KR101949611B1 - Chemically amplified binder resin and organic insulation layer composition including the same - Google Patents

Abstract

A chemically amplified binder resin comprises a repeating unit represented by chemical formula 1. In the chemical formula 1, R_1 is chemical formula A1 or chemical formula A2, R_2 and R_3 are one of an alkyl group, an aryl group, an aralkyl group and a cycloalkyl group having 1 to 20 carbon atoms, R_4 is a tetravalent aromatic or cycloaliphatic group containing a hetero element having 1 to 20 carbon atoms, and each of I, m, and n is a number between 0 and 1. A positive photosensitive organic insulating film composition according to embodiments of the present invention can have improved heat resistance.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified binder resin and an organic insulating film composition containing the same.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified type binder resin and an organic insulating film composition containing the same, and more particularly to a chemically amplified type binder resin contained in an organic insulating film included in a display device such as an organic light emitting display device or a liquid crystal display device, And an organic insulating film composition comprising a binder resin.

In a display device such as a thin film transistor (TFT) type liquid crystal display device, a protective film for protecting and insulating a thin film transistor (TFT) circuit is formed.

Conventionally, an inorganic material such as silicon oxide or silicon nitride (SiOx or SiNx) has been used as the protective film. However, when a protective layer is formed using an inorganic material, the dielectric constant of the protective layer is relatively high, which makes it difficult to increase the open area ratio. Furthermore, when the vacuum evaporation process for forming the protective film is performed, the process cost and the process time are excessively high.

In order to overcome the above-mentioned problem, studies have been made on a protective film using a liquid organic insulating material having a relatively low dielectric constant and capable of a coating process. Hereinafter, a protective film using an organic insulating material is referred to as an organic insulating film.

The organic insulating layer may be provided with a photosensitive function on the insulating layer itself, so that a separate additional process for forming a fine pattern for providing interconnecting paths between circuits may be omitted. That is, in the case of a protective film made of a conventional inorganic material, an exposure process is required for the photoresist film after forming a photoresist film on the protective film. On the other hand, when the organic insulating film is used as a protective film, It is not necessary to form a film. Therefore, there is an effect of higher productivity and cost reduction.

As the organic insulating material constituting such an organic insulating film, a photosensitive resin which is a macromolecule compound which is chemically reacted by light or electron beam to change its solubility to a specific solvent is generally used.

In addition, for micro-processing for forming a circuit pattern, a polarity change or cross-linking reaction of the polymer may occur due to a photoreaction with respect to a substance constituting the organic insulating film. Particularly, the organic insulating material constituting the organic insulating film utilizes the property of change in solubility in a developer such as an aqueous alkali solution after exposure.

The organic insulating material constituting the organic insulating film is classified into a positive type and a negative type depending on the solubility of the photosensitive portion in development. In the positive type photoresist, the exposed portion is dissolved by the developing solution due to the change in polarity, and the negative type photoresist is a method in which the exposed portion is dissolved in the developing solution through the crosslinking reaction and the unexposed portion is dissolved to form a pattern.

The negative type organic insulating film is disadvantageous in that foreign matter is generated when it is mixed with an alkali developing solution which is widely used in existing mass production processes.

On the other hand, the positive organic insulating film is not only advantageous from the viewpoint of work environment because there is no problem in the compatibility of the developer, but also has the advantage that the resolution is improved as the swelling phenomenon is theoretically suppressed at a portion not exposed to ultraviolet rays. Further, since the organic insulating film can be easily removed by using the removing liquid after forming the organic insulating film on the substrate, the substrate recovery and reusability can be significantly improved by removing the organic insulating film in the event of a defect.

In recent years, as a representative binder resin contained in the composition of the positive-type organic insulating film, a composition obtained by mixing an acrylic polymer resin with a quinonediazide photoactive compound (PAC) (photoactive compound) is used. Particularly, since a high aperture ratio can be realized, various high-brightness devices having organic insulating films widely applied are being developed.

However, the conventional positive type organic insulating film can not sufficiently satisfy the sensitivity problem, and has a limitation in resolution to cope with miniaturization for higher integration.

Recently, in order to solve the sensitivity problem of a positive organic insulating film including a PAC (Photo Active Compound), a protective agent of a polymer binder is removed through an acid catalysis reaction using an acid generated through exposed light, A chemically amplified positive organic insulating film for solubilizing a developing solution has been introduced (Korean Patent Registration No. 0964773).

