KR100522832B1 - Coating Solution Composition Having Anti-dust Property and Low Reflection Property and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to a coating liquid composition having fouling resistance and low reflectivity, and a method for preparing the same, including 4 to 15 parts by weight of alkoxysilane, 0.8 to 7 parts by weight of fluorine silane, 0.01 to 0.5 part by weight of surfactant, and 0.01 to 0.05 part by weight of acid catalyst. And 90 to 94 parts by weight of solvent, and exhibit low reflection and stain resistance at the same time. In particular, it exhibits a function of preventing adhesion of dust due to friction and the like, and when applied to the outermost layer of the display, the effect of reducing the reflectance and appearance can be easily managed. It works.

Description

Coating solution composition having anti-fouling property and low reflection property and its manufacturing method {Coating Solution Composition Having Anti-dust Property and Low Reflection Property and Method for Preparing the Same}

The present invention relates to a coating liquid composition having pollution resistance and low reflection properties and a method for producing the same. More particularly, the present invention relates to a fouling-resistant and low-reflective coating liquid composition suitable for use as a coating liquid for a display and a method for preparing the same, since the fluorine-based silane and a salt-type surfactant have both fouling resistance and low reflection property.

Various displays such as CRTs for monitors, CRTs such as CPTs for TVs, TFT-LCD polarizers, PDP filters, RPTS filters, mobile phone liquid crystals, watches, photographs, picture frames, etc. are closely related to our lives. When the display is exposed to light such as natural light, eye fatigue or headache may be caused by reflected light, and an image produced inside the display may not be clearly formed in the eye, resulting in a decrease in contrast.

In order to solve this problem, there have been studies to develop a low reflection coating layer which reduces the reflectance by inducing extinction interference. Japanese Patent Application Laid-Open Nos. 9-208898 and 8-122501 disclose a low reflection layer having a refractive index of 1.28 to 1.38 prepared using a silicic acid compound and magnesium fluoride (MgF ₂ ) metal oxide, and a European patent application No. 96118471 discloses a coating liquid prepared by using a compound having a fluorine-based silane and a fluorine-based alkyl group and having a low reflection function and a fouling-resistant function due to a decrease in surface energy.

However, the low reflection layer into which the metal oxide or fluorine is introduced has an electric charge on the surface by friction or the like, so that the dust adheres well, and the dust once adhered does not easily fall off. Therefore, it is not suitable for the low reflection layer which is located at the outermost part of the display and must be resistant to contamination sources such as fingerprints and dust. To be resistant to pollutants, the surface energy is low and fingerprints are not easily attached, and the charges on the surface flow without being offset or staying, so that dust does not get stuck by electrostatic attraction.

Therefore, there have been reported methods for preventing the adhesion of dust and the like by not charging the surface. Japanese Patent Publication No. 94-65529 discloses Indium doped Tin Oxide ITO, Antimony-doped Tin Oxide (ATO), Antimony-doped Zinc Oxide (Antimony doped Zinc Oxide) Japanese Patent Laid-Open Publication Nos. 93-295353 and 94-32997 use a method of using a conductive metal oxide filler such as AZO), and Japanese Patent Laid-Open Publication No. 93-339336 have a low molecular weight. It is published over the method of using surfactant of.

However, methods of preventing adhesion of dust and the like by using a conductive metal oxide or a conductive polymer cannot control a low refractive index and thus can not exhibit a low reflection function, and the used surfactant is released to the surface of the coating film with time, so that the effect is long. There is a problem that cannot be sustained.

In order to solve the above problems, the present invention has a low reflection function due to low refractive index and at the same time has a low surface energy and anti-fouling function through anti-static to have a pollution resistance and low reflection property that can be suitably applied to the front of the display. It is an object to provide a coating liquid composition.

In addition, an object of the present invention is to provide a method for producing a coating liquid composition having fouling resistance and low reflection.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is characterized by consisting of 4 to 15 parts by weight of alkoxysilane, 0.8 to 7 parts by weight of fluorine silane, 0.01 to 0.5 parts by weight of surfactant, 0.01 to 0.05 parts by weight of acid catalyst and 90 to 94 parts by weight of solvent. It provides a coating liquid composition having pollution resistance and low reflection.

