WO2015122109A1 - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
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- WO2015122109A1 WO2015122109A1 PCT/JP2014/084632 JP2014084632W WO2015122109A1 WO 2015122109 A1 WO2015122109 A1 WO 2015122109A1 JP 2014084632 W JP2014084632 W JP 2014084632W WO 2015122109 A1 WO2015122109 A1 WO 2015122109A1
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- 0 C*CC(*C)(C(O*C1CC2OC2CC1)=O)O* Chemical compound C*CC(*C)(C(O*C1CC2OC2CC1)=O)O* 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/305—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/306—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and polyethylene oxide chain in the alcohol moiety
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0006—Arrays
- G02B3/0012—Arrays characterised by the manufacturing method
- G02B3/0018—Reflow, i.e. characterized by the step of melting microstructures to form curved surfaces, e.g. manufacturing of moulds and surfaces for transfer etching
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Definitions
- the present invention relates to a thermosetting planarizing film or microlens resin composition, and a planarizing film and microlens formed from the resin composition.
- a CCD / CMOS image sensor In the process of manufacturing a CCD / CMOS image sensor, an immersion process using a chemical solution such as a solvent or an alkaline solution is performed. In order to prevent the element from being deteriorated or damaged by such a process, the process is resistant to the process.
- a protective film is provided on the element surface. Such a protective film has such properties as transparency, high heat resistance and light resistance, no deterioration such as coloring over a long period of time, excellent solvent resistance and alkali resistance. Is required (Patent Document 1).
- Patent Document 4 a technique using a dye instead of a pigment dispersion system has been proposed.
- Patent Document 5 a technique using a dye instead of a pigment dispersion system has been proposed.
- the conventional thermosetting protective film is baked at a temperature of 180 ° C. or higher, it is generally difficult to apply it on a color filter using a dye whose decomposition starts at about 180 ° C.
- the problem to be solved is a heat which is excellent in transparency, solvent resistance and flatness and can be cured at a desired temperature higher than 100 ° C. It is to provide a curable resin composition.
- a resin composition for a planarizing film or a microlens containing the component (A), the component (B) and a solvent a copolymer having a structural unit represented by the following formula (1) and further having a structural unit represented by the following formula (2) or formula (3):
- R 2 represents an epoxy group or an organic group having 5 to 12 carbon atoms having an epoxy ring
- R 3 represents an alkylene group having 1 to 3 carbon atoms
- n represents an integer of 0 to 5.
- the structural unit represented by the formula (1) is a structural unit represented by the following formula (1-1), and the resin composition for a planarizing film or microlens according to the first aspect .
- the copolymer further has a structural unit represented by the following formula (4), and is a resin composition for a planarizing film or a microlens according to the first aspect or the second aspect.
- X represents a cyclohexyl group or a phenyl group.
- the weight average molecular weight of the copolymer is 1,000 to 50,000, and the resin composition for a planarizing film or microlens according to any one of the first to third aspects. object.
- the thermal acid generator is contained in an amount of 0.1% by mass to 20% by mass based on the content in the solid content excluding the solvent from the resin composition.
- the resin composition of the present invention contains the thermal acid generator as the component (B), it is excellent in curability at a desired temperature higher than 100 ° C. and storage stability. Furthermore, the resin film formed from the resin composition of the present invention has excellent transparency, solvent resistance, and flatness. As mentioned above, the level
- the solid content obtained by removing the solvent from the resin composition of the present invention is usually 1% by mass to 50% by mass.
- the component (A) of the present invention is a copolymer having a structural unit represented by the following formula (1) and further having a structural unit represented by formula (2) or formula (3).
- each R 0 independently represents a hydrogen atom or a methyl group
- R 1 represents a single bond or an alkylene group having 1 to 5 carbon atoms
- the alkylene group may have an ether bond therein.
- R 2 represents an epoxy group or an organic group having 5 to 12 carbon atoms having an epoxy ring
- R 3 represents an alkylene group having 1 to 3 carbon atoms
- n represents an integer of 0 to 5.
- Examples of the formula (1) include structural units represented by the following formula (1-1). (Wherein R 0 represents a hydrogen atom or a methyl group, and R 1 represents a single bond or an alkylene group having 1 to 5 carbon atoms.)
- Specific examples of the compound (monomer) forming the structural unit represented by the formula (2) include 4-biphenyl (meth) acrylate, 2- (4-biphenyloxy) ethyl (meth) acrylate, 2- (2 -Biphenyloxy) ethyl (meth) acrylate, 2- (4-biphenyloxy) -2'-ethoxyethyl (meth) acrylate, 2- (2-biphenyloxy) -2'-ethoxyethyl (meth) acrylate, NK ester [Registered trademark] A-LEN-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.). These compounds may be used alone or in combination of two or more.
