Resin composition

Abstract

There is provided a thermosetting resin composition. A resin composition, comprising: (A) component, (B) component, and a solvent, wherein the content of the (B) component is 0.1 to 5.0% by mass with respect to the content of all components of the resin composition, except the solvent: (A) component: a self-crosslinking copolymer having a structural unit of Formula (1) below and a structural unit of Formula (2) below (B) component: a compound of Formula (3) below ##STR00001##
wherein R.sup.0 is each independently a hydrogen atom or a methyl group, X is O or NH, R.sup.1 is a single bond or an alkylene group, R.sup.2 is an alkyl group, a is an integer of 1 to 5, b is an integer of 0 to 4, R.sup.3 is a divalent organic group having an ether bond and/or an ester bond, R.sup.5 is an alkyl group, f is an integer of 1 to 5, g is an integer of 0 to 4, R.sup.6 is a single bond or an alkylene group, Y is a single bond or an ester bond, A is a mono- to tetra-valent organic group which optionally contain at least one hetero atom, or a hetero atom, and h is an integer of 1 to 4.

Claims

1. A resin composition, consisting of: (A) component below, (B) component below, a surfactant, and a solvent, wherein the content of the (B) component is 0.1 to 5.0% by mass with respect to the content of all components of the resin composition, except the solvent: (A) component: a self-crosslinking copolymer having a structural unit of Formula (1) below and a structural unit of Formula (2) below (B) component: a compound of Formula (3) below ##STR00011## wherein R.sup.0 is each independently a hydrogen atom or a methyl group, X is an O group or an NH group, R.sup.1 is a single bond or a linear or branched alkylene group having a carbon atom number of 1 to 6, R.sup.2 is a linear or branched alkyl group having a carbon atom number of 1 to 6, a is an integer of 1 to 5, b is an integer of 0 to 4, and a and b satisfy 1a+b5, and R.sup.2 are optionally different from each other when b is 2, 3 or 4, R.sup.3 is a divalent organic group of Formula (I), (II) or (III) below, the carbonyl group in Formula (I) is bonded to the main chain of the structural unit of Formula (2) when R.sup.3 is a divalent organic group of Formula (I) below, R.sup.4 is an organic group having an epoxy group, R.sup.5 is a linear or branched alkyl group having a carbon atom number of 1 to 6, f is an integer of 1 to 5, g is an integer of 0 to 4, and f and g satisfy 1f+g5, and R.sup.5 are optionally different from each other when g is 2, 3 or 4, R.sup.6 is a single bond or a linear or branched alkylene group having a carbon atom number of 1 to 6, Y is a single bond or an ester bond, A is a monovalent, divalent, trivalent or tetravalent organic group which optionally contain at least one hetero atom, or a hetero atom, and h is an integer of 1 to 4 ##STR00012## wherein c is an integer of 0 to 3, d is an integer of 1 to 3, and e in each formula is independently an integer of 2 to 6, wherein the self-crosslinking copolymer of the (A) component optionally further comprises a structural unit of Formula 4 below: ##STR00013## wherein Z is a phenyl group, a biphenylyl group or a naphthyl group, some or all of hydrogen atoms of the phenyl group, the biphenylyl group and the naphthyl group is optionally substituted with an alkyl group having a carbon atom number of 1 to 10, an alkoxy group having a carbon atom number of 1 to 10, a cyano group or a halogeno group.

2. The resin composition according to claim 1, wherein the structural unit of Formula 2 is a structural unit of Formula (2-1) or (2-2) below: ##STR00014##

3. The resin composition according to claim 1, wherein the self-crosslinking copolymer of the (A) component further comprises the structural unit of Formula 4 ##STR00015## .

4. The resin composition according to claim 1, wherein the self-crosslinking copolymer has a weight average molecular weight of the 1,000 to 100,000.

5. The resin composition according to claim 1, wherein the hetero atom is a nitrogen atom, an oxygen atom or a sulfur atom.

6. The resin composition according to claim 1, which is used as a protective film.

7. The resin composition according to claim 1, which is used as a planarization film.

8. The resin composition according to claim 1, which is used as a microlens.

9. A method for manufacturing a cured film, comprising: applying the resin composition according to claim 1 onto a base and baking the resulting resin composition at 80 to 300 C. for 0.3 to 60 minutes.

10. A method for manufacturing a microlens, comprising: applying the resin composition according to claim 1 onto a base and baking the resulting resin composition at a temperature in a range of from 80 to 300 C. for 0.3 to 60 minutes to manufacture a cured film; forming a resist pattern on the cured film reflowing the resist pattern by heat treatment to form a lens pattern; and performing etch-back of the cured film by using the lens pattern as a mask to transfer the shape of the lens pattern to the cured film.

