KR101688014B1 - Positive photosensitive resin composition, photosensitive resin film, and display device using the same - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.) (A) an alkali-soluble resin containing at least one urea group at the end thereof represented by the following formula (1); (B) a photosensitive diazoquanone compound; And (C) a solvent, a photosensitive resin film using the positive photosensitive resin composition, and a display device.
[Chemical Formula 1]

(Wherein each substituent is as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a positive photosensitive resin composition, a photosensitive resin film, and a display device using the same. BACKGROUND OF THE INVENTION < RTI ID =

The present invention relates to a positive photosensitive resin composition, a photosensitive resin film using the positive photosensitive resin composition, and a display device.

The polyimide or polybenzoxazole precursor used for ensuring the excellent heat resistance, electrical characteristics, and mechanical properties of the interlayer insulating film in semiconductors and display devices is used in the form of a composition to be easily applied and applied to semiconductor and display substrates Patterning by ultraviolet rays, development, heat curing treatment, or the like can be performed to easily form the surface protective film and the interlayer insulating film.

However, in the case of the polybenzoxazole precursor, the solubility of the polybenzimidazole precursor in the developing solution is lower than that of the polyimide precursor, and sensitivity is lowered due to a high exposure dose when the same critical dimension (CD) is realized.

As a method for improving the solubility of polybenzoxazole in a developing solution, there has been disclosed a method of decreasing the molecular weight of a polymer or adding an excess amount of a monomolecular dissolution control agent to the composition itself. However, in this case, although some sensitivity is improved, an excessive amount of oligomer and additives cause excessive reflow on the pattern side when the pattern is cured, thereby further reducing the pattern slope.

Therefore, in order to improve the sensitivity of the composition without decreasing the pattern slope, it is necessary to study a method of introducing a functional group which increases solubility in the developing solution into the resin itself.

One embodiment of the present invention is to provide a positive photosensitive resin composition which improves the solubility of an alkali-soluble resin in a developing solution to improve sensitivity, resolution, and residual film ratio.

Another embodiment of the present invention is to provide an alkali-soluble resin having high solubility in a developing solution.

Another embodiment of the present invention is to provide a photosensitive resin film produced using the above positive photosensitive resin composition.

Another embodiment of the present invention is to provide a display element comprising the photosensitive resin film.

One embodiment of the present invention is a photosensitive resin composition comprising (A) an alkali-soluble resin containing at least one urea group represented by the following formula (1) at the end thereof, (B) a photosensitive diazoquinone compound, and (C) Type photosensitive resin composition.

[Chemical Formula 1]

(In the formula 1,

X is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

The alkali-soluble resin may be a polybenzoxazole precursor, a polyimide precursor, or a combination thereof.

The alkali-soluble resin may be represented by the following general formula (2).

(2)

(In the formula (2)

A is O, CO, CR ³⁰⁰ R ³⁰¹ , SO ₂ , S or a single bond, R ³⁰⁰ and R ³⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group,

B is any one selected from the group consisting of the following formulas (3) to (5)

X is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹ and R ² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a hydroxyl group, a carboxyl group, or a thiol group,

and n is an integer of 2 to 100,000.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

(In the above formulas 3 to 5,

R ¹² to R ¹⁵ are each independently hydrogen or a substituted or unsubstituted alkyl group,

n1, n3, and n4 each independently may be an integer of 1 to 4, n2 is an integer of 1 to 3,

Y may be O, CR ⁴⁰⁰ R ⁴⁰¹ , CO, CONH, S, or SO ₂ , and R ⁴⁰⁰ and R ⁴⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group.

The alkali-soluble resin may have a weight average molecular weight of 3,000 to 300,000 g / mol.

The positive photosensitive resin composition may further comprise a dissolution controlling agent represented by the following formula (6).

[Chemical Formula 6]

(6)

R ³ is hydrogen, a hydroxy group, or a substituted or unsubstituted C1 to C30 alkyl group,

R ⁴ to R ⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group)

The solvent is selected from the group consisting of N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, Glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, or combinations thereof.

The positive photosensitive resin composition may further include an additive selected from the group consisting of a surfactant, a refilling agent, a thermal acid generator, and a combination thereof.