The alkoxysilane is a group consisting of tetraethylorthosilicate (TEOS), tetramethoxyorthosilicate (TMOS), methyltrimethoxysilane (MTMS) and methyltriethoxy silane (MTES). Can be selected from.

The fluorine silane is tridecafluorooctyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane May be selected from the group consisting of heptadecafluorodecyltriisopropoxysilane.

The surfactant is in the form of a salt having both positive and negative charges, and may have a molecular weight of 200 or more.

Non-fluorinated hydrocarbon salts, non-fluorine-based silane salts, fluorine-based hydrocarbon salts in which the surfactant in the form of a salt having both a positive charge and a negative charge include counter cations such as ions having a negative charge of a carboxyl group, a sulfone group or a hydroxyl group, and an ammonium group And fluorine silane salts.

In addition, the method for preparing a coating liquid composition having fouling resistance and low reflectivity according to the present invention includes (a) 40 to 60 parts by weight of an alkoxysilane, 6 to 20 parts by weight of a fluorine silane, and 0.1 to 5 parts by weight of a surfactant of 30 to 60 parts by weight of a solvent. Adding to; (B) adding 0.1 to 0.5 parts by weight of an acid catalyst to the added (a) to adjust the pH to 0.5 to 3; (C) adding water to adjust the pH to (2) 0.2 to 2 equivalents to the equivalent of water required to hydrolyze the entire silane; (D) subjecting the water to (d) to a sol-gel reaction for 20 to 40 hours at a temperature of 15 to 50 ° C .; And (e) diluting the sol-gel reactant of (d) with a mixed solvent and terminating the reaction at a temperature of 0 to 10 ° C. to prepare a coating solution.

The amount of the sol-gel reactant diluted by the mixed solvent may be 3 to 10 parts by weight of the total diluent.

The mixed solvent of (e) is one alcohol selected from the group consisting of methanol, ethanol, isopropanol and 2-butanol and methyl ethyl ketone, methyl iso One kind of ketone selected from the group consisting of methyl butyl ketone is 50 to 80 parts by weight with respect to the total solvent, methyl acetate, ethyl acetate, butylacetate, tetrahydrofuran (tetrahydrofuran), 2-methoxyethanol (aka methylcellosolve) and 2-butoxyethanol (2-buthoxyethanol (aka, butylcellosolve)) from 10 to 1 solvent based on the total solvent It may be 50 parts by weight.

Hereinafter, the present invention will be described in detail.

The present invention is characterized in that it comprises a fluorine-based silane and a salt-type surfactant in order to provide a coating liquid having a low reflectance and excellent resistance to contamination such as coating on the front surface of the display.

That is, the coating liquid composition having fouling resistance and low reflection of the present invention is 4 to 15 parts by weight of alkoxysilane, 0.8 to 7 parts by weight of fluorine silane, 0.01 to 0.5 part by weight of surfactant, 0.01 to 0.05 part by weight of acid catalyst and 90 to 94 solvent. It consists of parts by weight.

In order to realize the basic mechanical properties of the alkoxysilane coating film, in order to show the strength of the coating film that can be applied to the outermost display, tetraethoxy ortho silicate, tetramethoxy, trifunctional silane-based compound Methyltrimethoxysilane which is a compound, methyltriethoxysilane, etc. are preferable. In addition, the preferable content of the alkoxysilane is 40 to 60 parts by weight. If it is less than 40 parts by weight, the hardness of the coating film for display cannot be maintained, and if it is more than 60 parts by weight, the degree of curing of the coating film is high, causing a curl of the coating material, and the adhesion between the substrate and the coating film is lowered.

 The present invention employs a fluorine-based silane to give the display a low reflection function to the coating film of the display in order to prevent eye fatigue caused by the reflected light. The low reflection function depends on the difference between the refractive index of the substrate and the coating film and the thickness of the coating film, and the fluorine-based silane lowers the refractive index of the coating film for display to exhibit a low reflection function. In addition, the coating film containing a certain amount of fluorine exhibits a water-repellent property in which the surface energy is lowered and the contact angle of the surface and water droplets falls below 20 degrees. The fingerprint film is not stained well and is resistant to contamination such as dust.