- the compound (monomer) that forms the structural unit represented by the formula (3) include 3-vinylbiphenyl and 4-vinylbiphenyl. In addition, these compounds may be used independently or may be used in combination of 2 types.
- the compound (monomer) forming the structural unit represented by the formula (4) include N-cyclohexylmaleimide and N-phenylmaleimide. These compounds may be used alone or in combination of two or more.
- the content of the structural unit represented by the above formula (1) in the copolymer of the component (A) is 10 mol% to 90 mol%, preferably 20 mol% to 70 mol%.
- the weight average molecular weight of the copolymer is usually 1,000 to 50,000, preferably 3,000 to 30,000.
- the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
- the content of the copolymer in the resin composition of the present invention is usually 1% by mass to 99% by mass, preferably 5% by mass to based on the content in the solid content of the resin composition. 95% by mass.
- the method for obtaining the component (A) is not particularly limited, but generally, a monomer mixture containing the monomer species used for obtaining the above-mentioned copolymer is usually 50 ° C. to 120 ° C. in a polymerization solvent. It is obtained by carrying out a polymerization reaction at a temperature of The copolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the resin composition of the present invention without isolation in this state.
- the copolymer solution obtained as described above is poured into a stirred poor solvent such as hexane, diethyl ether, methanol, water and the like to reprecipitate the copolymer, and the generated precipitate is obtained.
- the copolymer can be made into powder by drying at normal temperature or reduced pressure at room temperature or by heating. By such an operation, a polymerization initiator and an unreacted compound that coexist with the copolymer can be removed.
- the powder of the copolymer may be used as it is, or the powder may be redissolved, for example, in a solvent described later and used as a solution.
- the thermal acid generator which is the component (B) of the present invention is a catalyst which generates an acid by heating and cationically polymerizes the epoxy group in the component (A) by the action of the acid.
- an organic onium salt compound in which a cation component and an anion component are paired is usually used.
- Examples of the cation component include organic cations such as organic sulfonium, organic oxonium, organic ammonium, organic phosphonium, and organic iodonium.
- Examples of the anion component include B (C 6 F 5 ) 4 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , PF 6 ⁇ , BF 4 ⁇ , and CF 3 SO 3 ⁇ .
- thermal acid generator examples include TA100, TA120, TA160 (manufactured by San Apro Co., Ltd.), K-PURE (registered trademark) TAG2690, TAG2690, CXC1614, CXC1738 (manufactured by King Industries Inc.). , Sun Aid SI-100L, SI-180L (manufactured by Sanshin Chemical Industry Co., Ltd.). These thermal acid generators may be used alone or in combination of two or more.
- the content of the component (B) in the resin composition of the present invention is usually 0.1% by mass to 20% by mass based on the content in the solid content of the resin composition.
- the method for preparing the resin composition of the present invention is not particularly limited.
- the copolymer (A) is dissolved in a solvent, and the thermal acid generator (B) is added to the solution in a predetermined ratio.
- the thermal acid generator (B) is added to the solution in a predetermined ratio.
- the solvent is not particularly limited as long as it dissolves the components (A) and (B).
- solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate.
- propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate are used from the viewpoint of improving the leveling property of a coating film formed by applying the resin composition of the present invention on a substrate.
- Butyl lactate and cyclohexanone are preferred.
- the resin composition of the present invention can also contain a surfactant for the purpose of improving the coating property.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rubitan monopalmitate, polyoxyethylene sorbit
- Fluorosurfactants such as Gent Series (manufactured by Neos Co., Ltd.) and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned. These surfactants may be used alone or in combination of two or more.
- content in the resin composition of this invention is 3 mass% or less based on content in the solid content of the said resin composition, Preferably it is 1 mass%. Or less, more preferably 0.5% by mass or less.
- the resin composition of the present invention is a cross-linking agent, a curing aid, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion aid, as necessary, as long as the effects of the present invention are not impaired. Etc. can be included.
- Substrate for example, a semiconductor substrate such as silicon covered with a silicon oxide film, a semiconductor substrate such as silicon covered with a silicon nitride film or a silicon oxynitride film, a semiconductor substrate such as silicon provided with a color filter, a silicon nitride substrate , Quartz substrate, glass substrate (including alkali-free glass, low alkali glass, crystallized glass), glass substrate on which ITO film is formed ⁇ on the resin composition of the present invention by an appropriate coating method such as a spinner or a coater. After the coating, a flattening film or a microlens resin film is formed by baking and curing using a heating means such as a hot plate.
