KR20190088779A - Positive-type photosensitive resin composition and insulation layer formed from the same - Google Patents

Abstract

The present invention relates to a positive-type photosensitive resin composition comprising a binder resin, a linear vinyl ether compound, a photoacid generator and a solvent. The interaction between the binder resin and the linear vinyl ether compound can form an insulation film having improved transmittance and reliability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a positive-type photosensitive resin composition and an insulating film formed from the positive-

The present invention relates to a positive photosensitive resin composition and an insulating film made therefrom. More particularly, the present invention relates to a positive photosensitive resin composition comprising a photosensitive resin and a photoacid generator, and an insulating film prepared from the positive photosensitive resin composition.

For example, a photosensitive resin composition is used to form various photocurable insulating patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer of a display device. For example, an inorganic insulating film such as silicon oxide or silicon nitride has a high dielectric constant, and the demand for a low dielectric organic insulating film is increasing, and the photosensitive resin composition can be used for forming the organic insulating film.

The organic insulating layer may be formed in a predetermined pattern through an exposure and development process after the photosensitive resin composition is coated and cured through a preliminary heat treatment.

The photosensitive resin composition is classified into a positive type and a negative type according to a portion removed by a developing process. In the positive-working composition, the exposed portion is dissolved by the developing solution, and in the negative-type composition, the unexposed portion may be dissolved to form a pattern.

In the case of the organic insulating film, it is necessary to form the organic insulating film so as to have mechanical properties such as heat resistance together with excellent insulating property, and the photosensitive resin composition needs to be prepared so as to have excellent sensitivity to the exposure process.

In addition, the optical characteristics of the organic insulating film may be deformed by the heat treatment, and the transmittance may be lowered, thereby deteriorating the image quality of the display device. Therefore, it is necessary to design the photosensitive resin composition in consideration of the optical characteristics of the organic insulating film.

For example, Korean Patent Laid-Open Publication No. 2013-0021324 discloses a positive resist composition, but does not provide an alternative for improving the mechanical and optical properties described above.

Korean Patent Publication No. 10-2013-0021324

An object of the present invention is to provide a photosensitive resin composition having excellent chemical, optical, and mechanical properties.

An object of the present invention is to provide an insulating film formed from the photosensitive resin composition and having excellent transparency and reliability.

An object of the present invention is to provide an image display device including the insulating film formed by the photosensitive resin composition.

1. Binder resin; Linear vinyl ether compounds; Photoacid generators; And a solvent.

2. The positive photosensitive resin composition according to 1 above, wherein the binder resin comprises a first resin containing a phenol unit protected with an acid-decomposable group.

3. The positive photosensitive resin composition according to 1 above, wherein said first resin comprises a structural unit represented by the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,

R ₃ represents an acid-decomposable group and is an alkyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkoxy group having 4 to 8 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, p is 40 to 80 mol%, and q is 20 to 60 mol%

4. The positive photosensitive resin composition according to 3 above, wherein the first resin comprises a structural unit represented by the following formula (1-1)

[Formula 1-1]

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,

R ₄ and R ₅ are each independently an alkyl group having 1 to 6 carbon atoms, p is from 40 to 80 mol%, and q is from 20 to 60 mol%

5. The positive photosensitive resin composition according to 2 above, wherein the binder resin further comprises a second resin containing an epoxy group-containing acrylic resin.

6. The positive photosensitive resin composition according to item 5, wherein the second resin is derived from at least one of monomers represented by the following general formula (2) or (3)

(2)

(3)

(Wherein Z ₁ is hydrogen or a methyl group, Z ₂ is an alkylene group having 1 to 6 carbon atoms, Z ₃ and Z ₄ are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, 3 to 8 rings, and m is an integer of 1 to 6)

7. The positive photosensitive resin composition according to 5 above, wherein the first resin is contained in an amount of about 30 to 55 parts by weight and the second resin is contained in about 10 to 55 parts by weight in 100 parts by weight of the total binder resin.

8. The positive photosensitive resin composition according to 1 above, wherein said linear vinyl ether compound comprises a compound represented by the following formula (4)

[Chemical Formula 4]

(Wherein R ¹ is an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms, and n is an integer of 1 to 6).

