WO2013108716A1 - Negative photosensitive resin composition - Google Patents
Negative photosensitive resin composition Download PDFInfo
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- WO2013108716A1 WO2013108716A1 PCT/JP2013/050428 JP2013050428W WO2013108716A1 WO 2013108716 A1 WO2013108716 A1 WO 2013108716A1 JP 2013050428 W JP2013050428 W JP 2013050428W WO 2013108716 A1 WO2013108716 A1 WO 2013108716A1
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- photosensitive resin
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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
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
Abstract
Description
すなわち、第1観点として、下記(A)成分、(B)成分及び(C)溶剤を含有するネガ型感光性樹脂組成物:
(A)成分:少なくとも(i)N-アルコキシメチル(メタ)アクリルアミドと、(ii)アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体、
(B)成分:光酸発生剤、
(C)成分:溶剤、
第2観点として、(A)成分の(ii)アルカリ可溶性基を有するモノマーがマレイミドである第1観点に記載のネガ型感光性樹脂組成物、
第3観点として、(D)成分として、増感剤をさらに感光性樹脂組成物100質量部に基づいて0.1乃至10質量部含有する、第1観点または第2観点に記載のネガ型感光性樹脂組成物、
第4観点として、(E)成分として、さらにヒドロキシ基を有するポリマーを含有する、第1観点または第2観点に記載のネガ型感光性樹脂組成物、
第5観点として、(A)成分はさらにヒドロキシ基を有するモノマーを含有するモノマー混合物を共重合した共重合体である、第1観点乃至第3観点に記載のネガ型感光性樹脂組成物、
第6観点として、(F)成分として、さらに架橋剤を含有する、第1観点乃至第5観点に記載のネガ型感光性樹脂組成物、
第7観点として、第1観点乃至第6観点のうちいずれかに記載のネガ型感光性樹脂組成物を用いて得られる硬化膜、
第8観点として、第7観点に記載の硬化膜からなる液晶ディスプレイ用層間絶縁膜、
第9観点として、第7観点に記載の硬化膜からなる光学フィルタ、
に関するものである。 As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a first aspect, a negative photosensitive resin composition containing the following component (A), component (B) and solvent (C):
(A) component: a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group,
(B) component: a photoacid generator,
(C) component: solvent,
As a second aspect, the negative photosensitive resin composition according to the first aspect, wherein (ii) the monomer having an alkali-soluble group of component (A) is maleimide,
As a third aspect, the negative photosensitive resin according to the first aspect or the second aspect, further containing 0.1 to 10 parts by mass of a sensitizer as component (D) based on 100 parts by mass of the photosensitive resin composition. Functional resin composition,
As a 4th viewpoint, the negative photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint containing the polymer which further has a hydroxyl group as (E) component,
As a fifth aspect, the negative photosensitive resin composition according to the first aspect to the third aspect, wherein the component (A) is a copolymer obtained by copolymerizing a monomer mixture containing a monomer having a hydroxy group,
As a sixth aspect, the negative photosensitive resin composition according to the first aspect to the fifth aspect, which further contains a crosslinking agent as the component (F),
As a seventh aspect, a cured film obtained using the negative photosensitive resin composition according to any one of the first aspect to the sixth aspect,
As an eighth aspect, an interlayer insulating film for a liquid crystal display comprising the cured film according to the seventh aspect,
As a ninth aspect, an optical filter comprising the cured film according to the seventh aspect,
It is about.
(A)成分:少なくとも(i)N-アルコキシメチル(メタ)アクリルアミドと、(ii)アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体、
(B)成分:光酸発生剤、
(C)溶剤。 The negative photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B) and solvent (C).
(A) component: a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group,
(B) component: a photoacid generator,
(C) Solvent.
(A)成分は、少なくとも(i)N-アルコキシメチル(メタ)アクリルアミドと、(ii)アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体である。 <(A) component>
Component (A) is a copolymer obtained by copolymerizing a monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer having an alkali-soluble group.
