Photosensitive resin composition and cured film prepared therefrom

Abstract

The present invention relates to a photosensitive resin composition and to a cured film formed therefrom, wherein the photosensitive resin composition can improve the sensitivity by using an alcoholic solvent, along with a siloxane polymer and a quinone diazide compound conventionally used, which enhances the solubility in a developer through an interaction between the alcohol and the diazonaphthoquinone (DNQ) group in the quinone diazide compound, as well as can form a cure film having excellent film retention rate even after post-bake.

Claims

1. A photosensitive resin composition comprising: (A) a siloxane polymer; (B) a 1,2-quinonediazide-based compound; and (C) a solvent comprising an alcohol, wherein the alcohol is at least one selected from the group consisting of isopropyl alcohol, n-propyl alcohol, sec-butyl alcohol, t-butyl alcohol, and allyl alcohol, wherein the alcohol is comprised in an amount of 5 to 60 wt % based on the total weight of the solvent (C), and wherein the resin composition is a positive-type photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein the siloxane polymer (A) comprises at least one structural unit derived from a silane compound represented by Formula 1:
(R.sup.1).sub.nSi(OR.sup.2).sub.4n[Formula 1] wherein R.sup.1 is C.sub.1-12 alkyl, C.sub.2-10 alkenyl, or C.sub.6-15 aryl, wherein, in case that a plurality of R.sup.1 are present in the same molecule, respective R.sup.1s may be the same or different, and in case that R.sup.1 is alkyl, alkenyl, or aryl, its hydrogen atoms may be substituted in part or entirely, and wherein R.sup.1 may comprise a structural unit containing a heteroatom; R.sup.2 is hydrogen, C.sub.1-6 alkyl, C.sub.2-6 acyl, or C.sub.6-15 aryl, wherein, in case that a plurality of R.sup.2 are present in the same molecule, respective Res may be the same or different, and in case that R.sup.2 is alkyl, acyl, or aryl, its hydrogen atoms may be substituted in part or entirely; and n is an integer of 0 to 3.

3. The photosensitive resin composition according to claim 2, wherein the siloxane polymer (A) comprises a structural unit derived from a silane compound represented by Formula 1 where n is 0, in an amount of 10 to 40 mole %, based on an Si atomic mole number.

4. The photosensitive resin composition according to claim 1, which further comprises an epoxy compound.

5. The photosensitive resin composition according to claim 1, which further comprises at least one silane compound represented by Formula 2:
(R.sup.3).sub.nSi(OR.sup.4).sub.4n[Formula 2] wherein R.sup.3 is C.sub.1-12 alkyl, C.sub.2-10 alkenyl, or C.sub.6-15 aryl, wherein, in case that a plurality of R.sup.3 are present in the same molecule, respective R.sup.3s may be the same or different, and in case that R.sup.3 is alkyl, alkenyl, or aryl, its hydrogen atoms may be substituted in part or entirely, and wherein R.sup.3 may comprise a structural unit containing a heteroatom; R.sup.4 is hydrogen, C.sub.1-6 alkyl, C.sub.2-6 acyl, or C.sub.6-15 aryl, wherein, in case that a plurality of R.sup.4 are present in the same molecule, respective R.sup.4s may be the same or different, and in case that R.sup.4 is alkyl, acyl, or aryl, its hydrogen atoms may be substituted in part or entirely; and n is an integer of 0 to 3.

Description

EXAMPLE

Synthesis Example 1

(1) Synthesis of a Siloxane Polymer (A-1)

(2) To a reactor equipped with a reflux condenser, 40 wt % of phenyltrimethoxysilane, 15 wt % of methyltrimethoxysilane, 20 wt % of tetraethoxysilane, and 20 wt % of pure water were added, and then 5 wt % of propylene glycol monomethyl ether acetate (PGMEA) were added thereto, followed by refluxing and stirring the mixture in the presence of 0.1 wt % of an oxalic acid catalyst for 7 hours and then cooling it. After that, the reaction product was diluted with PGMEA so that the solid content was 40 wt %. A siloxane polymer having a weight average molecular weight of about 5,000 to 8,000 Da was synthesized.

Synthesis Example 2

(3) Synthesis of a Siloxane Polymer (A-2) To a reactor equipped with a reflux condenser, 20 wt % of phenyltrimethoxysilane, 30 wt % of methyltrimethoxysilane, 20 wt % of tetraethoxysilane, and 15 wt % of pure water were added, and then 15 wt % of PGMEA were added thereto, followed by refluxing and stirring the mixture in the presence of 0.1 wt % of an oxalic acid catalyst for 6 hours and then cooling it. After that, the reaction product was diluted with PGMEA so that the solid content was 30 wt %. A siloxane polymer having a weight average molecular weight of about 8,000 to 13,000 Da was synthesized.