9. The positive photosensitive resin composition according to 1 above, wherein the content of the binder resin in the total weight of the composition is 5 to 50% by weight, and the linear vinyl ether compound is contained in 1 to 40 parts by weight of 100 parts by weight of the binder resin .

10. The photoacid generator according to 1 above, wherein the photoacid generator is 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 nitrobenzylsulfonate-based compound, and a tripazine-based compound.

11. An insulating film formed from the positive-type photosensitive resin composition according to any one of items 1 to 10 above.

12. In the above eleventh embodiment, the insulating film used as the interlayer insulating film or the via insulating film of the image display apparatus

13. An image display device comprising an upper insulating film.

The photosensitive resin composition according to the exemplary embodiments includes a linear vinyl ether compound, and oxidation of the phenol group can be prevented by heat treatment such as post-baking, for example, to prevent yellowing. Therefore, an insulating film can be formed which maintains excellent transparency even after curing.

Further, the linear vinyl ether compound can further improve the film properties such as the adhesion of the insulating film, the coating property, and the like.

The photosensitive resin composition may include a first resin containing a hydroxyl group and a protecting group and a second resin containing an epoxy group as a binder resin. The sensitivity of the exposure process and the resolution of the developing process are secured by the first resin, and the mechanical properties of the insulating film can be improved by the second resin.

1 to 5 are schematic cross-sectional views for explaining a method of forming an insulating film according to exemplary embodiments.

Embodiments of the present invention provide a positive photosensitive resin composition comprising a binder resin, a linear vinyl ether compound, a photoacid generator, and a solvent, and having excellent transparency and film forming reliability. An image display device including the insulating film formed from the positive photosensitive resin composition and the insulating film is also provided.

Hereinafter, embodiments of the present invention will be described in more detail.

≪ Positive photosensitive resin composition >

The positive photosensitive resin composition according to the embodiments of the present invention (hereinafter also abbreviated as photosensitive composition) may include a binder resin, a linear vinyl ether compound, a photo acid generator, and a solvent.

According to exemplary embodiments, the photosensitive composition may be provided in a chemically amplified resist (CAR) composition in which the solubility difference is caused by, for example, an acid generated by an exposure process. Therefore, an insulating film or an insulating pattern can be formed with improved sensitivity and resolution as compared with, for example, a composition based on Photo Active Compound (PAC) such as quinone diazide.

Binder resin

The photosensitive composition according to exemplary embodiments may comprise a binder resin as a base component. The binder resin provides the basic skeleton of the insulating film formed from the photosensitive composition and can provide a difference in solubility by the exposure process.

According to exemplary embodiments, the binder resin may comprise a first resin comprising a phenolic (or novolak) resin and a second resin comprising an epoxy group containing acrylic resin.

The first resin comprises a plurality of hydroxyl groups, and at least a part of the hydroxyl groups may be protected with an acid-decomposable group. For example, among the phenol units contained in the first resin, the hydroxyl group contained in at least part of the phenol unit may be protected with the acid-decomposable group.

For example, the first resin may include a structural unit (for example, a repeating unit) represented by the following formula (1).

[Chemical Formula 1]

In the formula (1), R ₁ and R ₂ each independently represent hydrogen or a methyl group. R ₃ represents an acid-decomposable group, and is an alkyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkoxy group having 4 to 8 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

 p and q may represent the molar ratio of the phenol unit and the phenol unit protected by the acid decomposable group, respectively. For example, p may be about 40 to 80 mole%, and q may be about 20 to 60 mole%. p and q represent the relative molar ratio of the phenol unit and the phenol unit protected by the acid decomposable group, and does not exclude the addition of other units.

In some embodiments, the first resin may include a structure represented by Formula 1-1 below.

[Formula 1-1]

R ₁ , R ₂ , p and q are as defined in the above formula (1). R ₄ and R ₅ each independently represent an alkyl group having 1 to 6 carbon atoms.

For example, the phenol unit may be derived from hydroxystyrene as the first monomer. The phenol unit protected by the acid-decomposable group may be derived from the following formula 1-2, and in one embodiment, the second monomer represented by formula 1-3.

[Formula 1-2]

[Formula 1-3]

In formulas (1-2) and (1-3), R ₃ , R ₄ and R ₅ are as defined in the above formulas (1) and (1-1).

