KR102539889B1 - Chemically amplified photosensitive resist composition and insulation layer prepared from the same - Google Patents

Abstract

The present invention relates to a chemically amplified photosensitive resin composition and an insulating film prepared therefrom, and more specifically, (a-1) a resin in which at least a part of a phenolic hydroxyl group or a carboxyl group is protected by an acid decomposable group, (a-2) (A) a binder resin containing an acrylic resin containing an epoxy group, and (a-3) a siloxane resin; (B) a photoacid generator; and (C) a chemically amplified photosensitive resin composition capable of obtaining an insulating film having excellent pattern adhesion and uniformity by including a solvent, and an insulating film prepared therefrom.

Description

Chemically amplified photosensitive resin composition and insulating film prepared therefrom

The present invention relates to a chemically amplified photosensitive resin composition and an insulating film prepared therefrom.

In a display device such as a thin film transistor (TFT) type liquid crystal display, an inorganic protective film such as silicon nitride has been conventionally used as a protective film to protect and insulate the TFT (Thin Film Transistor) circuit, but the dielectric constant value There is a problem in that it is difficult to improve the aperture ratio because the aperture ratio is high, and in order to overcome this problem, the demand for an organic insulating film having a low dielectric constant is increasing.

As such an organic insulating film, a photosensitive resin, which is a polymer compound whose solubility in a specific solvent is changed by chemical reaction with light and electron beams, is generally used, and the microfabrication of the circuit pattern is the polarity of the polymer caused by the photoreaction of the organic insulating film. by changes and cross-linking reactions. In particular, the organic insulating film material utilizes the change in solubility in a solvent such as an alkaline aqueous solution after exposure.

The organic insulating film is classified into a positive type and a negative type according to the solubility of the photosensitized portion in development. In the positive type photoresist, the exposed portion is dissolved by a developer, and in the negative type photoresist, the exposed portion is insoluble in the developer and the unexposed portion is dissolved to form a pattern.

Among them, since the positive organic insulating film uses an aqueous alkali solution, the use of the organic developer used in the negative organic insulating film can be excluded, which is not only advantageous in terms of the working environment, but also theoretically protects the area not exposed to ultraviolet rays. Since the swelling phenomenon can be prevented, there is an advantage in that the resolution is improved. In addition, since the organic film is easily removed by a stripper after forming, the recovery and reusability of the substrate is greatly improved by removing the organic film when a defective panel is generated during the process.

In particular, in constituting an insulating film of a liquid crystal display device as such an organic insulating film, the insulating film must have excellent insulating properties, as well as low thermal expansion to reduce stress at the interface when coated on a substrate, and also physically Must have strong character.

In addition, the insulating film or the protective film inevitably forms an interface with a metal, a silicon compound, or the like. At this time, excellent adhesion is a very important factor in terms of device reliability. The insulating film undergoes a fine pattern formation process to provide an interconnection path between circuits. At this time, if photosensitivity is given to the insulating film itself, the process of forming a pattern by applying a separate photoresist on the conventional insulating film can be reduced, making it easier A fine pattern can be formed.

For this reason, the positive organic insulating film composition is a compound (PAC (photo active compound)) that imparts photosensitivity to a binder resin, such as an acrylic photosensitive resin used as a typical binder resin, a novolac resin, a polyimide, or a siloxane. Research on the application of the added composition has been actively conducted, and recently, the insulating film has been commercialized and various devices using it have reached the point of being released.

In particular, when an insulating film is to be formed on a silicon nitride film, the surface of the silicon nitride film is previously treated with hexamethyldisilazane (HDMS) to improve adhesion, but HDMS is a very harmful material to the human body.

In order to solve this problem, Korean Patent Publication No. 10-2010-0049687 discloses a positive photosensitive resin composition containing a phenolic resin modified with a compound having an unsaturated hydrocarbon group, a compound that generates an acid by light, a thermal crosslinking agent and a solvent. is starting However, the sensitivity is poor and sufficient adhesion is still not obtained without using HDMS.

Korean Patent Publication No. 10-2010-0049687

An object of the present invention is to provide a chemically amplified photosensitive resin composition having excellent adhesion to a substrate.

Another object of the present invention is to provide a chemically amplified photosensitive resin composition having excellent sensitivity, transmittance and gradient of formed patterns.

In addition, an object of the present invention is to provide an insulating film made of the above chemically amplified photosensitive resin composition.

1. (a-1) a resin in which at least a part of a phenolic hydroxyl group or a carboxyl group is protected by an acid-decomposable group, (a-2) an acrylic resin containing an epoxy group, and (a-3) a siloxane resin (A) binder resin ; (B) a photoacid generator; and (C) a chemically amplified photosensitive resin composition comprising a solvent.

2. The chemically amplified photosensitive resin composition according to 1 above, wherein the resin (a-1) is polymerized by including at least one of the monomers represented by Formula 1, Formula 2, Formula 3, and Formula 4 below:

[Formula 1]

(Wherein, R is an alkyl group having 1 to 6 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms; a tetrahydropyranyl group; or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms It is an alkyl group having 1 to 6 carbon atoms)

[Formula 2]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms)

[Formula 3]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 3 to 8 carbon atoms, and R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms)

[Formula 4]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms, and R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms an alkyl group).

