KR102547175B1 - Aqueous anti-static high rigidity composition and its preparing method - Google Patents

Abstract

The present invention relates to an aqueous anti-static high-hardness composition and, more specifically, to an aqueous anti-static high-hardness composition that has excellent adhesion by applying a coating solution to a highly flexible material such as plastics and stably implements a dry coating film with the pencil hardness of 3H or more to form an anti-static high-hardness dry coating film having excellent anti-scratch properties, and to a manufacturing method thereof.

Description

Aqueous anti-static high rigidity composition and its preparing method

The present invention relates to a high-hardness composition for water-based antistatic, and more particularly, by applying a coating liquid to a material with high flexibility such as plastic, excellent adhesion, stable scratch resistance by realizing a dry coating film having a pencil hardness of 3H or more ( Anti-scratch) relates to a water-based antistatic high-hardness composition capable of forming a high-hardness antistatic dry coating film and a method for preparing the same.

In the field of the electronics industry, “ESD Work” (Electro static discharge work) is often classified as “anti-static industry” and is applied in various ways in the industrial field. Among them, the “antistatic coating agent” market, which is implemented through the coating process as part of the paint industry, is also demanding more technological progress as the microcircuit process in the electronics industry progresses precisely.

Among the new studies related to this, the most noteworthy new approach is to adopt an inorganic binder, “silane” or “silane coupling agent,” as a binder for the coating agent, and mix “Pedot-PSSA aqueous dispersion,” a representative material for conductive polymers. There is a method for preparing a water-based antistatic coating agent.

This is done by hydrolyzing "Tetra-Ethyl Ortho Silicate (hereinafter "TEOS"), a representative "silane" known theoretically, using water and an acid catalyst to form a hydroxyl group (-OH) in lipophilic TEOS. It is a method of preparing an antistatic water-based conductive coating liquid by adding a hydrophilic property to TEOS to improve compatibility with water, and then mixing the water-based dispersion, “Pedot-PSSA aqueous dispersion.”

The water-based conductive coating liquid prepared in this way is coated on the material, and then, in the drying process, the hydrolyzate of TEOS is heated and cured at a constant temperature to induce dehydration and condensation between the hydrolyzed TEOS molecules to form a crosslinked coating film, realizing a high degree of crosslinking. It is a method of realizing a high-hardness dry film.

However, the prior art described above has the following problems.

First, even at room temperature, the dehydration and condensation of “hydrolyzed TEOS” present in the coating liquid proceeds rapidly, resulting in poor storage stability of the coating liquid, problems such as thickening, seeding, layer separation, surface resistance increase, and gelation of the liquid. The shelf life of “aqueous antistatic coating liquid” is very short.

Second, if the dried coating film is left at room temperature for a long period of time based on 120 ° C x 1 hour, or if post-curing is performed by heating, unreacted hydroxyl groups (-OH) undergo additional dehydration condensation, resulting in cracks in the dry coating film. It happens gradually. This can be presumed to be the cause of the phenomenon that the "surface resistance" of the dry film that showed good surface resistance at the beginning is left for a long period of time later.

Third, because of the strong shrinkage occurring during the curing process of the inorganic binder, it can be applied to tempered glass with excellent heat resistance and low shrinkage, but it is applied to optical materials such as PET film or PI film, where numerical stability and flexibility are important. There are clearly limits.

Fourth, it exhibits excellent adhesion to materials such as glass and marble, but has poor adhesion to plastic materials.

Publication No. 10-2010-0047440 (published on May 10, 2010)

The present invention was derived to solve the above problems, and the present invention is to prepare a polythiophene-based (Pedot-PSSA-based) antistatic "water-based conductive polymer dispersion" and a hydrolyzed alkoxy silane compound to produce a PET film and a PI film. A water-based antistatic high-hardness composition having excellent adhesion to various flexible plastic materials such as anti-scratch, excellent storage stability of liquid and dry coating films, and a pencil hardness of 3H or higher and a method for producing the same It aims to provide

The high-hardness composition for aqueous antistatic use according to the present invention includes an aqueous conductive polymer dispersion, a binder, and a solvent, wherein the binder is a mixture of difunctional silane and trifunctional silane.

According to another preferred embodiment of the present invention, the aqueous conductive polymer dispersion is characterized by containing 20 to 30% by weight, 2 to 6% by weight of a binder, and 65 to 75% by weight of a solvent.

According to another preferred embodiment of the present invention, the mixing weight ratio of the difunctional silane and the trifunctional silane is 3 to 5: 1 based on the solid content.

According to another preferred embodiment of the present invention, the difunctional silane is dimethyl ethoxy silane (Di-methyl Di-Ethoxy Silane, “DMDES”).

According to another preferred embodiment of the present invention, the trifunctional silane is 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES).

According to another preferred embodiment of the present invention, the solvent is ethyl alcohol, and the aqueous conductive polymer dispersion is a Pedot-PSSA-based acidic aqueous dispersion that is not neutralized as a conductive polymer.

According to another preferred embodiment of the present invention, the aqueous conductive polymer dispersion serves as a catalyst.

The manufacturing method according to the present invention includes a mixing step of preparing a mixed solution by mixing 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) and dimethyldiethoxysilane (DMDES) in a solvent, and It is characterized in that it comprises a hydrolysis step of hydrolyzing by adding an aqueous conductive polymer dispersion to the mixed solution.

According to another preferred aspect of the present invention, the hydrolysis step proceeds for 24 hours or longer.

The high-hardness composition for water-based antistatic use according to the present invention,

First, anti-scratch is maintained while mitigating cracks generated in the process of implementing a high-hardness coating film to improve scratch resistance.

Second, the storage stability of the coating solution is secured.

Third, the change with time of the dry coating film due to the additional post-curing reaction after heat curing is minimized.

Fourth, adhesion to plastic materials requiring flexibility is excellent.

1 is a graph comparing the rate of solid content (%) loss by temperature of “composition No. 1”.
2 is a solid content (%) measurement value for each temperature converted to 100 g of TEOS input of “composition No. 1”.
Figure 3 is a graph of the solid content (%) reduction result by long-term heat curing of "composition No. 1"
4 and 5 are photographs of the “composition No. 1” dry film.

The high-hardness composition for water-based antistatic use according to the present invention,

① In order to realize a dry coating film with high hardness (3H or more) in an ultra-thin film (about 100 nm ± 50 nm), an inorganic binder is used,

② In order to realize stable surface resistance in dry film, use conductive polymer-based products instead of metal ions or surfactants.

③ The inorganic binder is hydrolyzed to give a hydroxyl group (-OH) to the molecular end, and through this, hydrophilicity is imparted to the lipophilic inorganic binder to improve compatibility with "aqueous conductive polymer",

④ It does not use a separate curing agent, initiator or catalyst, and uses heat curing (100 ℃ ~ 120 ℃) to realize a dry coating film.

⑤ It has been developed so that the physical properties (hardness, surface resistance) of the dry coating film can be stably maintained without change over time even after a long period of time.

Hereinafter, preferred embodiments of the present invention will be described. However, embodiments of the present invention may be modified in many different forms, and the scope of the present invention is not limited to the embodiments described below.

In addition, 'include' a component throughout the specification means that other components may be further included, rather than excluding other components unless otherwise stated.

The high-hardness composition for aqueous antistatic use according to the present invention includes an acidic aqueous conductive polymer dispersion, a binder, and a solvent.

The water-based conductive polymer dispersion uses unneutralized water-based Pedot-PSSA dispersion as an antistatic conductive material. Since this material is already widely known, a detailed description thereof will be omitted. The aqueous conductive polymer dispersion contains 20 to 30% by weight. If the content of the water-based conductive polymer is less than 20% by weight, problems may occur in conductivity, and if the content of the water-based conductive polymer exceeds 30% by weight, the hardness decreases and the possibility of cracking increases.

The solvent may be at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropanol, dimethylol propane, trimethylol propane, propylene glycol monomethyl ether, and water, and preferably ethanol. The solvent comprises 65 to 75% by weight of the total composition.

The binder in the present invention is characterized in that TEOS is not used, and a mixture of trifunctional silane and bifunctional silane is used.

Examples of trifunctional silanes include (triethoxysilane, trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriae Toxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, phenyltriethoxysilane, (3-(3-mercaptopropyl)trimethoxysilane, 3-(3-mercaptopropyl ) Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, and trimethoxy(2-phenylethyl)silane.

As the silane of the bifunctional group, (dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxy(methyl)phenylsilane, diethoxy(methyl)phenylsilane, cyclohexylmethyl-dimethoxysilane, dicyclopentyl-dimethoxysilane, Diphenyl dimethoxysilane is mentioned.

The content of the binder in the composition is 2 to 6% by weight.

On the other hand, in order to keep the physical properties of the dry film excellent, it is important to keep the ratio of the solid content of the binder and the solid content of the conductive polymer constant in the composition constituting the dry film. 15 parts by weight to 20 parts by weight.

In addition, the solid content of the binder is 1.5% to 2.5% by weight of the total composition.