The first resin may be prepared through a copolymerization reaction of the first monomer and the second monomer, and the number of moles of the first monomer and the second monomer may be controlled so as to correspond to a molar ratio expressed by p and q, respectively .

As described above, the first resin contains both a phenol unit in which a hydroxyl group remains and a phenol unit in which a hydroxyl group is protected by an acid-decomposable group, so that sensitivity to the exposure process and adhesion to a substrate can be realized at the same time .

In some embodiments, the first resin may further comprise units derived from a third monomer other than the first and second monomers. The third monomer may comprise, for example, a (meth) acrylate-based monomer. In this case, examples of the third monomer include, but not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Alkyl (meth) acrylates such as n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate and t-butyl (Meth) acrylate such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (Meth) acrylates; (Meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate and the like.

The third monomer may include a monomer containing a hydroxyl group. In this case, the third monomer may include, for example, an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid, hydroxymethylstyrene, and the like.

In some embodiments, the weight average molecular weight of the first resin may range from 5,000 to 35,000, preferably from 5,000 to 20,000. Within this range, the residual film ratio of the photosensitive composition is effectively improved, and the film residue can be reduced.

The binder resin may further comprise an epoxy resin-containing acrylic resin as the second resin. As the second resin is included, the thermosetting property is improved in a heat treatment process such as post-baking, for example, and the mechanical properties such as heat resistance and impact resistance of the insulating film can be further improved.

In some embodiments, the second resin may be derived from a monomer represented by the following formula (2).

(2)

In the general formula (2), Z ₁ is hydrogen or a methyl group, and Z ₂ is an alkylene group having 1 to 6 carbon atoms. Z ₃ and Z ₄ may independently be hydrogen or an alkyl group having 1 to 6 carbon atoms and may be connected to each other to form a ring having 3 to 8 carbon atoms. m may be an integer of 1 to 6,

A monomer represented by the above formula (2) Z ₂ may form an ether bond with an adjacent oxygen atom. Therefore, since rotation through the ether bond is possible, the glass transition temperature can be reduced, and the flowability of the photosensitive composition can be improved.

Also, the monomer length can be controlled by adjusting m in the above formula (2). By adjusting the monomer length, the sidewall slope of the insulation pattern generated after the development process can be controlled. For example, when the subsequent conductive pattern such as the transparent electrode is formed by reducing the inclination of the sidewall, damage to the insulation pattern and dropout of the conductive pattern can be prevented.

In some embodiments, the second resin may be derived from a monomer represented by the following formula (3).

(3)

In the formula (3), Z ₁ , Z ₃ , Z ₃ and Z ₄ are as defined in the above formula (2).

The transmittance of the second resin can be further improved through the monomer represented by the general formula (3).

In some embodiments, the second resin may be prepared using at least one of the monomers of formula (2) or the monomers of formula (3).

The second resin may be prepared by copolymerizing monomers represented by the general formula (2) or (3) and other monomers commonly used in the art capable of forming an acrylic resin.

In some embodiments, the other monomer may include a carboxyl group-containing ethylenically unsaturated monomer for improving developability and adhesion to a substrate. Examples of the carboxyl group-containing ethylenically unsaturated monomers include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid, and anhydrides thereof.

As additional non-limiting examples of the other monomers there may be mentioned styrene, vinyl toluene, methyl styrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- methoxystyrene, o- Aromatic vinyl compounds such as vinyl benzyl methyl ether and p-vinyl benzyl methyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Acrylate such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate and isobonyl Alicyclic (meth) acrylates; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like. These may be used alone or in combination of two or more.

For example, the second resin may be prepared by copolymerizing at least one of the monomers represented by the general formula (2) or (3) and the above-mentioned other monomers. The molar ratio of the monomer represented by the formula (2) or (3) may be about 5 to 60 mol% of the total monomers. In this case, improvements in developability, transparency, pattern slope, and the like can be effectively achieved through the second resin.

The weight average molecular weight of the second resin may be 5,000 to 40,000, preferably 15,000 to 30,000. The developability can be further improved and the film residue can be reduced in the above range.

As described above, the binder resin may include the first resin and the second resin, and the first resin is about 30 to 55 parts by weight and the second resin is about 10 parts by weight To 55 parts by weight. In this case, the residual film ratio after the exposure and development step and the stability with time of the composition can be further improved.