3. The chemically amplified photosensitive resin composition according to 1 above, wherein the repeating units formed by the monomers of Chemical Formulas 1 to 4 are contained in an amount of 20 to 60 mol% based on the total weight of the (a-1) resin.

4. The chemically amplified photosensitive resin composition according to 1 above, wherein the resin (a-1) has a weight average molecular weight of 5,000 to 35,000.

5. The chemically amplified photosensitive resin composition according to 1 above, wherein the resin (a-2) is polymerized by including a monomer represented by Formula 5 below:

[Formula 5]

(Wherein, R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R ₄ are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to have 3 carbon atoms may form a ring of from 1 to 8; m is an integer from 1 to 6).

6. The chemically amplified photosensitive resin composition according to 1 above, wherein the resin (a-2) is polymerized by including a monomer represented by the following formula (6):

[Formula 6]

(Wherein, R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R ₄ are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to have 3 carbon atoms to 8 rings).

7. The chemically amplified photosensitive resin composition according to 1 above, wherein the repeating unit formed by the monomers of Formula 5 or 6 is contained in an amount of 5 to 60 mol% based on the total amount of the resin (a-2).

8. The chemically amplified photosensitive resin composition according to 1 above, wherein the resin (a-2) has a weight average molecular weight of 5,000 to 40,000.

9. The chemically amplified photosensitive resin composition according to 1 above, wherein the resin (a-3) is a polymerized resin including monomers represented by the following Chemical Formulas 7, 8 and 9:

[Formula 7]

Si(OR ₁ ) ₄

(Wherein, R ₁ is each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms)

[Formula 8]

CH ₃ Si(OR ₂ ) ₃

(Wherein, R ₂ is each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms)

[Formula 9]

C ₆ H ₅ Si(OR ₃ ) ₃

(Wherein, R ₃ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms)

10. In the above 9, the repeating unit formed by the monomer of Formula 7 is 10 to 60 mol%, and the repeating unit formed by the monomer of Formula 8 is 10 to 60 mol%, with respect to the entire resin (a-3), The repeating unit formed by the monomer of 9 is contained in 10 to 60 mol%, a chemically amplified photosensitive resin composition.

11. The chemically amplified photosensitive resin composition according to 1 above, wherein the resin (a-3) has a weight average molecular weight of 500 to 20,000.

12. In the above 1, the binder resin, based on 100 parts by weight of the total binder resin, (a-1) 30 to 55 parts by weight of the resin, (a-2) 30 to 60 parts by weight of the resin and (a-3) A chemically amplified photosensitive resin composition comprising 1 to 25 parts by weight of a resin.

13. The photoacid generator according to 1 above, wherein the photoacid generator is a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, or ortho - At least one chemically amplified photosensitive resin composition selected from the group consisting of nitrobenzylsulfonate-based and triazine-based compounds.

14. The chemically amplified photosensitive resin composition according to 1 above, wherein the solvent is at least one selected from the group consisting of ethers, acetates, esters, ketones, amides and lactones.

15. An insulating film in which the chemically amplified photosensitive resin composition according to any one of 1 to 14 above is cured.

16. An image display device having the insulating film of 15 above.

The chemically amplified photosensitive resin composition of the present invention can obtain an insulating film having excellent pattern adhesion and uniformity.

In addition, the chemically amplified photosensitive resin composition of the present invention can obtain fast sensitivity and remarkably improved transmittance.

The chemically amplified photosensitive resin composition of the present invention has excellent resolution and improved flowability, so it is easy to process.

The present invention relates to (a-1) a resin in which at least a part of a phenolic hydroxyl group or a carboxyl group is protected by an acid-decomposable group, (a-2) an acrylic resin containing an epoxy group, and (a-3) (A) containing a siloxane resin. binder resin; (B) a photoacid generator; and (C) a chemically amplified photosensitive resin composition capable of obtaining an insulating film having excellent pattern adhesion and uniformity by including a solvent.

Hereinafter, the present invention will be described in detail.

<Chemically amplified photosensitive resin composition>

The chemically amplified photosensitive resin composition of the present invention comprises (a-1) a siloxane resin, (a-2) an acrylic resin containing an epoxy group, and (a-3) at least a part of a phenolic hydroxyl group or carboxy group protected by an acid-decomposable group. (A) a binder resin comprising a resin; (B) a photoacid generator; and (C) a solvent:

(A) binder resin

The binder resin according to the present invention is composed of (a-1) a siloxane resin, (a-2) an acrylic resin containing an epoxy group, and (a-3) a resin in which at least a part of the phenolic hydroxyl group or carboxyl group is protected by an acid-decomposable group. Contains the resin of the species.