Including 25 g of the conductive polymer (1.4% solid content, 98.6% water content) in 100 g of the composition is equivalent to containing about 25 g of water in 100 g of the composition.

In addition, the mixing weight ratio of the trifunctional silane and the bifunctional silane is 3 to 5:1, preferably 4:1, based on the solid content.

If the trifunctional group is excessively added, drying is fast, but cracks may occur over time, and if the bifunctional group is excessively added, the drying time is too slow and the hardness is reduced.

The present invention has the greatest feature of the binder, and the first feature is that a trifunctional silane is used instead of the tetrafunctional TEOS in order to improve the storage stability of the liquid phase.

The second characteristic is to artificially lower the degree of crosslinking of the dry coating film in order to prevent the change with time occurring in the dry coating film of trifunctional groups. To this end, the degree of crosslinking of the dry film is controlled by using a bifunctional silane, and the degree of crosslinking of the dry film is prevented from progressing to the third stage even when exposed to any conditions.

It is intended to provide a high-hardness dry coating film that does not generate cracks by adjusting the degree of crosslinking by mixing a theoretical crosslinking degree of 2-step "bifunctional" silane and a 3rd-step "trifunctional" silane.

For reference, the dry film curing method of a composition using an inorganic binder induces dehydration condensation by heat curing to form a crosslinking reaction. At this time, the dehydration condensation process is subdivided and defined as follows.

The case where all inorganic molecules present in the “degree of crosslinking 1” composition undergoes dehydration condensation once on average is defined as the “degree of crosslinking 1” step by dehydration condensation.

The case where all inorganic molecules present in the “degree of crosslinking 2” composition undergo dehydration condensation twice on average is defined as the “degree of crosslinking 2” step by dehydration condensation.

The case where all inorganic molecules present in the “degree of crosslinking 3” composition undergo dehydration condensation three times on average is defined as the “degree of crosslinking 3” step by dehydration condensation.

The case where all inorganic molecules present in the “degree of crosslinking 4” composition undergo dehydration condensation four times on average is defined as the “degree of crosslinking 4” step by dehydration condensation.

On the other hand, as the most preferred mode of the present invention, 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) was selected as the trifunctional silane.

This hydrolyzate of silane was heat-cured smoothly even in the range of 100°C to 120°C, had excellent adhesion to plastic materials as an epoxy-based silane coupling agent, and had excellent storage stability at room temperature.

In addition, as the bifunctional silane, Di-methyl Di-Ethoxy Silane (“DMDES”) was selected.

Compared to trifunctional silane having one alkyl group, bifunctional silane has two alkyl groups. This is the reason why the dehydration condensation of difunctional silane is too slow compared to trifunctional silane. Among bifunctional silanes, dimethyldiethoxysilane (DMDES) has a structure in which two methyl groups (-CH3) having the smallest size of an alkyl group are substituted, and can be said to have faster dehydration condensation compared to other bifunctional alkyl groups. And compared to the characteristics of polydimethylsiloxane (PDMS), which improves slip resistance and scratch resistance as the number of methyl groups in the molecule increases, dimethyl containing the most methyl groups in the polymer when the polymer is produced by dehydration condensation Diethoxysilane (DMDES) is expected to show the greatest effect in improving anti-scratch as a “reactive silicone”.

Structural formula and molecular weight of trifunctional silane and bifunctional silane. abbreviation 2-3,4 ECHETES DMDES name 2-(3,4epoxycyclohexyl)ethyltriethoxy silane
[2-(3,4-Epoxycyclohexyl)
ethyltrimethoxy silane ] Dimethyldiethoxysilane
(Dimethyldiethoxysilane)
Diethoxydimethylsilane
(Diethoxydimethylsilane) constitutional formula

chemical formula CH ₃ Si(OC ₂ H ₅ ) ₃ (CH ₃ ) ₂ Si(OC ₂ H ₅ ) ₂ Molecular Weight 288.46 g/mol 148.28g/mol

In the present invention, as a method for slowing down the dehydration condensation reaction rate in the coating liquid composition, unlike the coating liquid composition prepared using TEOS, which is a tetrafunctional group silane, a composition using trifunctional silane and bifunctional silane is used to prepare and store We want to improve stability, and we will explain this in detail.

Assuming the following five chemical formulas, molecular weights, and crosslinking levels including TEOS, the structural formula after hydrolysis and the solid content conversion rate in the dry film can be defined as follows.

Comparative table of 5 types of inorganic silanes. division Formula:
Molecular Weight (MW) after hydrolysis
structural diagram Step 3
After dehydration condensation
Molecular Weight bridging step 3
standard
Expected solid content (%) TES:Tri Ethoxy Silane H-Si-(OC ₂ H ₅ ) ₃
164.28 g/mol

H-Si-O _3x(1/2)
53.09 g/mol 32.32% TEOS: Tetra ethyl Ortho silicate Si-(OC ₂ H ₅ ) ₄
208.44 g/mol

HO-Si-O _3x(1/2)
69.09 g/mol 33.16%
(Step 4 of crosslinking:
28.84%) MTES: Methyl Tri Ethoxy
Silane H ₃ C-Si-(OC ₂ H ₅ ) ₃
178.30 g/mol

H3C-Si-O _3x(1/2)
67.12 g/mol 37.64% 2-(3,4ECHETES):2-(3,4-Epoxycyclohexyl) ethyltrimethoxy silane OH ₁₃ C ₈ -Si-(OC ₂ H ₅ ) ₃
288.46 g/mol

OH ₁₃ C ₈ -Si-O _3x(1/2)
177.27 g/mol 61.46% 3GPTES:3-Glycidoxy Propyl Tri Ethoxy Silane O ₂ H ₁₁ C ₆ -Si-(OC ₂ H ₅ ) ₃
278.42 g/mol

O ₂ H ₁₁ C ₆ -Si-O _3x(1/2)
167.24 g/mol 60.07%

Here, “expected solid content (%)” is a theoretical solid content (%) value that can be obtained through dehydration condensation after hydrolysis when 100 g of each silane is added by weight before hydrolysis. In this study, it was named as “solid content conversion rate (%)” or “expected solid content (%)”.

The above-described silanes upon completion of hydrolysis have structures of a similar type. If you look at it in a simple diagram, it has the following structure.

[Figure 1] Simplified structural diagram of hydrolyzed silanes

Here, comparing the functional group corresponding to the position of R-, two characteristics that affect the reactivity of hydrolyzed silane can be expected. First, in TEOS, the substance corresponding to the position of R- is a hydroxyl group (-OH) capable of dehydration condensation, and the remaining four species are -H, -CH ₃ , -C ₆ H ₁₁ O _2, - It is an alkyl group of C ₈ H ₁₃ O. Therefore, when dehydration condensation between hydrolyzed inorganic molecules proceeds in a three-dimensional space existing in a liquid, hydrolyzed TEOS has a very high reaction probability and is fast compared to other silanes, and can be said to be free without spatial restrictions. . This can cause dehydration and condensation of tetrafunctional group hydrolyzed TEOS to proceed rapidly even at room temperature compared to other silanes substituted with an alkyl group, and as a result, storage stability of the liquid may deteriorate rapidly.

[Figure 2] A schematic diagram of comparison of steric hindrance effects on the possibility of dehydration condensation.

Second, as the size of the alkyl group in the structure of the hydrolyzed molecule increases, the area occupied by the alkyl group in the three-dimensional space increases. At this time, the distance between the hydroxy groups (-OH) located on the other three axes is narrowed. Conversely, as the size of the alkyl group decreases, the distance of the three hydroxyl groups (-OH) will increase and occupy a free space. If the alkyl group does not exist, the three hydroxyl groups (-OH) position to secure the largest possible distance between the hydroxyl groups (-OH).

[Figure 3] Prediction of structural change of hydroxyl group (-OH) according to the size of R group (conceptual diagram)

That is, depending on the size of the alkyl group, the space occupied form of hydroxy (-OH) may change, which hinders physical access between molecules during the dehydration condensation reaction and induces steric hindrance, resulting in dehydration condensation will affect the "reaction rate" of

It can be expected that the hydrolyzate of the tetrafunctional group TEOS will hardly decrease the reaction rate due to the steric hindrance effect in the dehydration condensation reaction.

The hydrolyzate of triethoxysilane (TES) in which a hydrogen atom (H) is located at the position of the R group, which is a case where the size is very small at the position of the R group, has almost three hydroxyl groups (-OH) in the molecular structure. It will be widely distributed in the location of the plane. (See [Figure 3]) And in this case, the dehydration condensation reaction between different molecules can be expected to proceed very quickly compared to other trifunctional silanes compared in this study.

Conversely, when the size of R is very large, 3-glycidoxypropyltriethoxysilane (3-GPTES) or 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) The hydrolyzate will be distributed with the three hydroxyl groups (-OH) confined to a very narrow space in the molecular structure. Since the steric hindrance is relatively large, it can be predicted that the dehydration condensation reaction between molecules will be very slow.

Finally, as the size of the R group increases, the slowdown in the dehydration condensation reaction will be more affected by the second step dehydration condensation reaction than the first step dehydration condensation reaction, and will have a greater effect on the third step dehydration condensation reaction.