In exemplary embodiments, the binder resin may comprise from about 5 to about 50 weight percent, and preferably from about 10 to about 40 weight percent, of the total weight of the photosensitive composition. Within this range, the sensitivity to the exposure process and the resolution to the development process can be improved together.

Linear vinyl ether compound

According to exemplary embodiments, the photosensitive composition may comprise a linear vinyl ether compound. For example, the linear vinyl ether compound may be contained in the form of a monomer, and may function as a protecting agent or an antioxidant of a phenol unit or a hydroxyl group contained in the binder resin.

The linear vinyl ether compound may include a bifunctional vinyl compound having a vinyl group bonded to the terminal by a linear linker group containing an ether bond.

In some embodiments, the linear vinyl ether compound may include a compound represented by Formula 4 below.

[Chemical Formula 4]

In the general formula (4), R ¹ may represent an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms. and n may be an integer of 1 to 6.

Examples of the linear vinyl ether compound include diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, and cyclohexanedimethanol divinyl ether. These may be used alone or in combination of two or more.

In the linear vinyl ether compound, for example, the phenol unit or the acid-decomposable group is released in the post-baking process after the exposure and development process or the subsequent thermal process, and the resulting phenol unit is oxidized, for example, as quinone It is possible to prevent denaturation. When the binder resin is modified to include quinone, the yellowish phenomenon of the insulating film may be caused and the transmittance of the insulating film may be lowered.

For example, the linear vinyl ether compound may be combined with a hydroxyl group exposed to the phenol unit after the exposure and development processes to inhibit oxidation modification to the quinone unit. Therefore, the desired transparency and transmittance of the insulating film can be maintained after the post-baking or subsequent heat treatment process.

The linear vinyl ether compound includes vinyl groups at the ends thereof via a linear linker, so that the linear vinyl ether compounds can easily meet with the hydroxyl groups of adjacent binder resins without steric hindrance. If the length of the linear vinyl ether compound is excessively increased, the possibility of reaction or interaction with the hydroxyl group due to molecular folding or the like may be reduced. In view of the above-mentioned aspect, in the formula (4), n can be adjusted to 6 or less.

The linear vinyl ether bond may interact with the hydroxyl group contained in the binder resin as described above to improve the adhesion of the composition. In addition, the flowability of the composition is improved through the rotatable structure of the ether bond, and film formation properties such as coatability and flatness can be enhanced together.

In the exemplary embodiments, the content of the linear vinyl ether compound may be about 1 to 40 parts by weight, preferably about 10 to 40 parts by weight, based on 100 parts by weight of the binder resin. The above-described improvement in transmittance and adhesion of the insulating film within the above range can be effectively implemented.

Photoacid generator

The photosensitive composition according to exemplary embodiments may be a CAR type composition comprising a photoacid generator.

The photoacid generator is a compound which generates an acid (for example, proton (H ⁺ )) by an exposure process using ultraviolet rays or radiation, and a compound known in the field of photosensitive compositions can be used without any particular limitation.

For example, 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, Sulfonate-based compounds, and triprazine-based compounds. These may be used alone or in combination of two or more.

The content of the photo-acid generator may be, for example, about 0.1 to 20 parts by weight, and preferably about 0.5 to 10 parts by weight based on 100 parts by weight of the binder resin. Within this range, sufficient sensitivity to the exposure process can be obtained without impairing the transmittance and mechanical properties of the binder resin and the linear vinyl ether compound.

In some embodiments, a sensitizer may be used with the photo acid generator to improve the sensitivity of the exposure process. For example, the acid generator from the photo acid generator can be amplified by the sensitizer.

For example, the sensitizer may be at least one selected from the group consisting of polynuclear aromatic compounds, xanthines, xanthones, cyanines, oxonols, thiazines, acridines, acridones, anthraquinones, squaryliums, Coumarins, anthracene compounds, and the like. These may be used alone or in combination of two or more.

In one embodiment, the sensitizer may include a compound represented by Formula 5 below.

[Chemical Formula 5]

In formula (5), L ₁ and L ₂ may independently be an alkyl group having 1 to 6 carbon atoms.

For example, the sensitizer may include at least one of the compounds represented by the following formulas (5-1) to (5-3).