The photosensitive resin composition of the present invention can form a photosensitive pattern having excellent adhesion and uniformity with a substrate by including the above-described three types of resin as a binder resin. In particular, excellent adhesion to the silicon nitride film can be exhibited even without HMDS treatment.

[Resin (a-1) in which at least a part of phenolic hydroxyl group or carboxyl group is protected by acid decomposable group]

(a-1) The resin functions to impart solubility to the cured pattern by the photoacid generator during exposure.

(a-1) Resin is a resin containing a functional group in which at least a part of a phenolic hydroxyl group or a carboxy group is protected by an acid decomposable group, and the functional group is not particularly limited, but is represented by the following Formula 1, Formula 2, Formula 3 and Formula 4 A resin that is polymerized by including at least one of the monomers may be exemplified.

[Formula 1]

(Wherein, R is an alkyl group having 1 to 6 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms; a tetrahydropyranyl group; or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms It is an alkyl group having 1 to 6 carbon atoms)

[Formula 2]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms)

[Formula 3]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 3 to 8 carbon atoms, and R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms)

[Formula 4]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms, and R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms an alkyl group).

In Resin a-1, the repeating units formed by the monomers of Chemical Formulas 1 to 4 may be appropriately mixed according to the specific types of other copolymerized monomers, etc., so the content and mixing ratio are not particularly limited. For example, the entire Resin a-1 It is preferable in terms of pattern formation to be polymerized by being included in an amount of 20 mol% to 60 mol% relative to each other.

Resin a-1 may further include a repeating unit formed of a monomer having a phenolic hydroxyl group or a carboxyl group (unprotected with an acid-decomposable group). Examples of such monomers include the aforementioned ethylenically unsaturated monomers having a carboxyl group, hydroxystyrene, hydroxymethylstyrene, and the like.

Resin a-1 preferably has a weight average molecular weight of 5,000 to 35,000, preferably 5,000 to 20,000, in terms of improving the residual film rate and reducing residue.

[Acrylic resin (a-2) containing an epoxy group]

The acrylic resin (a-2) according to the present invention is a resin containing an epoxy group, and it is possible to form a more durable pattern by enabling thermal curing. Thermal curing can be performed, for example, in a post-bake process.

In order to introduce an epoxy group into the acrylic resin, in one embodiment of the present invention, the a-2 resin according to the present invention may be polymerized by including a monomer represented by Formula 5 below.

[Formula 5]

(Wherein, R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R ₄ are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to have 3 carbon atoms to form a ring; m is an integer from 1 to 6)

The monomer represented by Chemical Formula 5 contains an oxygen atom adjacent to R ₂ . When the chain contains an oxygen atom, the radius of gyration of the single bond increases, thereby lowering the glass transition temperature, thereby improving flowability and facilitating processing.

In addition, it is possible to adjust the length of the monomer by adjusting m in Chemical Formula 5, and through this, the slope of the formed pattern can be adjusted. can

In addition, as another embodiment of the present invention, the a-2 resin according to the present invention may include a monomer represented by Chemical Formula 6 and be polymerized to introduce an epoxy group.

[Formula 6]

(Wherein, R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R ₄ are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to have 3 carbon atoms to form a ring of 8)

The monomer represented by Formula 6 has the advantage of improving the transmittance of the polymerized resin.

In the a-2 resin, the repeating unit containing an epoxy group, for example, the repeating unit formed by the monomers of Formula 4 or 5 may be appropriately mixed according to the specific type of other monomers to be copolymerized, so the content and mixing ratio are not particularly limited. , For example, a-2 contained in 5 mol% to 60 mol% of the total resin and polymerized improves transparency, improves processability, and adjusts the inclination of the pattern to prevent cracking of the cured film during deposition of the transparent electrode. It is preferable in terms of maximizing the effect of

(a-2) The resin may be polymerized using monomers known in the art capable of forming an acrylic resin in addition to the monomers of Formula 5 or Formula 6 above.

For example, an ethylenically unsaturated monomer having a carboxyl group can be used. The type of ethylenically unsaturated monomer having a carboxyl group is not particularly limited, but examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid, and their anhydrides; and omega-carboxypolycaprolactone mono(meth)acrylate, and the like, mono(meth)acrylates of polymers having carboxy groups and hydroxyl groups at both ends, and the like, preferably acrylic acid and methacrylic acid. These can be used individually or in mixture of 2 or more types.

In addition, at least one other monomer copolymerizable with the above monomers may be further included for polymerization. For example, styrene, vinyltoluene, methyl styrene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p- Aromatic vinyl compounds, such as vinyl benzyl methyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-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, tricyclo[5.2.1.0 2,6]decan-8-yl (meth)acrylate, 2- alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate; 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. of unsaturated oxetane compounds; (meth)acrylates substituted with a cycloalkane, dicycloalkane or tricycloalkane ring having 4 to 16 carbon atoms; etc. can be mentioned. These can be used individually or in mixture of 2 or more types.

The acrylic resin (a-2) preferably has a weight average molecular weight of 5,000 to 40,000, preferably 15,000 to 30,000, from the standpoint of improving developability and reducing residue.

