KR20190094851A - Positive-type photosensitive resin composition and insulation layer formed from the same - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition comprising: a binder resin; an antioxidant containing a bifunctional epoxy compound; a photoacid generator; and a solvent. An insulation film having improved transmittance and reliability can be formed through the interaction between the binder resin and the antioxidant.

Description

Positive type photosensitive resin composition and insulating film formed therefrom {POSITIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION AND INSULATION LAYER FORMED FROM THE SAME}

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

For example, photosensitive resin compositions are used to form various photocurable insulating patterns such as photoresists, insulating films, protective films, black matrices, column spacers, and the like of display devices. For example, an inorganic insulating film such as silicon oxide or silicon nitride has a high dielectric constant, increasing the demand for a low dielectric organic insulating film, and the photosensitive resin composition may be used to form the organic insulating film.

The organic insulating layer may be formed in a predetermined pattern by coating the photosensitive resin composition, curing the film by preliminary heat treatment, and then performing exposure and development processes.

The said photosensitive resin composition is classified into positive type and negative type according to the part removed by a image development process. In the positive composition, the exposed part is dissolved by the developer, and in the negative composition, the unexposed part is dissolved to form a pattern.

In the case of the organic insulating layer, it is necessary to be formed to have mechanical properties such as heat resistance and the like with excellent insulation, and the photosensitive resin composition needs to be manufactured to have excellent sensitivity to the exposure process.

In addition, the optical properties of the organic insulating layer may be deformed by the heat treatment, resulting in a decrease in transmittance, thereby degrading an 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, although Korean Patent Publication No. 2013-0021324 discloses a positive resist composition, it does not provide an alternative for improving the mechanical and optical properties described above.

Korean Patent Publication No. 10-2013-0021324

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

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

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

1. binder resin; Antioxidant containing a bifunctional epoxy type compound; Photoacid generators; And a positive photosensitive resin composition containing a solvent.

2. The above 1, wherein the binder resin is a positive photosensitive resin composition comprising a first resin containing a phenol unit protected by an acid-decomposable group.

3. In the above 1, wherein the first resin is a positive photosensitive resin composition comprising a structural unit represented by the following formula (1):

[Formula 1]

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

R ₃ represents the acid-decomposable group, an alkyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, or an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms Substituted or unsubstituted C1-C10 alkyl group, p is 40-80 mol%, q is 20-60 mol%).

4. In the above 3, wherein the first resin comprises a structural unit represented by the following formula 1-1, the positive photosensitive resin composition:

[Formula 1-1]

(In formula 1-1, R <_1> and R <_2> is respectively 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%, q is 20 to 60 mol%).

5. In the above 2, wherein the binder resin further comprises at least one of a second resin containing an epoxy group-containing acrylic resin or a third resin containing an oxetane group-containing acrylic resin, the positive photosensitive resin composition.

6. In the above 5, wherein the second resin is derived from at least one of the monomers represented by Formula 2 or Formula 3, the positive photosensitive resin composition:

[Formula 2]

[Formula 3]

In Formulas 2 and 3, Z ₁ is hydrogen or a methyl group, Z ₂ is an alkylene group having 1 to 6 carbon atoms, and Z ₃ and Z ₄ are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, or are connected to each other to have carbon atoms. Forms a ring of 3 to 8,

m is an integer from 1 to 6).

7. In the above 5, wherein the third resin is a positive photosensitive resin composition comprising a structural unit derived from a monomer represented by the following formula (4):

[Formula 4]

(In Formula 4, Ra is hydrogen or a methyl group, Rb is a C1-C6 alkylene group, Rc is a C1-C6 alkyl group.).

8. according to the above 5, wherein about 30 to 55 parts by weight of the first resin, about 30 to 60 parts by weight of the second resin, and about 1 to 25 parts by weight of the third resin of the total 100 parts by weight of the binder resin, Positive photosensitive resin composition.

9. In the above 1, wherein the antioxidant is a positive photosensitive resin composition comprising a compound represented by the following formula (5):

[Formula 5]

(In formula 5, R <^1> is a C1-C6 alkylene group or a C3-C12 cycloalkylene group.).