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

For example, the content of the sensitizer may be about 0.01 to 60 parts by weight, and preferably about 0.5 to 10 parts by weight based on 100 parts by weight of the binder resin. Within this range, for example, the sensitivity to the exposure process can be improved without impairing the effect of improving the permeability from the linear vinyl ether compound.

menstruum

The photosensitive composition may use, as a solvent, an organic solvent having a sufficient solubility in an organic component such as the above-mentioned binder resin and linear vinyl ether compound.

For example, ethers, acetates, esters, ketones, amides, and lactones may be used. These solvents may be used alone or in combination of two or more.

Examples of the ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl Ether, and the like.

Examples of the acetate solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate, propylene glycol dialkyl acetate, and the like. .

Examples of the ester solvent include ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyric acid, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, and diethylene glycol methyl ethyl ester.

Examples of the ketone solvent include methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone.

Examples of the amide solvent include N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone. An example of a lactone solvent is gamma -butyrolactone.

Preferably, propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester, or a mixture thereof may be used in view of coating property and thickness uniformity of the insulating film.

The content of the solvent may be included in the balance excluding the above-mentioned components and additives described later. For example, the content of the solvent may be about 40-90 wt%, preferably about 50-80 wt% of the total weight of the photosensitive composition. Within this range, the solid content and viscosity can be appropriately maintained to improve the coating property of the composition.

additive

The photosensitive composition may further contain additives, for example, within a range that does not inhibit the interaction between the binder resin, the linear vinyl ether compound and the photoacid generator described above.

The additive may include a basic compound, a surfactant, a coupling agent, a heat crosslinking agent, a light stabilizer, a photocuring accelerator, a leveling agent, a defoaming agent, and the like.

For example, the basic compound may be included, for example, for developing control and may include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like have.

The surfactant can improve the adhesion between the substrate and the photosensitive composition.

The surfactant may include a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant, which are well known in the art. These may be used alone or in combination of two or more.

The coupling agent may be included to improve the adhesion between the photosensitive composition and the substrate including the inorganic material, and to adjust the taper angle of the insulation pattern.

The coupling agent may include, for example, a silane coupling agent or a thiol-based compound, and preferably a silane coupling agent may be used.

Examples of the silane coupling agent include? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacrylate (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane, Vinyltrialkoxysilane, and the like.

The thermal cross-linking agent can further improve the degree of crosslinking of the insulating film through heat treatment such as post-baking as a composition, thereby improving hardness and heat resistance.

The thermal cross-linking agent may include, for example, a polyacrylate resin, an epoxy resin, a phenol resin, a melamine resin, an organic acid, an amine compound, an anhydrous compound and the like.

The light stabilizer can improve the light resistance of the photosensitive composition. The light stabilizer may include, for example, benzotriazole-based, triazine-based, benzophenone-based, hindered aminoether-based, hindered amine-based compounds, and the like.

The content of the above-mentioned additives can be appropriately changed in consideration of process conditions, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the binder resin, respectively .

<Insulating Film and Image Display Device>

Embodiments of the present invention provide an insulating film formed from the above-described photosensitive composition and a method of manufacturing the same.

1 to 5 are schematic cross-sectional views for explaining a method of forming an insulating film according to exemplary embodiments.

Referring to FIG. 1, a first conductive pattern 110 may be formed on a substrate 100.

The substrate 100 may be, for example, a glass substrate or a resin substrate containing polyimide, polymethylmethacrylate (PMMA), or the like. For example, the substrate 100 may be a display panel substrate of an image display apparatus.

The first conductive pattern 110 may be formed by depositing a metal or a transparent conductive oxide such as ITO to form a first conductive layer and then etching the first conductive layer.

In some embodiments, a barrier film including silicon oxide, silicon nitride, silicon oxynitride, or the like may be formed on the upper surface of the substrate 100 before the first conductive pattern 110 is formed.

The first conductive pattern 110 may be provided, for example, as an electrode such as a gate electrode, a source electrode, or a drain electrode of a thin film transistor (TFT) included in an image display device. In some embodiments, the first conductive pattern 110 may be provided as a wiring such as a scan line, a data line, a power supply line, or the like of an image display apparatus.