This means that when heating hardening a hydrolyzate having a large R group, the drying of the coating film becomes very slow or a higher heating temperature than average may be required. As it will appear, it will be a more effective way to improve the room temperature stability of liquids.

In addition, this will be a sufficient reason for the fact that the hydrolyzed composition of trifunctional or bifunctional silanes has better storage stability at room temperature than the hydrolyzate of tetrafunctional TEOS.

On the other hand, in the present invention, it is necessary to prevent cracks in the dry coating film in order to use it for materials such as plastic rather than glass. For this purpose, a bifunctional silane was used as the binder of the present invention.

In the present invention, a bifunctional silane is used to prevent the degree of crosslinking of the dry film from progressing to the third step. In this case, the hardness of the dry film may decrease through proper crosslinking, but the anti-crack effect of the dry film may be realized.

The difunctional silane in the present invention may be variously adopted, but dimethyldiethoxysilane (DMDES) is preferably used.

The hydrolysis reaction and dehydration condensation reaction of dimethyldiethoxy silane (DMDES) can be explained as follows.

[Figure 4] Hydrolysis reaction of dimethyldiethoxy silane (DMDES)

[Figure 5] A schematic diagram of the dehydration condensation reaction and polymerization of hydrolyzed dimethyldiethoxy silane (DMDES).

When the hydrolyzed dimethyldiethoxy silane (DMDES) undergoes a dehydration condensation reaction, the molecular weight will increase in the form of a linear polymer. This is converted into a structure almost similar to the silicone additive used to impart slip and scratch resistance in the “solvent-based coating agent”.

Even if the hydrolyzate of dimethyldiethoxysilane (DMDES) proceeds with dehydration condensation, since it cannot form a three-dimensional network structure, it will form a very flexible coating film with low hardness.

Since the hydrolyzate of dimethyldiethoxysilane (DMDES) is a substance that participates in dehydration condensation, mixing it with the hydrolyzed tetrafunctional or trifunctional silane to form a dry coating film lowers the hardness of the dry coating film and lowers the threshold of crosslinking of the dry coating film. It is possible to prevent cracks in the dry coating film that may occur in the phosphorus situation, and as a result, it will be possible to consistently implement a dry coating film in which no cracks occur.

On the other hand, when polydimethylsiloxane (PDMS: Poly Di-Methyl Siloxane) is mixed with hydrolyzed tetrafunctional or trifunctional silane to form a dry film, polydimethylsiloxane (PDMS: Poly Di-Methyl Siloxane) participates in the dry film. Without doing so, it will float to the surface of the dry film, causing the above-described contamination-related problems.

However, the hydrolyzate of dimethyldiethoxysilane (DMDES), which undergoes the same dehydration condensation reaction as the hydrolyzed tetrafunctional or trifunctional silane, will participate as a component of the dry film and be permanently adhered to the dry film. This provides a theoretical background for hydrolyzed DMDES to act as a “reactive silicone” additive for improving scratch resistance in dry coating films of hydrolyzed inorganic silanes.

On the other hand, in the case of conventionally using TEOS as a binder, the catalyst is to add water to TEOS (Si-(OCH ₂ CH ₃ ) ₄ before hydrolysis to separate the alkoxy group and replace the hydroxyl group, which is a hydrophilic functional group, at the terminal of TEOS. It was an important factor in accelerating the hydrolysis reaction for

However, in the present invention, the Pedot-PSSA aqueous dispersion itself, which is an acidic material, serves as a catalyst, and a separate catalyst is not used.

In the case of preparing a composition using an acidic Pedot-PSSA aqueous dispersion as a catalyst, there is a problem in that the production process is prolonged due to low heat generation and low reactivity during the hydrolysis reaction of the composition, but in order to realize stable storage stability of the composition Most preferably, no catalyst is used.

Aqueous Pdot-PSSA dispersion can also work as an excellent catalyst, and mixing the aqueous Pdot-PSSA dispersion and catalyst causes the effect of increasing the catalyst content (catalyst + catalyst), which deteriorates the storage stability of the composition. works as

Therefore, this study intends to directly hydrolyze inorganic materials using an aqueous Pedot-PSSA dispersion without a separate catalyst.

On the other hand, when the temperature increases, the dehydration condensation rate in the composition liquid increases, and when the temperature decreases, the reactivity decreases, resulting in a slow dehydration condensation reaction rate. By lowering the temperature of the composition, the storage period can be extended.

Next, the method for producing a high-hardness composition for water-based antistatic use according to the present invention,

A mixing step of preparing a mixed solution by mixing 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) and dimethyldiethoxysilane (DMDES) in a solvent, and an aqueous conductive polymer dispersion in the mixed solution It includes a hydrolysis step of hydrolyzing by adding.

However, since the present invention uses a mixture of a bifunctional group and a trifunctional group, the reaction rate is slowed, so the hydrolysis step is preferably performed for 24 hours or more.

In addition, when the water-based antistatic high-hardness composition is coated on a substrate, the coated substrate is preferably heat-cured at 100 to 120 ° C. Here, if the curing temperature is too low, the reaction proceeds too slowly, and if the curing temperature is high, there is a problem of poor economic efficiency.

Hereinafter, a detailed description will be made based on specific experimental data, but first, basic experiments to derive the core content of the present invention, although not directly related to the present invention, will be described, and then experiments directly related to the present invention will be described.

[Basic experiment]

1. Basic experiment to understand the curing conditions of the binder.

In order to understand the curing speed of the binder, an experiment was conducted based on TESO.

As a binder, 99% or higher purity TEOS (ALDRICH, Tetraethyl orthosilicate, alias: Orthosilicic acid tetraethyl ester, Silicon tetraethoxide, Tetraethoxysilane, Tetraethoxysilicon (IV), Tetraethyl silicate,) (refractive index: 1.382 - 1.384) was selected.

A 35% hydrochloric acid (35% HCl) aqueous solution (boiling point: 108.584° C.) was selected as a catalyst.

As a mixed solvent, ethanol with a purity of 99.5% or higher (ALDRICH, ethyl alcohol, Pure. Alias: Ethanol, absolute alcohol, non-denatured ethanol) was selected.

De-ionized water (M.W: 18.015 g/mol) was used as the water used for hydrolysis.

- In order to adjust the final solid content (NV) of the composition to 4%, TEOS (Si-(OCH ₂ CH ₃ ) ₄ before hydrolysis was fixed at 13.870% among the total mixing amount (%) of the composition and added. (4% / 0.2884 =13.870%)

- In terms of parts by weight, the amount of TEOS added before hydrolysis is 13.870 g in 100 g of the total composition.

- The amount of water needed to hydrolyze it is 4.797g (molar mass of TEOS x 4 molecular weight of water = (13.870/208.33)x18.015x4 = 0.066577x18.015x4 = 4.797g).

- 35% aqueous hydrochloric acid solution was added in an arbitrary amount, and in this experiment, 0.02 g of 35% aqueous hydrochloric acid solution was added to 100 g of the entire composition.

- The insufficient weight in 100 g of the total composition was adjusted to 100 g by making up for the weight of the composition by using 81.313 g of ethanol.

- 1000 g of the hydrolysis composition was prepared according to the following formula.

Composition No. 1 formulation table % 1000g note Ethanol 81.313 813.13 TEOS (NV=28.84%) 13.870 138.70 (NV=28.84%) Di Water 4.797 47.97 35% HCL aqueous solution 0.020 0.20 Total 100.00 1000.00 NV (%) theoretical value 4

[Production process of composition No. 1] Hydrolysis process of TEOS.

① 813.13 g of ethanol and 138.7 g of TEOS before hydrolysis were added to a weighed 2-liter reaction vessel, and stirring was performed at a linear speed of 0.4 m/s.

② Put 47.97g of deionized water and 0.2g of 35% aqueous hydrochloric acid solution in another container and mix well.

③ Slowly add the mixture of deionized water and hydrochloric acid solution to the mixture of ethanol under stirring and TEOS before hydrolysis.

④ After sealing the reaction container well and adjusting the linear speed to 0.8 m/s, hydrolysis is performed by stirring at room temperature for 24 hours.

⑤ After 25 hours, measure the total weight of the reaction vessel containing the composition and supplement it with ethanol as much as the lost weight.

⑥ Filter with #300 fine mesh and pack in a plastic container.

[Test method for measuring solid content of “Composition No. 1”].

① Measure the solid content based on 10 g of the TEOS hydrolyzate prepared above.

② For complete curing, heat in an oven at 200℃ and measure the solid content every 30 minutes.

③ Measure until there is no further change in solid content.

④ Repeat the same experiment based on the oven temperatures of 150℃, 120℃, 100℃, and 80℃.