On the other hand, the composition of the positive organic insulating film includes a chemically amplified binder resin, an inhibitor, a photoacid generator, and a solvent.

In addition, it is also possible to use a unit comprising an acid-decomposable protecting group having a crosslinkable functional group by an active energy ray or heat as a binder resin, or a unit having a crosslinkable functional group by an active energy ray or heat and not containing an acid-decomposable protecting group, And a positive photosensitive organic insulating film composition capable of minimizing the amount of film used for coating an organic insulating film since the pattern shape can be maintained after the heat treatment and the film reduction can be remarkably reduced (Korean Patent Laid- 2012-0106086).

An object of the present invention is to provide a chemical amplification type binder resin capable of improving not only sensitivity and transparency but also heat resistance.

It is an object of the present invention to provide an organic insulating film composition comprising the chemical amplification type binder resin.

The present invention provides a chemically amplified binder resin comprising a repeating unit represented by the following general formula (1).

[Chemical Formula 1]

또는

이며,Wherein R < ₁ >

or

Lt;

R ₂ and R ₃ are one of an alkyl group, an aryl group, an aralkyl group and a cycloalkyl group having 1 to 20 carbon atoms,

R4 is a tetravalent aromatic or cycloaliphatic containing a heteroatom of 1 to 20 carbon atoms,

l, m and n are each a number between 0 and 1 (1 + m? 0),

A is a substituent represented by the general formula 1-3 or 1-4,

[Formula 1-3]

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[Formula 1-4]

Here, in the above formulas 1-3 and 1-4, x represents any one of O, S, N, Si and Se.

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The chemical amplification type binder resin according to the embodiments of the present invention includes an acetal group substituting a polyamic acid. Therefore, the chemical amplification type binder resin can be chemically amplified using a mineral acid dispersing agent.

The positive photosensitive organic insulating film composition according to the embodiments of the present invention can be improved in sensitivity and fineness using the chemically amplified binder resin, and can have improved heat resistance.

Hereinafter, the photosensitive resin composition according to an embodiment of the present invention will be described in detail with reference to tables, synthesis examples and examples. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

On the other hand, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

The chemical amplification type binder resin according to the present invention comprises a repeating unit represented by the following general formula (1) or (2).

[Chemical Formula 1]

또는

이며,Wherein R < ₁ >

or

Lt;

R ₂ and R ₃ are one of an alkyl group, an aryl group, an aralkyl group and a cycloalkyl group having 1 to 20 carbon atoms.

R4 is a tetravalent aromatic or cycloaliphatic containing a heteroatom of 1 to 20 carbon atoms,

l, m and n are each a number between 0 and 1 (1 + m? 0),

A is a substituent represented by the general formula 1-3 or 1-4,

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[Formula 1-3]

[Formula 1-4]

In the above formulas 1-3 to 1-4, x represents any one of O, S, N, Si and Se.

The chemical amplification type binder resin according to the present invention has a xanthene structure in its main chain. The chemically amplified binder resin according to the present invention has a xanthene structure excellent in photosensitivity, so that it can exhibit sufficient resolution in development and is advantageous for the formation of fine patterns. In addition, since the xanthene structure has a high heat-resistant property at a decomposition temperature of 350 ° C or higher, it has an effect of lowering out gassing, thereby securing the reliability of the applied panel.

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Further, carboxyl group and acetal group are bonded to the chemically amplified binder resin. In particular, when l + m + n = 1, the residue substituted with an acetal group from the carboxyl group contained in each repeating unit of the formula (1) or (2) may have a content ratio of the residue derived from the total anhydride to 0.15 to 0.8 have.

The carboxyl group and acetal group ratio of the chemically amplified binder resin are determined from an acid value analysis. Here, the ratio of the acetal group of the compound of Formula 1 may vary depending on the equivalent amount of the added acetal.

In order to obtain the desired effect of the present invention, the ratio of the acetal group when 1 + m + n = 1 for each of the repeating units 1, m and n in Chemical Formula 1 is preferably 0.015 to 0.8, , And the ratio of the acetal group may be 0.5 to 0.7. In this case, the solubility in the organic solvent is excellent and the solution processability is excellent. On the other hand, when the acetal group ratio is too low, the solution processability is poor, which is not preferable.

The chemical amplification type binder resin may have a weight average molecular weight ranging from 500 to 50,000 g / mol. When the weight average molecular weight is less than 500 g / mol, the patterning speed is so high that pattern formation is impossible and a desired film thickness ratio can not be obtained. On the other hand, if the weight average molecular weight exceeds 50,000 g / mol, development by a developer may not be possible.