The positive photosensitive resin composition may include 5 to 100 parts by weight of the photosensitive diazoquinone compound (B) and 100 to 900 parts by weight of the solvent (C), based on 100 parts by weight of the alkali-soluble resin (A) .

Another embodiment of the present invention provides an alkali-soluble resin represented by the general formula (2).

The weight average molecular weight of the alkali-soluble resin may be 3,000 to 300,000 g / mol.

Another embodiment of the present invention provides a photosensitive resin film produced using the above positive photosensitive resin composition.

Another embodiment of the present invention provides a display element comprising the photosensitive resin film.

Other details of the embodiments of the present invention are included in the following detailed description.

Soluble resin can be easily dissolved in the developing solution in the exposed part by incorporating at least one urea group at the terminal of the alkali-soluble resin to provide a photosensitive resin composition having improved sensitivity, resolution and residual film ratio, The photosensitive resin film produced by the composition can be usefully used in display devices.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, the terms " substituted "and" substituted ", unless otherwise defined, means that at least one hydrogen atom of the functional group of the present invention is a halogen atom (F, Cl, Br, or I), a hydroxy group, (Wherein R200, R201 and R202 are the same or different and are each independently a C1 to C10 alkyl group), an amidino group, a hydrazine group, a hydrazine group, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkyl group, Substituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C2 to C30 heteroaryl groups, and substituted or unsubstituted C2 to C30 heterocycloalkyl groups.

Means a C1 to C20 alkyl group, specifically, a C1 to C20 alkyl group, and the "cycloalkyl group" means a C3 to C30 cycloalkyl group, and specifically, C3 Refers to a C1 to C30 alkoxy group, specifically, a C1 to C18 alkoxy group, and an "aryl group" means a C6 to C30 aryl group, specifically, a C6 to C30 aryl group, C20 aryl group ", the" alkenyl group "means a C2 to C30 alkenyl group, specifically a C2 to C18 alkenyl group, the" alkylene group "means a C1 to C30 alkylene group, specifically C1 Means a C6 to C30 arylene group, and specifically refers to a C6 to C16 arylene group.

 Unless otherwise specified in the present specification, the term "aliphatic organic group" means a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C1 to C30 alkylene group, a C2 to C30 alkenylene group, Means a C1 to C15 alkyl group, a C2 to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15 alkylene group, a C2 to C15 alkenylene group, or a C2 to C15 alkynylene group, Means a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to C30 cycloalkynyl group, a C3 to C30 cycloalkylene group, a C3 to C30 cycloalkenylene group, or a C3 to C30 cycloalkynylene group And more specifically a C3 to C15 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C3 to C15 cycloalkynyl group, a C3 to C15 cycloalkylene group, a C3 to C15 cycloalkenylene group, or a C3 to C15 cyclo Means a C6 to C30 aryl group or a C6 to C30 arylene group, specifically a C6 to C16 aryl group or a C6 to C16 arylene group, and the "heterocyclic group" Is a C2 to C30 heterocycloalkyl group containing from 1 to 3 hetero atoms selected from the group consisting of O, S, N, P, Si, and combinations thereof, C2 to C30 heterocycloalkylene groups, C2 To C30 heterocycloalkenyl groups, C2 to C30 heterocycloalkenylene groups, C2 to C30 heterocycloalkynyl groups, C2 to C30 heterocycloalkynylene groups, C2 to C30 heteroaryl groups, and C2 to C30 heteroarylene groups, , Specifically C2 to C15 heterocycloalkyl groups containing 1 to 3 hetero atoms selected from the group consisting of O, S, N, P, Si and combinations thereof in one ring, C2 to C A C2 to C15 heterocycloalkylene group, a C2 to C15 heterocycloalkenyl group, a C2 to C15 heterocycloalkenylene group, a C2 to C15 heterocycloalkynylene group, a C2 to C15 heterocycloalkynylene group, a C2 to C15 heteroaryl group, C15 < / RTI > heteroarylene group.