Solid content (%) measurement result of “Composition No. 1”. elapsed time 200℃ 150℃ 120℃ 100℃ 80℃ 30 minutes 4.53 4.98 5.25 7.09 11.17 60 minutes 4.53 4.82 4.87 4.90 5.12 90 minutes 4.45 4.77 4.79 4.87 4.98 120 minutes 4.45 4.72 4.74 4.84 4.96

[Analysis of peculiarities and results]

Even after heating for 60 minutes (1 hour) or 120 minutes (2 hours) at temperatures of -200 ° C, 150 ° C, and 120 ° C, the theoretical calculated value of expected solid content of 4% was not reached.

- The lower the heating temperature, the higher the solid content (unevaporated content).

- As shown in Figure 1, the theoretical NV of the composition is 4%, but the actual measured solids value (NV (%)) was measured too high.

- This can be judged to be due to the purity of the reagent, but considering that the theoretically calculated solids value is a result that can be obtained only when the hydrolyzed TEOS undergoes 100% complete dehydration condensation, the temperature and heating In terms of time, it is reasonable to assume that 100% dehydration condensation of TEOS did not proceed, and as a result, the solid content measurement value increased.

- In this experiment, 13.870 g of TEOS before hydrolysis was added based on 100 g of the total composition, and at this time, the solid content conversion rate of TEOS was calculated as 28.84%, and the theoretical solid content value of 100 g of the composition was defined as about 4 g (4%). Since the actual measured solids value is a measured value obtained by adding 13.870g of TEOS before hydrolysis, the measured solids are converted into a case where the TEOS content before hydrolysis is 100g. It is possible to calculate the actual solids value, which can be directly compared with the water.

[Formula 1] The solid content (%) conversion calculation method is as follows.

TEOS input: measured solids content (%) = 100 g of TEOS: converted solids content (%)

⇒13.870g: Solid content measured value by temperature (%) = 100g : X (%).

⇒X(%) = (100g x measured solid content at each temperature (%)) / 13.870g

Solid content (%) measured value for each temperature calculated by converting TEOS 100g input amount of “Composition No. 1”. lapse
hour 200℃ 150℃ 120℃ 100℃ 80℃ Measures conversion value Measures conversion value Measures conversion value Measures conversion value Measures conversion value 30 minutes 4.53 32.66 4.98 35.90 5.25 37.85 7.09 51.12 11.17 80.53 60 minutes 4.53 32.66 4.82 34.75 4.87 35.11 4.90 35.33 5.12 36.91 90 minutes 4.45 32.08 4.77 34.39 4.79 34.53 4.87 35.11 4.98 35.90 120 minutes 4.45 32.08 4.72 34.03 4.74 34.17 4.84 34.90 4.96 35.76

Figure 2 is an experimental result of measuring the loss of solids by evaporation by heating the same composition at different temperatures.

① In neither case, the theoretical solid content value was reached. In addition, the solid content was measured differently depending on the temperature even though the composition was the same. Even when cured for 2 hours under a heating condition of 200 ° C., the solid content of the theoretical value was not reached.

② Under the general curing conditions of 120°C x 1 hr, a dry coating film of 300 nm has good appearance, excellent surface resistance, and can satisfy the conditions of 9H hardness. However, it can be seen that in such a drying environment, there is a possibility that a large amount of TEOS (uncured) in which dehydration condensation has not progressed remains in the formed dry film.

③ If these uncured (dehydration-condensation has not yet progressed) components remain, the dried coating film may be left at room temperature (25℃) for long-term storage, or at a low temperature (e.g., 60℃~80℃ temperature range). When heated for a long time, additional curing proceeds inside the dry film, which becomes a factor that can change the physical properties of the dry film.

In order to confirm this, the heating time was extended to measure the additional solid content (%) loss.

Reproducible experiment - Solid content measurement result of “Composition No. 1” (Measurement result and conversion value of solid content (%) of the composition in Formulation Table 1 at temperatures of 120℃ & 150℃.) 150℃ 120℃ elapsed time Measures conversion value Measures conversion value 1hr 4.86 35.01 4.97 35.82 2hr 4.83 34.84 4.86 35.07 3hr 4.75 34.26 4.81 34.66 4hr 4.73 34.09 4.78 34.49 24 hours 4.72 32.03 4.76 34.32

- The theoretical solids value of 28.84% that can be reached in 100% dehydration condensation of TEOS was not reached at temperatures of 200 °C, 150 °C or 120 °C.

- In other words, it can be assumed that the dried coating film by heating and curing the hydrolyzed TEOS composition at a temperature of 120 ° C for about 1 hour is in a very incomplete cross-linking state even if the dry coating film has excellent hardness and resistance.

- Considering that the remaining amount of solid content (%) of TEOS measured after heating at a temperature of 120℃ or 150℃ in the range of 1 hour to 4 hours is in the range of 34% to 36%, dehydration condensation proceeded within this curing condition range It can be seen that the number of is in the range of 2 or more and 3 or less.

- Also, in the case of curing at 200℃, it can be seen that the number of dehydration condensation reaches 3 or more in 30 minutes.

[Coating and drying method of “Composition No. 1”]

- The composition was coated to a thickness of 12.5 μm (about 500 nm) using Baker Applicator YBA-3 on tempered glass having a thickness of 5 mm and a size of 150 mm x 150 mm.

- The solvent was evaporated by preliminary heating at 80 ° C for 15 minutes.

- Drying was induced by heating at 120 ° C. for 1 hour.

- When the specific gravity value of the liquid is not corrected, the theoretical final dry film thickness is defined as wet film thickness x solid content (%), and in this experiment, the dry film thickness is 12.5 μm x (4/100 (%)) = 0.5 μm = 500 nm was expected.

[Special matters and results]

- Due to the occurrence of cracks, the hardness of the dry coating film could not be measured.

[How to adjust the dry film thickness of “Composition No. 1”]

- In order to obtain a dry film without cracks, the solid content of the composition was reduced by diluting the coating solution by adding 10% of ethanol, and the composition was coated with a wet film thickness of 12.5 μm using Baker Applicator YBA-3. did

- Then, heat curing was performed under drying conditions of 120 ° C x 60 min.

- The composition dilution and coating were repeated until the cracks were not visible to the naked eye, and a stable coating thickness without cracks was determined.

- After that, the cured film was repeatedly heated under the conditions of 120 ° C x 60 min, and it was confirmed whether or not cracks occurred in the dry film as the heat curing time increased.

Whether or not cracks occur due to the increase in the dry film thickness and heat curing time of “Composition No. 1” dry film thickness about 500 nm about 400 nm about 300 nm about 200 nm about 100 nm After drying at 120℃ x 1hr X X O O O After drying at 120℃ x 2hr X X △ O O After drying at 120℃ x 3hr X X X △ O After drying at 120℃ x 4hr X X X X △

Note: X = cracked, △ = fine crack, O = no crack (visual observation).

Hardness change of dry film according to heat curing progress at “Composition No. 1” dry film thickness of 300 nm. drying time 120℃ x 30min 120℃ x 60min 120℃ x 90min 120℃ x 120min pencil hardness 6H 9H 9H 9H

[Special matters and results]

- In the case of inducing dehydration condensation by heating at a temperature of 120° C. at a dry film thickness of about 300 nm, the drying time at which no cracks were observed with the naked eye was about 120 minutes.

- This section was divided into conditions of 120 ° C x 30 min, and drying was carried out, and the pencil hardness of the dry film was measured for each section.

- As a result of the experiment, when drying at 120 ° C for more than 60 min, the hardness of the dry film was 9H.

- In the solid content measurement experiment of TEOS hydrolyzate, it was found that the condition of 120 ° C x 60 min did not reach complete dehydration condensation. Based on this, if we estimate the correlation between the degree of dehydration and condensation and the hardness of the dry film, the hardness of the TEOS hydrolyzate can sufficiently reach the pencil hardness of 9H if the dehydration and condensation proceeds to some extent even if the dehydration condensation does not progress 100% can know

2. Basic Experiments to Determine Conductive Polymer Content.

As a binder, TEOS (ALDRICH, Tetraethyl orthosilicate, alias: Orthosilicic acid tetraethyl ester, Silicon tetraethoxide, Tetraethoxysilane, Tetraethoxysilicon (IV), Tetraethyl silicate,) with a purity of 99% or more (refractive index: 1.382 - 1.384) was selected.

Through previous experiments, the preferred solid content of TEOS for measuring the stable surface resistance of a dry coating film was determined to be 2%.

As a Pedot-PSSA-based conductive polymer, 1.4% solid Huclawn N3 aqueous dispersion (d50=75nm, Hub Global Co., Ltd., Korea) was selected.

A 35% hydrochloric acid (35% HCl) aqueous solution (boiling point: 108.584° C.) was selected as a catalyst.

As the mixed solvent, ethanol with a purity of 99.5% or higher (ALDRICH, ethyl alcohol, Pure. Alias: Ethanol, absolute alcohol, non-denatured ethanol) was selected.

In order to determine the amount or scope of use of the "conductive polymer aqueous dispersion" required for the preparation of the composition, the composition was prepared by sequentially increasing the content of the "conductive polymer aqueous dispersion (Huclawn N3)" included in the composition, and coated to form a coating film. After drying, the surface resistance was measured.