(A)成分の共重合体は、斯かる構造を有する共重合体であればよく、共重合体を構成する高分子の主鎖の骨格及び側鎖の種類などについて特に限定されない。 In the present invention, the copolymer refers to a polymer obtained by copolymerization using a monomer having an unsaturated double bond, such as acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and styrene.
The copolymer of component (A) may be any copolymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the copolymer.
(式中R1は水素原子、ハロゲン原子または炭素数1乃至6のアルキル基を表す。式中R2は水素原子または炭素数1乃至10のアルキル基を表す。) (I) N-alkoxymethyl (meth) acrylamide used for component (A) is represented by the structure of formula (1):
(Wherein R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
カルボキシル基を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、モノ-(2-(アクリロイルオキシ)エチル)フタレート、モノ-(2-(メタクリロイルオキシ)エチル)フタレート、N-(カルボキシフェニル)マレイミド、N-(カルボキシフェニル)メタクリルアミド、N-(カルボキシフェニル)アクリルアミド、4ビニル安息香酸等が挙げられる。
フェノール性水酸基を有するモノマーとしては、例えば、ヒドロキシスチレン、N-(ヒドロキシフェニル)アクリルアミド、N-(ヒドロキシフェニル)メタクリルアミド、N-(ヒドロキシフェニル)マレイミド等が挙げられる。
酸無水物基を有するモノマーとしては、例えば、無水マレイン酸、無水イタコン酸等が挙げられる。
マレイミド基を有するモノマーとしては、例えば、マレイミドが挙げられる。 (Ii) Monomers having an alkali-soluble group used for the component (A) include monomers having a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, 4-vinylbenzoic acid and the like.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.
Examples of the monomer having a maleimide group include maleimide.
そのようなモノマーの具体例としては、アクリル酸エステル化合物、メタクリル酸エステル化合物、N-置換マレイミド化合物、アクリロニトリル、アクリルアミド化合物、メタクリルアミド化合物、スチレン化合物及びビニル化合物等が挙げられる。
以下、上記モノマーの具体例を挙げるが、これらに限定されるものではない。 Moreover, in this invention, when obtaining the copolymer which has a specific functional group, the monomer which can be copolymerized with the monomer which has a specific functional group can be used together.
Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, N-substituted maleimide compounds, acrylonitrile, acrylamide compounds, methacrylamide compounds, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said monomer is given, it is not limited to these.
(B)成分は光酸発生剤である。本発明の熱硬化性樹脂組成物に用いられる酸の種類は特に限定されない。このような光酸発生剤の具体例としては、以下のものが挙げられる。 <(B) component>
The component (B) is a photoacid generator. The kind of acid used for the thermosetting resin composition of the present invention is not particularly limited. Specific examples of such a photoacid generator include the following.
The content of the component (B) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 2 to 10 parts by mass. When this ratio is less than 0.5 mass part, photoreactivity may fall and a sensitivity may fall. Moreover, when it exceeds 20 mass parts, the transmittance | permeability of the formed coating film may fall or the storage stability of a solution may fall.
本発明に用いる(A)成分および(B)成分を溶解し、且つ所望により添加される後述の(D)成分、(E)成分、(F)成分などを溶解するものであり、斯様な溶解能を有する溶剤であれば、その種類及び構造などは特に限定されるものでない。 <(C) Solvent>
The (A) component and the (B) component used in the present invention are dissolved, and the (D) component, (E) component, (F) component, etc., which will be added as required, are dissolved. If it is a solvent having solubility, its type and structure are not particularly limited.
(D)成分は、増感剤である。本発明のネガ型感光性樹脂組成物からなる塗膜を露光する波長に対し(B)成分である光酸発生剤の反応率が小さい場合、増感剤を添加することで反応率を向上させることができる。このような増感剤の具体例としては、9,10-ジブトキシアントラセン、9-ヒドロキシメチルアントラセン、チオキサントン、2-イソプロピルチオキサントン、4-イソプロピルチオキサントン、2-クロロチオキサントン、2,4-ジエチルチオキサントン、アントラキノン、1,2-ジヒドロキシアントラキノン、2-エチルアントラキノン、1,4-ジエトキシナフタレン等が挙げられる。 <(D) component>
(D) component is a sensitizer. When the reaction rate of the photoacid generator as the component (B) is small with respect to the wavelength at which the coating film made of the negative photosensitive resin composition of the present invention is exposed, the reaction rate is improved by adding a sensitizer. be able to. Specific examples of such a sensitizer include 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, Anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene and the like can be mentioned.
