KR102044944B1 - Photosensitive resin composition, photosensitive resin layer using the same and display device - Google Patents

Abstract

(A) alkali-soluble resins; (B) photosensitive diazoquinone compound; (C) a diol compound having a boiling point of 160 ° C to 400 ° C and a log P of -1.9 to 1.0; And (D) a photosensitive resin composition comprising a solvent, a photosensitive resin film prepared using the same, and a display device including the photosensitive resin film.

Description

Photosensitive resin composition, photosensitive resin film and display device using same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND DISPLAY DEVICE}

The present substrate relates to a photosensitive resin composition, a photosensitive resin film using the same, and a display device including the photosensitive resin film.

The photosensitive resin composition is a material essential for the production of display elements such as color filters, liquid crystal display materials, display devices such as organic light emitting elements, and display device panel materials. For example, in a color filter such as a color liquid crystal display, in order to increase the display contrast and the color development effect, photosensitivity such as a black pixel partition wall layer is formed at a boundary between colored layers such as red, green, and blue. A resin film is required, and this photosensitive resin film is mainly formed from the photosensitive resin composition.

In particular, a photosensitive resin film such as a pixel partition layer used as a material of a display device panel should have a low taper angle in order to have processability and device reliability. In addition, a colorant such as a pigment or a dye that absorbs light in the visible region for light shielding properties should be used.

In general, although a phenolic compound was used to control the developability of the photosensitive resin composition, it is difficult to solve the problem of lowering sensitivity and surface cracking after curing with the phenolic compound alone.

Therefore, the research to develop the photosensitive resin composition which can solve the said problem is continued.

One embodiment is to provide a photosensitive resin composition that is excellent in sensitivity and developability, and can minimize the occurrence of surface cracks (surface stains) after curing.

Another embodiment is to provide a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment is to provide a display device including the photosensitive resin film.

One embodiment includes (A) an alkali soluble resin; (B) photosensitive diazoquinone compound; (C) a diol compound having a boiling point of 160 ° C to 400 ° C and a log P of -1.9 to 1.0; And (D) provides a photosensitive resin composition comprising a solvent.

The diol compound may have a boiling point of 160 ° C. to 400 ° C., and a log P of −1.2 to 0.7.

The diol compound may be represented by any one selected from the group consisting of the following Chemical Formulas 1 to 4.

[Formula 1]

In Chemical Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, provided that at least one of R ¹ and R ² is a substituted or unsubstituted C1 to C10 alkyl group,

R ¹ and R ² may be bonded to each other to form a cycloalkane ring.

[Formula 2]

In Chemical Formula 2,

R ³ to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, provided that at least one of R ³ to R ⁵ is a substituted or unsubstituted C1 to C10 alkyl group.

[Formula 3]

In Chemical Formula 3,

R ⁶ to R ⁹ are each independently a C1 to C10 alkyl group unsubstituted or substituted with a hydrogen atom, a hydroxy group or a hydroxy group, provided that two of R ⁶ to R ⁹ are necessarily C1 to C10 alkyl groups substituted with a hydroxy group or a hydroxy group ,

L ¹ is * -CH ₂ -CH _2- * or * -CH = CH- *.

[Formula 4]

In Chemical Formula 4,

R ¹⁰ to R ¹³ are each independently a hydrogen atom or a hydroxy group, provided that any one of R ¹⁰ and R ¹¹ is a hydroxy group and any one of R ¹² and R ¹³ is a hydroxy group.

The diol compound may be represented by any one selected from the group consisting of the following Chemical Formulas 5 to 13.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

The alkali-soluble resin may be a polybenzoxazole precursor, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof.

The photosensitive resin composition includes 5 parts by weight to 100 parts by weight of the photosensitive diazoquinone compound, 3 parts by weight to 30 parts by weight of the diol compound, and 100 parts by weight of the alkali-soluble resin. It may include 400 parts by weight to 1000 parts by weight.