The chemical amplification type binder resin may have a degree of dispersion ranging from 1.0 to 5.0. On the other hand, when the average dispersion degree exceeds 5.0, the resolution may be lowered.

According to the method for producing a chemical amplification type binder resin, a xanthene polyimide precursor having a xanthene structure is synthesized. Then, xanthene polyamic ester is synthesized through acetal substitution on the xanthene polyimide precursor. A detailed description thereof will be given later with reference to a synthesis example.

Positive photosensitive high-refractive-index organic insulating film composition

The positive photosensitive organic insulating film composition according to embodiments of the present invention includes a chemical amplification type binder resin, a photo acid generator, and an organic solvent.

1. Chemically amplified binder resin

Since the chemical amplification type binder resin has been described above, a detailed description thereof will be omitted.

2. Photo acid generator

The photoacid generator is a compound which generates an acid by irradiation with an actinic ray or radiation. The photoacid generator may be at least one selected from the group consisting of a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, A sultonate-based compound and a triazine-based compound may be used singly or two or more of them may be used in combination. Any material other than the above-described photoacid generator may be used as long as the photoacid generator does not adversely affect the film formation. However, the photoacid generator may have appropriate light absorption at a wavelength of 250 nm to 400 nm and maintain transparency of the organic insulating material at a visible light range of 400 nm or more It is preferable to use a material which can be used.

Preferably, photoacid generators represented by the following formula (3) or (4) can be used.

(3)

[Chemical Formula 4]

According to one embodiment of the present invention, it is preferable that the photoacid generator comprises 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the chemical amplification type binder resin. When the content of the photoacid generator is less than 0.1 part by weight, acid generation is difficult. When the amount is more than 10 parts by weight, there is a fear of precipitation due to a decrease in solubility in the composition.

3. Organic solvent

The organic solvent is not particularly limited as long as it can dissolve the polymer in an organic solvent such as acetate, ether, glycol, ketone, alcohol, or carbonate used in a general photopolymerizable composition. Examples of the solvent include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, butylcarbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, N, N-dimethylacetamide , N-methylpyrrolidone, N-methylcaprolactam, and the like, or a mixture of two or more thereof.

The content of the organic solvent is 20 to 95 parts by weight, preferably 30 to 90 parts by weight based on 100 parts by weight of the total composition. When the content of the solvent is less than 20 parts by weight, it is difficult to form a thin film by the conventional coating method. When the amount of the solvent is more than 95 parts by weight, a thin film having a desired thickness can not be obtained after coating.

4. Additives

The positive photosensitive organic insulation film composition according to the present invention may further include additives. Examples of the additives include heat stabilizers, heat crosslinking agents, photocuring accelerators, surfactants, base quenchers, antioxidants, adhesion promoters, adhesion promoters, light stabilizers and antifoaming agents. If necessary, the above-mentioned additives may be used alone or in combination.

Among the additives that are typically included among the above additives, the adhesion promoting agent acts to improve the adhesion with the substrate. The adhesive enhancer includes, for example, a silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an epoxy group. Specifically, the adhesive enhancer may be at least one member selected from the group consisting of trimethoxysilylbenzoic acid,? -Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The content of the adhesion promoting agent is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the chemically amplified binder resin.

The surfactant acts to improve coatability, coatability, uniformity and stain removal on the substrate. As the surfactant, one or more selected from the group consisting of a fluorine-based surfactant, a silicon-based surfactant and a nonionic surfactant may be used in combination. The content of the surfactant is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the binder resin.

Hereinafter, a method of preparing the compounds according to the present invention will be described.

Synthesis Example 1; Xanthene polyimide precursor synthesis

35.20 g of 4,4 '- (spiro [fluorene-9,9'-xanthene] -3', 6'-diylbis (oxy)] dianiline was dissolved in 246 g of gamma-butyrolactone in a mechanical stirrer and a 500 mL round bottom flask 25.77 g of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride and 0.63 g of maleic anhydride were charged and heated at room temperature for 4 hours and 30 minutes to obtain polyimide precursor 1.

Synthesis Example 2; Chemically amplified xanthene polyimide precursor synthesis

0.02 g of phosphoric acid and 2.7 g of 3,4-Dihydro-2H-pyran were mixed with the solution of the xanthene polyimide precursor 1 obtained in Synthesis Example 1 and reacted at room temperature for 24 hours to obtain a resin.