(E)成分は、ヒドロキシ基を有するポリマーである。ヒドロキシ基を有するポリマーとしては例えば、ヒドロキシ基を有するモノマーを重合した重合体、セルロース、ヒドロキシプロピルセルロース、ジエポキシとジカルボン酸を共重合して得られるポリマー、ジエポキシとジフェノールを共重合して得られるポリマー、ポリエステルポリオール、ポリエーテルポリオール、ポリカプロラクトンポリオール等が挙げられるが、好ましくはヒドロキシ基を有するモノマーを重合した重合体、またはヒドロキシプロピルセルロースである。 <(E) component>
The component (E) is a polymer having a hydroxy group. Examples of the polymer having a hydroxy group include a polymer obtained by polymerizing a monomer having a hydroxy group, cellulose, hydroxypropyl cellulose, a polymer obtained by copolymerizing diepoxy and dicarboxylic acid, and obtained by copolymerizing diepoxy and diphenol. Examples thereof include polymers, polyester polyols, polyether polyols, polycaprolactone polyols, and the like, and a polymer obtained by polymerizing a monomer having a hydroxy group, or hydroxypropyl cellulose is preferable.
本発明の(F)成分である架橋剤としては(B)成分で発生した酸により(A)成分と反応し得る架橋剤であればよい。このような架橋剤としてはエポキシ化合物、メチロール化合物等の化合物が挙げられるが、好ましくはメチロール化合物である。 <(F) component>
The crosslinking agent that is the component (F) of the present invention may be any crosslinking agent that can react with the component (A) by the acid generated in the component (B). Examples of such a crosslinking agent include compounds such as an epoxy compound and a methylol compound, and a methylol compound is preferred.
更に、本発明のネガ型感光性樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、クエンチャー、界面活性剤、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、または多価フェノール、多価カルボン酸等の溶解促進剤等を含有することができる。 <Other additives>
Furthermore, the negative photosensitive resin composition of the present invention can be used as necessary as a quencher, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, as long as the effects of the present invention are not impaired. Or a dissolution accelerator such as a polyhydric phenol or polyvalent carboxylic acid.
本発明のネガ型感光性樹脂組成物は、(A)成分の重合体及び(B)成分の光酸発生剤を(C)溶剤に溶解したものであり、且つ、それぞれ所望により(D)成分の増感剤、(E)成分のヒドロキシ基を有するポリマー、(F)成分の架橋剤、及びその他添加剤のうち一種以上を更に含有することができる組成物である。
<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present invention is obtained by dissolving the polymer of component (A) and the photoacid generator of component (B) in solvent (C), and each component (D) as desired. (E) component-containing polymer having a hydroxy group, component (F) a cross-linking agent, and other additives.
[1]:(A)成分100質量部に基づいて、0.5乃至20質量部の(B)成分を含有し、これら成分が(C)溶剤に溶解されたネガ型感光性樹脂組成物。
[2]:上記[1]の組成物において、更に(D)成分を(A)成分100質量部に基づいて、0.1乃至10質量部含有するネガ型感光性樹脂組成物。
[3]:上記[1]又は[2]の組成物において、更に(E)成分を(A)成分100質量部に基づいて、5乃至150質量部含有するネガ型感光性樹脂組成物。
[4]:上記[1]乃至[3]の組成物において、更に(F)成分を(A)成分100質量部に基づいて5乃至100質量部含有するネガ型感光性樹脂組成物。 Especially, the preferable example of the negative photosensitive resin composition of this invention is as follows.
[1]: A negative photosensitive resin composition containing 0.5 to 20 parts by mass of the component (B) based on 100 parts by mass of the component (A) and dissolving these components in the solvent (C).