The photosensitive resin composition may further include additives of malonic acid, 3-amino-1,2-propanediol, leveling agent, fluorine-based surfactant, radical polymerization initiator, or a combination thereof.

Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

Another embodiment provides a display device including the photosensitive resin film.

The display device may be an organic light emitting diode (OLED).

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

The photosensitive resin composition according to the embodiment includes a diol compound having a boiling point of 160 ° C. to 400 ° C. and a log P of −1.9 to 1.0, and thus has high transmittance with respect to the exposure wavelength, thereby lowering the packing density, thereby providing excellent sensitivity and developability. Have In addition, the thick film coating can effectively control cracks or stains occurring on the surface of the film after curing.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, and "cycloalkenyl group" means a C3 to C20 cycloalkenyl group , "Heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" Is a C1 to C20 alkylene group, and "arylene group" refers to a C6 to C20 arylene group, and "alkylarylene group" refers to a C6 to C20 alkylarylene group, and a "heteroarylene group" to C3 to C20 hetero It means an arylene group and a "alkoxy group" means a C1-C20 alkoxylene group.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group, Azido, amidino, hydrazino, hydrazono, carbonyl, carbamyl, thiol, ester, ether, carboxyl or salts thereof, sulfonic acid or salts thereof, phosphoric acid or salts thereof, C1 To C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 To C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.

In addition, unless otherwise specified in the present specification, "hetero" means that at least one hetero atom of N, O, S, and P is included in a chemical formula.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

Unless otherwise defined herein, “combination” means mixed or copolymerized. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymerization.

Unless stated otherwise in the present specification, unsaturated bonds include not only multiple bonds between carbon-carbon atoms, but also include other molecules such as carbonyl bonds, azo bonds, and the like.

Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at the position where the chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

Unless otherwise defined herein, "*" means the part connected with the same or different atoms or formulas.

“Log P” herein is the octanol-water partition coefficient, which is a coefficient representing the distribution of solutes in two non-mixed phases, octanol and water, and is one of the representative parameters of the hydrophobicity of a compound.

Photosensitive resin composition according to one embodiment is (A) alkali-soluble resin; (B) photosensitive diazoquinone compound; (C) a diol compound having a boiling point of 160 ° C to 400 ° C and a log P of -1.9 to 1.0; And (D) a solvent.

The diol compound having a boiling point of 160 ° C. to 400 ° C. and a log P of −1.9 to 1.0 is included as an additive in the photosensitive resin composition, thereby controlling the development rate of the photosensitive resin composition and controlling cracks or stains during thick film coating. Can be done. For example, when the diol compound is used as an additive in the positive photosensitive resin composition, the dissolution rate in the developer is improved, and the development time is reduced, and the crack or stain on the surface after curing (prebaking or postbaking) can be effectively controlled. Can be.

Each component is demonstrated concretely below.

(C) Dior  compound

The photosensitive resin composition according to one embodiment includes a diol compound having a boiling point of 160 ° C. to 400 ° C. and a log P of −1.9 to 1.0. By including the diol compound, the transmittance with respect to the exposure wavelength is increased, the packing density can be lowered to improve the sensitivity. In addition, it is possible to effectively control the occurrence of cracks and stains generated on the surface of the coating film after curing.

For example, the diol compound may have a boiling point of 160 ° C. to 400 ° C., and a log P of −1.2 to 0.7.

The diol compound having a boiling point of 160 ° C. to 400 ° C. and a log P of −1.9 to 1.0 may be represented by any one selected from the group consisting of Formulas 1 to 4.

 [Formula 1]

In Chemical Formula 1,

R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, provided that at least one of R ¹ and R ² is a substituted or unsubstituted C1 to C10 alkyl group,

R ¹ and R ² may be present independently, or may be bonded to each other to form a cycloalkane ring.

 [Formula 2]

In Chemical Formula 2,

R ³ to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, provided that at least one of R ³ to R ⁵ is a substituted or unsubstituted C1 to C10 alkyl group.