As described above, fluorine-based silanes for imparting low reflectance and fouling resistance to a coating film for a display include tridecafluorooctyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, Heptadecafluorodecyltriisopropoxysilane, etc. are preferable. The preferred content of fluorine-based silane is 0.8 to 7 parts by weight. This is 20 to 50 parts by weight based on the whole alkoxy silane and the fluorine-based silane. If it is less than 20 parts by weight, it is difficult to control the refractive index and to ensure contamination resistance, and when it exceeds 50 parts by weight, it is difficult to control the appropriate molecular weight by the sol-gel reaction. The strength of the coating film is lowered.

In addition, the present invention adopts a salt-type surfactant having both a positive charge and a negative charge in order to impart a function of preventing adhesion of dust due to friction among the display coating film. The coating film including the surfactant prevents the positive charge and the negative charge from coexisting in the local part and easily carries a charge by friction with a material having a different electronegativity. Therefore, it is possible to prevent the adhesion of dust or static electricity by blocking the penetration of charges that can occur from the outside. This is different from a general coating film that provides an antistatic function using a conductive metal oxide or a conductive polymer, and is also different from a low resistance coating film for the purpose of shielding electromagnetic waves generated inside a display.

Salt type surfactants having both positive and negative charges as described above include non-fluorinated hydrocarbon salts and non-fluorine silane salts containing negatively charged ions such as carboxyl groups, sulfone groups, hydroxyl groups, and counter cations such as ammonium groups. , Fluorine hydrocarbon salts, fluorine silane salts, and the like, and the molecular weight of the surfactants is preferably 200 or more. This is because the high molecular weight surfactant of 200 or more is included in the structure in which the coating film is formed by the sol-gel reaction of the silane, and the effect can be maintained for a long time. Because.

Among the salt-type surfactants, fluorine-based surfactants are effective in preventing dust adhesion because of easy surface migration due to fluorine, and silane-type surfactants are sol-gel reactions with other alkoxysilanes and fluorine-based silanes of the present invention. By performing the curing, as the curing proceeds, the coating film may be fixed in the structure of the coating film to completely prevent surface detachment with time. In addition, since the surfactant containing a carboxyl group, a sulfone group, etc. is hydrophilic, although the mechanism is not clear, it synergizes with the hydrophobic property by fluorine, and increases pollution resistance.

Surfactants containing salts such as carboxyl groups, sulfone groups, and ammonium groups can be divided into the case where the carboxyl group and the like exist together with the relative cation in the terminal group and the case in which they exist inside the molecular structure. Specific examples of the former is _{Me 3 Si (CH 2) 3} SO 3 - Na +, C 12 H 25 OSO 2 - Na +, R f CH 2 CH 2 SO 3 H, R f CH 2 CH 2 SO 3 - NH 4 ^+, and _{R f CH 2 CH 2 s CH} 2 CH 2 CO 2 - it may be made of Li ^+, wherein R _f is a fluorinated alkyl group. Specific examples of the latter include R _f1 SO ₃ R _f2 , and R _f1 CO ₂ R _f2 , wherein R _f1 and R _f2 are fluorine alkyl groups, fluorine silanes or fluorine alkoxysilanes. Surfactants containing sulfone or carboxyl groups in the molecular structure are easily dissociated into ions of the form R _f1 SO ₃ ^- and R _f2 ⁺ or ions of the form R _f1 CO ₂ ^- and R _f2 ⁺ , dissociated anions and cations Permanent antistatic effect is realized by physical or chemical bonding with the silicon compound that forms the backbone of the coating.

The content of the surfactant as described above is 0.01 to 0.5 parts by weight is suitable for the present invention for imparting a dust adhesion prevention function by friction or the like.

In addition, the coating liquid composition of the present invention is added 40 to 60 parts by weight of alkoxysilane, 6 to 20 parts by weight of fluorine-based silane and 0.1 to 5 parts by weight of the surfactant 30 to 60 parts by weight of the solvent, and then 0.1 to 0.5 parts by weight of the acid catalyst to add pH Is adjusted to 1 to 3, and water is added so as to be 0.2 to 2 times the equivalent of water required to hydrolyze the entire silane, and the sol-gel reaction is carried out for 20 to 40 hours at a temperature of 15 to 50 ° C. After execution, the sol-gel reactant is prepared by diluting with a mixed solvent and maintaining the temperature at 0 to 10 ° C. to terminate the reaction.