[siloxane resin (a-3)]

The siloxane resin (a-3) according to the present invention functions to improve adhesion to a substrate.

The siloxane resin (a-3) may be a polymerized resin including monomers represented by Chemical Formulas 7, 8, and 9 below.

[Formula 7]

Si(OR ₁ ) ₄

(Wherein, R ₁ is each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms)

[Formula 8]

CH ₃ Si(OR ₂ ) ₃

(Wherein, R ₂ is each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms)

[Formula 9]

C ₆ H ₅ Si(OR ₃ ) ₃

(Wherein, R ₃ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms)

The repeating unit formed by the monomer of Formula 7 may be included in 10 to 60 mol% with respect to the entire siloxane resin, and the repeating unit formed by the monomer of Formula 8 may be included in 10 to 60 mol% with respect to the entire siloxane resin, The repeating unit formed by the monomer of Chemical Formula 9 may be included in an amount of 10 to 60 mol% based on the total amount of the siloxane resin. Adhesion to the substrate, pattern angle, developability, etc. may be most excellent in the above content range.

The siloxane resin (a-3) preferably has a weight average molecular weight of 500 to 20,000, preferably 1,000 to 7,000, from the standpoint of improving developability and reducing residue.

The binder resin according to the present invention can remarkably increase adhesion to a substrate without reducing pattern forming ability by mixing the above-described three types of resins. In the case of a silicon nitride film, excellent adhesion is maintained even without HDMS treatment.

In the binder resin according to the present invention, the mixing ratio of the three resins is not particularly limited, but the mixing weight ratio of the resins a-1, a-2, and a-3 is based on 100 parts by weight of the total binder resin, (a- 1) 30 to 55 parts by weight of the resin, (a-2) 30 to 60 parts by weight of the resin, and 1 to 25 parts by weight of the resin (a-3) are preferred in view of improving the remaining film rate and adhesion.

The content of the binder resin according to the present invention is not particularly limited as long as it can function, and for example, may be included in 5 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of the composition. can be included When the content of the binder resin is included at 5% by weight or more and 50% by weight or less of the total weight of the composition, there is an advantage in that the effect of improving sensitivity and resolution can be maximized with appropriate viscosity.

(B) photoacid generator

A photoacid generator is a compound that generates an acid by irradiating actinic rays or radiation.

The type of photoacid generator is not particularly limited, and examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, Ortho-nitrobenzyl sulfonate type, triazine type compound, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

The content of the photoacid generator is not particularly limited as long as it can function, and for example, may be included in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. there is. When the content of the photoacid generator is 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the binder resin, chemical changes by acid catalysis can sufficiently occur and the composition can be applied uniformly. there is.

In the present invention, a sensitizer may be further included along with the photoacid generator, if necessary.

The sensitizer is a component that improves the sensitivity by accelerating the decomposition of the photoacid generator. The sensitizer according to the present invention is not particularly limited, and examples thereof include polynuclear aromatics, xanthenes, xanthones, cyanines, oxonols, thiazines, acridines, acridones, anthraquinones, squaliums, Styryls, base styryls, coumarins, anthracene compounds, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Preferably, the sensitizer according to the present invention may be a compound of Formula 10 below.

[Formula 10]

(In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms).

The sensitizer of Formula 10 may preferably be a compound of Formulas 11 to 13 below.

[Formula 11]

[Formula 12]

[Formula 13]

The content of the sensitizer is not particularly limited within the range capable of performing the function, and for example, may be included in an amount of 0.01 to 60 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. . When the content of the sensitizer is included in an amount of 0.1 to 20 parts by weight or less based on 100 parts by weight of the binder resin, the effect of improving sensitivity or transmittance by spectral sensitization can be maximized.

(C) Solvent

The type of solvent is not particularly limited, and any solvent can be used as long as it can dissolve the above-mentioned components, has a suitable drying speed, and can form a uniform and smooth coating film after evaporation of the solvent.

Specific examples include ethers, acetates, esters, ketones, amides and lactones. These can be used individually or in mixture of 2 or more types.

Specific examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether; and the like.

Specific examples of the acetates include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monobutyl ether acetate; and dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, and dipropylene glycol monobutyl ether acetate.

Specific examples of esters include methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, n-butyl acetate, isobutyl acetate, and acetic acid. n-amyl, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate , 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl -3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyrbate, ethyl pyrbate, diethylene glycol methyl ethyl ester and the like.

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

Specific examples of amides include N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Specific examples of lactones include γ-butyrolactone.

Preferably, propylene glycol methyl ether acetate, diethylene glycol methyl ethyl ester or a mixture thereof is preferably used in terms of applicability and uniformity of film thickness of the insulating film.

The content of the solvent is not particularly limited as long as it can function, and for example, may be included in 40 to 90% by weight, preferably 50 to 80% by weight, based on the total weight of the composition. When the content of the solvent is included at 40% by weight or more and 90% by weight or less based on the total weight of the composition, the solid content and viscosity can be maintained at an appropriate level, thereby increasing the coating property.