[Formula 3]

In Chemical Formula 3,

R ⁶ to R ⁹ are each independently a C1 to C10 alkyl group unsubstituted or substituted with a hydrogen atom, a hydroxy group or a hydroxy group, provided that two of R ⁶ to R ⁹ are necessarily C1 to C10 alkyl groups substituted with a hydroxy group or a hydroxy group ,

L ¹ is * -CH ₂ -CH _2- * or * -CH = CH- *.

[Formula 4]

In Chemical Formula 4,

R ¹⁰ to R ¹³ are each independently a hydrogen atom or a hydroxy group, provided that any one of R ¹⁰ and R ¹¹ is a hydroxy group and any one of R ¹² and R ¹³ is a hydroxy group.

The diol compound represented by Chemical Formula 4 may be specifically represented by Chemical Formula 13, and more specifically, may be represented by Chemical Formula 4-1.

[Formula 4-1]

Specifically, the diol compound may be represented by any one selected from the group consisting of the following Chemical Formulas 5 to 13.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

The diol compound may be used in 3 parts by weight to 30 parts by weight, such as 5 parts by weight to 20 parts by weight, such as 5 parts by weight to 15 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the diol compound is included in the content range, the sensitivity and surface properties of the photosensitive resin composition are excellent.

(A) alkali-soluble resin

As said alkali-soluble resin, a polybenzoxazole precursor, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof can be used.

The polybenzoxazole precursor may include a structural unit represented by the following Formula 14, and the polyimide precursor may include a structural unit represented by the following Formula 15.

[Formula 14]

(In Formula 14,

X ¹ may be a substituted or unsubstituted C6 to C30 aromatic organic group,

Y ¹ may be a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group have.)

[Formula 15]

(In Chemical Formula 15,

X ² may be a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted divalent to hexavalent C1 to C30 aliphatic organic group, or a substituted or unsubstituted divalent to hexavalent C3 to C30 alicyclic organic group There is,

Y ² may be a substituted or unsubstituted C6 to C30 aromatic organic group, a substituted or unsubstituted tetravalent to hexavalent C1 to C30 aliphatic organic group or a substituted or unsubstituted tetravalent to hexavalent C3 to C30 alicyclic organic group have.)

In Formula 14, X ¹ may be a residue derived from an aromatic diamine as an aromatic organic group.

Examples of the aromatic diamine include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino- 4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2 , 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoro rope Ropan, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-pentafluoroethyl Phenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoro Propane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3 -Amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy Hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-2-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-2-trifluoro Rhomethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane and 2- (3-a No-4-hydroxy-6-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane can be used, but is not limited thereto It doesn't happen.

Examples of the X ¹ may be a functional group represented by Formula 16 and Formula 17, but are not limited thereto.

[Formula 16]

[Formula 17]

(In the above formula 16 and 17,

A ¹ may be a single bond, O, CO, CR ⁴⁷ R ⁴⁸ , SO ₂ or S, wherein R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, and specifically, May be a C1 to C30 fluoroalkyl group,

R ⁵⁰ to R ⁵² may each independently be a hydrogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxy group or a thiol group,

n10 may be an integer from 0 to 2, and n11 and n12 may each be an integer from 0 to 3)

In Formula 14, Y ¹ is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic organic group, and may be a residue of a dicarboxylic acid or a residue of a dicarboxylic acid derivative. Specifically, Y ¹ may be an aromatic organic group or a divalent to hexavalent alicyclic organic group.

Specific examples of the dicarboxylic acid derivatives include 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether, bis (phenylcarbonyl chloride). ) Phenone, phthaloyldichloride, terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride, diphenyloxydicarboxylate dibenzotriazole or combinations thereof, but is not limited thereto.

Examples of the Y ¹ may include a functional group represented by the following Chemical Formulas 18 to 20, but are not limited thereto.