Synthesis Example 3

(4) Synthesis of a Siloxane Polymer (A-3)

(5) To a reactor equipped with a reflux condenser, 20 wt % of phenyltrimethoxysilane, 30 wt % of methyltrimethoxysilane, 20 wt % of tetraethoxysilane, and 15 wt % of pure water were added, and then 15 wt % of PGMEA were added thereto, followed by refluxing and stirring the mixture in the presence of 0.1 wt % of an oxalic acid catalyst for 5 hours, and then cooling it. After that, the reaction product was diluted with PGMEA so that the solid content was 30 wt %. A siloxane polymer having a weight average molecular weight of about 9,000 to 15,000 Da was synthesized.

(6) TABLE-US-00001 TABLE 1 Siloxane Phenyl- Methyl- Solid Wt. avg. polymer trimethoxy- trimethoxy- Tetraethoxy- Pure content M.W. (A) silane silane silane water PGMEA (wt %) (Da) Syn. Ex. 1 40 15 20 20 5 40 5,000-8,000 (A-1) Syn. Ex. 2 20 30 20 15 15 30 8,000-13,000 (A-2) Syn. Ex. 3 20 30 20 15 15 30 9,000-15,000 (A-3)

Synthesis Example 4

(7) Synthesis of an Epoxy Compound

(8) A three-necked flask equipped with a condenser was placed on a stirrer with an automatic temperature controller. 100 parts by weight of a monomer including glycidyl methacrylate (100 mole %), 10 parts by weight of 2,2-azobis(2-methylbutyronitrile), and 100 parts by weight of PGMEA were put in the flask, and the flask was charged with nitrogen. The flask was heated to 80 C. while stirring the mixture slowly, and the temperature was maintained for 5 hours to obtain an epoxy compound having a weight average molecular weight of about 6,000 to 10,000 Da. Then PGMEA was added thereto to adjust the solid content thereof to 20 wt %.

EXAMPLES AND COMPARATIVE EXAMPLES

(9) Preparation of Photosensitive Resin Compositions

(10) Photosensitive resin compositions of the following Examples and Comparative Examples were prepared using the compounds obtained in the above Synthesis Examples.

(11) Besides, the following compounds were used in the Examples and Comparative

EXAMPLES

(12) TABLE-US-00002 TABLE 2 Solid content Component (wt %) Manufacturer 1,2-Quinonediazide- B-1 TPA-517 100 Miwon based compound Commercial B-2 BIOC 25 100 Miwon Commercial B-3 TPA-523 100 Miwon Commercial Solvent Alcohol C-1 Isopropyl alcohol Solvent Sigma- (boiling point: 82.4 C.) Aldrich C-2 Propylene glycol monomethyl Chemtronics ether (boiling point: 118 C.) C-3 Methanol Sigma- (boiling point: 64.6 C.) Aldrich C-4 Ethanol Fisher (boiling point: 78.4 C.) C-5 Diacetone ethanol Sigma- (boiling point: 166 C.) Aldrich C-6 Dipropylene glycol dimethyl Hannong ether (boiling point: 175 C.) Chemicals Non- C-7 PGMEA Chemtronics Alcohol Epoxy compound D GHPO3 20 Miwon Commercial Silane compound E Z-6124 Silane 100 Xiameter (phenyltrimethoxysilane) Surfactant F Silicon-based leveling 100 Dow Corning surfactant, FZ-2122 Tory

Example 1

(13) 32.85 parts by weight of a solution of the siloxane polymer (A-1) prepared in Synthesis Example 1, 32.85 parts by weight of a solution of the siloxane polymer (A-2) prepared in Synthesis Example 2, and 34.3 parts by weight of a solution of the siloxane polymer (A-3) prepared in Synthesis Example 3 were mixed. Then, 16.7 parts by weight of TPA-517 (B-1) as a 1,2-quinonediazide-based compound, 0.7 part by weight of BIOC 25 (B-2), 14.3 parts by weight of the epoxy compound (D) prepared in Synthesis Example 4, 6.9 parts by weight of a silane monomer (E), and 0.3 part by weight of a surfactant based on 100 parts by weight of the total siloxane polymers were uniformly mixed. This mixture was dissolved in a mixture of an alcohol and PGMEA (isopropyl alcohol (C-1):PGMEA=15:85 by weight) as a solvent such that the solid content was 22 wt %. The mixture was stirred for 5 hours and filtered through a membrane filter having 0.2 m pores to obtain a composition solution having a solid content of 22 wt %.

Examples 2 to 4 and Comparative Examples 1 to 5

(14) Composition solutions were prepared in the same manner as in Example 1, except that the components and/or their amounts were changed as described in Table 3 below.