[2]: The negative photosensitive resin composition further comprising 0.1 to 10 parts by mass of component (D) based on 100 parts by mass of component (A) in the composition of [1] above.
[3] A negative photosensitive resin composition containing 5 to 150 parts by mass of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2].
[4] A negative photosensitive resin composition containing 5 to 100 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the compositions [1] to [3].
本発明のネガ型感光性樹脂組成物を半導体基板(例えば、シリコン/二酸化シリコン被覆基板、シリコンナイトライド基板、金属例えばアルミニウム、モリブデン、クロムなどが被覆された基板、ガラス基板、石英基板、ITO基板等)の上に、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布などによって塗布し、その後、ホットプレートまたはオーブン等で予備乾燥することにより、塗膜を形成することができる。その後、この塗膜を加熱処理することにより、ネガ型感光性樹脂膜が形成される。 <Coating film and cured film>
The negative photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a negative photosensitive resin film is formed by heat-treating this coating film.
以下の実施例で用いる略記号の意味は、次のとおりである。
MAA:メタクリル酸
MI:マレイミド
MMA:メタクリル酸メチル
BMAA:N-(n-ブトキシメチル)アクリルアミド
HEMA:2-ヒドロキシエチルメタクリレート
GMA:グリシジルメタクリレート
ST:スチレン
AIBN:アゾビスイソブチロニトリル
PAG1:TPS-TF(東洋合成(株)製)(化合物名:トリフェニルスルホニウムトリフルオロメタンスルホネート)
PAG2: GSID-26-1(BASF製)(前記式(79)で表される化合物)
PAG3:イルガキュア369(BASF製)(光重合開始剤)
CYM:サイテックジャパン製サイメル303(製品名)(化合物名:ヘキサメトキシメチルメラミン)
HMA:9-ヒドロキシメチルアントラセン
HPC:ヒドロキシプロピルセルロース
DPHA:ジペンタエリスリトールペンタ/ヘキサアクリレート
BTEAC:ベンジルトリエチルアンモニウムクロライド
PGME:プロピレングリコールモノメチルエーテル
PGMEA:プロピレングリコールモノメチルエーテルアセテート
JE:ジャパンエポキシレジン(株)製 JER157S70 [Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MI: maleimide MMA: methyl methacrylate BMAA: N- (n-butoxymethyl) acrylamide HEMA: 2-hydroxyethyl methacrylate GMA: glycidyl methacrylate ST: styrene AIBN: azobisisobutyronitrile PAG1: TPS-TF (Toyo Gosei Co., Ltd.) (Compound name: Triphenylsulfonium trifluoromethanesulfonate)
PAG2: GSID-26-1 (manufactured by BASF) (compound represented by the formula (79))
PAG3: Irgacure 369 (manufactured by BASF) (photopolymerization initiator)
CYM: Cytech Japan-made Cymel 303 (product name) (compound name: hexamethoxymethylmelamine)
HMA: 9-hydroxymethylanthracene HPC: hydroxypropyl cellulose DPHA: dipentaerythritol penta / hexaacrylate BTEAC: benzyltriethylammonium chloride PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate JE: manufactured by Japan Epoxy Resins Co., Ltd. JER157S70
以下の合成例に従い得られた特定共重合体及び特定架橋体の数平均分子量及び重量平均分子量を、日本分光(株)製GPC装置(Shodex(登録商標)カラムKF803LおよびKF804L)を用い、溶出溶媒テトラヒドロフランを流量1ml/分でカラム中に(カラム温度40℃)流して溶離させるという条件で測定した。なお、下記の数平均分子量(以下、Mnと称す。)及び重量平均分子量(以下、Mwと称す。)は、ポリスチレン換算値にて表される。 [Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the specific copolymer and specific cross-linked product obtained in accordance with the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was flowed through the column at a flow rate of 1 ml / min (column temperature: 40 ° C.) for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
共重合体を構成するモノマー成分として、MI(26.0g)、BMAA(45.0g)、ST(29.0g)を使用し、ラジカル重合開始剤としてAIBN(2g)を使用し、これらを溶剤PGME(238g)中において重合反応させることにより、Mn4,300、Mw9,800である共重合体溶液(共重合体濃度:30質量%)を得た(P1)。なお、重合温度は、温度60℃乃至90℃に調整した。 <Synthesis Example 1>