11. The method for manufacturing a microlens according to claim 10, wherein the base is a substrate having a color filter formed thereon.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited thereto.

MEASUREMENT OF WEIGHT AVERAGE MOLECULAR WEIGHT OF COPOLYMER OBTAINED IN FOLLOWING SYNTHESIS EXAMPLE

(2) Apparatus: GPC System (produced by JASCO Corporation)

(3) Column: Shodex [Registered trademark] KF-804L and 803L

(4) Column Oven: 40 C.

(5) Flow rate: 1 mL/min

(6) Eluent: Tetrahydrofuran

(7) [Synthesis of Self-Crosslinking Copolymer]

Synthesis Example 1

(8) 300 g of styrene, 205 g of 4-hydroxyphenyl methacrylate, 246 g of a monomer of Formula (2-7) shown above and 47.0 g of 2,2-azobisisobutyronitrile were dissolved in 976 g of propylene glycol monomethylether, and then the solution was added dropwise to a flask containing 222 g of propylene glycol monomethylether being kept at 70 C. over 4 hours. After the dropwise addition, reaction was further performed for 18 hours, thereby obtaining a copolymer solution (concentration of a solid content: 40% by mass). The copolymer obtained thereby had a weight average molecular weight (Mw) of 21,000 (conversion to polystyrene).

(9) [Preparation of Resin Composition]

Example 1

(10) 50.0 g of the self-crosslinking copolymer solution (concentration of a solid content: 40% by mass) obtained in Synthesis Example 1 as (A) component, 0.6 g of a compound of Formula (3-10) shown above as (B) component, and 0.01 g of MEGAFACE [registered trademark] R-30 (produced by DIC Corp.) as a surfactant were dissolved in 3.6 g of propylene glycol monomethylether acetate and 14.4 g of propylene glycol monomethylether, thereby forming a solution. Afterward, the solution was filtered using a polyethylene-based microfilter having a pore diameter of 0.10 m, thereby preparing a resin composition

Example 2

(11) A resin composition was prepared under the same conditions as described in Example 1, except that 1.0 g of the compound of Formula (3-10) described above as (B) component, 4.3 g of propylene glycol monomethylether acetate and 14.7 g of propylene glycol monomethylether were used.

Example 3

(12) A resin composition was prepared under the same conditions as described in Example 1, except that 0.1 g of the compound of Formula (3-8) described above as (B) component, 2.8 g of propylene glycol monomethylether acetate and 14.1 g of propylene glycol monomethylether were used.

Example 4

(13) A resin composition was prepared under the same conditions as described in Example 1, except that 0.6 g of the compound of Formula (3-6) described above was used as (B) component.

Comparative Example 1

(14) 50.0 g of a self-crosslinking copolymer solution (concentration of a solid content: 40% by mass) as (A) component obtained in Synthesis Example 1 and 0.01 g of MEGAFACE [Registered trademark] R-30 (produced by DIC Corp.) as a surfactant were dissolved in 2.7 g of propylene glycol monomethylether acetate and 14.0 g of propylene glycol monomethylether, thereby forming a solution. Afterward, the solution was filtered using a polyethylene-based microfilter having a pore diameter of 0.10 thereby preparing a resin composition.

Comparative Example 2

(15) A resin composition was prepared under the same conditions as used in Example 1, except that 1.6 g of the compound of Formula (3-10) described above as (B) component, 5.3 g of propylene glycol monomethylether acetate and 15.1 g of propylene glycol monomethylether were used.

(16) [Chemical Resistance Test]

(17) Each of the resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was applied onto a silicon wafer using a spin coater, and baked on a hot plate at 100 C. for 1 minute and at 150 C. for 10 minutes, thereby forming a cured film having a film thickness of 4 m. A test of dipping the cured film in each of propylene glycol monomethylether, propylene glycol monomethylether acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, acetone, methylisobutylketone, 2-heptanone, 2-propanol, N-methylpyrrolidone and a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 2.38% by mass was performed at 23 C. for 10 minutes. A change in film thickness was estimated between before and after dipping by measuring a film thickness before and after dipping. When 10% or more increase or decrease in film thickness with respect to the film thickness before dipping was shown in at least one of the dipping solvents, chemical resistance was evaluated as , and when less than 10% increase or decrease in film thickness was shown in all solvents, chemical resistance was evaluated as . Evaluation results are shown in Table 1.