(15) TABLE-US-00003 TABLE 3 Based on 100 parts by Sur- weight of Siloxane polymer (A) 1,2-Quinonediazide Solvent (C) Epoxy Silane fac- siloxane (sum = 100) compound (B) C-7 Comp. Comp. tant polymers A-1 A-2 A-3 B-1 B-2 B-3 Alcohol (PGMEA) (D) (E) (F) Ex. 1 32.85 32.85 34.3 16.7 0.7 0 C-1 15 85 14.3 6.9 0.3 Ex. 2 32.85 32.85 34.3 16.7 0.7 0 C-1 20 80 14.3 6.9 0.3 Ex. 3 100 0 0 0 3.9 8.4 C-2 20 80 0 0 0.3 Ex. 4 100 0 0 0 3.9 8.4 C-2 50 50 0 0 0.3 C. Ex. 1 32.85 32.85 34.3 16.7 0.7 0 100 14.3 6.9 0.3 C. Ex. 2 100 0 0 0 3.9 8.4 100 0 0 0.3 C. Ex. 3 32.85 32.85 34.3 16.7 0.7 0 C-3 20 80 14.3 6.9 0.3 C. Ex. 4 100 0 0 0 3.9 8.4 C-4 20 80 0 0 0.3 C. Ex. 5 100 0 0 0 3.9 8.4 C-5 20 80 0 0 0.3 C. Ex. 6 32.85 32.85 34.3 16.7 0.7 0 C-6 20 80 14.3 6.9 0.3

Test Example 1: Evaluation of Sensitivity

(16) The compositions prepared in the Examples and in the Comparative Examples above each were coated on a glass substrate by spin coating. The coated substrate was then pre-baked on a hot plate kept at 110 C. for 90 seconds to form a dried film in a thickness of 3 m. The dried film was exposed, through a mask having a pattern of square holes in sizes ranging from 1 m to 30 m, to light at an exposure rate of 0 to 200 mJ/cm.sup.2 based on a wavelength of 365 nm for a certain time period using an aligner (model name: MA6), which emits light having a wavelength of 200 nm to 450 nm. It was then developed with an aqueous developer of 2.38 wt % tetramethylammonium hydroxide through puddle nozzles at 23 C. The exposed film thus obtained was then heated in a convection oven at 230 C. for 30 minutes to prepare a cured film.

(17) For the hole pattern formed through a mask having a size of 10 m, the amount of exposure energy required for attaining a critical dimension (CD, unit: m) of 10 m was measured. The lower the exposure energy is, the better the sensitivity of a cured film is. The sensitivity was also converted to a percent unit for the same composition. Here, Comparative Examples 1 and 2 were used as references. The lower the sensitivity % converted is, the better the sensitivity in mJ/cm.sup.2 is.
Sensitivity (% converted)=sensitivity (mJ/cm.sup.2)100/reference sensitivity for the same composition (mJ/cm.sup.2)

Test Example 2: Evaluation of Film Retention Rate

(18) The compositions prepared in the Examples and in the Comparative Examples above each were coated on a silicon nitride substrate by spin coating. The coated substrate was then pre-baked on a hot plate kept at 110 C. for 90 seconds to form a dried film in a thickness of 3 m. The dried film was developed with an aqueous developer of 2.38 wt % tetramethylammonium hydroxide through puddle nozzles at 23 C. The developed film was then heated in a convection oven at 230 C. for 30 minutes to prepare a cured film. The film retention rate (%) was yielded by calculating the ratio in percent of the thickness of the finally cured film to that of the film immediately after the pre-bake by using a non-contact type film thickness measurement equipment (SNU Precision). The higher the numerical value is, the better the film retention rate is.
Film retention rate (%)=(thickness of finally cured film/thickness of film after pre-bake)100

(19) The test results are shown in Table 4 below.

(20) TABLE-US-00004 TABLE 4 Sensitivity Film mJ/cm.sup.2 % converted retention (10 m/10 m) (10 m/10 m) rate (%) Ex. 1 28 80 relative to Comp. Ex. 1 93 Ex. 2 17.5 50 relative to Comp. Ex. 1 92 Ex. 3 19.3 69 relative to Comp. Ex. 2 94 Ex. 4 21 75 relative to Comp. Ex. 2 93 Comp. Ex. 1 35 100 relative to Comp. Ex. 1 92 Comp. Ex. 2 28 100 relative to Comp. Ex. 2 94 Comp. Ex. 3 35 100 relative to Comp. Ex. 1 92 Comp. Ex. 4 28 100 relative to Comp. Ex. 2 94 Comp. Ex. 5 21 75 relative to Comp. Ex. 2 83 Comp. Ex. 6 19.3 55 relative to Comp. Ex. 1 76

(21) As shown in Table 4 above, all the cured films formed from the compositions of the Examples, which fall within the scope the present invention, had excellent sensitivity and film retention rate. In contrast, the cured films formed from the compositions according to the Comparative Examples, which do not fall within the scope of the present invention, showed at least one unfavorable property.