[Formula 18]

[Formula 19]

[Formula 20]

(In Formula 18 to Formula 20,

R ⁵³ to R ⁵⁶ may each independently be a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group,

n13 and n14 may each be an integer of 0 to 4, n15 and n16 may each be an integer of 0 to 3,

A ² may be a single bond, O, CR ⁴⁷ R ⁴⁸ , CO, CONH, S or SO ₂ , and R ⁴⁷ and R ⁴⁸ may each independently be a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, and Specifically, may be a C1 to C30 fluoroalkyl group)

In Formula 15, X ² is an aromatic organic group, a divalent to hexavalent aliphatic organic group, or a divalent to hexavalent alicyclic organic group. Specifically, X ² may be an aromatic organic group or a divalent to hexavalent alicyclic organic group.

Specifically, X ² may be a residue derived from aromatic diamine, alicyclic diamine or silicone diamine. At this time, the aromatic diamine, alicyclic diamine and silicone diamine may be used alone or in combination of one or more thereof.

Examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine , Bis [4- (4-aminophenoxy) phenyl] sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] Ether, 1, 4-bis (4-aminophenoxy) benzene, the compound in which the alkyl group or the halogen atom was substituted by these aromatic rings, or a combination thereof is mentioned, But it is not limited to these.

Examples of the alicyclic diamine include, but are not limited to, 1,2-cyclohexyl diamine, 1,3-cyclohexyl diamine, or a combination thereof.

Examples of the silicone diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane , 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, 1,3-bis (aminopropyl) tetra Methyldisiloxane or combinations thereof, but is not limited thereto.

In Formula 15, Y ² is an aromatic organic group, a tetravalent to hexavalent aliphatic organic group, or a tetravalent to hexavalent alicyclic organic group. Specifically, Y ² may be an aromatic organic group or a tetravalent to hexavalent alicyclic organic group.

Y ² may be a residue derived from an aromatic acid dianhydride or an alicyclic acid dianhydride. In this case, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in combination of one or more thereof.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride; Benzophenone tetracarboxylic dianhydride such as benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride ; Oxydiphthalic dianhydride such as 4,4'-oxydiphthalic dianhydride; Biphthalic dianhydrides such as 3,3 ', 4,4'-biphthalic dianhydride (3,3', 4,4'-biphthalic dianhydride); (Hexafluoroisopropyledene) diphthalic dianhydride, such as 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (4,4'-(hexafluoroisopropyledene) diphthalic dianhydride) ; Naphthalene-1,4,5,8-tetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride) and the like, but are not limited thereto.

Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1,2,3,4-cyclobutanetetracarboxylic dianhydride), 1,2,3,4-cyclopentanetetracarboxyl Acid dianhydrides (1,2,3,4-cyclopentanetetracarboxylic dianhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic dianhydride (5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexane-1,2-dicarboxylic anhydride), 4- (2,5-dioxotetrahydrofuran-3-yl) -tetraline-1,2-dicar Acid dianhydride (4- (2,5-dioxotetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (bicyclooctene- 2,3,5,6-tetracarboxylic dianhydride), bicyclooctene-1,2,4,5-tetracarboxylic dianhydride (bicyclooctene-1,2,4,5-tetracarboxylic dianhydride), and the like. It is not limited to this.

The alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 g / mol to 300,000 g / mol, specifically, may have a weight average molecular weight (Mw) of 5,000 g / mol to 30,000 g / mol. When having a weight average molecular weight (Mw) in the above range can be obtained a sufficient residual film ratio in the non-exposed part when developing with an aqueous alkali solution, it can be efficiently patterned.

(B) photosensitive Diazoquinone  compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure can be preferably used.

Representative examples of the photosensitive diazoquinone compound include compounds represented by the following Chemical Formula 21 and the following Chemical Formulas 23 to 25, but are not limited thereto.