Composition Table 2. division 2-1 2-2 2-3 2-4 2-5 2-6 Conductive polymer content 5% 10% 15% 20% 25% 30% One Ethanol 606.46 606.46 606.46 606.46 606.46 606.46 2 TEOS (NV=28.84%) 69.35 69.35 69.35 69.35 69.35 69.35 3 Di Water 23.99 23.99 23.99 23.99 23.99 23.99 4 35% HCL aqueous solution 0.20 0.20 0.20 0.20 0.20 0.20 5 Huclawn N3 50.00 100.00 150.00 200.00 250.00 300.00 6 Di Water (for water correction) 250.00 200.00 150.00 100.00 50.00 0.00 Total 1000.00 1000.00 1000.00 1000.00 1000.00 1000.00 TEOS NV (%) theoretical value 2.00 2.00 2.00 2.00 2.00 2.00 Conductive polymer NV (%) 0.07 0.14 0.21 0.28 0.35 0.42 NV (%) Sum 2.07 2.14 2.21 2.28 2.35 2.42

- In order to correct the effect of the water contained in the conductive polymer when the "conductive polymer aqueous dispersion" is added, water is added during the reduction of the conductive polymer to correct the water content in the entire composition to be the same.

[Manufacturing process of “Composition No. 2” series]

Process of pre-hydrolyzing TEOS with a catalyst and post-adding Pedot-PSSA

[Step 1: Pre-hydrolysis process of TEOS].

① 606.46 g of ethanol and 69.35 g of TEOS before hydrolysis were added to a weighed 2-liter reaction vessel, and stirring was performed at a linear speed of 0.4 m/s.

② Put 23.99g of deionized water and 0.2g of 35% aqueous hydrochloric acid solution in another container and mix well.

③ Slowly add the mixture of deionized water and hydrochloric acid solution to the mixture of ethanol under stirring and TEOS before hydrolysis.

④ After sealing the reaction vessel well and adjusting the linear speed to 0.8 m/s, hydrolysis is performed by stirring at room temperature for 24 hours.

[Step 2: Conductive polymer (Pedot-PSSA aqueous dispersion) post-addition process]

⑤ After 25 hours, the total weight of the reaction vessel containing the composition is measured and supplemented with ethanol as much as the lost weight.

⑥ Conductive polymer (Huclawn N3) or a mixture of conductive polymer and water is added as much as specified and stirred.

⑦ Filter with #300 fine mesh and pack in a plastic container.

[Coating and drying method of “Composition No. 2” series]

- The composition was coated to a thickness of 12.5 μm (300 nm) using Baker Applicator YBA-3 on tempered glass having a thickness of 5 mm and a size of 150 mm x 150 mm.

- The solvent was evaporated by preliminary heating at 80 ° C for 15 minutes.

- Drying was induced by heating at 120 ° C for 60 minutes.

- When the specific gravity value of the liquid is not corrected, the theoretical final dry film thickness is defined as wet film thickness x solid content (%), and in this experiment, 12.5 μm x (2/100 (%)) = 0.25 μm = 250 nm A range of 300 nm was anticipated and defined.

-

Pencil hardness measurement result of “Composition No. 2” series (Based on dry film thickness of 250 ~ 300nm.) division 2-1 2-2 2-3 2-4 2-5 2-6 Conductive polymer content 5% 10% 15% 20% 25% 30% 120℃ x 1hr crack 9H 7~8H 6H 5~6H 5H 120℃ x 2hr crack crack crack 7~8H 7H crack 120℃ x 3 hours crack crack crack fine crack 8H crack 120℃ x 4hr severe crack severe crack severe crack fine crack fine crack crack

[Special matters and results]

- Compared to the TEOS hydrolyzate alone, the composition containing the Pedot-PSSA dispersion reduced cracking of the dry film.

- As the content of the conductive polymer increases, the hardness tends to decrease.

- The best surface condition was shown at 20% conductive polymer content (Formulation Table No. 2-4), and then cracking increased as the conductive polymer content increased to 30%.

- However, it is estimated that the conductive polymer content with the best cracking phenomenon is in the range of 20 to 25% based on the binder solid content of 2%.

[Method of measuring surface resistance of dry film]

Surface resistance was measured using SIMCO ST-4 (Voltage: 100V, Simco, Japan).

Surface resistance is a logarithmic function and is usually expressed in the form of a number*EX. In the present invention, it is expressed in the form of EX.

It should be determined that the higher the measured value is, the higher the surface resistance value is, and the lower the measured value is, the lower the surface resistance value is.

Surface resistance measurement results of “Composition No. 2” series. division 2-1 2-2 2-3 2-4 2-5 2-6 Inorganic solid content (%)
(theoretical value) 2 2 2 2 2 2 Pedot-PSSA aqueous dispersion (%) content 5% 10% 15% 20% 25% 30% Surface resistance (Ω/□) (after 120℃ x 1 hr) 13.1 7.5 6.4 5.3 4.8 4.3

[Special matters and results]

- Based on the case where the content of the binder in the composition is 2%, it was confirmed that the content of the conductive polymer realizing the surface resistance of E7 (7th power) or less, which is the development goal of the composition, is 15% or more.

- It was confirmed that the hardness of the dry film decreased as the content of the conductive polymer increased.

- Considering the inversely proportional relationship between hardness and surface resistance, it can be seen that the content of the conductive polymer in the entire composition is advantageously in the range of 20 to 25%.

3. Experiment to determine the effect of the catalyst on the storage properties of the coating liquid composition.

Composition Table No. 3. number division 3-1 3-2 3-3 One Ethanol 656.16 656.46 656.66 2 TEOS (NV=28.84%) 69.35 69.35 69.35 3 Di Water 23.99 23.99 23.99 4 35% HCL aqueous solution 0.500 0.20 0.00 5 Huclawn N3 250.00 250.00 250.00 Total 1000.00 1000.00 1000.00 TEOS NV (%) theoretical value 2.00 2.00 2.00 Conductive polymer NV (%) 0.35 0.35 0.35 NV (%) Sum 2.35 2.35 2.35

[Manufacturing process of Composition Table No. 3].

① It was prepared in the same way as in the composition manufacturing process 2.

② The composition of 3-1 and 3-2 is a conductive polymer post-addition process after pre-hydrolysis

③ 3-3 is the direct hydrolysis process.

Surface resistance and storage test results of Composition No. 3 series. item 3-1 3-2 3-3 One surface resistance after manufacturing 4.9 4.8 4.9 1 week later 6.5 4.9 4.9 2 weeks later 11.2 5.2 5.1 3 weeks later OVER 12.3 6.2 4 weeks later OVER can't measure 2 liquid safety after manufacturing seeding occurs Good Good 1 week later floor separation Good Good 2 weeks later seeding occurs Good 3 weeks later floor separation Good 4 weeks later floor separation

([Note:] The surface resistance value OVER is a customary term that expresses the surface resistance value of E13.5 (13.5 power) or higher.)

- As the content of the catalyst increases, the storage stability of the liquid phase quickly deteriorates.

- As the content of the catalyst increases, seeding and precipitation occur faster.

- As the content of the catalyst increases, the surface resistance of the dry coating film quickly deteriorates in coating experiments conducted at intervals of one week after storage of the composition.

- The best storage stability was shown when an acidic Pedot-PSSA aqueous dispersion was used as a catalyst and no additional catalyst was used.

- When preparing a composition using an acidic Pedot-PSSA aqueous dispersion as a catalyst, there is a problem in that the production process is prolonged due to low heat generation and low reactivity during the hydrolysis reaction of the composition, but it is difficult to realize stable storage stability of the composition. It was concluded that it is most preferable not to use a catalyst for this purpose.

4. Storage stability comparison experiment according to functional groups

Composition Table 4. - Comparison of storage stability of compositions according to silane functional groups (based on 5% solid content) division 4-1 4-2 4-3 4-4 4-5 (expected degree of crosslinking) (3.0) (3.0) (3.0) (3.0) (3.0) One Ethanol 790.10 794.02 811.96 863.45 861.56 2 TES (NV: 32.32%) 154.70 3 TEOS (NV: 33.16%) 150.78 4 MTES (37.64%) 132.84 5 2-3,4 ECHETES (NV: 61.46%) 6 3GPTES (NV: 60.07%) 81.35 83.24 7 Di-Water (1) (for hydrolysis) 50.89 52.13 40.26 15.24 16.16 8 35% HCL aqueous solution 0.20 0.20 0.20 0.20 0.20 9 Di-Water (2) (for replenishment) 4.11 2.87 14.74 39.76 38.84 Total 1000.00 1000.00 1000.00 1000.00 1000.00 Composition solid content (theoretical value, %) 5.0 5.0 5.0 5.0 5.0

[Hydrolysis method of composition No. 4 series]

- As described above, the input amount of TEOS was calculated as 33.16% of the expected solid content (%) based on the degree of crosslinking 3.

- The higher the inorganic binder content of the composition, the faster the storage property deteriorates. The solid content (%) of the composition was prepared at 5% in order to compare the storability of the composition and the cracking tendency of the dry film.

