in the case of the coating composition of Example 1, only condensation rate change of 0.5% or so occurred during 60 days, and the residual rate of SiOH was maintained in a stable state of more than 98%.

Test Example 2: Stability Test of Coating Composition

(36) TGA measurement was carried out regarding the coating compositions prepared in above Example 1 and Comparative Example 1 to establish curing sections by heat, and the results are shown in FIG. 1.

(37) As shown in FIG. 1, the beginning point of the first condensation and curing by heat was confirmed to be 80 C.

(38) Further, surfaces prepared by coating the coating compositions on a glass substrate, and then curing them at 80 C. for one hour were observed for 60 days in the same manner as in Test Example 1, and a change in the surface hardness is shown in Table 2 below and its surface pictures are shown in FIG. 2.

(39) TABLE-US-00002 TABLE 2 Pencil Hardness Change (H).sup.a 10 days 20 days 40 days 60 days Beginning after after after after Ex. 1 9H 9H 9H 9H 9H Com. 1 8H 6H 5H 3H .sup.aMitsubishi pencil, 1 kgf, fail in the event that two times or more scratches out of five experiments occur

(40) As shown in Table 2 above, the TEOS based coating film of Comparative Example 1 showed a phenomenon in which the hardness was reduced due to the high film shrinkage and residual SiOH. On the other hand, in Example 1, high hardness was maintained for a long time, and stable results could be obtained. This is a phenomenon resulting from the electronic stability of organic functional groups and silicon, and it is considered because a re-formation reaction of the produced siloxane did not occur. In addition, as shown in FIG. 2, it was confirmed that the coating film of Example 1 showed a very flat characteristic without cracking, but the TEOS based coating film of Comparative Example 1 was all shattered after 60 days.

Example 2: Preparation of Functional Coating Composition Using Graphene

(41) A commercially available graphene manufactured by Hummers method of Korea Patent Application No. 2011-0119354 as an organic functional material was mixed in an amount of 0.1% by weight with the coating composition prepared in Example 1 and stirred for one day to prepare a functional coating composition.

Comparative Example 2: Preparation of Mixture Composition of Coating Composition of Comparative Example 1 and Graphene

(42) With the exception that the coating composition obtained in Comparative Example 1 was used instead of the coating composition prepared in Example 1, a mixture composition was prepared in the same manner as in Example 2.

Test Example 3: Characterization of Mixture Composition

(43) For the characterization of the mixture compositions of above Example 2 and Comparative Example 2, the compositions were coated on a glass substrate. The coating films were cured under the same curing conditions as in Test Example 2 and then, transmittance and sheet resistance were measured for 60 days, and the results are shown in Table 3 below.

(44) TABLE-US-00003 TABLE 3 Transmittance (%).sup.a Sheet Resistance (ohm/sq).sup.b 10 20 40 60 10 20 40 60 days days days days days days days days Beginning after after after after Beginning after after after after Ex. 2 95 94 95 95 94 6.8 6.8 6.7 6.8 6.8 Com. 91 92 90 89 89 6.4 7.0 7.5 8.1 8.3 Ex. 2 .sup.ameasurement equipment is based on UV/visible light 500 nm, and the glass substrate is defined as a baseline. .sup.bindicating exponent values in 1 10.sup.x.

(45) As shown in Table 3 above, it was confirmed that the coating film of Example 2 derived constant values in transmittance and sheet resistance which is a change value of electrical properties whereas the coating film of mixture of Comparative Example 2 showed a large-scale change in transmittance and sheet resistance due to the re-formation reaction of siloxane and unstable surface stability, etc.

Example 3: Preparation of Functional Coating Composition Using Conductive Polymer

(46) Doped poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) as a commercially available conductive polymer was dissolved in 1% by weight aqueous solution of HG-KL15 of Hube Globe, Inc. and then, the thus prepared conductive polymer solution was mixed in an amount of 40% by weight with the coating composition obtained in Example 1 and stirred for one day to prepare a mixture composition.

Comparative Example 3: Preparation of Mixture Composition of Coating Composition of Comparative Example 1 and Conductive Polymer

(47) With the exception that the coating composition of Comparative Example 1 was used instead of the coating composition of Example 1, a mixture composition was prepared in the same manner as in Example 3.

Test Example 4: Characterization of Mixture Composition

(48) For the characterization of the mixture compositions of above Example 3 and Comparative Example 3, the compositions were coated on a glass substrate. The coating films were cured under the same curing conditions as in Test Example 2 and then, transmittance and sheet resistance were measured for 60 days, and the results are shown in Table 4 below.

(49) TABLE-US-00004 TABLE 4 Transmittance (%).sup.a Sheet Resistance (ohm/sq).sup.b 10 20 40 60 10 20 40 60 days days days days days days days days Beginning after after after after Beginning after after after after Ex. 3 92 92 92 92 92 7.5 7.5 7.6 7.6 7.6 Com. 91 92 92 90 90 6.4 76 7.9 8.4 9.2 Ex. 3 .sup.ameasurement equipment is based on UV/visible light 500 nm, and the glass substrate is defined as a baseline. .sup.bindicating exponent values in 1 10.sup.x.

(50) As shown in Table 4 above, it was confirmed that the coating film of mixture of Example 3 derived constant values in transmittance and sheet resistance which is a change value of electrical properties whereas the coating film of mixture of Comparative Example 3 showed a large-scale change in transmittance and sheet resistance due to the re-formation reaction of siloxane and unstable surface stability, etc.

(51) Taken together the above results, the bis-type precursor of the present invention has a high transmittance and high strength property and also shows a stable performance with little change in physical properties even when combined with organic functional materials and therefore, it can be applied without limits in a variety of fields.

(52) The coating composition of the invention enables a solution process, has excellent storage stability, and exhibits a high transmittance and high strength property when cured. In addition, when combined with organic functional materials, it exhibits high compatibility and excellent physical property. Furthermore, when the functional coating composition of the invention is applied across the industry, it can be widely used in a variety of fields such as a heat resistant light-sensitive material, a high refraction property based flexible substrate material, and a material for manufacturing special film.