- a heating means such as a hot plate.
- Baking conditions are appropriately selected from baking temperatures of 80 ° C. to 300 ° C. and baking times of 0.3 minutes to 60 minutes. Further, two or more steps may be performed at different baking temperatures within the above temperature range. In the case of the resin composition of the present invention, a desired resin film can be formed at a baking temperature of less than 200 ° C.
- the film thickness of the resin film formed from the resin composition of the present invention is 0.005 ⁇ m to 5.0 ⁇ m, preferably 0.01 ⁇ m to 3.0 ⁇ m.
- a resist solution is applied onto the resin film for microlenses formed from the resin composition of the present invention, exposed through a predetermined mask, and post-exposure heating (PEB) is performed as necessary, followed by alkali development, rinsing And a predetermined resist pattern is formed by drying.
- PEB post-exposure heating
- g-line, i-line, KrF excimer laser, ArF excimer laser can be used.
- the resist pattern is reflowed by heat treatment (usually a temperature not exceeding 200 ° C.) to form a lens pattern.
- heat treatment usually a temperature not exceeding 200 ° C.
- the underlying microlens resin film is etched back, and the lens pattern shape is transferred to the microlens resin film to produce a microlens.
- Example 2 10.0 g (containing 2.5 g of solid content) of the copolymer (A) component obtained in Synthesis Example 2 and K-PURE (registered trademark) TAG2688 (B) as a thermal acid generator.
- King Industries Inc. 0.4 g
- Megafac registered trademark
- R-30 DIC Corporation
- ⁇ Comparative example 2 10.0 g (including 3.0 g of solid content) of the copolymer (A) component obtained in Synthesis Example 3 and Megafac [registered trademark] R-30 (manufactured by DIC Corporation) as a surfactant. ) 0.003 g was dissolved in 11.0 g of propylene glycol monomethyl ether acetate to form a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.10 micrometer, and prepared the resin composition.
- the film thickness change was measured before and after immersion, and even if one of the above immersion solvents had a film thickness increase or decrease of 5% or more with respect to the film thickness before immersion, the film thickness increased or decreased for all the solvents. Was less than 5%, the solvent resistance was evaluated as “ ⁇ ”. The evaluation results are shown in Table 1.
- Step flatness The resin composition prepared in Example 1 and Example 2 was applied onto a stepped substrate (see FIG. 1) having a height of 0.3 ⁇ m, a line width of 10 ⁇ m, and a space between lines of 10 ⁇ m using a spin coater, and a hot plate Above, baking was performed at 100 ° C. for 1 minute and further at 140 ° C. for 10 minutes to form a resin film having a thickness of 0.6 ⁇ m. From h1 (step difference of the stepped substrate 1) and h2 (step difference of the resin film 2, that is, the height difference between the height of the resin film on the line and the height of the resin film on the space) shown in FIG. The flattening rate was determined using (h2 / h1)) ⁇ 100 ′′. The evaluation results are shown in Table 1.
- the resin film formed from the resin composition of the present invention was highly solvent-resistant and highly transparent. Furthermore, it was found that the resin composition of the present invention is excellent in storage stability. Furthermore, the resin films formed from the resin composition of the present invention all have a leveling flatness with a flattening rate of 50% or more, and among them, the resin film formed from the resin composition prepared in Example 1 Had excellent step flatness with a flattening rate of 80% or more. On the other hand, since the resin film formed from the resin composition prepared in Comparative Example 1 does not contain a thermal acid generator, the resin film formed from the resin composition prepared in Comparative Example 2 is baked at less than 200 ° C. Since the film was formed at a temperature, the solvent resistance was not satisfied, and it was found that the film was not suitable for either a planarizing film or a microlens resin film.
- FIG. 1 is a schematic view showing a resin film formed by applying and baking the resin composition of the present invention on a stepped substrate.
