Positive photosensitive material
View Patent ↗The invention relates to a novel positive working photosensitive composition having: at least one photoacid generator; at least one novolak polymer; at least one polymer, having a polymer backbone, said polymer comprising a structure of the following formula: wherein R 1 -R 5 are, independently, —H or —CH 3 , A is a linear or branched C 1 -C 10 alkylene group, B is a C 1 -C 12 alkyl or alicyclic group, D is a linking group that may be a chemical bond, a carboxylate group, wherein the carbonyl carbon is bonded to the polymer backbone, or a —COOCH 2 — group, wherein the carbonyl carbon is bonded to the polymer backbone, Ar is a substituted or unsubstituted aromatic group or heteroaromatic group, E is a linear or branched C 2 -C 10 alkylene group, G is an acid cleavable group. The invention further relates to a process for using the novel composition for forming an image.
1. A positive working photosensitive composition comprising:
a) at least one photoacid generator;
b) at least one novolak polymer, which comprises one or more cresylic repeat units chosen from o-cresol, p-cresol or m-cresol;
c) at least one polymer, having a polymer backbone, said polymer consisting of a structure of the following formula:
wherein R 1 -R 5 are, independently, —H, F or —CH 3 , A is an ethylene group or a 1,2-propylene group, B is a C 1 -C 12 alkyl or alicyclic group, D is a —COOCH 2 — group or —COO— group wherein the carbonyl carbon is bonded to the polymer backbone and Ar is a phenyl group, E is a linear or branched C 2 -C 10 alkylene group, G is an acid cleavable group, v is 0-10 mole %, w is 7 mole %-15 mole %, x is 14 mole %-80 mole %, y is 25 mole %-35 mole % and z is 20 mole %-50 mole %.
2. The positive working photosensitive material of claim 1 , wherein the at least one photoacid generator is an onium salt, a dicarboximidyl sulfonate ester, an oxime sulfonate ester, a diazo(sulfonyl methyl) compound, a disulfonyl methylene hydrazine compound, a nitrobenzyl sulfonate ester, a biimidazole compound, a diazomethane derivative, a glyoxime derivative, a β-ketosulfone derivative, a disulfone derivative, a sulfonic acid ester derivative, an imidoyl sulfonate derivative, or a halogenated triazine compound.
3. The positive working photosensitive composition of claim 1 , wherein at least one novolak polymer comprises one or more cresylic repeat units chosen from p-cresol or m-cresol.
4. The positive working photosensitive material of claim 3 , wherein at least one novolak polymer is a cresylic novolak comprising at least 80 mole percent m-cresol.
5. The positive working photosensitive composition of claim 1 , wherein A is an ethylene group and B is a methyl group, an ethyl group, a propyl group or a butyl group.
6. The positive working photosensitive composition of claim 1 , wherein G is an acid cleavable group chosen from the group consisting of a t-butyl group, a tetrahydropyran-2-yl group, a tetrahydrofuran-2-yl group, a 4-methoxytetrahydropyran-4-yl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-propoxyethyl group, a 3-oxocyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 8-methyl-8-tricyclo[5.2.1.0 2,6]decyl group, a 1,2,7,7-tetramethyl-2-norbornyl group, a 2-acetoxymenthyl group, a 2-hydroxymethyl group, a 1-methyl-1-cyclohexylethyl group, a 4-methyl-2-oxotetrahydro-2H-pyran-4-yl group, a 2,3-dimethylbutan-2-yl group, a 2,3,3-trimethylbutan-2-yl group, a 1-methyl cyclopentyl group, a 1-ethyl cyclopentyl group, a 1-methyl cyclohexyl group, 1-ethyl cyclohexyl group, a 1,2,3,3-tetramethylbicyclo[2.2.1]heptan-2-yl group, a 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-yl group, a 2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl group, a 2,3-dimethylpentan-3-yl group, and a 3-ethyl-2-methylpentan-3-yl group.
7. The positive working photosensitive composition of claim 1 , wherein G is an acid cleavable group chosen from a t-butyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 8-methyl-8-tricyclo[5.2.1.0 2,6]decyl group, a 1,2,7,7-tetramethyl-2-norbomyl group, a 2-acetoxymenthyl group, a 1-methyl-1-cyclohexylethyl group, a 2,3-dimethylbutan-2-yl group, a 2,3,3-trimethylbutan-2-yl group, a 1-methyl cyclopentyl group, a 1-ethyl cyclopentyl group, a 1-methyl cyclohexyl group, 1-ethyl cyclohexyl group, a 1,2,3,3-tetramethylbicyclo[2.2.1]heptan-2-yl group, a 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-yl group, a 2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl group, a 2,3-dimethylpentan-3-yl group, or a 3-ethyl-2-methylpentan-3-yl group.
8. The positive working photosensitive composition of claim 1 , wherein A is a ethylene group, and D is a —COOCH 2 .
9. The positive working photosensitive composition of claim 8 , wherein, when y>0 mole %, E is a 1,2-propylene group.
10. A method of forming a positive relief image comprising:
a) forming a photosensitive layer by applying the positive working photosensitive composition of claim 1 to a substrate;
b) image-wise exposing the photosensitive layer to actinic radiation to form a latent image;
c) developing the latent image in a developer,
d) wherein the image-wise exposed photosensitive layer is optionally thermally treated.
11. The method of claim 10 , wherein the developer comprises at least one compound chosen from tetra (C1-C4 alkyl)ammonium hydroxide, choline hydroxide, lithium hydroxide, sodium hydroxide, or potassium hydroxide.
12. The method of claim 10 , wherein the wavelength of the actinic radiation is from about 240 nm to about 450 nm.
13. The positive working photosensitive composition of claim 1 wherein in the polymer's structure formula, v is 3 mole %-8 mole %.
14. The positive working photosensitive composition of claim 1 wherein in the polymer's structure formula, v is 4 mole %-6 mole %, w is 9 mole %-12 mole %, and y is 28 mole %-33 mole %.
15. The positive working photosensitive composition of claim 1 wherein in the polymer's structure formula, w is 9 mole %-12 mole %, and y is 28 mole %-33 mole %.
16. The positive working photosensitive composition of claim 1 wherein the photoacid generator is selected from the group consisting of a dicarboximidyl sulfonate ester, an oxime sulfonate ester, a diazo(sulfonyl methyl) compound, a disulfonyl methylene hydrazine compound, a nitrobenzyl sulfonate ester, a biimidazole compound, a diazomethane derivative, a glyoxime derivative, a β-ketosulfone derivative, a disulfone derivative, a sulfonic acid ester derivative, an imidoyl sulfonate derivative, and a halogenated triazine compound.
17. The positive working photosensitive composition of claim 16 wherein the imidoyl sulfonate derivative is selected from the group consisting of 1,3-dioxoisoindolin-2-yl trifluoromethanesulfonate, 1,3-dioxoisoindolin-2-yl nonafluoro-n-butane sulfonate, 1,3-dioxoisoindolin-2-yl perfluoro-n-octane sulfonate, 3-dioxoisoindolin-2-yl 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 3-dioxoisoindolin-2-yl N-[2-(tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecan-3-yl)-1,1-difluoroethanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl nonafluoro-n-butane sulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl perfluoro-n-octanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, and 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl N-[2-(tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecan-3-yl)-1,1-difluoroethanesulfonate.
18. The positive working photosensitive composition of claim 16 wherein the imidoyl sulfonate derivative is selected from the group consisting of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl nonafluoro-n-butane sulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl perfluoro-n-octanesulfonate, 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, and 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl N-[2-(tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecan-3-yl)-1,1-difluoroethanesulfonate.