10. In the above 9, wherein the antioxidant is a positive photosensitive resin composition comprising a compound represented by the following formula 5-1:

[Formula 5-1]

11. In the above 1, wherein the content of the binder resin in the total weight of the composition is 5 to 50% by weight, the antioxidant is included in 1 to 10 parts by weight of 100 parts by weight of the binder resin, the positive type photosensitive resin composition.

12. In the above 1, the photoacid generator is a diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazo disulfone, disulfone, ortho A positive photosensitive resin composition comprising at least one selected from the group consisting of nitrobenzylsulfonate-based and triazine-based compounds.

13. The insulating film formed from the positive photosensitive resin composition of any one of 1 to 12 above.

14. The insulating film according to the above 13, used as an interlayer insulating film or a via insulating film of an image display device.

15. An image display device including the insulating film of 13 above.

The photosensitive resin composition according to the exemplary embodiments may include an antioxidant including a bifunctional epoxy-based compound. For example, yellowing may be prevented by oxidation of a phenol group by heat treatment such as post-baking. Can be prevented. Therefore, an insulating film which maintains excellent transmittance even after curing can be formed.

In addition, the antioxidant may further improve film properties such as adhesion, coating property, and the like of the insulating film.

The binder resin of the photosensitive resin composition may include a first resin including a hydroxyl group and a protecting group, and may further include a second resin containing an epoxy group and / or a third resin containing an oxetane group. The sensitivity of the exposure process and the resolution of the development process may be secured by the first resin, and the curing and mechanical properties of the insulating film may be improved by the second resin and / or the third resin.

1 to 5 are schematic cross-sectional views illustrating a method of forming an insulating film according to example embodiments.

Embodiments of the present invention include a binder resin, an antioxidant including a bifunctional epoxy-based compound, a photoacid generator and a solvent, and provide a positive photosensitive resin composition having excellent transmittance and film formation reliability. Further, an image display device including an insulating film formed from the positive photosensitive resin composition and the insulating film is provided.

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

<Positive Photosensitive Resin Composition>

The positive photosensitive resin composition (hereinafter, may also be abbreviated as photosensitive composition) according to embodiments of the present invention may include a binder resin, an antioxidant, a photoacid generator, and a solvent.

According to exemplary embodiments, the photosensitive composition may be provided as a chemically amplified resist (CAR) composition in which solubility difference occurs due to an acid generated by an exposure process, for example. Thus, for example, an insulating film or an insulating pattern may be formed with improved sensitivity and resolution compared to a photo active compound (PAC) based composition such as quinonediazide.

Binder resin

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

According to exemplary embodiments, the binder resin includes a first resin including a phenol-based (or novolac-based) resin, and a second resin and / or an oxetane group-containing acrylic resin including an epoxy group-containing acrylic resin. It may further include a third resin comprising a.

The first resin may include a plurality of hydroxyl groups, and at least some of the hydroxyl groups may be protected with an acid-decomposable group. For example, among the included phenol units of the first resin, the hydroxyl group included in at least some of the phenol units 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 Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ may each independently represent a hydrogen or a methyl group. R ₃ represents the acid-decomposable group, an alkyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, or an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms 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 ratios of phenol units and phenol units protected with acid-decomposable groups, respectively. For example, p may be about 40 to 80 mol%, q may be about 20 to 60 mol%. p and q represent the relative molar ratios of the phenolic units and phenolic units protected with acid-decomposable groups and do not exclude the addition of other units.

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

[Formula 1-1]

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

For example, the phenolic unit can be derived from hydroxy styrene as the first monomer. The phenol unit protected by the acid-decomposable group may be derived from the second monomer represented by the following Chemical Formula 1-2, in one embodiment.

[Formula 1-2]

[Formula 1-3]

In Formulas 1-2 and 1-3, R ₃ , R ₄ and R ₅ are as defined in Formulas 1 and 1-1.

The first resin may be prepared through copolymerization of the first monomer and the second monomer, and the number of moles of the first monomer and the second monomer may be adjusted to correspond to the molar ratios represented by desired p and q. .