(D) additives

In addition, the photosensitive resin composition of the present invention includes additives such as a basic compound, a surfactant, an adhesion improver, a thermal crosslinking agent, a light stabilizer, a photocuring accelerator, a halation inhibitor (leveling agent), and an antifoaming agent that are generally used for the purpose of the present invention. It can be further included within a range that does not deviate.

The type of basic compound is not particularly limited, and may be arbitrarily selected from those used as chemically amplified resists. Specific examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. These can be used individually or in mixture of 2 or more types.

Specific examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanol An amine, dicyclohexylamine, dicyclohexylmethylamine, etc. are mentioned.

Specific examples of the aromatic amine include aniline, benzylamine, N,N-dimethylaniline, diphenylamine and the like.

Specific examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4- Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline , pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0]-7 - Undecene etc. can be mentioned.

Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide and the like.

Specific examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.

The content of the basic compound is not particularly limited as long as it can function, but may be included in an amount of 0.001 to 1 part by weight, preferably 0.005 to 0.5 part by weight, based on 100 parts by weight of the binder resin. When the amount of the basic compound is 0.001 parts by weight or more and 1 part by weight or less with respect to 100 parts by weight of the binder resin, an interlayer insulating film having good heat resistance and solvent resistance can be formed.

A surfactant is a component that improves adhesion between a substrate and the photosensitive resin composition.

The type of surfactant is not particularly limited, and various surfactants such as fluorine-containing surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. These can be used individually or in mixture of 2 or more types.

Specific examples of fluorine-containing surfactants include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781 (trade names, manufactured by DIC Corporation); FLUORAD FC430, FC431 and FC171 (trade name, product of Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH- 40 (trade name, product of Asahi Glass Co., Ltd.), SOLSPERSE 20000 (trade name, product of Lubrizol Japan Limited), and the like.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane and trimethylolethane, and their ethoxylates or propoxylates (eg, glycerol propoxylate or glycerine ethoxylate); polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2, and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, product of BASF); polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester and the like.

Specific examples of cationic surfactants include phthalocyanine-modified compounds such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.), organo compounds such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) siloxane polymers; (meth)acrylic acid-based (co)polymers such as POLYFLOW No.75, No.90, and No.95 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), W001 (trade name, manufactured by Yusho Co., Ltd.), etc. can be heard

Specific examples of the anionic surfactant include W004, W005, and W017 (trade name, manufactured by Yusho Co., Ltd.).

Specific examples of silicone surfactants include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade names, manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460 and 4452 ( Trade name, manufactured by Momentive Performance Materials Inc.), KP341, KF6001 and KF6002 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, 323 and 330 (trade name, manufactured by BYK Chemie), and the like.

The content of the surfactant is not particularly limited as long as it can function, but may be included in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the binder resin. When the content of the surfactant is 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the binder resin, there is an advantage in that the effect of improving the adhesion between the substrate and the resin composition can be maximized.

Adhesion improvers improve adhesion between an inorganic material as a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, and a metal such as gold, copper, and aluminum, and an insulating film, and are also useful for adjusting the taper angle with the substrate. do.

The type of adhesion improving agent is not particularly limited, and specific examples include a silane coupling agent or a thiol-based compound, preferably a silane coupling agent.

The type of silane coupling agent is not particularly limited, and specific examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldi Alkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclo hexyl)ethyltrialkoxysilane, vinyltrialkoxysilane, etc. are mentioned, preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, more preferably γ-glycidoxy It is propyltrialkoxysilane. These can be used individually or in mixture of 2 or more types.

The content of the adhesion improver is not particularly limited as long as it can function, but may be included in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. If the content of the adhesion modifier is 0.1 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the binder resin, there is an advantage in that adhesion with the insulating film can be improved and the effect of adjusting the taper angle with the substrate can be maximized.

The thermal crosslinking agent is a component that allows a smooth crosslinking reaction to occur through UV irradiation and heat treatment when forming an insulating film as a composition and improves heat resistance.

The type of thermal crosslinking agent is not particularly limited, and specific examples include polyacrylate resins, epoxy resins, phenolic resins, melamine resins, organic acids, amine compounds, anhydride compounds, and the like. These can be used individually or in mixture of 2 or more types.

The content of the thermal crosslinking agent is not particularly limited within the range capable of performing the function, but may be included in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the binder resin. When the content of the thermal crosslinking agent is included in an amount of 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the binder resin, the effect of improving heat resistance is maximized.

A light stabilizer is a component that improves the light resistance of the photosensitive resin composition.

The type of light stabilizer is not particularly limited, and specific examples include benzotriazole-based, triazine-based, benzophenone-based, hindered aminoether-based, and hindered amine-based compounds. These may be used alone or in combination of two or more.

The content of the light stabilizer is not particularly limited within the range capable of performing the function, but may be included in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the binder resin. When the content of the light stabilizer is included in an amount of 0.01 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the binder resin, the effect of improving light resistance is maximized.