[Formula 21]

In Chemical Formula 21,

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

D ¹ to D ³ may be each independently OQ, wherein Q may be a hydrogen atom, a functional group represented by the following Chemical Formula 22a, or a functional group represented by the following Chemical Formula 22b, wherein Q may not be a hydrogen atom at the same time,

n31 to n33 may be each independently an integer of 1 to 5.

[Formula 22a]

[Formula 22b]

[Formula 23]

In Chemical Formula 23,

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

D ⁴ to D ⁶ may be each independently OQ, wherein Q is the same as defined in Formula 16,

n34 to n36 may be each independently an integer of 1 to 5.

[Formula 24]

In Chemical Formula 24,

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

D ⁷ to D ¹⁰ may be each independently a hydrogen atom, a substituted or unsubstituted alkyl group, OQ or NHQ, wherein Q is the same as defined in Formula 21,

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

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

However, at least one of the D ⁷ to D ¹⁰ may be OQ, one aromatic ring may include one to three OQ, and the other aromatic ring may include one to four OQ.

[Formula 25]

In Chemical Formula 25,

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

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

Q is the same as defined in Formula 21 above.

The photosensitive diazoquinone compound is preferably included in an amount of 5 parts by weight to 100 parts by weight, such as 10 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is well formed without residue by exposure, and there is no film thickness loss during development, and a good pattern can be obtained.

(D) solvent

The photosensitive resin composition may include a solvent capable of easily dissolving each component such as the alkali-soluble resin, the photosensitive diazoquinone compound, and the diol compound.

The solvent is an organic solvent, specifically N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol di Ethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate (methyl lactate), ethyl lactate (ethyl lactate), butyl lactate (butyl Lactate), methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate (methyl pyruvate), ethyl pyruvate (ethyl pyruvate), methyl-3-me A oxy propionate or a combination thereof may be used, but is not limited thereto.

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

The solvent is preferably used in 400 parts by weight to 1000 parts by weight, such as 500 parts by weight to 900 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the content of the solvent is within the above range, a film of sufficient thickness can be coated, and solubility and coating property are excellent.

For example, the solvent is mixed with an ether solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and gamma-butyrolactone. It may be one solvent. At this time, the ether solvent may be included in more content than gamma-butyrolactone. For example, the ether solvent may be included in an amount of 50 parts by weight to 100 parts by weight, such as 60 parts by weight to 80 parts by weight, based on 10 parts by weight of the gamma-butyrolactone.

(E) other additives

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

The positive photosensitive resin composition may be malonic acid, 3-amino-1,2-propanediol, leveling agent, or fluorine-based surfactant in order to prevent stains or spots, leveling properties, or generation of residues due to undeveloped coatings. , Additives of a radical polymerization initiator or a combination thereof, and the like. The amount of these additives to be used can be easily adjusted according to the desired physical properties.

In addition, the positive photosensitive resin composition may further include an epoxy compound as an additive to improve adhesion and the like. As the epoxy compound, an epoxy novolac acrylic carboxylate resin, an ortho cresol novolac epoxy resin, a phenol novolac epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A type epoxy resin, an alicyclic epoxy resin or a combination thereof may be used. Can be.

When the epoxy compound is further included, a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator may be further included.

The epoxy compound may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the positive photosensitive resin composition. When the epoxy compound is included in the above range it is possible to improve the adhesion and other properties in storage and economical.

In addition, the positive photosensitive resin composition may further include a heat latent acid generator. Examples of the heat latent acid generator include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid, trifluorobutanesulfonic acid and the like; Alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid and the like; Or combinations thereof, but is not limited thereto.

The heat latent acid generator can smoothly proceed the cyclization reaction even if the curing temperature is lowered as a catalyst for the dehydration reaction of the phenolic hydroxyl group-containing polyamide of the polybenzoxazole precursor and the cyclization reaction.

In addition, suitable surfactants or leveling agents may be further used as additives in order to prevent staining of the film thickness or to improve developability.

(F) other additives

Meanwhile, the photosensitive resin composition may further include additives of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

The silane coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, or the like to improve adhesion to a substrate.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycol. Cidoxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the above range, it is excellent in adhesion, storage property and the like.