The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 3; Xanthene polyimide precursor synthesis

35.20 g of 4,4 '- (spiro [fluorene-9,9'-xanthene] -3,6-diylbis (oxy)) dianiline was dissolved in 246 g of gamma-butyrolactone and stirred in a 4-neck round- , 25.77 g of 4 '- (hexafluoroisopropylidene) diphthalic anhydride and 0.63 g of maleic anhydride were heated at room temperature for 4 hours and 30 minutes to obtain a polyimide precursor 2.

Synthesis Example 4; Chemically amplified xanthene polyimide precursor synthesis

0.02 g of phosphoric acid and 2.7 g of 3,4-Dihydro-2H-pyran were mixed with the solution of the xanthene polyimide precursor 2 obtained in Synthesis Example 3 and reacted at room temperature for 24 hours to obtain a resin.

The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 5 Synthesis of xanthene polyimide precursor

35.20 g of spiro [fluorene-9,9'-xanthene] -3 ', 6'-diamine was dissolved in 246 g of gamma-butyrolactone in a mechanical stirrer and a 500 mL round bottom flask, and 4,4' - (hexafluoroisopropylidene) diphthalic anhydride was added to 25.77 g and Maleic anhydride (0.63 g) were added and heated at room temperature for 4 hours and 30 minutes to obtain polyimide precursor 3.

Synthesis Example 6 Synthesis of xanthene polyamic ester

0.02 g of phosphoric acid and 2.7 g of 3,4-Dihydro-2H-pyran were mixed with the xanthene polyimide precursor 3 solution obtained in Synthesis Example 5 and reacted at room temperature for 24 hours to obtain a resin.

The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Synthesis Example 7 Synthesis of xanthene polyimide precursor

35.20 g of spiro [fluorene-9,9'-xanthene] -3,6-diamine was dissolved in 246 g of gamma-butyrolactone in a mechanical stirrer and a 500 mL round bottom flask, and 25.77 g of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, Maleic anhydride (0.63 g) was added and heated at room temperature for 4 hours and 30 minutes to obtain polyimide precursor 4.

Synthesis Example 8 Synthesis of xanthene polyamic ester

0.02 g of phosphoric acid and 2.7 g of 3,4-Dihydro-2H-pyran were mixed with the xanthene polyimide precursor 4 solution obtained in Synthesis Example 7 and reacted at room temperature for 24 hours to obtain a resin.

The product was confirmed to have undergone the reaction through IR by changing the absorption peaks derived from the carboxyl group and the allyl group.

Example 1

35 g of the chemically amplified binder resin prepared in Synthesis Example 2 and 0.08 g of 1,3-dioxo-1H-benzo [de] isoquinolin-2 (3H) -yl trifluoromethanesulfonate photoacid generator (Formula 3) (BYK333) and 0.02 g of adhesive preparation (KBM303) were added to the solution and mixed. Thus, a positive photosensitive organic insulating film composition was prepared.

Example 2

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 4 was used.

Example 3

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 6 was used.

Example 4

A positive photosensitive organic insulating film composition was prepared in the same manner as in Example 1 except that 35 g of the chemically amplified binder resin prepared in Synthesis Example 8 was used.

Comparative Example 1

35.5 g of a novolac resin and 10.5 g of a photoactive compound (PAC) compound containing a naphthoquinone diazide group were dissolved in an amount of 35 parts by weight based on the organic solvent PGMEA. To this solution, 0.03 g of a surfactant (BYK333) 0.02 g were added and mixed.

Property evaluation

Each of the positive photosensitive organic insulating film compositions obtained through Examples 1 to 4 and Comparative Example 1 was applied to a transparent glass substrate through a spin coater to form a preliminary organic insulating film. Thereafter, the preliminary organic insulating film was dried through a hot plate at 100 DEG C for 90 seconds. Using a predetermined mask, the resist film was exposed as a light source using an ultra-high pressure mercury lamp, and then developed in a TMAH 2.38% developer at 25 캜 for 60 seconds, and then washed with water. After washing with water and drying in an oven at 250 캜 for 60 minutes, an organic insulating film pattern was formed.