Referring to FIG. 2, a preliminary insulating layer 120 may be formed on the substrate 100 to cover the first conductive pattern 110. The preliminary insulating layer 120 may be formed by applying the above-described photosensitive composition through a spin coating process, a slit coating process, a roll coating process, or the like, followed by drying and / or a soft baking process. For example, the soft bake process may be performed at a temperature range of about 60 to 150 &lt; 0 &gt; C.

As described above, since the photosensitive composition contains a linear vinyl ether compound, the flowability of the composition is improved and the film flatness and coating properties can be further improved. Further, the adhesion with the substrate 100 can be further improved through the combination of the first resin and the second resin.

Referring to FIG. 3, the preliminary insulating layer 120 can be converted into an insulating layer including the exposed portion 123 and the non-exposed portion 125 through an exposure process.

According to exemplary embodiments, a mask including a light shielding portion and a transmissive portion may be disposed on the preliminary insulation layer 120, and then an excimer laser, deep ultraviolet light, ultraviolet light, visible light, electron beam, X- (Wavelength: 436 nm), i-line (wavelength: 365 nm), and h-line (wavelength: 405 nm).

For example, the transmissive portion of the mask may overlap with the first conductive pattern 110, and the portion of the preliminary insulation layer 120 irradiated with light through the transmissive portion may be converted into the exposure portion 123.

According to exemplary embodiments, an acid is generated from the photoacid generator contained in the photosensitive composition by the exposure process, and the acid-decomposable group contained in the binder resin (for example, the first resin) can be released. As a result, the hydroxyl group of the phenol unit protected by the acid-decomposable group is exposed, and the solubility of the exposed portion 123 in the developer can be increased.

In some embodiments, a post exposure baking (PEB) process may be further performed to prevent diffusion of the acid generated after the exposure process.

Referring to FIG. 4, the exposure process can be performed to remove the exposed portion 123. Accordingly, the insulating pattern can be defined by the remaining non-visible portion 125. [ The developing process can be performed using, for example, an alkali developing solution such as tetramethylammonium hydroxide (TMAH).

In the space in which the exposing portion 123 is removed by the developing process, for example, an opening 127 for exposing the first conductive pattern 110 at least partially may be formed.

In the exemplary embodiments, a post-baking process may be further performed to improve the mechanical characteristics through additional curing of the insulation pattern (for example, the remaining unexposed portions 125) after the development process. The post-baking process may be performed at a temperature of about 150 to 350 ° C.

When a high-temperature heat treatment such as the post-baking process is performed, the phenol units included in the binder resin may be oxidized (for example, in quinone units) to cause yellowing of the insulation pattern.

However, according to exemplary embodiments, the phenol unit may be protected by the linear vinyl ether compound to suppress the yellowing and maintain the transmittance of the insulation pattern.

Referring to FIG. 5, the second conductive pattern 130 may be formed in the opening 127 shown in FIG.

For example, after forming a second conductive film that sufficiently fills the opening 127 and includes a metal or a transparent conductive oxide on the non-visible portion 125, the second conductive film is patterned to form a second conductive pattern 130 Can be,

Even when the heat treatment process such as the high-temperature deposition process is performed for forming the second conductive film, the yellowing and dropping of the non-visible portion 125 can be suppressed through the action of the linear vinyl ether compound.

The second conductive pattern 130 may be provided, for example, as a pixel electrode of an image display device, or may be provided as various wiring structures. For example, the second conductive pattern 130 may be provided as a pixel electrode including a via structure passing through the insulating pattern to be electrically connected to the first conductive pattern 110. In this case, the first conductive pattern 110 may be provided as a drain electrode connected to the pixel electrode.

Embodiments of the present invention provide an image display device including the above-described insulating film or an insulating pattern. The insulating film may be provided as a gate insulating film, an interlayer insulating film, a via insulating film, or the like of the image display apparatus. For example, the second conductive pattern 130 shown in FIG. 5 is provided as a pixel electrode, and a display layer including a liquid crystal layer or an organic light emitting layer is formed on the second conductive pattern 130 to form an LCD device or an OLED Device, etc. may be implemented.

A counter electrode (for example, a cathode) facing the pixel electrode may be disposed on the display layer, and additional structures such as an encapsulation layer, a hard coating layer, and a window substrate may be stacked on the counter electrode .