<Insulation film>

The present invention provides an insulating film made of the above composition.

A method of forming an insulating film according to the present invention includes applying the photosensitive resin composition of the present invention on a substrate of a display device or on a source/drain or silicon nitride layer formed on a substrate; pre-baking the photosensitive resin composition; Forming a pattern by selectively exposing and developing the photosensitive resin composition; Heat treatment of the formed pattern may be included.

As the substrate, glass or transparent plastic resin commonly used in liquid crystal displays, organic EL, etc. is mainly used, but is not particularly limited according to the characteristics of the display device used. For example, a metal film constituting a gate electrode is formed on an insulating substrate such as a glass substrate, and the metal film can be used as a surface layer.

The method of applying the photosensitive resin composition to the top of a substrate is not particularly limited, and examples thereof include a coating method using a slit nozzle such as a spray coating method, a roll coating method, and a discharge nozzle type coating method, and a rotational coating method such as a center dropping spin method. method, extrusion coating method, bar coating method, etc., and coating can be performed by combining two or more coating methods.

The applied film thickness varies depending on the application method, solid content concentration of the composition, viscosity, etc., but is usually applied so that the film thickness after drying is 0.5 to 100 μm.

The prebaking step performed thereafter is a process of volatilizing the solvent by applying vacuum, infrared rays, or heat to obtain a non-flowable coating after forming the coating. Heating conditions vary depending on the type or mixture of each component, but in the case of hot plate (hot plate) heating, it can be performed at 60 to 130 ° C for 5 to 500 seconds, and in the case of using a heat oven, 60 to 140 It can be carried out for 20 to 1,000 seconds at ° C.

Next, the selective exposure process is an excimer laser, far ultraviolet ray, ultraviolet ray, visible ray, electron beam, X-ray or g-ray (wavelength 436 nm), i-ray (wavelength 365 nm), h-ray (wavelength 405 nm), or a mixture of these rays is carried out while investigating Exposure may be performed by a contact, proximity, projection, or the like exposure method.

In the present invention, a step of heat-treating (high-temperature sintering) the photosensitive resin composition after alkali development is performed. A thermal cross-linking agent or the like is applied to the composition of the photosensitive resin composition for high-temperature firing. The heat treatment step may be performed for 30 minutes to 3 hours at a temperature of 150 to 350° C. using a heating device such as a hot plate or an oven. After completing the heat treatment, a completely cross-linked and cured pattern is obtained.

<Image display device>

In addition, the present invention provides an image display device having the insulating film.

The insulating film of the present invention can be applied to various image display devices such as an electroluminescence display, a plasma display, and a field emission display as well as a typical liquid crystal display.

The image display device may have a configuration commonly used in the art other than the insulating film.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but these embodiments are only illustrative of the present invention and do not limit the scope of the appended claims, and embodiments within the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications to the are possible, and it is natural that these variations and modifications fall within the scope of the appended claims.

Examples and Comparative Examples

A photosensitive resin composition having the composition and content shown in Table 1 was prepared.

binder resin
(A) photoacid generator
(B)/
sensitizer menstruum
(C) basicity
compound coupling agent Surfactants type parts by weight parts by weight type parts by weight parts by weight parts by weight type parts by weight Example 1 A1-1/A2-1/A2-3/A3-1 50/25/20/5 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 2 A1-1/A2-1/A2-3/A3-1 45/25/20/10 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 3 A1-1/A2-1/A2-3/A3-2 45/25/20/10 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 4 A1-1/A2-1/A2-3/A3-3 45/25/20/10 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 5 A1-2/A2-1/A2-3/A3-1 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 6 A1-2/A2-2/A2-4/A3-1 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 7 A1-2/A2-1/A2-3/A3-2 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 8 A1-2/A2-1/A2-3/A3-3 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 9 A1-3/A2-1/A2-3/A3-1 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 10 A1-3/A2-2/A2-4/A3-1 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 11 A1-3/A2-1/A2-3/A3-2 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 12 A1-3/A2-1/A2-3/A3-3 40/25/20/15 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 13 A1-4/A2-1/A2-3/A3-1 45/25/20/10 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 14 A1-4/A2-2/A2-4/A3-1 45/25/20/10 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 15 A1-4/A2-1/A2-3/A3-2 45/25/20/10 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 16 A1-4/A2-1/A2-3/A3-3 45/25/20/10 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 17 A1-1/A2-1/A2-3/A3-4 50/25/20/5 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 18 A1-1/A2-1/A2-3/A3-5 50/25/20/5 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 19 A1-1/A2-1/A2-3/A3-6 50/25/20/5 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 20 A1-1/A2-1/A2-3/A3-7 50/25/20/5 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Example 21 A1-1/A2-1/A2-3/A3-1 40/15/15/30 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/A2-3 50/25/25 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/A2-4 50/25/25 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Comparative Example 3 A1-2/A2-1/A2-3 50/25/25 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Comparative Example 4 A1-3/A2-1/A2-3 50/25/25 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Comparative Example 5 A1-4/A2-1/A2-3 50/25/25 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Comparative Example 6 A1-1/A3-1/A3-2 50/25/25 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1 Comparative Example 7 A1-1/A2-5/A3-1 50/25/20/5 1.0/0.5 D1/D2 120/80 0.01 1.0 G1/G2 0.1/0.1