As described above, the first resin may include a phenol unit in which the hydroxyl group remains and a phenol unit in which the hydroxyl group is protected with an acid-decomposable group, thereby realizing both sensitivity to the exposure process and adhesion to the substrate. .

In some embodiments, the first resin may further include a unit derived from a third monomer in addition to the first and second monomers. The third monomer may include, for example, a (meth) acrylate-based monomer. In this case, as a non-limiting example of the third monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth Alkyl (meth) acrylates such as acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth) acrylate; Alicyclic compounds such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate Group (meth) acrylates; Aryl (meth) acrylates, such as phenyl (meth) acrylate and benzyl (meth) acrylate, etc. are mentioned.

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

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

The binder resin may further include an epoxy group-containing acrylic resin as the second resin. As the second resin is included, for example, thermal curing properties may be improved in a heat treatment process such as post-baking, thereby further improving mechanical properties such as heat resistance and impact resistance of the insulating film.

In some embodiments, the second resin may be derived from a monomer represented by Formula 2 below.

[Formula 2]

In Formula 2, Z ₁ is hydrogen or a methyl group, Z ₂ may be an alkylene group having 1 to 6 carbon atoms. Z ₃ and Z ₄ may be independently of each other 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 from 1 to 6,

In the monomer represented by Formula 2, Z ₂ may form an ether bond through an adjacent oxygen atom. Therefore, since rotation through the ether bond is possible, the glass transition temperature can be reduced to improve the flowability of the photosensitive composition.

In addition, the monomer length may be adjusted through the adjustment of m in Chemical Formula 2. By adjusting the monomer length, the sidewall slope of the insulation pattern generated after the developing process may be controlled. For example, the sidewall slope may be reduced to prevent damage to the insulating pattern and dropout of the conductive pattern when forming a subsequent conductive pattern such as a transparent electrode.

In some embodiments, the second resin may be derived from a monomer represented by Formula 3 below.

[Formula 3]

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

Through the monomer represented by Formula 3, the transmittance of the second resin may be further improved.

In some embodiments, the second resin may be prepared using at least one of the monomer of Formula 2 or the monomer of Formula 3.

The second resin may be prepared by copolymerizing other monomers commonly used in the art that may form an acrylic resin in addition to the monomer represented by Formula 2 or Formula 3.

In some embodiments, the other monomer may include a carboxyl group-containing ethylenically unsaturated monomer to improve developability and adhesion to the substrate. As an example of the said carboxyl group-containing ethylenically unsaturated monomer, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid; Dicarboxylic acids, such as fumaric acid, mesaconic acid, and itaconic acid, these anhydrides, etc. are mentioned.

Further non-limiting examples of such other monomers include styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m 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 compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-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; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. Alicyclic (meth) acrylates; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds. These can be used individually or in mixture of 2 or more types.

For example, the second resin may be prepared by copolymerizing at least one of the monomers represented by Formula 2 or Formula 3 and other monomers described above. The molar ratio of the monomer represented by Formula 2 or Formula 3 may be about 5 to 60 mol% of the total monomers. In this case, improvement of developability, transparency, pattern slope, etc. through the second resin can be effectively implemented.

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

In some embodiments, the third resin may further include an oxetane group-containing acrylic resin (eg, a third resin). In this case, the thermal crystallization process may be promoted by the crosslinking reaction through the oxetane group.

The third resin may include, for example, a structural unit derived from a monomer represented by Formula 4 below.

[Formula 4]

In Formula 4, Ra may be hydrogen or a methyl group. Rb is an alkylene group having 1 to 6 carbon atoms, Rc may be an alkyl group having 1 to 6 carbon atoms.

In some embodiments, the third resin may further include a structural unit derived from at least one of monomers represented by the following formulas (1) to (3).

In some embodiments, the third resin is (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) It may further comprise a structural unit derived from at least one of acryloyloxyethyl phthalate or 2- (meth) acryloyloxyethyl succinate.

The weight average molecular weight of the third resin may be 5,000 to 30,000, preferably 8,000 to 20,000, developability and stability over time within the above range, the film residue after development may be reduced.