In addition, unless otherwise specified, the terms "fluoroalkyl group", "fluoroalkylene group", "fluorocycloalkylene group", "fluoroarylene group", "fluoroalkoxy group" and " Group may be any substituent containing a fluorine atom in the substituent present in the alkyl group, alkylene group, cycloalkylene group, arylene group, alkoxy group and alcohol group.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

An embodiment of the present invention is a resin composition comprising: (A) an alkali-soluble resin including at least one urea group represented by the following formula (1) at the terminal; (B) a photosensitive diazoquinone compound; And (C) a solvent.

[Chemical Formula 1]

In Formula 1,

X is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

For example, X may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The alkali-soluble resin includes at least one urea group represented by the above-mentioned formula (1) at the end thereof, thereby increasing the solubility of the alkali-soluble resin in a developing solution such as tetramethylammonium hydroxide (TMAH) Can be improved. This is because the urea group represented by the formula (1) exhibits a high polarity.

The urea group has an effect similar to an amine group in that the slope of the pattern side of the patterned side of the substrate coated with the photosensitive resin composition is prevented from being reduced. However, unlike the amine group, the urea group can improve the storage stability of the composition. In addition, the urea group improves the bonding strength between the photosensitive diazoquinone compound present in the composition and the alkali-soluble resin in the unexposed portion, thereby reducing the film loss and increasing the dissolution rate of the alkali-soluble resin in the exposed portion, And the contrast ratio of the unexposed portion can be maximized.

Hereinafter, each component constituting the positive photosensitive resin composition will be described in detail.

(A) an alkali-soluble resin

The alkali-soluble resin includes at least one urea group represented by the formula (1) at one end thereof, thereby improving the sensitivity, resolution, and residual film ratio of the photosensitive resin film formed from the alkali-soluble resin.

The alkali-soluble resin may be a polybenzoxazole precursor, a polyimide precursor, or a combination thereof.

The alkali-soluble resin may be represented by the following general formula (2).

(2)

In Formula 2,

A is O, CO, CR ³⁰⁰ R ³⁰¹ , SO ₂ , S or a single bond, R ³⁰⁰ and R ³⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group,

B is any one selected from the group consisting of the following formulas (3) to (5)

X is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹ and R ² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a hydroxyl group, a carboxyl group, or a thiol group,

and n is an integer of 2 to 100,000.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,

R ¹² to R ¹⁵ are each independently hydrogen or a substituted or unsubstituted alkyl group,

n1, n3, and n4 each independently may be an integer of 1 to 4, n2 is an integer of 1 to 3,

Y may be O, CR ⁴⁰⁰ R ⁴⁰¹ , CO, CONH, S, or SO ₂ , and R ⁴⁰⁰ and R ⁴⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group.

For example, A may be CR ³⁰⁰ R ³⁰¹ , B may be represented by formula 5, and X is a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, Or an unsubstituted C6 to C20 aryl group.

The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 to 300,000 g / mol, for example, a weight average molecular weight of 5,000 to 50,000 g / mol. When the alkali-soluble resin has a weight average molecular weight within the above range, a sufficient residual film ratio can be obtained in an unexposed area at the time of development with an aqueous alkali solution, and patterning can be efficiently performed.

(B) Photosensitive Diazoquinone  compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure can be preferably used.

Representative examples of the photosensitive diazoquinone compound include compounds represented by the following general formulas (19) and (21) to (23), but are not limited thereto.

[Chemical Formula 19]

In the above formula (19)

R ₃₁ to R ₃₃ may be, independently of each other, hydrogen or a substituted or unsubstituted alkyl group, specifically CH ₃ ,

D ₁ to D ₃ may independently be OQ and Q may be hydrogen or the following formulas 20a to 20d in which Q can not be hydrogen at the same time,

n31 to n33 may be an integer of 1 to 3 independently of each other.

[Chemical Formula 20a]

[Chemical Formula 20b]

[Chemical Formula 20c]

[Chemical Formula 20d]

[Chemical Formula 21]

In Formula 21,

R ₃₄ may be hydrogen or a substituted or unsubstituted alkyl group,

D ₄ to D ₆ may independently be OQ, Q is the same as defined in the above formula (19)

n34 to n36 may be an integer of 1 to 3, independently of each other.

