Photosensitive resin composition and manufacturing method of display device using the same

1 . A photosensitive resin composition comprising:

a silsesquioxane-based copolymer obtained by copolymerizing:

a first monomer,

a second monomer represented by Chemical Formula 2,

a third monomer represented by Chemical Formula 3, and

a fourth monomer represented by Chemical Formula 4; and

a quinonediazide-based photosensitive compound,

(R 4 ) n —Si(R 5 ) 4-n   Chemical Formula 2

Si(R 6 ) 4   Chemical Formula 3

(R 7 ) 3 —Si—R 8 —Si—(R 7 ) 3   Chemical Formula 4

wherein, in Chemical Formulas 2 to 4,

R 5 to R 7 are each independently a substituted or unsubstituted alkoxy group having one to three carbon atoms,

R 4 is a substituted or unsubstituted alkyl group having one to three carbon atoms, or a substituted or unsubstituted aryl group having six to twelve ring-forming carbon atoms,

R 8 is a substituted or unsubstituted arylene group having six to twelve ring-forming carbon atoms, and

n is an integer from one to three, and

wherein the first monomer, the second monomer, the third monomer, and the fourth monomer are different from each other,

wherein the third monomer comprises at least one of tetramethoxysilane, tetraethoxysilane, or tetrapropoxysilane,

wherein the first monomer comprises a (1-1)-st monomer and a (1-2)-nd monomer different from the (1-1)-st monomer, and

the (1-1)-st monomer is represented by Chemical Formula 1-1, and the (1-2)-nd monomer is represented by Chemical Formula 1-2,

R 1 —R 2 —Si(R 3 ) 3   Chemical Formula 1-1

R 1 —R 2 —Si(R 3 ) 3 , and  Chemical Formula 1-2

wherein, in Chemical Formula 1-1 and Chemical Formula 1-2, R 1-1 is a substituted or unsubstituted mercapto group, R 1-2 is a substituted or unsubstituted furanyl group, R 2 is a direct linkage, or a substituted or unsubstituted divalent alkyl group having three to six carbon atoms, and R 3 is a substituted or unsubstituted alkoxy group having one to three carbon atoms.

2 . The photosensitive resin composition of claim 1 , wherein the silsesquioxane-based copolymer has a weight average molecular weight of about 5000 to about 15000.

3 . The photosensitive resin composition of claim 1 , wherein the silsesquioxane-based copolymer has a dispersity of about 2.0 to about 4.0.

4 . The photosensitive resin composition of claim 1 , wherein the silsesquioxane-based copolymer comprises a repeating unit in which the combination order of the first monomer, the second monomer, the third monomer, and the fourth monomer is random.

5 . The photosensitive resin composition of claim 1 , wherein the second monomer represented by Chemical Formula 2 is represented by Chemical Formula 2-1 or Chemical Formula 2-2,

R 4 —Si(R 5 ) 3   Chemical Formula 2-1

(R 4 ) 2 —Si(R 5 ) 2 , and  Chemical Formula 2-2

wherein, in Chemical Formula 2-1 and Chemical Formula 2-2, R 4 and R 5 are the same as defined in Chemical Formula 2.

6 . The photosensitive resin composition of claim 1 , wherein the first monomer comprises 3-(mercapto)propyltrimethoxysilane and trimethoxy (2-furanyl) silane.

7 . The photosensitive resin composition of claim 1 , wherein the second monomer comprises at least one of methyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, or diphenyldiethoxysilane.

8 . The photosensitive resin composition of claim 1 , wherein the fourth monomer comprises at least one of 1,4-bis(triethoxysilyl)benzene, 1,3bis(triethoxysilyl)benzene, or 4,4-bis(triethoxysilyl)-1,1′-biphenyl.

9 . The photosensitive resin composition of claim 1 , wherein the silsesquioxane-based copolymer comprises a repeating unit represented by Chemical Formula 5,

10 . The photosensitive resin composition of claim 1 , wherein, with respect to the total amount of the first monomer, the second monomer, the third monomer, and the fourth monomer, about 5% to about 25% by weight of the first monomer, about 20% to about 60% by weight of the second monomer, about 20% to about 40% by weight of the third monomer, and about 5% to about 25% by weight of the fourth monomer are included.

11 . The photosensitive resin composition of claim 1 , further comprising a glycol-based solvent,

wherein, with respect to the total amount of the photosensitive resin composition, about 10% to about 40% by weight of the silsesquioxane-based copolymer, about 5% to about 20% by weight of the quinonediazide-based photosensitive compound, and about 40% to about 85% by weight of the glycol-based solvent are included.

12 . The photosensitive resin composition of claim 11 , wherein the quinonediazide-based photosensitive compound comprises at least one of 1,4-benzenediol, 1,2-benzenediol, 4,4′-dihydroxy-biphenyl, bisphenol-A, α,α-bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl)-ethylbenzene, or 4,4′,4″-trihydroxyphenylmethane which contains, as a substituent, a naphthoquinone-1,2-diazide-4-sulfonic acid ester group or a naphthoquinone-1,2-diazide-5-sulfonic acid ester group.