As described above, since the insulating film is suppressed in yellowing due to the heat treatment and has excellent transparency, the image quality of the image display device can be improved.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Examples and Comparative Examples

A positive photosensitive resin composition having the composition and the content (parts by weight) shown in Table 1 below was prepared.

division The binder resin (A) /
The linear vinyl ether compound (B) Photoacid generator
(C1) /
Sensitizer (C2) menstruum
(D) additive Basic
compound
(E) The coupling agent (F) Surfactants Example 1 A1-1 / A2-1 / B1 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 2 A1-1 / A2-1 / B2 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 3 A1-1 / A2-1 / B3 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 4 A1-1 / A2-2 / B1 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 5 A1-1 / A2-2 / B2 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 6 A1-1 / A2-2 / B3 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 7 A1-2 / A2-1 / B1 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 8 A1-2 / A2-1 / B2 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 9 A1-2 / A2-1 / B3 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 10 A1-2 / A2-2 / B1 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 11 A1-2 / A2-2 / B2 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Example 12 A1-2 / A2-2 / B3 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Comparative Example 1 A1-1 / A2-1 / B4 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Comparative Example 2 A1-1 / A2-2 / B4 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Comparative Example 3 A1-1 / A2-1 / - 70/30 / - 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Comparative Example 4 A1-1 / A2-2 / - 70/30 / - 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Comparative Example 5 A1-2 / A2-1 / B4 45/30/25 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1 Comparative Example 6 A1-2 / A2-2 / B4 45/35/20 1.0 / 0.5 D1 / D2 120/80 0.01 1.0 G1 / G2 0.1 / 0.1

Specific ingredients are as follows. The numerical value of each unit included in the binder resin (A) means mol%.

p/q = 60/40, Mw=12,000A1-1)

p / q = 60/40, Mw = 12,000

p/q/r = 60/25/15, Mw=12,000 A1-2)

p / q / r = 60/25/15, Mw = 12,000

A2-1, A2-2

A2-1) a / b / c / d = 15/10/50/25, Mw = 25,000

A2-2) a / b / c / d = 15/15/40/30, Mw = 24,000

(TCI사 제조)B1)

(Manufactured by TCI)

(TCI사 제조)B2)

(Manufactured by TCI)

(Sigma-Aldrich사 제조)B3)

(Sigma-Aldrich)

(Sigma-Aldrich사 제조)B4)

(Sigma-Aldrich)

C1)

C2)

D1) Propylene glycol methyl ethyl acetate

D2) Diethylene glycol methyl ethyl ester

E) Dicyclohexylmethylamine

F)? -Glycidoxypropyltrialkoxysilane

G1) SH-8400 (manufactured by Dow Corning)

G2) F-475 (manufactured by DIC)

Experimental Example

The following evaluations were carried out on the greenish compositions prepared according to Examples and Comparative Examples in Table 1, and the results are shown in Table 2 below.

(1) Sensitivity measurement

The photosensitive resin compositions of Examples and Comparative Examples were coated on a 0.7 mm thick glass substrate (Corning 1737, Corning) with a spinner and heated on a hot plate at 100 캜 for 125 seconds to volatilize the solvent, Thereby forming an insulating layer.

Thereafter, in order to obtain a contact hole pattern having a diameter of 10 mu m, the exposure portion was exposed with an i-line stepper (NSR-205i11D, Nikon Corporation) using a mask having a square pattern opening with sides of 10 mu m.

The substrate after exposure was subjected to a puddle development in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 40 seconds using a developer and heated in an oven at 230 DEG C for 30 minutes to form a cured insulating pattern.

Subsequently, the substrate was cut vertically and the sensitivity was evaluated by measuring the amount of exposure required to form 10 占 퐉 contact holes in each insulating pattern.

(2) Pattern angle

The insulating patterns formed for the sensitivity measurement were cut vertically and the angle with the substrate was calculated from the optical photographs.

(3) Measurement of transmittance

The transmittance at 400 nm was measured with a spectrophotometer for the insulating patterns formed for the sensitivity measurement.

(4)

The photosensitive resin compositions prepared in Examples and Comparative Examples were coated on a 0.7 mm thick glass substrate (Corning 1737, manufactured by Corning) with a spinner and heated on a hot plate at 100 ° C for 125 seconds to volatilize the solvent. A) was measured. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was subjected to a puddle development at 23 DEG C for 40 seconds using a developing solution, and an insulating pattern was formed by heating in an oven at 230 DEG C for 30 minutes. Then, the film thickness (B) The film residual ratio was calculated according to the following equation (1).