- For accurate observation of liquid phase stability, water was used instead of colored “conductive polymer” as much as the expected amount of conductive polymer.

- The water content required for hydrolysis was marked as “Di-water (1)”, and water was additionally added to adjust the water content deviation between the comparative test groups to the same content, and this was referred to as “Di-Water (2)” marked.

- As the catalyst, 0.02% of 35% aqueous hydrochloric acid was used.

- Hydrolysis was carried out at room temperature for 24 hours.

Results of liquid storage test of Composition No. 4 series. division 4-1 4-2 4-3 4-4 4-5 (Inorganic type) TES TEOS MTES 2-3,4
ECHETES 3GPTES One after manufacturing Haze occurs Good Good Good Good 2 3 days (72 hours) gel generation Good Good Good Good 3 1 week later X settling, seeding Good Good Good 4 2 weeks later X gel generation Good Good Good 5 3 weeks later X X Good Good Good 6 After 4 weeks (1 month) X X fine seeding Good Good 7 6 weeks later X X floor separation Good Good 8 After 8 weeks (2 months) X X X Good Good 9 After 25 weeks (6 months) X X X Good Good

[Analysis of the results of composition No. 4 series]

- Gelation of triethoxy silane (TES) hydrolyzate proceeded at a very rapid rate compared to tetraethoxy silane (TEOS) hydrolyzate.

- The hydrolyzate of methyltriethoxysilane (MTES) showed significantly improved storage stability at room temperature compared to the hydrolyzate of tetraethoxysilane (TEOS).

- 2-3,4 ECHETES showed excellent solution storage stability compared to methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS), and maintained stability even after a storage period of 6 months or more.

[Composition No. 4 series dry film thickness and crack test method]

- Instead of a plastic film material with weak thermal stability, a coating was applied on tempered glass to conduct a high-temperature curing experiment.

- The composition was coated with a wet film thickness of 12.5 μm using Baker Applicator YBA-3 on tempered glass having a thickness of 5 mm and a size of 150 mm x 150 mm.

- If the specific gravity value of the liquid is not corrected, the theoretical final dry film thickness is defined as wet film thickness x solid content (%), and in this experiment, 12.5 μm x (5/100 (%)) = 0.625μm = about 625nm It was assumed that the dry film thickness of

- In general, the dry film of “antistatic coating” is between 100nm and 300nm, but in the thin film below 300nm, cracks tend to appear late, so a dry film of about 600nm thick was formed.

- Curing was performed by heating immediately after coating without performing a preheating process according to each drying temperature.

- As for the heat curing condition, curing was performed at room temperature (25 ° C), and then the temperature was raised by 20 ° C from 60 ° C to 200 ° C, and curing was performed for 1 hour each.

- When cracks did not occur after drying, the dry state was predicted by measuring pencil hardness, and when cracks occurred, pencil hardness was not measured.

Pencil hardness and crack test results by temperature of Composition No. 4 series. (Dry film thickness: about 600 ~ 650nm) division 4-1 4-2 4-3 4-4 4-5 (Inorganic type) TES TEOS MTES 2-3,4
ECHETES 3GPTES One Normal temperature (25℃) X/after drying
crack Crack after 7 days 2 months later
micro crack slow drying undried 2 60℃ x 1hr X/crack 2B/ 3 day hook rack 3B/Good 3B/Good undried 3 80℃ x 1hr X/crack Crack after 4H/1 day 3H/Good H/Good undried 4 100℃ x 1hr X/crack 6H/crack 4H/Good 2H/Good undried 5 120℃ x 1hr X/crack X/crack 5H/Good 3H/Good 2H/Good 6 150℃ x 1hr X/crack X/crack 7H/Good 4H/fine crack 6H/Good 7 180℃ x 1hr X/crack X/crack X/crack X/crack 7H/fine crack 8 200℃ x 1hr X/crack X/crack X/crack X/crack X/crack

(*Note: X = Unmeasurable)

Result of pencil hardness and crack test when heat curing at 120 ℃ of composition No. 4 series (dry film thickness: about 600 ~ 650 nm) division 4-1 4-2 4-3 4-4 4-5 (Inorganic type) TES TEOS MTES 2-3,4
ECHETES 3GPTES One 120℃ x 1hr X/crack X/crack 5H/Good 3H/Good 2H/Good 2 120℃ x 2hr X/crack X/crack 7H/Good 4H/Good 3H/Good 3 120℃ x 3hr X/crack X/crack 8H/Good 6H/Good 4-5H/Good 4 120℃ x 4hr X/crack X/crack X/fine crack 6H/Good 6H/Good 5 120℃ x 24hr X/crack X/crack X/crack X/crack 8H/fine crack 6 120℃ x 48hr X/crack X/crack X/crack X/crack 8H/fine crack

(*Note: X = Unmeasurable)

[Analysis of test results of composition No. 4 series]

① Triethoxy silane (TES) hydrolyzate was unstable due to haze and high viscosity after 24 hours of hydrolysis. In addition, when drying after coating, it showed a very fast drying speed, but the coating film was poor, so it could not be meaningful as a comparison group.

② The tetraethoxysilane (TEOS) hydrolyzate showed a drying speed fast enough to measure pencil hardness even under the drying conditions of 60 ° C x 1 hour, but cracks occurred when the dried film was left at room temperature for a certain period of time.

③ Tetraethoxysilane (TEOS) hydrolyzate does not crack when the dry film thickness is less than about 300 nm and under the drying conditions of 120 ° C x 1 hour. However, as in this experiment, when the dry film thickness is about 600 nm, it Cracks occurred immediately after drying for 1 hour.

④ The hydrolyzate of methyltriethoxysilane (MTES) showed a very fast drying rate at a temperature of 80 ° C based on heating for 1 hour at a dry film thickness of about 600 nm. And cracks did not occur until the temperature of 150 ℃. However, considering that the hardness of the dry film is lower than that of TEOS, it can be seen that the dehydration condensation reaction is significantly slower than that of the hydrolyzate of tetraethoxysilane (TEOS).

⑤ 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) shows a slower drying rate than methyltriethoxysilane (MTES), but at a drying temperature of 100℃ and 120℃ It showed a satisfactory drying speed.

⑥ 3-Glycidoxypropyl triethoxysilane (3GPTES) was undried at a temperature of 120 ° C or lower and cured by heating for 1 hour. Even at 150 ° C x 1 hour, insufficient drying was shown, and it was found that heat curing conditions of 150 ° C x 2 hours or 180 ° C x 1 hour were required for sufficient curing.

⑦ There is a difference in drying speed depending on heating temperature and time, but when sufficient heating temperature and time are provided and the degree of crosslinking of the dry film approaches 3, high hardness of pencil hardness of 7H or more is measured for all trifunctional silanes, and cracks It was confirmed that this occurred.

⑧ Compared to the hydrolyzate of tetrafunctional silane, it was found that the dehydration condensation reactivity of the hydrolyzate of trifunctional silane increases as the size of the substituted alkyl group (-R) increases, and the storage stability of the liquid phase is improved. In addition, it was found that such a decrease in dehydration and condensation reactivity required a higher heating temperature and heating time in the drying process of the coating solution.

Next, based on the basic experiments described above, direct experiments related to the present invention were conducted.

5-1. Experiments to determine the amount of dimethyldiethoxysilane (DMDES).

The following experiment was conducted to determine an appropriate mixing ratio of dimethyldiethoxysilane (DMDES) and 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES).

Composition Table No. 5 - Mixed Hydrolysis Table of 2-3,4ECHETES and DMDES. division 5-1 5-2 5-3 5-4 5-5 Expected degree of crosslinking 2 2.7 2.8 2.9 3 One Ethanol 844.82 857.86 859.72 861.58 863.45 2 2-3,4 ECHETES (61.46%) 0.00 56.95 65.08 73.22 81.35 3 DMDES (NV: 50.01%) 99.98 29.99 20.00 10.00 0.00 4 Di-Water (for hydrolysis) 28.55 19.23 17.90 16.57 15.24 5 35% HCL aqueous solution 0.20 0.20 0.20 0.20 0.20 6 Di-Water (additional amount) 21.45 30.77 32.10 33.43 34.76 Total 1000.00 1000.00 1000.00 1000.00 1000.00 Solid content in 2-3,4ECHETES composition (theoretical value, %) 0.0 3.5 4.0 4.5 5.0 Solid content in DMDES composition (theoretical value, %) 5 1.5 One 0.5 0

[Hydrolysis method of composition No. 5 series]

① The expected solid content of 2-3,4ECHETES (NV: 61.46%) and the expected solid content of DMDES (NV: 50.01%) were added to calculate the solid content of the binder in the entire composition to be 5%.

② The expected crosslinking degree of the mixture was calculated using [Equation 2] crosslinking degree calculation method.

[Formula 2] Method for Calculating Composition Crosslinking Degree

③ The solid content in the composition was calculated using the expected solid content values in [Table 18].

④ In order to correct the experimental error due to the deviation of the water content, the water content was adjusted in the same way as in the composition formulation table No. 4 of [Table 14], and the water content was corrected to 5% of the entire composition.