In addition, the photosensitive resin composition may further include a surfactant, a surfactant, for example, a fluorine-based surfactant and / or a silicone-based surfactant, in order to improve coating properties and prevent defects.

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like from BM Chemie Co .; Mechapack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^®, etc. from Dai Nippon Inki Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Co., Ltd .; Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^{® from} Asahi Glass Co., Ltd .; May be selected from commercially available under the name, such as Toray Silicone ^® (Note)社SH-28PA, the copper ^® -190, copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

As the silicone surfactant, BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, Commercially available products such as BYK-325 can be used.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the above range, coating uniformity is secured, staining does not occur, and wetting of the IZO substrate or the glass substrate is excellent.

In addition, the photosensitive resin composition may be added a certain amount of other additives such as antioxidants, stabilizers, etc. within a range that does not impair the physical properties.

The photosensitive resin composition according to one embodiment may be positive type or negative type.

Another embodiment provides a photosensitive resin film prepared by exposing, developing, and curing the above-described photosensitive resin composition. For example, the photosensitive resin film may be a black pixel partition layer.

The photosensitive resin film manufacturing method is as follows.

(1) application and coating film forming step

After apply | coating the said photosensitive resin composition to a desired thickness on the board | substrate, such as a glass substrate or an ITO board | substrate which gave predetermined | prescribed pretreatment, using a method, such as a spin or a slit coat method, a roll coat method, the screen printing method, an applicator method, 70 A coating film is formed by heating at 1 degreeC-150 degreeC for 1 to 10 minutes, removing a solvent.

(2) exposure step

After the mask is formed to form a pattern necessary for the obtained photosensitive resin film, active rays of 200 nm to 500 nm are irradiated. As a light source used for irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used, and X-rays, an electron beam, etc. can also be used as needed.

The exposure amount varies depending on the kind of each component of the composition, the compounding amount and the dry film thickness, but when using a high pressure mercury lamp, the exposure amount is 500 mJ / cm ² or less (by a 365 nm sensor).

(3) developing stage

In the developing method, following the exposure step, an alkaline aqueous solution is used as a developing solution to dissolve and remove unnecessary portions, thereby remaining only the exposed portions to form a pattern.

(4) post-processing steps

There is a post-heating step for obtaining an image pattern obtained by development in the above process in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability. For example, it may be heated for 1 hour in a convection oven at 250 ℃ after development.

Another embodiment provides a display device including the photosensitive resin film.

The display device may be an organic light emitting diode (OLED).

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

( Example )

(Alkali Soluble Resin Synthesis)

2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler 12.4 g of 3-hexafluoropropane and 125 g of N-methyl-2-pyrrolidone (NMP) were added and dissolved.

When the solid was completely dissolved, 4.2 g of pyridine was added as a catalyst and 9.4 g of 4,4'-oxydibenzoyl chloride was added to NMP 100 g while maintaining the temperature at 0 ° C to 5 ° C. It was dripped slowly for a minute. After the dropping was completed, the reaction was performed at 0 ° C. to 5 ° C. for 1 hour, and the reaction was performed for 1 hour by raising the temperature to room temperature.

1.1 g of 5-novorene-2,3-dicarboxylic hydride was added thereto, stirred at 70 ° C. for 24 hours, and then the reaction was completed. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed sufficiently with water, and then dried under vacuum at 80 ° C. for at least 24 hours to prepare a polybenzoxazole precursor. Got it.

(Photosensitive resin composition production)

Example  One

10 g of the polybenzoxazole precursor was added to and dissolved in a mixed solvent of 70 g of propylene glycol monomethyl ether and 10 g of γ (gamma) -butyrolactone (GBL), followed by photosensitive diazo having a structure of Formula A 3 g of quinone compounds and 1 g of a diol compound (boiling point: 188.2 ° C, log P: -1.008) represented by the following Formula 5 were added, dissolved, and filtered through a 0.45 µm fluororesin filter to obtain a photosensitive resin composition.