As described above, the present invention is prepared by the low temperature thermal curing method by sol-gel reaction by adding a fluorine silane in order to facilitate the modification of the substrate and the convenience of the process. It is advantageous that the molecular weight of the final reactant by sol-gel reaction is 3000 to 20000 at the time of drying and curing the coating film for display. In addition, it is preferable to maintain a pH of 1 to 3 in order to prepare a coating film having suitable physical properties by the sol-gel reaction, because it is suitable for the rate of hydrolysis and condensation reaction at the pH. In order to maintain the pH as described above, the content of the acid catalyst is preferably 0.01 to 0.05 parts by weight. Preferred acid catalysts include nitric acid, hydrochloric acid, acetic acid, and the like.

In addition, the amount of the sol-gel reactant diluted by the mixed solvent in the method for preparing a coating liquid composition of the present invention is preferably 3 to 10 parts by weight in the total dilution liquid. In addition, the mixed solvent is one alcohol selected from the group consisting of methanol, ethanol, isopropanol and 2-butanol and one ketone selected from the group consisting of methyl ethyl ketone and methyl isobutyl ketone with respect to the total solvent from 50 to 80 By weight, one organic solvent selected from the group consisting of methyl acetate, ethyl acetate, butyl acetate, tetrahydrofuran, methylcellosolve, and butylcellosolve is added to the total solvent. It is preferable that it is 50 weight part.

The coating liquid composition prepared by the above method may be dried and cured for 20 to 40 hours at a temperature of 70 to 120 ° C. after coating using a wire bar or the like on the film to be coated.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

Examples 1-2 and Comparative Examples 1-2

Example 1

40 parts by weight of tetraethoxy orthosilicate (TEOS) which is an alkoxysilane, 15 parts by weight of KBM-7803 (Shinatsu) which is a fluorine silane, and 5 parts by weight of ethanol which is a solvent, 5 parts by weight of Zeffle GH-700 (Daikin) which is a surfactant. After the addition, the acid catalyst hydrochloric acid was added to 0.2 parts by weight to adjust the pH to 2, 15.3 parts by weight of water was added to make 1 equivalent of water, and then a sol-gel reaction was performed at a temperature of 30 ° C. for 24 hours. .

In order to terminate the sol-gel reaction, a mixed solvent of 60 g of ethanol, 30 g of tetrahydrofuran (THF) and 10 g of butylcellosolve (BC) was added to 10 g of the sol-gel reactant, followed by dilution. Refrigerated at temperature.

Example 2

40 parts by weight of methyltrimethoxysilane (MTMS), which is an alkoxysilane, 10 parts by weight of KBM-7103 (Shinatsu), which is a fluorine silane, and 2 parts by weight, Zeffle GH-700 (Daikin), which is a surfactant, and Zonyl FSA (DuPont, Ltd.) ) 1 part by weight was added to 31 parts by weight of tetrahydrofuran (THF) as a solvent, 0.2 parts by weight of hydrochloric acid as an acid catalyst was adjusted to pH 2, and 14.8 parts by weight of water was added to give 1 equivalent of water. Sol-gel reaction was performed for 24 hours at the temperature of ℃.

In order to terminate the sol-gel reaction, a mixed solvent of 60 g of ethanol, 30 g of tetrahydrofuran, and 10 g of butyl cellosol moiety (BC) was added to 10 g of the sol-gel reactant, and then refrigerated at a temperature of 0 to 10 ° C. .

Comparative Example 1

A coating solution was prepared in the same manner as in Example 1 except that Zeffle GH-700 (Daikin) was not added.

Comparative Example 2

A coating solution was prepared in the same manner as in Example 2 except that Zeffle GH-700 (Daikin) and Zonyl FSA (DuPont) were not added.

Pollution Resistance Evaluation Experiments for Coating Liquids of Examples and Comparative Examples

The coating solution prepared in Examples 1 and 2 and Comparative Examples 1 and 2 was coated on a polyethylene terephthalate (PET) film using a wire bar and then cured at 100 ° C. for 24 hours to complete the coating. The coated PET film was cut and prepared to have a length of 10 cm and then rubbed 20 times with a silk cloth, and then sprayed five times at a distance of 30 cm at a distance of 1 minute. After spraying the coating surface where the powder has settled down with 2 atmospheres of air for 10 seconds, the remaining powder was visually observed. The smallest amount of powder remaining by visual observation was evaluated as A, and as the amount was increased, B, C, and D were evaluated, and the results are shown in Table 1.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Rating B A D D

As shown in Table 1, the coating film coated with the coating solution of Examples 1 and 2 prepared by adding fluorinated silicate was compared with the coating film coated with the coating solution of Comparative Examples 1 and 2 prepared without the addition of fluorinated silicate. It can be seen that the resistance to contamination such as dust is excellent.