MI (26.0 g), BMAA (45.0 g), ST (29.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator. By carrying out a polymerization reaction in PGME (238 g), a copolymer solution (copolymer concentration: 30% by mass) as Mn 4,300 and Mw 9,800 was obtained (P1). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
共重合体を構成するモノマー成分として、MAA(20.0g)、BMAA(50.0g)、ST(30.0g)を使用し、ラジカル重合開始剤としてAIBN(2g)を使用し、これらを溶剤PGME(238g)中において重合反応させることにより、Mn4,000、Mw9,200である共重合体溶液(共重合体濃度:30質量%)を得た(P2)。なお、重合温度は、温度60℃乃至90℃に調整した。 <Synthesis Example 2>
MAA (20.0 g), BMAA (50.0 g), and ST (30.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator. By carrying out a polymerization reaction in PGME (238 g), a copolymer solution (copolymer concentration: 30% by mass) of Mn 4,000 and Mw 9,200 was obtained (P2). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
共重合体を構成するモノマー成分として、MAA(20.0g)、BMAA(50.0g)、HEMA(30.0g)を使用し、ラジカル重合開始剤としてAIBN(2g)を使用し、これらを溶剤PGME(238g)中において重合反応させることにより、Mn4,800、Mw10,500である共重合体溶液(共重合体濃度:30質量%)を得た(P3)。なお、重合温度は、温度60℃乃至90℃に調整した。 <Synthesis Example 3>
MAA (20.0 g), BMAA (50.0 g) and HEMA (30.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator, and these are used as solvents. By carrying out a polymerization reaction in PGME (238 g), a copolymer solution (copolymer concentration: 30% by mass) having Mn 4,800 and Mw 10,500 was obtained (P3). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
共重合体を構成するモノマー成分として、MAA(20.0g)、HEMA(40.0g)MMA(40.0g)を使用し、ラジカル重合開始剤としてAIBN(2g)を使用し、これらを溶剤PGME(238g)中において重合反応させることにより、Mn3,900、Mw8,500である共重合体溶液(共重合体濃度:30質量%)を得た(P4)。なお、重合温度は、温度60℃乃至90℃に調整した。
<Synthesis Example 4>
MAA (20.0 g), HEMA (40.0 g), MMA (40.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are used as a solvent PGME. (238 g) was subjected to a polymerization reaction to obtain a copolymer solution (copolymer concentration: 30% by mass) of Mn 3,900 and Mw 8,500 (P4). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
共重合体を構成するモノマー成分として、MAA(50.0g)、MMA(50.0g)を使用し、ラジカル重合開始剤としてAIBN(2g)を使用し、これらを溶剤PGMEA(120g)中において重合反応させることにより共重合体溶液(共重合体濃度:40質量%)を得た。なお、重合温度は、温度60℃乃至90℃に調整した。この共重合体200gにGMA(33.0g)、BTEAC(1.1g)、PGMEA(49.5g)を加えて反応させることによりMn8,700、Mw22,000の(A)成分(特定共重合体)の溶液(特定共重合体濃度:40.5質量%)を得た(P5)。なお、反応温度を90乃至120℃に調整した。 <Comparative Synthesis Example 1>
MAA (50.0 g) and MMA (50.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are polymerized in a solvent PGMEA (120 g). By reacting, a copolymer solution (copolymer concentration: 40% by mass) was obtained. The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C. By adding GMA (33.0 g), BTEAC (1.1 g), and PGMEA (49.5 g) to 200 g of this copolymer and reacting them, the (A) component of Mn8,700 and Mw22,000 (specific copolymer) ) (Specific copolymer concentration: 40.5% by mass) was obtained (P5). The reaction temperature was adjusted to 90 to 120 ° C.