[Formula A]

로 치환되어 있고, 나머지 하나는 수소 원자이다.)(In Formula A, among Q ¹ , Q ² and Q ³ , two are

And the other is a hydrogen atom.)

[Formula 5]

Example  2

In Example 1, except that the diol compound represented by the following formula (6) (boiling point: 182 ℃, log P: -0.655) instead of the diol compound represented by the formula (5) was used in the same manner as in Example 1 And the photosensitive resin composition was manufactured.

[Formula 6]

Example  3

In Example 1, except that the diol compound represented by the following formula (7) (boiling point: 202 ℃, log P: 0.266) instead of the diol compound represented by the formula (5), in the same manner as in Example 1, The photosensitive resin composition was prepared.

[Formula 7]

Example  4

In Example 1, except that the diol compound represented by the formula (8) (boiling point: 160 ℃, log P: -0.863) instead of the diol compound represented by the formula (5) was used in the same manner as in Example 1 And the photosensitive resin composition was manufactured.

[Formula 8]

Example  5

In Example 1, except that the diol compound represented by the formula (9) (boiling point: 195 ℃, log P: -0.740) in place of the diol compound represented by the formula (5) was used in the same manner as in Example 1 And the photosensitive resin composition was manufactured.

[Formula 9]

Example  6

In Example 1, except that the diol compound represented by the following formula (10) (boiling point: 252.9 ℃, log P: 0.374) instead of the diol compound represented by the formula (5), in the same manner as in Example 1, The photosensitive resin composition was prepared.

[Formula 10]

Example  7

In Example 1, except that the diol compound represented by the following formula (11) (boiling point: 291.5 ℃, log P: 0.656) instead of the diol compound represented by the formula (5), in the same manner as in Example 1, The photosensitive resin composition was prepared.

[Formula 11]

Example  8

In Example 1, except that the diol compound represented by the following formula 12 (boiling point: 283.9 ℃, log P: -0.265) instead of the diol compound represented by the formula (5) was used in the same manner as in Example 1 And the photosensitive resin composition was manufactured.

[Formula 12]

Example  9

In Example 1, except that the diol compound represented by the following formula (13) (boiling point: 372.1 ℃, log P: -1.194) instead of the diol compound represented by the formula (5) was used in the same manner as in Example 1 And the photosensitive resin composition was manufactured.

[Formula 13]

Comparative example  One

In Example 1, a photosensitive resin composition was manufactured in the same manner as in Example 1, except that the diol compound represented by Chemical Formula 5 was not used.

Comparative example  2

Example 1, except that the diol compound represented by the following formula C-1 (boiling point: 146.0 ° C., log P: -0.692) instead of the diol compound represented by the formula (1-1) was used In the same manner as in Example 1, a photosensitive resin composition was prepared.

[Formula C-1]

Comparative example  3

Example 1, except that the diol compound represented by the following formula C-2 (boiling point: 228 ° C, log P: -2.203) instead of the diol compound represented by the formula (1-1) was used In the same manner as in 1, a photosensitive resin composition was prepared.

[Formula C-2]

Comparative example  4

Example 1, except that the diol compound represented by the following formula C-3 (boiling point: 488.8 ° C, log P: 5.947) instead of the diol compound represented by the formula 1-1, Example 1 In the same manner as in the above, a photosensitive resin composition was prepared.

[Formula C-3]

Evaluation 1: Sensitivity

The photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 4 were applied to 10 cm * 10 cm ITO glass (30 kΩ resistance), heated to a contact type for 1 minute on a 120 ° C hotplate, A 1.8 mu m thick coating film was formed. After exposing the coating-coated substrate with a change in the amount of exposure to Ushio's UX-1200SM-AKS02 using a mask engraved with patterns of various sizes, it was developed by dissolving the exposed part by developing with a TMAH solution of 2.38% at room temperature. After that, washing with pure water for 50 seconds to form a pattern.