[Chemical Formula 22]

In Formula 22,

A ₃ may be CO or CR ⁵⁰⁰ R ⁵⁰¹ , and R ⁵⁰⁰ and R ⁵⁰¹ may be, independently of each other, a substituted or unsubstituted alkyl group,

D ₇ to D ₁₀ may be, independently of each other, hydrogen, a substituted or unsubstituted alkyl group, OQ or NHQ, Q is the same as defined in the above formula (19)

n37, n38, n39 and n40 may be independently an integer of 1 to 4,

n37 + n38 and n39 + n40 may independently be an integer of 5 or less,

Provided that at least one of the D ₇ to D ₁₀ are OQ, one aromatic ring has an OQ can contain 1 to 3, there is OQ can contain one to four and one of the aromatic ring.

(23)

In the formula (23)

R ₃₅ to R ₄₂ may be, independently of each other, hydrogen or a substituted or unsubstituted alkyl group,

n41 and n42 may be, independently of each other, an integer of 1 to 5, more specifically an integer of 2 to 4,

Q is the same as defined in the above formula (19).

The photosensitive diazoquinone compound is preferably included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is formed well without residue by exposure, and there is no loss of film thickness during development, and a good pattern can be obtained.

(C) Solvent

The positive photosensitive resin composition may include a solvent capable of easily dissolving each component.

Examples of the solvent include organic solvents such as N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol di Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butyleneglycol acetate, propyleneglycol monomethyl ether, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, and the like. These solvents may be used alone or in combination.

The solvent may be appropriately selected and used depending on the step of forming a photosensitive resin film such as spin coating, slit die coating and the like.

The solvent may be used in an amount of 100 to 900 parts by weight, for example, 200 to 700 parts by weight, based on 100 parts by weight of the polybenzoxazole precursor. When the content of the solvent is within the above range, a film having a sufficient thickness can be coated, and the solubility and coatability can be excellent.

Specifically, the solvent may be used such that the solids content of the positive photosensitive resin composition is 3 to 50% by weight, for example, 5 to 30% by weight.

(D) Dissolution regulator

The positive photosensitive resin composition according to one embodiment may further include a dissolution regulator.

The dissolution regulator may generally comprise a phenolic compound.

The phenolic compound increases the dissolution rate and sensitivity of the exposed portion during development with an alkaline aqueous solution, and helps to pattern at a high resolution.

Representative examples of such phenol compounds include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl- However, the present invention is not limited thereto.

For example, the dissolution controlling agent may be represented by the following formula (6).

[Chemical Formula 6]

In Formula 6,

R ³ is hydrogen, a hydroxy group, or a substituted or unsubstituted C1 to C30 alkyl group,

R ⁴ to R ⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group.

For example, R ³ may be a hydroxy group, and each of R ⁴ to R ⁶ may independently be a substituted or unsubstituted C 1 to C 20 alkyl group.

When the compound represented by Formula 6 is added as a dissolution regulator in the positive photosensitive resin composition, a photosensitive resin film such as an organic insulating film having high sensitivity and having no scum after development in the pattern formation process and excellent in chemical resistance can be obtained have.

The dissolution controlling agent may be included in an amount of 5 to 35 parts by weight, for example, 10 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the dissolution control agent is contained within the above range, a photosensitive resin film such as an organic insulating film having high sensitivity, no scum after development, and excellent chemical resistance and moisture barrier properties can be obtained.

(E) Other additives

The positive photosensitive resin composition according to one embodiment may further include other additives.

Other additives include thermal acid generators. Examples of the thermal acid generator include arylsulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid and the like; Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid, trifluorobutanesulfonic acid and the like; Methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid and the like; Or combinations thereof, but are not limited thereto.

The thermal acid generator is a catalyst for the dehydration reaction of a phenolic hydroxyl group-containing polyamide of an alkali-soluble resin and a cyclization reaction, and the cyclization reaction can proceed smoothly even if the curing temperature is lowered.

Further, a surfactant or leveling agent may be added as an additive in order to prevent unevenness in film thickness or to improve developability.

The thermal acid generator, surfactant, and leveling agent may be used alone or in combination.