共重合体を構成するモノマー成分として、MAA(30.0g)、GMA(50.0g)、ST(20.0g)を使用し、ラジカル重合開始剤としてAIBN(2g)を使用し、これらを溶剤PGME(238g)中において温度60℃乃至90℃にて重合反応させたが、重合反応中にゲル化してしまいその後の評価に使用することが出来なかった。 <Comparative Synthesis Example 2>
MAA (30.0 g), GMA (50.0 g), and ST (20.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator. The polymerization reaction was carried out at a temperature of 60 ° C. to 90 ° C. in PGME (238 g), but it was gelled during the polymerization reaction and could not be used for subsequent evaluation.
次の表1に示す組成に従い、(A)成分の溶液に、(B)成分、(C)溶剤、及び(D)成分、更に(E)成分及び(F)成分を所定の割合で混合し、室温で3時間撹拌して均一な溶液とすることにより、各実施例及び各比較例のネガ型感光性樹脂組成物を調製した。 <Examples 1 to 7 and Comparative Examples 1 and 2>
According to the composition shown in the following Table 1, the component (A) is mixed with the component (B), the solvent (C), the component (D), and the component (E) and the component (F) at a predetermined ratio. The negative photosensitive resin composition of each Example and each Comparative Example was prepared by stirring at room temperature for 3 hours to obtain a uniform solution.
ネガ型感光性樹脂組成物をシリコンウェハ上にスピンコーターを用いて塗布した後、温度110℃で120秒間ホットプレート上においてプリベークを行い、塗膜を形成した。この塗膜の膜厚をFILMETRICS製 F20を用いて測定した。 [Evaluation of film thickness after pre-baking]
The negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. The film thickness of this coating film was measured using F20 manufactured by FILMETRICS.
ネガ型感光性樹脂組成物を石英基板上にスピンコーターを用いて塗布した後、温度110℃で120秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキャノン製紫外線照射装置PLA-600FAにより365nmにおける光強度が5.5mW/cm2の紫外線を36秒間照射した。この膜を温度95℃にて120秒間ホットプレート上にて露光後加熱を行った後、温度150℃で15分間オーブン中においてポストベークを行い硬化膜を形成した。この硬化膜を紫外線可視分光光度計((株)島津製作所製SIMADSU UV-2550型番)を用いて400nmの波長の透過率を測定した。 [Evaluation of transmittance]
The negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. This coating film was irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm 2 for 36 seconds using a Canon UV irradiation device PLA-600FA. This film was heated after exposure on a hot plate at a temperature of 95 ° C. for 120 seconds and then post-baked in an oven at a temperature of 150 ° C. for 15 minutes to form a cured film. The cured film was measured for transmittance at a wavelength of 400 nm using a UV-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).
ネガ型感光性樹脂組成物を無アルカリガラス上にスピンコーターを用いて塗布した後、温度110℃で120秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキヤノン(株)製紫外線照射装置PLA-600FAにより365nmにおける光強度が5.5mW/cm2の紫外線をライン&スペースパターンのマスクを介して190mJ/cm2照射した。その後温度110℃で120秒間ホットプレート上において露光後加熱を行った。その後2.38質量%の水酸化テトラメチルアンモニウム(以下、TMAHと称す)水溶液に60秒間浸漬することで現像を行った後、超純水で20秒間流水洗浄を行うことでパターンを形成した。作製したパターンを150℃のオーブンにて15分焼成したものについてSEM観察し、パターンの線幅がマスクの線幅と一致する最小パターンサイズを解像度とした。 [Resolution Evaluation]
The negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. The coating light intensity at 365nm by UV irradiation apparatus PLA-600FA manufactured by Canon Inc. in was 190 mJ / cm 2 irradiation through a mask of the UV line and space pattern of 5.5 mW / cm 2. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds. Thereafter, development was performed by immersing in a 2.38% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, and then washing was performed with ultrapure water for 20 seconds to form a pattern. SEM observation was performed on the prepared pattern that was baked in an oven at 150 ° C. for 15 minutes, and the minimum pattern size at which the line width of the pattern coincided with the line width of the mask was defined as the resolution.