Sensitivity was calculated by confirming the energy to implement the 10 ㎛ pattern based on the size of the 10 ㎛ L / S pattern measured using the Olympus MX51T-N633MU, the results are shown in Table 1 below.

Evaluation 2: Surface crack (stain)

The photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 4 were applied to 10 cm * 10 cm ITO glass (30 kΩ resistance) and heated to a contact type for 4 minutes on a hot plate at 140 ° C. A 5.0 μm thick coating film was formed. The coated substrate was observed with a surface crack (stain) in the polarization mode using the Olympus MX51T-N633MU, the results are shown in Table 1 below.

surface crack (Stain) Criteria

○: hardly observed surface cracks (stains)

X: Many surface cracks (stains) are observed

Developing time (seconds) Sensitivity (mJ / cm ² ) Surface Cracks Example 1 60 100 ○ Example 2 60 95 ○ Example 3 60 95 ○ Example 4 60 100 ○ Example 5 60 95 ○ Example 6 60 90 ○ Example 7 60 90 ○ Example 8 60 90 ○ Example 9 60 90 ○ Comparative Example 1 60 150 X Comparative Example 2 60 145 X Comparative Example 3 60 140 X Comparative Example 4 60 150 X

Through the above Table 1, the photosensitive resin composition according to one embodiment has a boiling point of 160 ℃ to 400 ℃, by including a diol compound having a log P of -1.9 to 1.0, the photosensitive resin composition not containing the diol compound It can be seen that it has better sensitivity and surface properties.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (10)

(A) alkali-soluble resins;
(B) photosensitive diazoquinone compound;
(C) a diol compound having a boiling point of 195 ° C to 400 ° C and a log P of -1.9 to 1.0; And
(D) solvent
Including,
The diol compound is a photosensitive resin composition represented by any one of the following formulas (2) to (4) and (7):
[Formula 2]

In Chemical Formula 2,
R ³ to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, provided that at least one of R ³ to R ⁵ is a substituted or unsubstituted C1 to C10 alkyl group,
[Formula 3]

In Chemical Formula 3,
R ⁶ to R ⁹ are each independently a C1 to C10 alkyl group unsubstituted or substituted with a hydrogen atom, a hydroxy group or a hydroxy group, provided that two of R ⁶ to R ⁹ are necessarily C1 to C10 alkyl groups substituted with a hydroxy group or a hydroxy group ,
L ¹ is * -CH ₂ -CH _2- * or * -CH = CH- *,
[Formula 4]

In Chemical Formula 4,
R ¹⁰ to R ¹³ are each independently a hydrogen atom or a hydroxyl group, provided that any one of R ¹⁰ and R ¹¹ is a hydroxy group and any one of R ¹² and R ¹³ is a hydroxy group:
[Formula 7]

.
The method of claim 1,
The photosensitive resin composition whose log P of the said diol compound is -1.2-0.7.
delete The method of claim 1,
The diol compound represented by any one of Formulas 2 to 4 is a photosensitive resin composition represented by any one selected from the group consisting of the following formulas (9) to (13).
[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

The method of claim 1,
The alkali-soluble resin is a polybenzoxazole precursor, a polyimide precursor, a novolak resin, a bisphenol A resin, a bisphenol F resin, an acrylate resin, or a combination thereof.
The method of claim 1,
The photosensitive resin composition,
Per 100 parts by weight of the alkali-soluble resin
5 to 100 parts by weight of the photosensitive diazoquinone compound,
3 to 30 parts by weight of the diol compound,
Photosensitive resin composition comprising 400 parts by weight to 1000 parts by weight of the solvent.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
The photosensitive resin film manufactured using the photosensitive resin composition of any one of Claims 1, 2, and 4-7.
A display apparatus comprising the photosensitive resin film of claim 8.
The method of claim 9,
The display device is an organic light emitting device (OLED).