⑤ The water content required for hydrolysis was marked as “Di-water (1)”, and water was additionally added to adjust the water content deviation between the comparative test groups to the same content, and this was referred to as “Di-Water (2)”. marked.

⑥ As a catalyst, 0.02% of 35% aqueous hydrochloric acid was used.

⑦ Hydrolysis was carried out at room temperature for 24 hours.

[Heat drying conditions and crack test method of composition No. 5 series]

- Instead of a plastic film material with weak thermal stability, a high-temperature curing experiment was conducted by coating on tempered glass.

- The composition was coated with a wet film thickness of 12.5 µm using Baker Applicator YBA-3 on tempered glass having a thickness of 5 mm and a size of 150 mm x 150 mm.

- If the specific gravity value of the liquid is not corrected, the theoretical final dry film thickness is defined as wet film thickness x solid content (%), and in this experiment, 12.5 μm x (5/100 (%)) = 0.625μm = about 625nm It was assumed that the dry film thickness of

- In general, the dry film of “antistatic coating” is between 100nm and 300nm, but in the thin film below 300nm, cracks tend to appear late, so a dry film of about 600nm thick was formed.

- Without performing a preheating process, immediately after coating, it was put into an oven at 120 ° C., and pencil hardness and cracks were checked at intervals of 1 hour up to 4 hours.

- Thereafter, the temperature of the oven was lowered to 80 ° C and the presence or absence of cracks was checked at intervals of 24 hours.

- When cracks did not occur after drying, the dry state was predicted by measuring pencil hardness, and when cracks occurred, pencil hardness was not measured.

Pencil hardness and crack test results according to curing time at 120 ℃ temperature of composition No. 5 series. (Dry film thickness: about 600 to 650 nm) division 5-1 5-2 5-3 5-4 5-5 Expected degree of crosslinking 2 2.7 2.8 2.9 3 One 120℃ x 1hr undried 2H/Good 3H/Good 2H/Good 3H/Good 2 120℃ x 2hr undried 2H/Good 3H/Good 3H/Good 4H/Good 3 120℃ x 3hr undried 2H/Good 3H/Good 3H/Good 6H/Good 4 120℃ x 4hr H/Good 2H/Good 3H/Good 3H/Good 6H/Good 5 80℃ x 24hr H/Good 2H/Good 3H/Good 4H/Good 7H/fine crack 6 80℃ x 240hr H/Good 2H/Good 3H/Good 4H/Good X/crack 7 80℃ x 480hr H/Good 2H/Good 3H/Good 4H/Good X/crack

(*Note: X = Unmeasurable)

["Composition No. 5" series - adhesion test method]

- Coat the composition to a thickness of 12.5 μm (about 300 nm) using Baker Applicator YBA-3 on PET film with an average thickness of 100 μm.

- Evaporate the solvent by preliminary heating at 80℃ for 10 minutes.

- In order to minimize thermal deformation of PET film, heat it at 100℃ for 1 hour to induce hardening.

- Then, store the specimen at room temperature (25℃) for 72 hours (3 days) to induce post-curing (Aging).

- Test the adhesion (100/100) using the ISO2409 standard adhesion test tape after cutting with a 2mm cross hatch cutter.

Adhesion test result of “Composition No. 5” series. division 5-1 5-2 5-3 5-4 5-5 Expected degree of crosslinking 2 2.7 2.8 2.9 3 One adhesion
(100/100) X 95/100 100/100 100/100 100/100

(*Note: X = Unable to judge due to insufficient dryness.)

[Analysis of test results of composition No. 5 series]

① The hydrolyzate of 2-3,4ECHETES alone (composition 5-5) dries quickly, but when heated at 80 ° C, the hardness gradually rises, and cracks occur after about 10 days (240 hours).

② The drying of the hydrolyzate of DMDES alone was very slow, and it was found that the hardness gradually increased.

③ It was expected that DMDES would act as a major factor in slowing down the heating and drying speed in mixed hydrolytes.

④ The mixed hydrolyzate of DMDES and 2-3,4ECHETES showed different pencil hardness according to the difference in “degree of crosslinking” of each composition, but no cracks occurred when heated at 80℃ for a long time (20 days). , Compositions Nos. 5-4 with a degree of crosslinking of 2.9 showed a very slow increase in hardness only among the mixed anhydrides.

⑤ Compared to the hydrolyzate of 2-3,4ECHETES alone, the mixed hydrolyzate of DMDES and 2-3,4ECHETES reached the highest dry film hardness earlier than expected. This is a very different phenomenon from the gradual increase in hardness of the hydrolyzate of DMDES alone or the hydrolyzate of 2-3,4ECHETES alone during heat curing.

⑥ As the solid content (%) of DMDES among the total solids of the dry film increased, the dry film became softer and the adhesion decreased.

⑦ In particular, composition Nos. 5-2 with a crosslinking degree of 2.7 and compositions No. 5-3 with a crosslinking degree of 2.8 achieved faster pencil hardness at the beginning of drying than compositions No. 5-4 with a crosslinking degree of 2.9, but the amount of DMDES Considering the phenomenon that the drying speed slows down as the increase increases, this is not the result of a fast crosslinking reaction, but it is judged by DMDES to be “fake hardness” that reflects an effect similar to that of silicone additives. It is close to the characteristics of the initial dry film of oil-based coatings with improved “scratch resistance” as slipperiness is imparted by additives.

⑧ Based on a composition with a solid content of 5%, the dry film was coated on a glass plate with a thick film of about 600 nm and cured and dried. ) based on the mixing ratio of 4: 1, and it was confirmed that step 2.8 was the most stable based on the degree of crosslinking.

5-2. Final Composition Examples and Comparative Examples.

Tetraethyl orthosilicate (ALDRICH, TEOS, Tetraethyl orthosilicate, alias: Orthosilicic acid tetraethyl ester, Silicon tetraethoxide, Tetraethoxysilane, Tetraethoxysilicon (IV), Tetraethyl silicate,) was selected as a tetrafunctional silane-based binder.

2-(3,4epoxycyclohexyl)ethyltriethoxysilane (Coatosil 1770, Momentive, USA, 2-(3,4ECH)ETES, β-(3,4epoxycyclohexyl)ethyltriethoxy silane) as a trifunctional silane-based binder selected

Dimethyldiethoxysilane (KBE-22, Shinetsu Co., Japan, Dimethyldiehtoxy silane) was selected as a bifunctional silane-based binder.

As the non-neutralized acid Pedot-PSSA-based water-based conductive polymer, 1.4% solid Huclawn® N3 aqueous dispersion (d50=75nm, water content 98.6%, Huve Global Co., Ltd., Korea) was selected.

- [Table 9] Referring to “Composition Table 2,” the expected solid content of the binder in the composition was determined to be 2%, and 25% of the conductive polymer was used based on 100% of the composition. (Expected solid content of conductive polymer (%): 0.35%) At this time, the total expected solid content is 2.35%.

- [Table 14] Among the 5 types of silanes used in “Composition Table 4”, triethoxysilane (TES), tetraethyl orthosilicate (TEOS), and methyl triethoxysilane (MTES) showed the highest adhesion to plastic materials. It is a silane that does not meet the purpose of the development of this study because it is insufficient and the shelf life of the composition is poor.

- However, as a comparative example of tetrafunctional silane, tetraethyl orthosilicate (TEOS), the most representative silane among inorganic silanes, was selected and tested.

- The input amount of TEOS was calculated as 33.16% of the expected solid content (%) based on the degree of crosslinking 3.

- As a comparative example of a trifunctional silane, a composition prepared using only 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) without using DMDES was selected.

- In the case of hydrolysis by mixing DMDES in Examples and Comparative Examples, the ratio of DMDES in the total solid content of the inorganic binder for each silane is adjusted to 20%, and the ratio is calculated to be 4: 1 based on the weight ratio "Mixed hydrolyzed composition" was prepared, and "room temperature storage, adhesion, surface resistance, hardness, and change in dry coating film of the prepared composition were compared and tested.

- To improve room temperature storage stability, a separate catalyst was not used, and Pedot-PSS-based “aqueous conductive polymer dispersion” was used as a catalyst.

- Since the amount of water included in the “water-based conductive polymer” and added to the composition is greater than the amount of water required for hydrolysis of inorganic silane, additional water was not supplied.

Composition Table 6. - Preparation Table of Examples and Comparative Examples. number division Example Comparative Example 1 Comparative Example 2 Comparative Example 3 One Ethanol 715.97 717.46 693.75 689.69 2 2-(3,4ECH)ETES (NV: 61.46%) 26.03 32.54 - - 3 TEOS (NV: 33.16%) - - 48.25 60.31 4 DMDES (NV: 50.01%) 8.00 - 8.00 - 5 Huclawn N3 (Pedot-PSSA, NV: 1.4%) 250.00 250.00 250.00 250.00 Total 1000.00 1000.00 1000.00 1000.00 Main binder silane solid content (theoretical value, %) 1.60 2.00 1.60 2.00 DMDES solid content (theoretical value, %) 0.40 0.00 0.40 0.00 Conductive polymer NV (%) 0.35 0.35 0.35 0.35

[“Composition No. 6” series examples and comparative examples-hydrolysis method] Direct hydrolysis method using Pedot-PSSA.