In some embodiments, the binder resin may include a mixture of the first resin, the second resin, and the third resin described above. In this case, the first resin may include about 30 to 55 parts by weight of the first resin, about 30 to 60 parts by weight of the second resin, and about 1 to 25 parts by weight of the third resin.

In exemplary embodiments, the binder resin may be included in an amount of about 5 to 50% by weight, preferably about 10 to 40% by weight, based on the total weight of the photosensitive composition. Within this range, the sensitivity for the exposure process and the resolution for the development process can be improved together.

Antioxidant

The photosensitive composition may include an antioxidant and may inhibit modification and oxidation by oxidation of the binder resin.

The antioxidant may be included in the form of a monomer, and may function as a protecting agent of a phenol unit or a hydroxyl group included in the binder resin. According to exemplary embodiments, the antioxidant may include a bifunctional epoxy compound. For example, the antioxidant may have a structure in which epoxy groups are bonded to a terminal by a linker group.

In some embodiments, the antioxidant may include a compound represented by Formula 5 below.

[Formula 5]

In formula (5), R ¹ may represent an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms. When R ¹ is an alkylene group, it may be linear or branched, and when branched, it may have 3 to 6 carbon atoms.

In one embodiment, the antioxidant may include a compound represented by Formula 5-1.

[Formula 5-1]

The antioxidant may be, for example, a phenol unit or an acid-decomposable group is removed from the post-baking process or a subsequent heat treatment process after the exposure and development process is oxidized to quinone (quinone), for example. Can be prevented. When the binder resin is modified to include quinone, a yellowish phenomenon of the insulating film may be caused, thereby decreasing the transmittance of the insulating film.

For example, the antioxidant may combine with a hydroxyl group exposed to the phenol unit after the exposure and development process through an epoxy group to inhibit oxidation denaturation to the quinone unit. Thus, the desired transparency and transmittance of the insulating film can be maintained even after the post bake or subsequent heat treatment process.

For example, since the antioxidant includes epoxy groups at each end through a linear linker, hydroxyl groups of adjacent binder resins may easily meet without steric hindrance. When the length of the linear linker is excessively increased, the possibility of reaction or interaction with the hydroxyl group may be reduced due to molecular folding or the like. In addition, when the epoxy functional number of the antioxidant is 3 or more, as the molecular structure becomes bulky, the possibility of binding to the hydroxyl group of the binder resin may be lowered.

The antioxidant may improve the adhesion of the composition by interacting with the hydroxyl group contained in the binder resin as described above. In addition, as shown in the formula (5), through the rotatable structure of the ether bonds, such as ethylene oxide (EO) groups, the flowability of the composition is improved, thereby improving the film-forming properties such as coating, flatness Can be.

In exemplary embodiments, the amount of the antioxidant may be about 1 to 30 parts by weight, preferably about 1 to 10 parts by weight, based on 100 parts by weight of the binder resin. Within the above range, the above-described transmittance and adhesion improvement of the insulating film can be effectively implemented.

Photoacid generator (C)

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

The photoacid generator is a compound that generates an acid (eg, proton (H ⁺ )) by an exposure process utilizing ultraviolet rays or radiation, and compounds known in the art of photosensitive compositions may be used without particular limitation.

For example, the photoacid generator is a diazonium salt type, a phosphonium salt type, a sulfonium salt type, an iodonium salt type, an imide sulfonate type, an oxime sulfonate type, a diazodisulfone type, a disulfone type, ortho-nitrobenzyl Sulfonate-based, triazine-based compounds, and the like. These can be used individually or in mixture of 2 or more types.

The content of the photoacid generator may be, for example, about 0.1 to 20 parts by weight, and preferably 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 inhibiting transmittance and mechanical properties through the binder resin and the antioxidant.

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

For example, the sensitizers are polynuclear aromatics, xanthenes, xanthones, cyanines, oxonols, thiazines, acridines, acridones, anthraquinones, squalariums, styryls, base styryls, Coumarins, anthracene compounds, and the like. These may be used alone or in combination of two or more thereof.

In one embodiment, the sensitizer may include a compound represented by the following formula (6).

[Formula 6]

In Formula 6, L ₁ and L ₂ may be independently 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 Chemical Formulas 6-1 to 6-3.