[Equation 1]

Residual film ratio (%) = B / A * 100

division Sensitivity (mJ / cm ² ) Pattern angle ( ^o ) Transmittance (%) Remaining film ratio (%) Example 1 24 53 98 79 Example 2 24 52 99 79 Example 3 25 51 98 77 Example 4 25 53 98 76 Example 5 27 52 99 78 Example 6 26 53 99 80 Example 7 26 51 98 77 Example 8 27 52 98 78 Example 9 25 50 99 79 Example 10 26 51 98 78 Example 11 27 52 99 76 Example 12 26 50 99 78 Comparative Example 1 50 64 97 65 Comparative Example 2 53 60 97 63 Comparative Example 3 40 64 94 80 Comparative Example 4 43 60 93 82 Comparative Example 5 54 60 97 68 Comparative Example 6 56 55 94 65

Referring to Table 2, all of the embodiments in which the linear vinyl ether compound was included together with the binder resin exhibited a transmittance of 98% or more, and the sensitivity and pattern profile characteristics were also improved.

In the case of Comparative Examples 1, 2, 5 and 6 in which a compound having an acrylate group at the terminal thereof was used, the sensitivity and the residual film ratio decreased together. In the case of Comparative Examples 3 and 4 in which the linear vinyl ether compound was omitted, the transmittance was decreased due to the yellowing phenomenon.

100: substrate 110: first conductive pattern
120: preliminary insulating film 123:
125: Non-visible portion 127:
130: second conductive pattern

Claims (13)

Binder resin;
Linear vinyl ether compounds;
Photoacid generators; And
A positive photosensitive resin composition comprising a solvent.
The positive photosensitive resin composition according to claim 1, wherein the binder resin comprises a first resin containing a phenol unit protected with an acid-decomposable group.
[2] The positive photosensitive resin composition according to claim 1, wherein the first resin comprises a structural unit represented by the following formula (1)
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,
R ₃ represents an acid-decomposable group and is an alkyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkoxy group having 4 to 8 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
p is 40 to 80 mol%, and q is 20 to 60 mol%).
4. The positive photosensitive resin composition according to claim 3, wherein the first resin comprises a structural unit represented by the following formula (1-1)
[Formula 1-1]

(Wherein R ₁ and R ₂ are each independently hydrogen or a methyl group,
R ₄ and R ₅ are each independently an alkyl group having 1 to 6 carbon atoms,
p is 40 to 80 mol%, and q is 20 to 60 mol%).
The positive photosensitive resin composition according to claim 2, wherein the binder resin further comprises a second resin including an epoxy resin containing an epoxy group.
The positive photosensitive resin composition according to claim 5, wherein the second resin is derived from at least one of monomers represented by the following general formula (2) or (3)
(2)

(3)

(Wherein Z ₁ is hydrogen or a methyl group, Z ₂ is an alkylene group having 1 to 6 carbon atoms, Z ₃ and Z ₄ are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, Form a ring of 3 to 8,
and m is an integer of 1 to 6).
The positive photosensitive resin composition according to claim 5, wherein the first resin is contained in an amount of about 30 to 55 parts by weight and the second resin is contained in about 10 to 55 parts by weight in 100 parts by weight of the total binder resin.
The positive photosensitive resin composition according to claim 1, wherein the linear vinyl ether compound comprises a compound represented by the following formula (4):
[Chemical Formula 4]

(Wherein R ¹ is an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms, and n is an integer of 1 to 6).
The positive photosensitive resin composition according to claim 1, wherein the content of the binder resin in the total weight of the composition is 5 to 50% by weight, and the linear vinyl ether compound is contained in 1 to 40% by weight in 100 parts by weight of the binder resin.
The photoacid generator according to claim 1, wherein the photoacid generator is 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 benzylsulfonate-based compound, and a triprazine-based compound.
An insulating film formed from the positive photosensitive resin composition according to any one of claims 1 to 10.
The method of manufacturing a semiconductor device according to claim 11, wherein the insulating film used as an interlayer insulating film or a via insulating film of an image display apparatus
An image display device comprising the insulating film of claim 11.

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