ネガ型感光性樹脂組成物を無アルカリガラス上にスピンコーターを用いて塗布した後、温度110℃で120秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキヤノン(株)製紫外線照射装置PLA-600FAにより365nmにおける光強度が5.5mW/cm2の紫外線を20μmのライン&スペースパターンのマスクを介して50mJ/cm2刻みで照射した。その後温度110℃で120秒間ホットプレート上において露光後加熱を行った。その後2.38質量%のTMAH水溶液に60秒間浸漬することで現像を行った後、超純水で20秒間流水洗浄を行うことでパターンを形成した。20μmのパターンが形成できている最低の露光量を感度とした。 [Evaluation of sensitivity]
The negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. This coating film was irradiated with ultraviolet rays having a light intensity of 365 m at 5.5 mW / cm 2 at a rate of 50 mJ / cm 2 through a 20 μm line & space pattern mask by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds. Thereafter, development was performed by immersing in a 2.38 mass% TMAH aqueous solution for 60 seconds, and then washing was performed with ultrapure water for 20 seconds to form a pattern. The minimum exposure amount at which a 20 μm pattern was formed was defined as sensitivity.
以上の評価を行った結果を、次の表2に示す。 [Evaluation results]
The results of the above evaluation are shown in Table 2 below.
比較例1については、厚膜化できず、ポストベーク後の残膜率も90%以下と低かった。比較例2についてはプリベーク後にタックが入り、アルカリ現像液で現像することも出来なかった。 As can be seen from the results shown in Table 2, each of the negative photosensitive resin compositions of Examples 1 to 7 can be applied with a thick film of 10 μm or more, and high transmittance and alkali development are possible even with a thick film. And maintained high resolution and sensitivity.
In Comparative Example 1, the film thickness could not be increased, and the remaining film ratio after post-baking was as low as 90% or less. In Comparative Example 2, the tack entered after pre-baking, and development with an alkaline developer was not possible.
Claims (9)
- 下記(A)成分、(B)成分及び(C)溶剤を含有するネガ型感光性樹脂組成物。
(A)成分:少なくとも(i)N-アルコキシメチル(メタ)アクリルアミドと、(ii)アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体、
(B)成分:光酸発生剤、
(C)溶剤。 Negative photosensitive resin composition containing the following (A) component, (B) component, and (C) solvent.
(A) component: a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group,
(B) component: a photoacid generator,
(C) Solvent. - (A)成分の(ii)アルカリ可溶性基を有するモノマーがマレイミドである請求項1に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, wherein the monomer (A) of component (A) having an alkali-soluble group is maleimide.
- (D)成分として、増感剤をさらに感光性樹脂組成物100質量部に基づいて0.1乃至10質量部含有する、請求項1または2に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1 or 2, further comprising 0.1 to 10 parts by mass of a sensitizer as a component based on 100 parts by mass of the photosensitive resin composition.
- (E)成分として、さらにヒドロキシ基を有するポリマーを含有する、請求項1乃至3に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, further comprising a polymer having a hydroxy group as component (E).
- (A)成分はさらにヒドロキシ基を有するモノマーを含有するモノマー混合物を共重合した共重合体である、請求項1乃至3に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, wherein the component (A) is a copolymer obtained by copolymerizing a monomer mixture containing a monomer having a hydroxy group.
- (F)成分として、さらに架橋剤を含有する、請求項1乃至5のいずれか一項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 5, further comprising a crosslinking agent as the component (F).
- 請求項1乃至6のうちいずれか一項に記載のネガ型感光性樹脂組成物を用いて得られる硬化膜。 The cured film obtained using the negative photosensitive resin composition as described in any one of Claims 1 thru | or 6.
- 請求項7に記載の硬化膜からなる液晶ディスプレイ用層間絶縁膜。 The interlayer insulation film for liquid crystal displays which consists of a cured film of Claim 7.
- 請求項7に記載の硬化膜からなる光学フィルタ。 An optical filter comprising the cured film according to claim 7.
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CN110412829A (en) * | 2018-04-26 | 2019-11-05 | 东友精细化工有限公司 | Negative light-sensitive resin combination, photocuring pattern and image display device |
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