(1) Sensitivity evaluation

Each positive photosensitive organic insulating film composition thus formed was applied to a glass substrate with a spin coater and dried at 100 DEG C for 90 seconds with a hot plate. After drying, the thickness of the organic insulating film sample was measured by measuring with a contact-type film thickness meter (Veeco, DEKTAK150). Next, the sample was exposed through a mask with a high-pressure mercury lamp. Thereafter, spraying was performed using TMAH 2.38% developer to obtain an organic insulating film pattern. (MJ / sq cm) capable of forming the same dimensions as the mask pattern of 10 micron. That is, a resist having a small exposure dose can be said to have a high sensitivity characteristic since an image can be formed with a small exposure dose and optical energy.

(2)

The photosensitive resin composition was coated on the glass substrate to form a thin film having a thickness of 3 μm and the thickness was measured before and after the development using a contact type thickness meter (DEKTAK 6M, manufacturer VECCO, USA) after the photolithography process was performed. Were measured.

(3) Transmittance

The composition was spin-coated on the organic substrate to form an organic insulating film having the same thickness of 3 mu m and then post-baked at 250 DEG C / 60 min. Using a UV-spectrometer at each step, The average transmittance for light having a wavelength was measured.

(4) Evaluation of heat resistance

The organic insulating film composition was spin-coated on the organic substrate to form a thin film having the same thickness of 3 占 퐉, followed by post-baking at 250 占 폚 / 60min to obtain a cured film. The obtained sample was subjected to 5% decomposition The temperature was measured.

The comparative examples for the above items (1) to (4) and the evaluation results of the respective examples are shown in Table 1 below.

Example Polymer compound Sensitivity
(mJ / sqcm) Remaining film ratio (%) Permeability (%) Heat Resistance (° C) Example 1 Synthesis Example 1 70 91 86 329 Example 2 Synthesis Example 2 70 91 88 330 Example 3 Synthesis Example 3 80 92 87 328 Example 4 Synthesis Example 4 80 92 87 325 Comparative Example 1 Novolac resin 120 86 85 70

It is confirmed that the organic insulating film according to the present invention has excellent sensitivity, heat resistance, and transparency according to Table 1 and Comparative Examples.

Claims (12)

A chemical amplification type binder resin comprising a repeating unit represented by the following formula (1).
[Chemical Formula 1]

Wherein R < ₁ >

or

Lt;
R ₂ and R ₃ are one of an alkyl group, an aryl group, an aralkyl group and a cycloalkyl group having 1 to 20 carbon atoms,
R4 is a tetravalent aromatic or cycloaliphatic containing a heteroatom of 1 to 20 carbon atoms,
l, m and n are each a number between 0 and 1 (1 + m? 0),
A is a substituent represented by the general formula 1-3 or 1-4,
[Formula 1-3]

[Formula 1-4]

In the above formulas 1-3 and 1-4, x represents any one of O, S, N, Si and Se. The method according to claim 1, wherein, when l + m + n = 1, the residue substituted with an acetal group in the carboxyl group contained in each repeating unit is 0.15 to 0.8 ratio with respect to the residue derived from the total anhydride. Type binder resin. The chemically amplified binder resin according to claim 1, which has a weight average molecular weight ranging from 500 to 50,000 g / mol. The chemical amplification type binder resin according to claim 1, which has a dispersion degree in the range of 1.0 to 5.0. delete A chemical amplification type binder resin according to any one of claims 1 to 4;
Photoacid generators; And
And the remaining organic solvent. The positive photosensitive organic insulating film composition according to claim 6, wherein the mineral acid dissipator is in a range of 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin. The photoacid generator according to claim 6, wherein the photoacid generator is at least one compound selected from the group consisting of a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, A nitrobenzylsulfonate-based compound, and a triazine-based compound. The positive photosensitive organic insulating film composition according to claim 8, wherein the photoacid generator is represented by any one of Chemical Formulas (3) and (4).
(3)

[Chemical Formula 4]

The positive photosensitive organic insulating film composition according to claim 6, wherein the organic solvent comprises at least one of acetate, ether, glycol, ketone, alcohol, and carbonate. The method according to claim 6,
Which further comprises at least one of the group consisting of a heat stabilizer, a thermal crosslinking agent, a photocuring accelerator, a surfactant, a base quencher, an antioxidant, an adhesion promoter, an adhesion promoter, a light stabilizer and a defoaming agent, Insulator composition. 12. The method of claim 11,
Wherein the mineral acid dispersing agent has a range of 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin,
Wherein the additive is in a range of 0.01 to 10 parts by weight based on 100 parts by weight of the binder resin.