① Into a weighed 2-liter reaction container according to the composition table of Examples and Comparative Examples, the raw materials corresponding to 1 to 4 are put in order and stirred at a linear speed of 0.4 m/s. (A liquid)

② After adjusting the stirring speed of Liquid A to a linear speed of 0.8m/s, quantify 250g of Pedot-PSSA aqueous dispersion (Huclawn®N3, Hub Global) and slowly add it to “Liquid A”.

③ Seal the reaction container well and proceed with hydrolysis by stirring at room temperature for 24 hours.

④ After 24 hours, measure the total weight of the reaction container containing the composition and supplement it with ethanol as much as the lost weight.

⑤ Again, proceed with re-agitation at a linear speed of 0.8 m/s to mix, filter with a #300 fine silver net, and pack in a plastic container.

[“Composition No. 6” series Examples and Comparative Examples-Method of measuring surface resistance, hardness, and cracks of dry coating film]

- Coat the composition to a thickness of 12.5 μm (about 300 nm) using Baker Applicator YBA-3 on tempered glass with a thickness of 5 mm and a size of 150 mm x 150 mm.

- Evaporate the solvent by preliminary heating at 80℃ for 10 minutes.

- Induce hardening by heating at 120℃ for 1 hour.

- Then leave it at room temperature for 30 minutes and measure cracks, pencil hardness, and surface resistance after cooling.

- Thereafter, additional heating is performed at 120 ° C for 1 hour intervals, and pencil hardness and cracks are checked.

- If cracks do not occur, store the coated specimen in an oven at 80 ° C and measure cracks, pencil hardness, and surface resistance every 24 hours.

Cracks by curing time of composition No. 6 series, pencil hardness (heating temperature: 120 ℃, dry film thickness: about 300 nm, glass plate) division Example Comparative Example 1 Comparative Example 2 Comparative Example 3 crack Hardness crack Hardness crack Hardness crack Hardness One 120℃ x 1hr O 3H O 3H O 4H O 8H 2 120℃ x 2hr O 3H O 4H O 5H X X 3 120℃ x 3hr O 3H O 6H O 6H X X 4 120℃ x 4hr O 3H O 6H △ 6H X X 5 80℃ x 24hr O 3H △ 7H △ X X X 6 80℃ x 240hr O 3H △ X △ X X X 7 80℃ x 480hr O 3H X X △ X X X

(*Note: O=good, △=fine crack, X=crack or not measurable)

Surface resistance (Ω/□) measurement result by curing time of composition No. 6 series (heating temperature: 120℃, dry film thickness: about 300nm, glass plate) division Example Comparative Example 1 Comparative Example 2 Comparative Example 3 One 120℃ x 1hr 4.8 5.1 4.5 4.8 2 120℃ x 2hr 4.7 4.9 6.7 X 3 120℃ x 3hr 4.9 5.0 9.9 X 4 120℃ x 4hr 4.8 5.3 12.5 X 5 80℃ x 24hr 4.9 5.5 OVER X 6 80℃ x 240hr 5.0 5.6 X X 7 80℃ x 480hr 5.1 X X X

(*Note: X = Unable to measure, Over = Exceeding the measurement range)

[“Composition No. 6” Series Examples and Comparative Examples-Adhesion Test Method]

- Coat the composition to a thickness of 12.5 μm (about 300 nm) using Baker Applicator YBA-3 on PET film with an average thickness of 100 μm.

- Evaporate the solvent by preliminary heating at 80℃ for 10 minutes.

- In order to minimize thermal deformation of PET film, heat it at 100℃ for 1 hour to induce hardening.

- Then, store the specimen at room temperature (25℃) for 72 hours (3 days) to induce post-curing (Aging).

- Test the adhesion (100/100) using the ISO2409 standard adhesion test tape after cutting with a 2mm cross hatch cutter.

“Composition No. 6” Series Examples and Comparative Examples - Adhesion Test Result division Example Comparative Example 1 Comparative Example 2 Comparative Example 3 One 120℃ x 1hr 100/100 100/100 5/100 X

(*Note: X = Unmeasurable)

[“Composition No. 6” series Examples and Comparative Examples-room temperature storage stability test method of the composition]

- Coat the composition to a thickness of 12.5 μm (about 300 nm) using Baker Applicator YBA-3 on tempered glass with a thickness of 5 mm and a size of 150 mm x 150 mm.

- Evaporate the solvent by preliminary heating at 80℃ for 10 minutes.

- Induce hardening by heating at 120℃ for 1 hour.

- The prepared composition is re-coated at intervals of 1 week, 4 weeks and 7 days immediately after preparation, and cured by heating under conditions of 120 ° C x 1 hr.

- Measure the change in physical properties of the composition by measuring “pencil hardness” and “surface resistance” for each specimen.

“Composition No. 6” series Examples and Comparative Examples - Room temperature storage stability test results of the composition (recoating interval: 1 week (7 days), heating temperature: 120 ° C, dry film thickness: about 300 nm, glass plate) division Surface resistance (Ω/□) Example Comparative Example 1 Comparative Example 2 Comparative Example 3 One coating after manufacturing 4.8 5.1 4.5 4.8 2 Re-coating after 1 week 4.3 4.9 8.5 8.9 3 Re-coating after 2 weeks 4.5 5.3 11.9 12.3 4 Re-coating after 3 weeks 4.9 5.2 Over Over 5 Recoating after 4 weeks 5.1 5.8 No coating No coating 6 Recoating after 8 weeks 5.3 6.5 No coating No coating

(*Note: X = Unable to measure, Over = Exceeding the measurement range)

[Experimental results of “Comparative Example” and “Example”]

① In preparing a “hydrolyzed composition” of a conductive polymer aqueous dispersion (Pedot-PSSA aqueous dispersion) and an inorganic binder, a silane-based compound, rather than using a tetrafunctional TEOS, a trifunctional silane with an alkyl group substituted The composition prepared by mixing with the inorganic material had low dehydration condensation reactivity, so the "composition" had excellent "room temperature storage".

② The composition containing the bifunctional group DMDES has improved storage stability compared to the composition without DMDES.

③ In the case of the hydrolyzed composition by mixing the tetrafunctional group DMDES with the tetrafunctional group TEOS (Comparative Example 3), the “crack prevention” effect of the dry film was significantly improved compared to “Comparative Example 4”, but the dry film adhesion could not improve.

④ Compared to “Comparative Example 1,” the composition containing DMDES in the trifunctional silane (Example) hardly changes the dry film over time even after post-curing (heat curing) by exposing the dry film to 80 ° C. did not

⑤ Trifunctional silane (2- (3,4 epoxycyclohexyl) ethyltriethoxy silane, 2-3,4 ECHETES) Drying of trifunctional silane and DMDES mixed composition (Example) than composition using alone (Comparative Example 1) The coating film was more stable, and at this time, the range of stable mixing ratio can be seen as 2.7 or more and 2.9 or less based on the degree of crosslinking. More preferably, the range of 2.8 is stable.

The present invention is not limited by the above-described embodiments. Therefore, various forms of substitution, modification, and change will be possible by those skilled in the art within the scope of the technical spirit of the present invention described in the claims, which also falls within the scope of the present invention. something to do.

Claims (9)

Including acidic water-based conductive polymer dispersions, binders and solvents,
The binder is a mixture of bifunctional silane and trifunctional silane,
Water-based antistatic high-hardness composition, characterized in that the acidic aqueous conductive polymer dispersion acts as a catalyst The water-based antistatic high-hardness composition according to claim 1, wherein the acidic aqueous conductive polymer dispersion comprises 20 to 30% by weight, 2 to 6% by weight of a binder, and 65 to 75% by weight of a solvent. The water-based antistatic high-hardness composition according to claim 1, wherein the mixed weight ratio of the difunctional silane and the trifunctional silane is 3 to 5:1 based on solid content. The water-based antistatic high-hardness composition according to claim 1, wherein the bifunctional silane is dimethyl diethoxy silane ("DMDES") The water-based antistatic high-hardness composition according to claim 1, wherein the trifunctional silane is 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) The aqueous antistatic high-hardness composition according to claim 1, wherein the solvent is ethyl alcohol, and the acidic aqueous conductive polymer dispersion includes an unneutralized Pedot-PSSA-based acidic aqueous dispersion as a conductive polymer. delete A mixing step of preparing a mixed solution by mixing 2-(3,4epoxycyclohexyl)ethyltriethoxysilane (2-3,4ECHETES) and dimethyldiethoxysilane (DMDES) in a solvent, and
Method for producing a water-based antistatic high-hardness composition comprising a hydrolysis step of hydrolyzing by adding an acidic aqueous conductive polymer dispersion to the mixed solution According to claim 8,
Method for producing a water-based antistatic high-hardness composition, characterized in that the hydrolysis step proceeds for more than 24 hours

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