13 . The photosensitive resin composition of claim 11 , wherein the glycol-based solvent comprises at least one of butyl acetate, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate, ethyl lactate, propylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, diethylene glycol ethyl ether, or dipropylene glycol methyl ether.

14 . A photosensitive resin composition comprising:

a silsesquioxane-based copolymer obtained by copolymerizing

a first monomer,

a second monomer,

a third monomer, and

a fourth monomer,

which are different from each other;

a quinonediazide-based photosensitive compound;

a surfactant; and

a glycol-based solvent,

wherein the third monomer is represented by Chemical Formula 3,

Si(R 6 ) 4 , and  Chemical Formula 3

wherein

R 6 is a substituted or unsubstituted alkoxy group having one to three carbon atoms,

wherein the third monomer comprises at least one of tetramethoxysilane, tetraethoxysilane, or tetrapropoxysilane,

wherein the first monomer comprises a (1-1)-st monomer and a (1-2)-nd monomer different from the (1-1)-st monomer, and

the (1-1)-st monomer is represented by Chemical Formula 1-1, and the (1-2)-nd monomer is represented by Chemical Formula 1-2,

R 1 —R 2 —Si(R 3 ) 3   Chemical Formula 1-1

R 1 —R 2 —Si(R 3 ) 3 , and  Chemical Formula 1-2

wherein, in Chemical Formula 1-1 and Chemical Formula 1-2, R 1-1 is a substituted or unsubstituted mercapto group, R 1-2 is a substituted or unsubstituted furanyl group, R 2 is a direct linkage, or a substituted or unsubstituted divalent alkyl group having three to six carbon atoms, and R 3 is a substituted or unsubstituted alkoxy group having one to three carbon atoms.

15 . The photosensitive resin composition of claim 14 , wherein the second monomer is represented by Chemical Formula 2, and the fourth monomer is represented by Chemical Formula 4,

(R 4 ) n —Si(R 5 ) 4-n   Chemical Formula 2

(R 7 ) 3 —Si—R 8 —Si—(R 7 ) 3 , and  Chemical Formula 4

wherein, in Chemical Formulas 2 to 4, R 4 is a substituted or unsubstituted alkyl group having one to three carbon atoms, or a substituted or unsubstituted aryl group having six to twelve ring-forming carbon atoms,

R 5 and R 7 are each independently a substituted or unsubstituted alkoxy group having one to three carbon atoms,

R 8 is a substituted or unsubstituted arylene group having six to twelve ring-forming carbon atoms, and

n is an integer from one to three.

16 . A manufacturing method of a display device, the manufacturing method comprising:

forming an organic insulating layer on a base layer; and

forming a pixel-defining film on the organic insulating layer,

wherein at least one of the organic insulating layer or the pixel-defining film is formed of a photosensitive resin composition, and

the photosensitive resin composition comprises a silsesquioxane-based copolymer obtained by copolymerizing a first monomer comprising a (1-1)-st monomer and a (1-2)-nd monomer different from the (1-1)-st monomer, the (1-1)-st monomer being represented by Chemical Formula 1-1, and the (1-2)-nd monomer being represented by Chemical Formula 1-2, a second monomer represented by Chemical Formula 2, a third monomer represented by Chemical Formula 3, and a fourth monomer represented by Chemical Formula 4,

R 1-1 —R 2 —Si(R 3 ) 3   Chemical Formula 1-1

R 1-2 —R 2 —Si(R 3 ) 3   Chemical Formula 1-2

(R 4 ) n —Si(R 5 ) 4-n   Chemical Formula 2

Si(R 6 ) 4   Chemical Formula 3

(R 7 ) 3 —Si—R 8 —Si—(R 7 ) 3 , and  Chemical Formula 4

wherein, in Chemical Formulas 1-1, 1-2, and 2 to 4,

R 2 is a direct linkage, or a substituted or unsubstituted divalent alkyl group having three to six carbon atoms,

R 3 , and R 5 to R 7 are each independently a substituted or unsubstituted alkoxy group having one to three carbon atoms,

R 4 is a substituted or unsubstituted alkyl group having one to three carbon atoms, or a substituted or unsubstituted aryl group having six to twelve ring-forming carbon atoms,

R 8 is a substituted or unsubstituted arylene group having six to twelve ring-forming carbon atoms, and

n is an integer from one to three,

R 1-1 is a substituted or unsubstituted mercapto group, and

R 1-2 is a substituted or unsubstituted furanyl group.

17 . The manufacturing method of claim 16 , wherein the forming of the organic insulating layer comprises:

forming a preliminary organic insulating layer by coating the base layer with the photosensitive resin composition; and

selectively exposing and developing the preliminary organic insulating layer.

18 . The manufacturing method of claim 16 , wherein the forming of the pixel-defining film comprises:

forming a preliminary pixel-defining film by coating the organic insulating layer with the photosensitive resin composition; and

selectively exposing and developing the preliminary pixel-defining film.