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

For example, the content of the sensitizer may be about 0.01 to 60 parts by weight, 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 inhibiting the effect of improving the transmittance through the antioxidant.

menstruum

As the photosensitive composition, an organic solvent having sufficient solubility in organic components such as the binder resin and the antioxidant described above may be used as the solvent.

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

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

Examples of the acetate solvent 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. Can be mentioned.

Examples of the solvents of the esters are ethyl hydroxy acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate and methyl 3-methoxypropionate. , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylprop Cypionate, 3-methyl-3- methoxy butyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pirbate, ethyl pirbate, diethylene glycol methyl ethyl ester, etc. are mentioned.

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

Examples of the amide solvents include N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like. (Gamma) -butyrolactone is mentioned as an example of a lactone solvent.

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

The amount of the solvent may be included in the remaining amount except for the above components and the additives described below. For example, the content of the solvent may be about 40 to 90% by weight of the total weight of the photosensitive composition, preferably about 50 to 80% by weight. By properly maintaining the content and viscosity of the solid content within the above range can improve the coating properties of the composition.

additive

For example, the photosensitive composition may further include an additive within a range that does not inhibit the interaction of 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 thermal crosslinking agent, a light stabilizer, a photocuring accelerator, a leveling agent, an antifoaming agent, and the like, and compounds commonly used in the field of photosensitive compositions may be used.

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

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

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

The coupling agent may be included to improve adhesion between the photosensitive composition and the substrate including the inorganic material and to control the taper angle of the insulating 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 γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyl dialkoxysilane, and γ-methacryl Oxypropyltrialkoxysilane, γ-methacryloxypropylalkyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, Vinyltrialkoxysilane etc. are mentioned.

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

The thermal crosslinking agent may include, for example, a polyacrylate resin, an epoxy resin, a phenol resin, a melamine resin, an organic acid, an amine compound, an anhydride compound, or the like.

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

The content of the above-described additives may be appropriately changed in consideration of process conditions, for example, may be included in 0.01 to 10 parts by weight, and preferably included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the binder resin, respectively. .

<Insulation film and image display device>

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

1 to 5 are schematic cross-sectional views illustrating a method of forming an insulating film according to example embodiments.

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

The substrate 100 may be, for example, a glass substrate or a resin substrate including polyimide, polymethyl methacrylate (PMMA), or the like. For example, the substrate 100 may be a display panel substrate of an image display device.

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

In some embodiments, a barrier layer 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.

For example, the first conductive pattern 110 may be provided as an electrode such as a gate electrode, a source electrode, or a drain electrode of the thin film transistor TFT included in the 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 line, or the like of the image display device.

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

As described above, since the photosensitive composition includes a bifunctional epoxy compound as an antioxidant, the flowability of the composition may be enhanced to further improve film flatness and coating property. In addition, adhesion to the substrate 100 may be further enhanced through the combination of the first resin to the third resin.

Referring to FIG. 3, the preliminary insulating film 120 may be converted into an insulating film including the exposure part 123 and the non-exposure part 125 through an exposure process.

In example embodiments, a mask including a light blocking part and a transmitting part may be disposed on the preliminary insulating layer 120, and then excimer laser, far ultraviolet ray, ultraviolet ray, visible light, electron beam, X-ray, or g-ray may be disposed through the mask. (436 nm wavelength), i-ray (365 nm wavelength), h-ray (wavelength 405 nm), etc. can be irradiated.

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

In example embodiments, an acid may be generated from the photoacid generator included in the photosensitive composition by the exposure process, thereby leaving the acid-decomposable group included in the binder resin (eg, the first resin). Accordingly, the hydroxyl group of the phenol unit protected by the acid-decomposable group is exposed, so that the solubility of the exposed portion 123 in the developer may be increased.

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

Referring to FIG. 4, the developing part may be removed to remove the exposure part 123. Accordingly, an insulation pattern may be defined by the remaining non-exposed portion 125. The developing process can be carried out using an alkaline developer, for example tetramethylammonium hydroxide (TMAH).

For example, an opening 127 for at least partially exposing the first conductive pattern 110 may be formed in a space where the exposure part 123 is removed by the developing process.