(18) [Evaluation of Heat Resistance]

(19) Each of the resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was applied onto each of a quartz substrate and a silicon wafer using a spin coater, and baked on a hot plate at 100 C. for 1 minute and at 150 C. for 10 minutes, thereby forming a cured film having a film thickness of 4 m. Transmittance was measured for each cured film formed on the quartz substrate by changing a wavelength by 2 nm within a range of 400 to 800 nm using a UV-visible spectrophotometer UV-2550 (produced by Shimadzu Corp.). The lowest value of the measured transmittances was determined as the lowest transmittance, which is shown in Table 1. In addition, a surface of each cured film formed on the silicon wafer was observed using an optical microscope at a magnification of 100 to confirm that there were no impurities. Further, each of the cured films formed on the quartz substrate and the silicon wafer was heated in an oven at 150 C. for 1,000 hours. Afterward, transmittances were measured again for each cured film formed on the quartz substrate by changing a wavelength by 2 nm within a range of 400 to 800 nm, and the lowest value of the measured transmittances was determined as the lowest transmittance, which is shown in Table 1. In addition, a surface of each cured film formed on the silicon wafer was observed using an optical microscope at a magnification of 100. When there was 5% or more decrease in transmittance with respect to the lowest transmittance before heating for 1,000 hours, heat resistance was evaluated as , when there was less than 5% decrease in transmittance, heat resistance was evaluated as , when impurities were generated on the surface of the cured film after heating for 1,000 hours, heat resistance was evaluated as , and when no impurities were generated, heat resistance was evaluated as . Evaluation results are shown in Table 1.

(20) [Evaluation of Heat and Moisture Resistance]

(21) Each of the resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was applied onto each of a quartz substrate and a silicon wafer using a spin coater, and baked on a hot plate at 100 C. for 1 minute and then at 150 C. for 10 minutes, thereby forming a cured film having a film thickness of 4 m. Transmittances were measured for each cured film formed on the quartz substrate by changing a wavelength by 2 nm within a range of 400 to 800 nm using a UV-visible spectrophotometer UV-2550 (produced by Shimadzu Corp.). The lowest value of the measured transmittances was determined as the lowest transmittance, which is shown in Table 1. In addition, a surface of each cured film formed on the silicon wafer was observed using an optical microscope at a magnification of 100x to confirm that there were no impurities. Further, the cured films formed on the quartz substrate and the silicon wafer were left in a thermo-hygrostat at 85 C. and 85% RH for 1,000 hours. Afterward, the lowest transmittance was measured again for each cured film formed on the quartz substrate by changing a wavelength by 2 nm within a range of 400 to 800 nm, and the lowest value of the measured transmittances was determined as the lowest transmittance, which is shown in Table 1. In addition, a surface of each cured film formed on the silicon wafer was observed using an optical microscope at a magnification of 100. When there was 5% or more decrease in transmittance with respect to the lowest transmittance before leaving for 1,000 hours, heat and moisture resistance were evaluated as , when there was less than 5% decrease in transmittance, heat and moisture resistance were evaluated as , when impurities were generated on the surface of the cured film after leaving for 1,000 hours, heat and moisture resistance were evaluated as , and when no impurities were generated, heat and moisture resistance were evaluated as . Evaluation results are shown in Table 1.

(22) TABLE-US-00001 TABLE 1 Heat resistance Heat and moisture resistance (150 C./1,000 hrs) (85 C., 85% RH/1,000 hrs) Lowest transmittance/% Lowest transmittance/% (Wavelength (Wavelength 400-800 nm) 400-800 nm) Before Before Chemical heating for After heating Surface of leaving for After leaving Surface of resistance 1,000 hrs for 1,000 hrs cured film 1,000 hrs for 1,000 hrs cured film Example 1 97 95 97 97 Example 2 97 95 97 97 Example 3 97 94 97 97 Example 4 97 94 97 97 Comparative 97 92 x 97 97 Example 1 Comparative 97 96 97 97 x Example 2

(23) From the results shown in Table 1, it is shown that the cured film formed from the resin composition of the present invention exhibited high heat resistance and high heat and moisture resistance, so that the cured film did not color and did not have impurities even after being heated at 150 C. for 1,000 hours and then left at 85 C. and 85% RH for 1,000 hours, as well as high chemical resistance and high transparency. In contrast, the cured film formed from the resin composition prepared in Comparative Example 1 did not exhibit satisfactory heat resistance, and the cured film formed from the resin composition prepared in Comparative Example 2 did not exhibit satisfactory heat and moisture resistance, and therefore it has been identified that these cured films are not suitable for any of a protective film, a planarization film and a microlens.

BRIEF DESCRIPTION OF THE DRAWINGS

(24) FIG. 1 shows the results of observation of the surface of a cured film using an optical microscope after heating in an oven at 150 C. for 1,000 hours.

(25) FIG. 2 shows the results of observation of the surface of a cured film using an optical microscope after being left in a thermo-hygrostat at 85 C. and 85% RH for 1,000 hours.