- Step substrate 2 Resin film 3: Line width 4: Space between lines h1: Step difference of step substrate h2: Step of resin film
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Abstract
Description
すなわち、第1観点として、
(A)成分、(B)成分及び溶剤を含有する平坦化膜用又はマイクロレンズ用樹脂組成物。
(A)成分:下記式(1)で表される構造単位を有し、さらに、下記式(2)又は式(3)で表される構造単位を有する共重合体
(B)成分:熱酸発生剤
第2観点として、前記式(1)で表される構造単位は下記式(1-1)で表される構造単位である、第1観点に記載の平坦化膜用又はマイクロレンズ用樹脂組成物。
第3観点として、前記共重合体はさらに下記式(4)で表される構造単位を有する、第1観点又は第2観点に記載の平坦化膜用又はマイクロレンズ用樹脂組成物。
第4観点として、前記共重合体の重量平均分子量は1,000乃至50,000である、第1観点乃至第3観点のうちいずれか一つに記載の平坦化膜用又はマイクロレンズ用樹脂組成物。
第5観点として、前記熱酸発生剤は、前記樹脂組成物から前記溶剤を除いた固形分中の含有量に基づいて0.1質量%乃至20質量%含まれる、第1観点乃至第4観点のうちいずれか一つに記載の平坦化膜用又はマイクロレンズ用樹脂組成物。
第6観点として、第1観点乃至第5観点のうちいずれか一つに記載の樹脂組成物から作製される平坦化膜。
第7観点として、第1観点乃至第5観点のうちいずれか一つに記載の樹脂組成物から作製されるマイクロレンズ。
本発明の(A)成分は、前述の下記式(1)で表される構造単位を有し、さらに、式(2)又は式(3)で表される構造単位を有する共重合体である。
本発明の(B)成分である熱酸発生剤は、加熱によって酸が発生し、酸の作用によって前記(A)成分中のエポキシ基をカチオン重合させる触媒である。熱酸発生剤としては、通常カチオン成分とアニオン成分とが対になった有機オニウム塩化合物が用いられる。
基板{例えば、酸化珪素膜で被覆されたシリコン等の半導体基板、窒化珪素膜又は酸化窒化珪素膜で被覆されたシリコン等の半導体基板、カラーフィルターが形成されたシリコン等の半導体基板、窒化珪素基板、石英基板、ガラス基板(無アルカリガラス、低アルカリガラス、結晶化ガラスを含む)、ITO膜が形成されたガラス基板}上に、スピナー、コーター等の適当な塗布方法により本発明の樹脂組成物を塗布後、ホットプレート等の加熱手段を用いてベークして硬化させて平坦化膜又はマイクロレンズ用樹脂膜を形成する。
〔下記合成例で得られた共重合体の重量平均分子量の測定〕
装置:日本分光(株)製GPCシステム
カラム:Shodex〔登録商標〕KF-804L及びKF-803L
カラムオーブン:40℃
流量:1mL/分
溶離液:テトラヒドロフラン
<合成例1>
3,4-エポキシシクロヘキシルメチルメタクリレート(サイクロマー〔登録商標〕M100((株)ダイセル製))19.7g、エトキシ化オルトフェニルフェノールアクリレート(NKエステル〔登録商標〕A-LEN-10(新中村化学工業(株)製))40.0g、及び2,2’-アゾビスイソブチロニトリル1.6gをプロピレングリコールモノメチルエーテルアセテート114.0gに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテルアセテート70.2gを70℃に保持したフラスコ中に3時間かけて滴下した。滴下終了後、15時間反応させることにより、前記式(1)で表される構造単位及び前記式(2)で表される構造単位を有する共重合体の溶液(固形分濃度25質量%)を得た。得られた共重合体の重量平均分子量Mwは32,000(ポリスチレン換算)であった。
3,4-エポキシシクロヘキシルメチルメタクリレート20.0g、4-ビニルビフェニル11.0g、及び2,2’-アゾビスイソブチロニトリル0.64gをプロピレングリコールモノメチルエーテルアセテート43.9gに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテルアセテート27.0gを70℃に保持したフラスコ中に3時間かけて滴下した。滴下終了後、15時間反応させることにより、前記式(1)で表される構造単位及び前記式(3)で表される構造単位を有する共重合体の溶液(固形分濃度25質量%)を得た。得られた共重合体の重量平均分子量Mwは17,000(ポリスチレン換算)であった。
グリシジルメタクリレート6.5g、1-n-ブトキシエチルメタクリレート8.5g、スチレン38.0g、及び2,2’-アゾビスイソブチロニトリル2.3gをプロピレングリコールモノメチルエーテルアセテート103.0gに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテルアセテート26.0gを75℃に保持したフラスコ中に4時間かけて滴下した。滴下終了後、18時間反応させることにより、前記式(2)で表される構造単位及び前記式(3)で表される構造単位のいずれも有さない共重合体の溶液(固形分濃度30質量%)を得た。得られた共重合体の重量平均分子量Mwは14,000(ポリスチレン換算)であった。