The step of forming a pattern using the positive photosensitive resin composition includes a step of applying a positive photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing or the like; Drying the applied positive photosensitive resin composition to form a positive photosensitive resin composition film; Exposing the positive photosensitive resin composition film; A step of developing the exposed positive photosensitive resin composition film with an alkali aqueous solution to prepare a photosensitive resin film; And a step of heat-treating the photosensitive resin film. The conditions of the process for forming the pattern, and the like are well known in the art, so that detailed description thereof will be omitted herein.

According to another embodiment of the present invention, there is provided an alkali-soluble resin represented by the general formula (2).

The above-mentioned alkali-soluble resin is as described above.

According to another embodiment of the present invention, there is provided a photosensitive resin film produced using a positive photosensitive resin composition. The photosensitive resin film may be, for example, an organic insulating film.

According to still another embodiment of the present invention, there is provided a display device comprising the photosensitive resin film. The display device may be an organic light emitting diode (OLED) or a liquid crystal display device (LCD). For example, the display device may be an organic light emitting diode (OLED).

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited to the following Examples.

( Example )

Polybenzoxazole  Precursor ( PBO ) Synthesis of

Synthetic example  One. Polybenzoxazole  Synthesis of precursor

5 g of N-methylpyrrolidone was charged into a 1 L flask equipped with a stirrer and a thermometer and 89 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BHAF) , And dissolved. Subsequently, 35 g of pyridine was added to the solution while maintaining the temperature at 0 캜 to 5 캜. To this solution, 60 g of dioxybenzoyl chloride was dissolved in 200 g of N-methylpyrrolidone, and the mixture was added dropwise for 30 minutes, followed by stirring for 2 hours. After confirming that the monomers were completely exhausted after confirming the GPC, 11 g of isobenzothyanate was dissolved in 60 g of N-methylpyrrolidone, and the solution was added dropwise for 10 minutes. Subsequently, the reaction is continued for 2 hours while maintaining the temperature at 0 캜 to 5 캜. After completion of the reaction, the reaction solution was added dropwise to 4 L of water, and the resulting precipitate was recovered. The precipitate thus obtained was washed with pure water three times and then reduced in pressure to obtain polybenzoxazole represented by the following formula (7) in the form of a polyhydroxyamide A precursor was obtained. The polymer had a weight average molecular weight of 10,520 g / mol as determined by GPC standard standard polystyrene conversion.

(7)

Synthetic example  2. Polybenzoxazole  Synthesis of precursor

A polybenzoxazole precursor represented by the following formula (8) was obtained in the same manner as in Synthesis Example 1, except that 12 g of cyclohexylisothianate was added instead of 11 g of isobenzothiocyanate. The weight average molecular weight of the polymer as determined by GPC standard standard polystyrene conversion was 10,900 g / mol.

[Chemical Formula 8]

Synthetic example  3. Polybenzoxazole  Synthesis of precursor

A polybenzoxazole precursor represented by the following formula (9) was obtained in the same manner as in Synthesis Example 1, except that 28 g of octadecyl isothiocyanate was added instead of 11 g of isobenzothianate. The weight average molecular weight of the polymer as determined by GPC standard standard polystyrene conversion was 12,500 g / mol.

[Chemical Formula 9]

Synthetic example  4. Polybenzoxazole  Synthesis of precursor

Instead of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BHAF) , A polybenzoxazole precursor represented by the following formula (10) was obtained in the same manner as in Synthesis Example 1. The polymer had a weight average molecular weight of 8,350 g / mol as determined by GPC standard standard polystyrene conversion.

[Chemical formula 10]

Synthetic example  5. Polybenzoxazole  Synthesis of precursor

Instead of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BHAF) A polybenzoxazole precursor represented by the following general formula (11) was obtained in the same manner as in Synthesis Example 1, except that 12 g of cyclohexylisothianate was added instead of 11 g of isobenzothyanate. The weight average molecular weight of the polymer as determined by GPC standard standard polystyrene conversion was 7,900 g / mol.

(11)

Synthetic example  6. Polybenzoxazole  Synthesis of precursor

Instead of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BHAF) A polybenzoxazole precursor represented by the following general formula (12) was obtained in the same manner as in Synthesis Example 1, except that 28 g of octadecyl isothiocyanate was added instead of 11 g of isobenzothyanate. The polymer had a weight average molecular weight of 10,060 g / mol as determined by GPC standard standard polystyrene conversion.