In example embodiments, a post-baking process may be further performed to improve mechanical properties through further curing of the insulating pattern (eg, the remaining non-exposed part 125) after the developing 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, phenol units included in the binder resin may be oxidized (for example, in quinone units) to cause yellowing of the insulating pattern.

However, according to exemplary embodiments, the phenol unit is protected by the bifunctional epoxy compound to suppress yellowing to maintain transmittance of the insulating pattern.

Referring to FIG. 5, a second conductive pattern 130 may be formed in the opening 127 illustrated in FIG. 4.

For example, after forming the second conductive film on the non-exposed part 125 sufficiently filling the opening 127 and including the metal or the transparent conductive oxide, the second conductive film is patterned to form the second conductive pattern 130. Can be,

Even when a heat treatment process such as a high temperature deposition process is performed to form the second conductive film, yellowing and dropping of the non-exposed part 125 may be suppressed through the action of the bifunctional epoxy compound described above.

For example, the second conductive pattern 130 may be provided as a pixel electrode of the 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 penetrating 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 insulating film or 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 device. For example, the second conductive pattern 130 illustrated 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. Apparatus and the like can be implemented.

An opposite electrode (eg, 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 opposite electrode. .

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

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Examples and Comparative Examples

A positive photosensitive resin composition having a composition and content (parts by weight) described in Table 1 was prepared.

A positive photosensitive resin composition having a composition and content (parts by weight) described in Table 1 was prepared.

division Binder Resin (A) Antioxidant (B) Photoacid generator
(C1) /
Sensitizer (C2) menstruum
(D) Coupling Agent (F) Interface
Active agent
(G) Example 1 A1-1 / A2-1 / A3-1 50/15/30 B1 1.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 2 A1-2 / A2-1 / A3-1 50/15/30 B1 1.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 3 A1-1 / A2-2 / A3-1 50/15/30 B1 1.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 4 A1-2 / A2-2 / A3-1 50/15/30 B1 1.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 5 A1-1 / A2-1 / A3-2 50/15/30 B1 1.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 6 A1-2 / A2-2 / A3-2 50/15/30 B1 1.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 7 A1-1 / A2-1 / A3-1 50/15/30 B1 5.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 8 A1-2 / A2-1 / A3-1 50/15/30 B1 5.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 9 A1-1 / A2-2 / A3-1 50/15/30 B1 5.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 10 A1-2 / A2-2 / A3-1 50/15/30 B1 5.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 11 A1-1 / A2-1 / A3-2 50/15/30 B1 5.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 12 A1-2 / A2-2 / A3-2 50/15/30 B1 5.0 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 13 A1-1 / A2-1 / A3-1 50/15/30 B1 0.1 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Example 14 A1-1 / A2-1 / A3-1 50/15/30 B1 10 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Comparative Example 1 A1-1 / A2-1 / A3-1 50/15/30 B1 - 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Comparative Example 2 A1-1 / A2-1 / A3-1 50/15/30 B2 3 1.0 / 0.5 D1 / D2 120/80 1.0 0.1 Comparative Example 3 A1-1 / A2-1 / A3-1 50/15/30 B3 3 1.0 / 0.5 D1 / D2 120/80 1.0 0.1

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

A1-1, A1-2

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

A2-2) p / q = 70/30, Mw = 12,000

A2-1, A2-2

A2-1) (a) / (b) / (c) = 60/20/20, Mw = 8,000

A2-2) (a) / (b) / (c) = 60/10/30, Mw = 8,000

A3-1, A3-2

A3-1: (a) / (b) / (c) / (d) = 15/10/50/25, Mw = 25,000

A3-2: (a) / (b) / (c) / (d) = 25/15/30/30, Mw = 25,000

(ED-523T, Adeka사 제조)B-1)

(ED-523T, manufactured by Adeka)

(Epolight 100MF, kyoeisha사 제조)B-2)

(Epolight 100MF, kyoeisha company)

(S-400, Synasia사 제조)B-3)

(S-400, manufactured by Synasia)

C-1)

C-2)

D1) Propylene Glycol Methyl Ethyl Acetate

D2) diethylene glycol methyl ethyl ester

F) γ-glycidoxypropyltrialkoxysilane

G) SH-8400 (Dow Corning Corporation)

Experimental Example

The following evaluation of the gwanggwang composition prepared according to the Examples and Comparative Examples of Table 1, the results are shown in Table 2 below.