<実施例1>
合成例1で得られた(A)成分である共重合体の溶液10.0g(固形分2.5g含む)、(B)成分である熱酸発生剤としてK-PURE〔登録商標〕TAG2689(King Industries Inc.製)0.04g、及び界面活性剤としてメガファック〔登録商標〕R-30(DIC(株)製)0.003gを、プロピレングリコールモノメチルエーテルアセテート7.5gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例2で得られた(A)成分である共重合体の溶液10.0g(固形分2.5g含む)、(B)成分である熱酸発生剤としてK-PURE〔登録商標〕TAG2689(King Industries Inc.製)0.04g、及び界面活性剤としてメガファック〔登録商標〕R-30(DIC(株)製)0.003gを、プロピレングリコールモノメチルエーテルアセテート7.5gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例1で得られた(A)成分である共重合体の溶液10.0g(固形分2.5g含む)、及び界面活性剤としてメガファック〔登録商標〕R-30(DIC(株)製)0.003gを、プロピレングリコールモノメチルエーテルアセテートル7.5gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例3で得られた(A)成分である共重合体の溶液10.0g(固形分3.0g含む)、及び界面活性剤としてメガファック〔登録商標〕R-30(DIC(株)製)0.003gを、プロピレングリコールモノメチルエーテルアセテートル11.0gに溶解させて溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
実施例1、実施例2、比較例1及び比較例2で調製した樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに140℃で10分間ベークを行い、膜厚0.6μmの樹脂膜を形成した。これらの樹脂膜に対して、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、シクロヘキサノン、乳酸エチル、酢酸ブチル、アセトン、γ-ブチロラクトン、メチルエチルケトン、2-ヘプタノン、2-プロパノール、及び2.38質量%濃度の水酸化テトラメチルアンモニウム(TMAH)水溶液に、それぞれ23℃の温度条件下、5分間浸漬する試験を行った。浸漬前後において膜厚変化を測定し、上記浸漬溶剤のうち1つでも、浸漬前の膜厚に対して5%以上の膜厚増減があった場合は“×”、全ての溶剤について膜厚増減が5%未満であった場合は“○”として耐溶剤性を評価した。評価結果を表1に示す。
実施例1及び実施例2で調製した樹脂組成物をそれぞれ、石英基板上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに140℃で10分間ベークを行い、膜厚0.6μmの樹脂膜を形成した。これらの樹脂膜に対し、紫外線可視分光光度計UV-2550((株)島津製作所製)を用いて、波長400nmの透過率を測定した。評価結果を表1に示す。
実施例1及び実施例2で調製した直後の樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに140℃で10分間ベークを行うことにより樹脂膜を形成し、光干渉式膜厚測定装置ラムダエースVM-2110(大日本スクリーン製造(株)製)を用いてこれらの樹脂膜の膜厚を測定した。さらに、同じ樹脂組成物を35℃(加速試験)にて1ヶ月保管し、保管後の樹脂組成物から同様の方法にて形成した樹脂膜の膜厚を測定した。調製直後の樹脂組成物から形成した樹脂膜の膜厚と比較して、膜厚変化が10%未満であるものを“○”、10%以上であるものを“×”とした。評価結果を表1に示す。
実施例1及び実施例2で調製した樹脂組成物を、それぞれ高さ0.3μm、ライン幅10μm、ライン間スペース10μmの段差基板(図1参照)上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに140℃で10分間ベークを行い、膜厚0.6μmの樹脂膜を形成した。図1に示すh1(段差基板1の段差)とh2(樹脂膜2の段差、即ちライン上の樹脂膜の高さとスペース上の樹脂膜の高さとの高低差)から、“式:(1-(h2/h1))×100”を用いて平坦化率を求めた。評価結果を表1に示す。
2:樹脂膜
3:ライン幅
4:ライン間スペース
h1:段差基板の段差
h2:樹脂膜の段差
Claims (7)
- 前記共重合体の重量平均分子量は1,000乃至50,000である、請求項1乃至請求項3のうちいずれか一項に記載の平坦化膜用又はマイクロレンズ用樹脂組成物。
- 前記熱酸発生剤は、前記樹脂組成物から前記溶剤を除いた固形分中の含有量に基づいて0.1質量%乃至20質量%含まれる、請求項1乃至請求項4のうちいずれか一項に記載の平坦化膜用又はマイクロレンズ用樹脂組成物。
- 請求項1乃至請求項5のうちいずれか一項に記載の樹脂組成物から作製される平坦化膜。
- 請求項1乃至請求項5のうちいずれか一項に記載の樹脂組成物から作製されるマイクロレンズ。
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