As described above, the coating liquid composition having fouling resistance and low reflectivity according to the present invention simultaneously exhibits low reflectivity and fouling resistance, including a fluorine-based silane and a surfactant in the form of a salt, and when applied to the outermost layer of the display, It has an effect of reducing and facilitating appearance management. In particular, it exhibits a function of preventing adhesion of dust due to friction and the like and can be applied to the front surface of a display regardless of the type of substrate such as CRT or display film, and other coating layers such as hard coating or antistatic coating or anti-glare coating.

Although the present invention will be described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and modifications fall within the scope of the appended claims. It is also natural.

Claims (8)

a) selected from the group consisting of tetraethylorthosilicate (TEOS), tetramethoxyorthosilicate (TMOS), methyltrimethoxysilane (MTMS) and methyltriethoxy silane (MTES) 4 to 15 parts by weight of an alkoxysilane; b) tridecafluorooctyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriisopropoxysilane 0.8 to 7 parts by weight of a fluorine-based silane selected from the group consisting of (heptadecafluorodecyltriisopropoxysilane); c) 0.01 to 0.5 parts by weight of a surfactant having both a positive charge and a negative charge, and having a molecular weight of 200 or more; d) 0.01 to 0.05 parts by weight of an acid catalyst; And e) 90 to 94 parts by weight of the solvent Coating liquid composition having a fouling resistance and low reflection, characterized in that consisting of. delete delete delete The method of claim 1, Non-fluorinated hydrocarbon salts, non-fluorine-based silane salts, fluorine-based hydrocarbon salts in which the surfactant in the form of a salt having both a positive charge and a negative charge include counter cations such as ions having a negative charge of a carboxyl group, a sulfone group or a hydroxyl group, and an ammonium group And a fluorine-based silane salt, wherein the coating liquid composition has fouling resistance and low reflectivity. (A) adding 40 to 60 parts by weight of the alkoxysilane, 6 to 20 parts by weight of the fluorine-based silane and 0.1 to 5 parts by weight of the surfactant to 30 to 60 parts by weight of the solvent; (B) adding 0.1 to 0.5 parts by weight of an acid catalyst to the added (a) to adjust the pH to 1 to 3; (C) adding water to adjust the pH to (2) 0.2 to 2 equivalents to the equivalent of water required to hydrolyze the entire silane; (D) subjecting the water to (d) to a sol-gel reaction at a temperature of 15 to 50 ° C. for 20 to 40 hours; And (E) preparing a coating solution composition by diluting the sol-gel reaction product of (D) with a mixed solvent and terminating the reaction at a temperature of 0 to 10 ℃, The alkoxy silane is a group consisting of tetraethylorthosilicate (TEOS), tetramethoxyorthosilicate (TMOS), methyltrimethoxysilane (MTMS) and methyltriethoxy silane (MTES) Selected from The fluorine silane is tridecafluorooctyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane Posisilane (heptadecafluorodecyltriisopropoxysilane), The surfactant is in the form of a salt having both positive and negative charges, the molecular weight is 200 or more method of producing a coating liquid composition having a fouling resistance and low reflection. The method of claim 6, Method for producing a coating liquid composition having fouling resistance and low reflection, characterized in that the amount of the sol-gel reactant diluted by the mixed solvent is 3 to 10 parts by weight in the total diluent. The method of claim 6, The mixed solvent of (e) is one alcohol selected from the group consisting of methanol, ethanol, isopropanol and 2-butanol and methyl ethyl ketone, methyl iso One kind of ketone selected from the group consisting of methyl butyl ketone is 50 to 80 parts by weight with respect to the total solvent, methyl acetate, ethyl acetate, butylacetate, tetrahydrofuran (tetrahydrofuran), methylcellosolve (methylcellosolve) and butylcellosolve (butylcellosolve) of the organic solvent selected from the group consisting of 10 to 50 parts by weight of the total solvent having a fouling resistance and low reflection Method of producing a coating liquid composition.