[Chemical Formula 12]

Comparative Synthetic Example  One. Polybenzoxazole  Synthesis of precursor

18.3 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BHAF) was added to a four-necked flask equipped with a stirrer, a temperature controller, Norbornene-2,3-dicarboxylic anhydride (1.6 g) was added, and 164 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve. The solid content in the obtained solution was 15 wt%.

When the solid was completely dissolved, 8.1 g of pyridine was added, the temperature was raised to 50 캜, and the mixture was stirred at a temperature of 5 hours. Thereafter, the temperature was lowered to 0 ° C to 5 ° C, and a solution prepared by dissolving 13.3 g of 4,4'-deoxybenzoyl chloride in 75 g of N-methyl-2-pyrrolidone (NMR) was slowly dropped for 30 minutes. After the dropwise addition, the reaction was carried out at a temperature of 0 ° C to 5 ° C for 1 hour, followed by stirring at room temperature for 1 hour, and then the reaction was terminated. The reaction mixture was poured into water to form a precipitate. The precipitate was filtered and sufficiently washed with water, and dried at a temperature of 80 캜 under vacuum for at least 24 hours to prepare a polybenzoxazole precursor represented by the following formula (13). The polymer had a weight average molecular weight of 10,500 g / mol as determined by GPC standard standard polystyrene conversion.

[Chemical Formula 13]

Comparative Synthetic Example  2. Polybenzoxazole  Synthesis of precursor

6 g of N-methylpyrrolidone was charged into a 1 L flask equipped with a stirrer and a thermometer, 89 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BHAF) Lt; / RTI > Subsequently, 35 g of pyridine was added to the solution while maintaining the temperature at 0 캜 to 5 캜. To this solution, 60 g of 4,4'-dioxybenzoyl chloride was dissolved in 200 g of N-methylpyrrolidone and the mixture was added dropwise for 30 minutes. Respectively. After confirming GPC, confirm that all the monomer is exhausted. After completion of the reaction, the reaction solution was added dropwise to 4 L of water, and the resulting precipitate was recovered. The precipitate thus obtained was washed three times with pure water and then reduced in pressure to obtain polybenzoxazole represented by the following formula (14) in the form of a polyhydroxyamide A precursor was obtained. The polymer had a weight average molecular weight of 9,800 g / mol as determined by GPC standard standard polystyrene conversion.

[Chemical Formula 14]

Rating 1: Tetramethylammonium To the hydroxide (TMAH)  Solubility assessment

The solubility of polybenzoxazole precursors of Synthesis Examples 1 to 6, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 was evaluated. The results are shown in Table 1 below.

3 g of the polybenzoxazole precursors of Synthesis Examples 1 to 6, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 were added to 12 g of a solution of PGME / EL / GBL = 7/2/1 to prepare a solution having a solid content of 20% . The prepared solutions were coated on a 4-inch wafer using a spin-coater and baked at 120 ° C for 100 seconds to a final thickness of 2 탆. The coated samples were cut into 2 cm x 2 cm and put into a 2.38 wt% tetramethylammonium hydroxide (TMAH) solution at 23 [deg.] C to confirm the dissolution rate. The evaluation results are shown in Table 1 below.

Time dissolved (s) DR (A / s) Synthesis Example 1 35 571 Synthesis Example 2 30 666 Synthesis Example 3 33 606 Synthesis Example 4 28 714 Synthesis Example 5 26 769 Synthesis Example 6 29 689 Comparative Synthesis Example 1 42 476 Comparative Synthesis Example 2 39 512

From the above Table 1, polybenzoxazole precursors containing urea groups at the terminals according to Synthesis Examples 1 to 6 were found to have tetramethylammonium hydroxide (TMAH) in comparison with polybenzoxazole precursors according to Comparative Synthesis Examples 1 and 2 ) Was found to be high. This is a result depending on whether or not the urea group is contained at the terminal of the alkali-soluble resin.