(1) sensitivity measurement

On a 0.7 mm-thick glass substrate (Corning 1737, manufactured by Corning), the photosensitive resin compositions of Examples and Comparative Examples were each applied with a spinner, heated for 125 seconds on a 100 ° C hotplate to volatilize the solvent, and preliminary having a thickness of 4.0 µm. An insulating layer was formed.

Then, in order to obtain the contact hole pattern of 10 micrometers in diameter, exposure was performed with the i-line stepper (NSR-205i11D, Nikon Corporation) using the mask which has a square pattern opening part with a 10 micrometers edge part.

The board | substrate after exposure was puddle-developed for 40 second at 23 degreeC with the 2.38% tetramethylammonium hydroxide aqueous solution, and it heated for 30 minutes in 230 degreeC oven, and formed the hardened insulation pattern.

Subsequently, the substrate was vertically cut and the exposure amount required to form the 10 μm contact hole in each insulating pattern was measured to evaluate sensitivity.

(2) residual film rate

The photosensitive resin compositions prepared in Examples and Comparative Examples were applied onto a 0.7 mm thick glass substrate (Corning 1735, manufactured by Corning) with a spinner, and heated on a hot plate at 100 ° C. for 125 seconds to volatilize the solvent, followed by film thickness ( A) was measured. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was subjected to a puddle development at 23 ° C. for 40 seconds with a developer, and heated in an oven at 230 ° C. for 30 minutes to form an insulation pattern, and then the film thickness (B) was measured. The remaining film ratio was calculated according to Equation 1.

[Equation 1]

Residual Rate (%) = B / A * 100

(3) pattern angle

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

(4) adhesion

The photosensitive compositions of Examples and Comparative Examples were applied directly onto the glass substrate on which the silicon nitride film (SiNx) was deposited, respectively, and heated for 125 seconds on a 100 ° C. hot plate to volatilize the solvent to form a preliminary insulating film having a thickness of 4.0 μm. It was. Thereafter, exposure was performed using an i-line stepper (NSR-205i11D, Nikon Corporation) using a mask containing a hole pattern in the range of 5-20 μm. The substrate after exposure was subjected to puddle development at 23 ° C. for 40 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, and it was confirmed whether the pattern was peeled off. Evaluation criteria are as follows.

◎: pattern does not peel off at all

○: The pattern is exfoliated finely in some areas

(Triangle | delta): A considerable part pattern is peeled off

X: All areas of the pattern are peeled off

(5) transmittance measurement

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

(6) transmittance after additional baking

After measuring the transmittance as in (5), further baking was carried out in an oven at 230 ° C. for 30 minutes, and the transmittance at 400 nm was remeasured with a spectrophotometer.

division Sensitivity
(mJ / cm ² ) Residual rate
(%) Pattern angle ( ^o ) Adhesion Transmittance (%) After additional baking
Transmittance (%) Example 1 24 72 50 ◎ 97 95 Example 2 24 72 51 ◎ 97 94 Example 3 24 72 53 △ 97 94 Example 4 25 73 52 ◎ 96 94 Example 5 27 74 51 ○ 96 94 Example 6 27 74 52 ○ 96 94 Example 7 26 73 53 ◎ 96 94 Example 8 27 74 50 ◎ 96 94 Example 9 25 73 53 ◎ 96 94 Example 10 30 76 52 ◎ 96 94 Example 11 29 75 51 ○ 96 94 Example 12 23 71 51 △ 96 94 Example 13 23 74 52 △ 96 92 Example 14 21 69 51 X 96 94 Comparative Example 1 33 77 53 ○ 96 91 Comparative Example 2 35 76 54 ○ 96 92 Comparative Example 3 40 77 56 X 96 91

Referring to Table 2, the examples in which the bifunctional epoxy-based compound was included together with the binder resin as the antioxidant showed excellent sensitivity and pattern characteristics as compared with the comparative examples, and a good transmittance was obtained even after additional baking. For Example 13, which was somewhat reduced in antioxidants, the transmittance was somewhat lower after further baking. In Example 14, in which the amount of the antioxidant was somewhat excessive, the pattern adhesion was deteriorated.