1. Binder resin (a, b, c are molar ratios)

a/b = 60/40, Mw=12,000A1-1:

a/b = 60/40, Mw = 12,000

a/b/c = 60/25/15, Mw=12,000 A1-2:

a/b/c = 60/25/15, Mw=12,000

a/b/c = 55/15/30, Mw=11,000A1-3:

a/b/c = 55/15/30, Mw=11,000

a/b/c = 55/15/30, Mw=11,000A1-4:

a/b/c = 55/15/30, Mw=11,000

A2-1, A2-2:

A2-1: a/b/c/d = 15/15/40/30, Mw=25,000

A2-2: a/b/c/d = 20/15/30/35, Mw=25,000

A2-3, A2-4:

A2-3: a/b/c/d = 15/15/40/30, Mw=25,000

A2-4: a/b/c/d = 20/15/30/35, Mw=25,000

A2-5: a/b/c/d = 30/30/0/40, Mw=25,000

A3:

A3-1: a/b/c = 30/30/40 [R=H] , Mw=4,000

A3-2: a/b/c = 35/35/30 [R=H] , Mw=4,000

A3-3: a/b/c = 30/30/40 [R=CH ₃ ] , Mw=4,000

A3-4: a/b/c = 35/35/30 [R=CH ₃ ] , Mw=4,000

A3-5: a/b/c = 30/30/40 [R= C ₂ H ₅ ] , Mw=4,000

A3-6: a/b/c = 35/35/30 [R= C ₂ H ₅ ] , Mw=4,000

A3-7: a/b/c = 5/30/65 [R=H] , Mw=4,000

2. Photoacid Generator:

3. Photosensitizers:

4. Solvent

D1: propylene glycol methyl ethyl acetate

D2: diethylene glycol methyl ethyl ester

5. Basic Compound: Dicyclohexylmethylamine

6. Coupling agent: γ-glycidoxypropyltrialkoxysilane

7. Surfactants:

G1: SH-8400 (Dow Corning), G2: F-475 (DIC)

Experimental example

The resin compositions prepared according to Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 2 below.

(1) Sensitivity measurement

On a glass substrate (Corning 1737, Corning Co.) having a thickness of 0.7 mm, the photosensitive resin compositions of Examples and Comparative Examples were applied with a spinner, respectively, and heated on a hot plate at 100 ° C. for 125 seconds to volatilize the solvent to form a photosensitive film having a thickness of 4.0 μm. A resin composition layer was formed.

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

The substrate after exposure was subjected to puddle development at 23° C. for 40 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developer, and then heated in an oven at 230° C. for 30 minutes to obtain a cured film.

Thereafter, the substrate was vertically cut, and an exposure amount resulting in a 10 μm contact hole in each composition was selected as a sensitivity.

(2) pattern angle

The pattern obtained in Experimental Example (1) was cut vertically, and the angle with the substrate was calculated from an optical photograph.

(3) transmittance measurement

The transmittance at 400 nm of the film obtained in Experimental Example (1) was measured with a spectrophotometer.

(4) Adhesion evaluation

On the glass substrate on which SiNx was deposited, the photosensitive resin compositions of Examples and Comparative Examples were applied with a spinner in a state where HMDS (Hexamethyldisilazane) solution was not applied, and heated on a hot plate at 100 ° C. for 125 seconds to volatilize the solvent, A 4.0 μm photosensitive resin composition layer was formed.

Thereafter, exposure was performed with an i-line stepper (NSR-205i11D, Nikon Co., Ltd.) using a mask having a 5-20 μm hole pattern.

After exposure, the substrate was subjected to puddle development using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer at 23° C. for 40 seconds, and peeling of the pattern was confirmed.

◎: The pattern does not peel at all in all areas

○: The pattern is finely peeled off in some areas

△: A significant part of the pattern peeled off

X: All areas of the pattern are peeled off

division Transmittance (%) Sensitivity (mJ/cm ² ) Pattern angle (°) adhesion Example 1 97 24 53 ◎ Example 2 97 24 52 ◎ Example 3 97 24 54 ◎ Example 4 97 25 53 ◎ Example 5 96 27 52 ◎ Example 6 96 27 53 ◎ Example 7 95 26 54 ◎ Example 8 95 27 51 ◎ Example 9 95 23 54 ◎ Example 10 95 23 53 ◎ Example 11 94 24 52 ◎ Example 12 94 25 52 ◎ Example 13 95 28 53 ◎ Example 14 94 29 51 ◎ Example 15 95 28 53 ◎ Example 16 93 27 52 ◎ Example 17 94 28 53 ◎ Example 18 93 27 51 ◎ Example 19 95 28 52 ◎ Example 20 94 27 52 ○ Example 21 92 21 48 ◎ Comparative Example 1 97 22 56 X Comparative Example 2 97 21 57 X Comparative Example 3 97 23 56 X Comparative Example 4 97 22 56 X Comparative Example 5 97 22 55 X Comparative Example 6 78 22 32 ◎ Comparative Example 7 76 20 34 X

Referring to Table 2, it can be seen that the insulating films formed of the photosensitive resin compositions of Examples 1 to 21 have excellent adhesion. In addition, the sensitivity and transmittance also showed effects equal to or higher than those of the prior art, and showed an appropriate pattern angle.