Preparation of positive photosensitive resin composition

≪ Example 1 >

15 g of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1 was added to and dissolved in 80 g of PGME / EL / g-GBL, and then 3 g of the photosensitive diazoquinone compound represented by the following formula (A) 2 g of a dissolution control agent and 0.05 g of a surfactant F-544, and sufficiently dissolved. Thereafter, the resultant was filtered with a filter made of fluororesin of 0.45 mu m to obtain a positive photosensitive composition.

(A)

R=

R =

[Chemical Formula B]

≪ Example 2 >

Except that the polybenzoxazole precursor (Formula 8) prepared in Synthesis Example 2 was used instead of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1, the positive-type photosensitive resin composition ≪ / RTI >

≪ Example 3 >

Except that the polybenzoxazole precursor (Formula 9) prepared in Synthesis Example 3 was used instead of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1, the positive photosensitive resin composition ≪ / RTI >

<Example 4>

Except that the polybenzoxazole precursor (Formula 10) prepared in Synthesis Example 4 was used instead of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1, the positive photosensitive resin composition &Lt; / RTI &gt;

&Lt; Example 5 >

Except that the polybenzoxazole precursor (Formula 11) prepared in Synthesis Example 5 was used in place of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1, the positive-type photosensitive resin composition &Lt; / RTI &gt;

&Lt; Example 6 >

Except that the polybenzoxazole precursor (Formula 12) prepared in Synthesis Example 6 was used instead of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1, the positive photosensitive resin composition &Lt; / RTI &gt;

&Lt; Comparative Example 1 &

Except that the polybenzoxazole precursor (Formula 13) prepared in Comparative Synthesis Example 1 was used in place of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1, a positive photosensitive resin A composition was obtained.

&Lt; Comparative Example 2 &

Except that the polybenzoxazole precursor (Formula 14) prepared in Comparative Synthesis Example 2 was used in place of the polybenzoxazole precursor (Formula 7) prepared in Synthesis Example 1, the positive photosensitive resin A composition was obtained.

The sensitivity, resolution, and residual film ratio of the positive photosensitive resin compositions of Examples 1 to 6, Comparative Example 1, and Comparative Example 2 were evaluated. The results are shown in Table 1 below.

Evaluation 2: Resolution, Residual film ratio , Sensitivity evaluation

The positive photosensitive resin compositions prepared according to Examples 1 to 6, Comparative Examples 1 and 2 were coated on an 8-inch wafer or ITO substrate using a spin coater made by Mikasa (1H-DX2) The plate was heated on the plate at 120 DEG C for 100 seconds to form a photosensitive polybenzoxazole precursor film.

 The photosensitive polybenzoxazole precursor film was exposed to light with different exposure times using an i-line stepper (NSR i10C) manufactured by Mikon Co., Ltd., using a mask having a pattern of various sizes, and then exposed to 2.38% by weight of tetramethylammonium (TMAH) solution for 80 seconds to dissolve and remove the exposed portions, and then washed with pure water for 30 seconds to obtain a pattern. Subsequently, the pattern thus obtained was cured at 250 DEG C / 40 minutes at an oxygen concentration of 1000 ppm or less by using an electric furnace to produce a patterned film. The resolution of the pattern of the finished film was confirmed by optical microscope.

The change in film thickness after preliminary firing, development and curing was measured using a K-mac (ST4000-DLX) equipment and the change in film thickness was measured to calculate the retention rate (thickness after development / thickness before development, unit%) .

 The sensitivity was determined by measuring the exposure time at which a 10 占 퐉 L / S pattern was formed with a line width of 1: 1 after exposure and development, and measuring the optimum exposure time as the sensitivity of the photosensitive resin composition.

 The storage stability (or storage stability) is calculated by calculating the number of days passed until the time when the same coating thickness and exposure performance are exhibited, that is, the coating thickness and exposure performance of the composition show abnormal behavior while the composition is stored at room temperature Table 2 shows the results.