In Comparative Example 1, which lacked an antioxidant, the sensitivity decreased and the permeability was also significantly degraded after the baking process. Comparative Examples 2 and 3, which contain a tri- or tetra-functional epoxy compound, also exhibited a desired transmittance improvement effect due to steric hindrance in the antioxidant.

100: substrate 110: first conductive pattern
120: preliminary insulating film 123: exposed portion
125: non-exposed part 127: opening
130: second conductive pattern

Claims (15)

Binder resins;
Antioxidant containing a bifunctional epoxy type compound;
Photoacid generators; And
Positive photosensitive resin composition containing a solvent.
The positive type photosensitive resin composition of Claim 1 in which the said binder resin contains the 1st resin containing the phenol unit protected by the acid-decomposable group.
The positive type photosensitive resin composition according to claim 1, wherein the first resin comprises a structural unit represented by Formula 1 below:
[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group,
R ₃ represents the acid-decomposable group, an alkyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, or an alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms 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%, q is 20 to 60 mol%).
The positive photosensitive resin composition of claim 3, wherein the first resin comprises a structural unit represented by the following Chemical Formula 1-1:
[Formula 1-1]

(In formula 1-1, R <_1> and R <_2> is respectively 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%, q is 20 to 60 mol%).
The positive photosensitive resin composition according to claim 2, wherein the binder resin further comprises at least one of a second resin containing an epoxy group-containing acrylic resin or a third resin containing an oxetane group-containing acrylic resin.
The positive type photosensitive resin composition according to claim 5, wherein the second resin is derived from at least one of monomers represented by the following Chemical Formula 2 or Chemical Formula 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, Z ₁ is hydrogen or a methyl group, Z ₂ is an alkylene group having 1 to 6 carbon atoms, and Z ₃ and Z ₄ are independently hydrogen or an alkyl group having 1 to 6 carbon atoms, or are connected to each other to have carbon atoms. Forms a ring of 3 to 8,
m is an integer from 1 to 6).
The positive type photosensitive resin composition according to claim 5, wherein the third resin comprises a structural unit derived from a monomer represented by the following general formula (4):
[Formula 4]

(In Formula 4, Ra is hydrogen or a methyl group, Rb is a C1-C6 alkylene group, Rc is a C1-C6 alkyl group.).
The positive type according to claim 5, comprising about 30 to 55 parts by weight of the first resin, about 30 to 60 parts by weight of the second resin, and about 1 to 25 parts by weight of the third resin, in 100 parts by weight of the binder resin. Photosensitive resin composition.
The positive type photosensitive resin composition of claim 1, wherein the antioxidant comprises a compound represented by Formula 5 below:
[Formula 5]

(In formula 5, R <^1> is a C1-C6 alkylene group or a C3-C12 cycloalkylene group.).
The positive type photosensitive resin composition according to claim 9, wherein the antioxidant comprises a compound represented by the following Chemical Formula 5-1:
[Formula 5-1]

The positive type photosensitive resin composition of claim 1, wherein a content of the binder resin in the total weight of the composition is 5 to 50% by weight, and the antioxidant is included in 1 to 10 parts by weight of 100 parts by weight of the binder resin.
The photoacid generator according to claim 1, wherein the photoacid generator is a diazonium salt type, a phosphonium salt type, a sulfonium salt type, an iodonium salt type, an imide sulfonate type, an oxime sulfonate type, a diazodisulfone type, a disulfone type, ortho-nitro A positive photosensitive resin composition comprising at least one selected from the group consisting of benzylsulfonate-based and triazine-based compounds.
The insulating film formed from the positive photosensitive resin composition of any one of Claims 1-12.
The insulating film of Claim 13 used as an interlayer insulation film or a via insulation film of an image display apparatus.
An image display device comprising the insulating film of claim 13.

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