However, the compositions of Comparative Examples 1 to 5 without using a siloxane binder showed very poor adhesion.

In addition, in the case of Comparative Example 6, which does not contain an acrylic resin, there was a problem that the transmittance was seriously lowered, and in the case of Comparative Example 7, which used an acrylic resin that did not contain an epoxy group, there was a problem that not only the transmittance was lowered but also the pattern angle was too low. .

Claims (16)

(a-1) a resin in which at least a part of the phenolic hydroxyl group or carboxy group is protected by an acid-decomposable group, (a-2) an acrylic resin containing an epoxy group, and (a-3) a siloxane resin (A) a binder resin;
(B) a photoacid generator; and
(C) contains a solvent;
The (a-3) resin is a polymerized resin including monomers represented by the following Chemical Formulas 7, 8 and 9, chemically amplified photosensitive resin composition:
[Formula 7]
Si(OR ₁ ) ₄
[Formula 8]
CH ₃ Si(OR ₂ ) ₃
[Formula 9]
C ₆ H ₅ Si(OR ₃ ) ₃
(In Formulas 7 to 9, R ₁ , R ₂ and R ₃ are all hydrogen atoms).
The chemically amplified photosensitive resin composition according to claim 1, wherein the resin (a-1) is polymerized by including at least one of the monomers represented by Formula 1, Formula 2, Formula 3, and Formula 4 below:
[Formula 1]

(Wherein, R is an alkyl group having 1 to 6 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms; a tetrahydropyranyl group; or a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms or a cycloalkoxy group having 4 to 8 carbon atoms It is an alkyl group having 1 to 6 carbon atoms)
[Formula 2]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms)
[Formula 3]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 3 to 8 carbon atoms, and R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms)
[Formula 4]

(Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 1 to 6 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms, and R ₃ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 8 carbon atoms an alkyl group).
The chemically amplified photosensitive resin composition according to claim 1, wherein the repeating unit formed by the monomers of Chemical Formulas 1 to 4 is included in an amount of 20 to 60 mol% based on the total weight of the (a-1) resin.
The chemically amplified photosensitive resin composition according to claim 1, wherein the resin (a-1) has a weight average molecular weight of 5,000 to 35,000.
The chemically amplified photosensitive resin composition according to claim 1, wherein the resin (a-2) is polymerized by including a monomer represented by Formula 5 below:
[Formula 5]

(Wherein, R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R ₄ are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to have 3 carbon atoms may form a ring of from 1 to 8; m is an integer from 1 to 6).
The chemically amplified photosensitive resin composition according to claim 1, wherein the resin (a-2) is polymerized by including a monomer represented by Formula 6 below:
[Formula 6]

(Wherein, R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 1 to 6 carbon atoms; R ₃ and R ₄ are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to have 3 carbon atoms to 8 rings).
The chemically amplified photosensitive resin composition according to claim 1, wherein the repeating unit formed by the monomers of Chemical Formula 5 or 6 is included in an amount of 5 to 60 mol% based on the total weight of the (a-2) resin.
The chemically amplified photosensitive resin composition according to claim 1, wherein the resin (a-2) has a weight average molecular weight of 5,000 to 40,000.
delete The method according to claim 1, with respect to the entire resin (a-3), the repeating unit formed by the monomer of Formula 7 is 10 to 60 mol%, the repeating unit formed by the monomer of Formula 8 is 10 to 60 mol%, The repeating unit formed by the monomer is contained in 10 to 60 mol%, a chemically amplified photosensitive resin composition.
The chemically amplified photosensitive resin composition according to claim 1, wherein the resin (a-3) has a weight average molecular weight of 500 to 20,000.
The method according to claim 1, wherein the binder resin, based on 100 parts by weight of the total binder resin, (a-1) 30 to 55 parts by weight of resin, (a-2) 30 to 60 parts by weight of resin, and (a-3) resin 1 to 25 parts by weight, chemically amplified photosensitive resin composition.
The method according to claim 1, wherein the photoacid generator is diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, ortho-nitro A chemically amplified photosensitive resin composition comprising at least one selected from the group consisting of benzylsulfonate-based and triazine-based compounds.
The chemically amplified photosensitive resin composition of claim 1, wherein the solvent is at least one selected from the group consisting of ethers, acetates, esters, ketones, amides, and lactones.
An insulating film in which the chemically amplified photosensitive resin composition according to any one of claims 1 to 8 and 10 to 14 is cured.
An image display device having the insulating film of claim 15.