Film thickness (占 퐉) Sensitivity
L / S = 10 탆 (mJ / cm ² ) Resolution (탆) Residual film ratio
(%) Storage stability (days) taper angle (°) Preliminary firing After development Example 1 4.4 3.80 113 3 86.5 12 44 Example 2 4.5 3.83 100 3 85.2 11 43 Example 3 4.3 3.70 105 3 86.1 12 45 Example 4 4.5 3.79 98 2.6 84.2 13 42 Example 5 4.3 3.61 95 2.5 83.9 13 41 Example 6 4.5 3.82 100 2.5 84.8 13 42 Comparative Example 1 4.6 3.79 120 3.5 82.5 10 36 Comparative Example 2 4.5 3.73 116 3.2 83.1 6 44

From Table 2, when the photosensitive resin compositions according to Examples 1 to 6 were used, the sensitivity, the resolution, the residual film ratio, and the storage stability were superior to those of the photosensitive resin compositions according to Comparative Examples 1 and 2, It can be confirmed that it is excellent. That is, an alkali-soluble resin including a urea group at the terminal thereof can be patterned more efficiently than conventional alkali-soluble resins, thereby forming a photosensitive resin film having excellent performance, for example, an organic insulating film.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (12)

(A) an alkali-soluble resin represented by the following formula (2);
(B) a photosensitive diazoquinone compound; And
(C) Solvent
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.
(2)

(In the formula (2)
A is O, CO, CR ³⁰⁰ R ³⁰¹ , SO ₂ , S or a single bond, R ³⁰⁰ and R ³⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group,
B is any one selected from the group consisting of the following formulas (3) to (5)
X is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,
R ¹ and R ² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a hydroxyl group, a carboxyl group, or a thiol group,
and n is an integer of 2 to 100,000)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

(In the above formulas 3 to 5,
R ¹² to R ¹⁵ are each independently hydrogen or a substituted or unsubstituted alkyl group,
n1, n3, and n4 each independently may be an integer of 1 to 4, n2 is an integer of 1 to 3,
Y may be O, CR ⁴⁰⁰ R ⁴⁰¹ , CO, CONH, S or SO ₂ , and R ⁴⁰⁰ and R ⁴⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group.
The method according to claim 1,
The alkali-soluble resin is a polybenzoxazole precursor, a polyimide precursor, or a combination thereof.
delete The method according to claim 1,
The alkali-soluble resin has a weight average molecular weight of 3,000 to 300,000 g / mol.
The method according to claim 1,
Wherein the positive photosensitive resin composition further comprises a dissolution controlling agent represented by the following formula (6).
[Chemical Formula 6]

(6)
R ³ is hydrogen, a hydroxy group, or a substituted or unsubstituted C1 to C30 alkyl group,
R ⁴ to R ⁶ are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkyl group)
The method according to claim 1,
The solvent is selected from the group consisting of N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, Glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, or a combination thereof.
The method according to claim 1,
Wherein the positive photosensitive resin composition further comprises an additive selected from the group consisting of a surfactant, a refilling agent, a thermal acid generator, and a combination thereof.
The method according to claim 1,
The positive photosensitive resin composition
With respect to 100 parts by weight of the alkali-soluble resin (A)
5 to 100 parts by weight of the photosensitive diazoquinone compound (B), and
100 to 900 parts by weight of the above (C) solvent
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.
An alkali-soluble resin represented by the following formula (2).
(2)

(In the formula (2)
A is O, CO, CR ³⁰⁰ R ³⁰¹ , SO ₂ , S or a single bond, R ³⁰⁰ and R ³⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group,
B is any one selected from the group consisting of the following formulas (3) to (5)
X is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,
R ¹ and R ² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a hydroxyl group, a carboxyl group, or a thiol group,
and n is an integer of 2 to 100,000)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

(In the above formulas 3 to 5,
R ¹² to R ¹⁵ are each independently hydrogen or a substituted or unsubstituted alkyl group,
n1, n3, and n4 each independently may be an integer of 1 to 4, n2 is an integer of 1 to 3,
Y may be O, CR ⁴⁰⁰ R ⁴⁰¹ , CO, CONH, S or SO ₂ , and R ⁴⁰⁰ and R ⁴⁰¹ are each independently hydrogen, a substituted or unsubstituted alkyl group, or a fluoroalkyl group.
10. The method of claim 9,
Wherein the alkali-soluble resin has a weight average molecular weight of 3,000 to 300,000 g / mol.
A photosensitive resin film produced by using the positive photosensitive resin composition of any one of claims 1, 2, and 4 to 8.
A display element comprising the photosensitive resin film of claim 11.