JPH0748424A - Epoxyacrylate resin - Google Patents
Epoxyacrylate resinInfo
- Publication number
- JPH0748424A JPH0748424A JP8376794A JP8376794A JPH0748424A JP H0748424 A JPH0748424 A JP H0748424A JP 8376794 A JP8376794 A JP 8376794A JP 8376794 A JP8376794 A JP 8376794A JP H0748424 A JPH0748424 A JP H0748424A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy acrylate
- epoxy
- formula
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性、溶剤溶解性、
感光性に優れた新規なエポキシアクリレート樹脂に関す
るものである。The present invention relates to heat resistance, solvent solubility,
The present invention relates to a novel epoxy acrylate resin having excellent photosensitivity.
【０００２】本発明のエポキシアクリレート樹脂は、そ
れ自体で重合させるか、又は、各種のオレフィン性二重
結合を有する化合物と共重合させることによって、種々
のエポキシアクリレートポリマーとなり、熱的、化学
的、光学的安定性などに優れた高分子材料として種々の
用途に供することができる。The epoxy acrylate resin of the present invention is polymerized by itself or is copolymerized with a compound having various olefinic double bonds to form various epoxy acrylate polymers, which are thermally, chemically, It can be used for various purposes as a polymer material having excellent optical stability.
【０００３】[0003]
【従来の技術】従来、エポキシアクリレート樹脂は、感
光材料、光学材料、歯科材料、各種高分子の架橋剤な
ど、機能性高分子材料として広い分野で用いられてきた
が、近年ますます高い機能、例えば高耐熱性、耐候性、
高屈折性などが要求されるようになってきている。2. Description of the Related Art Epoxy acrylate resins have been used in a wide range of fields as functional polymer materials such as photosensitive materials, optical materials, dental materials, and cross-linking agents for various polymers. For example, high heat resistance, weather resistance,
High refractivity is required.
【０００４】このような要求に対して、これまでのエポ
キシアクリレート樹脂は必ずしも満足のいくものではな
いのが実情である。The epoxy acrylate resins up to now are not always satisfactory for such requirements.
【０００５】また、感光性樹脂について言えば、精密加
工業界、例えば印刷配線板製造などに於て、メッキある
いはエッチングのためのレジスト形成に、感光性樹脂組
成物を用いることは良く知られている。As for the photosensitive resin, it is well known to use the photosensitive resin composition for forming resist for plating or etching in the precision processing industry, for example, in the production of printed wiring boards. .
【０００６】また、最近では無電解メッキマスク、ソル
ダーマスクなどの永久マスクの分野にも感光性樹脂組成
物が用いられてきている。Recently, photosensitive resin compositions have also been used in the field of permanent masks such as electroless plating masks and solder masks.
【０００７】特開昭５２―１１７９８５号公報、特開昭
５４―１０１８号公報、特開昭５３―５６０１８号公報
等には、永久マスクとして使用可能な感光性樹脂組成物
が開示されている。JP-A-52-117985, JP-A-54-1018 and JP-A-53-56018 disclose a photosensitive resin composition usable as a permanent mask.
【０００８】しかし、これらの感光性樹脂組成物は高分
子結合剤およびモノマーを主成分としており厚膜の保護
被膜の形成には不向きである。However, these photosensitive resin compositions are not suitable for forming a thick protective film because they contain a polymer binder and a monomer as main components.
【０００９】すなわち、これらの感光性樹脂組成物では
ガラス転移温度の高い、高分子結合剤が用いられている
ため、感光層を形成する場合には、まず感光性樹脂組成
物をトルエン、エチルセロソルブ、メチルエチルケト
ン、塩化メチレン等の有機溶剤に均一に溶解または分散
させ、次に塗布、乾燥して感光層を形成する。That is, since a polymer binder having a high glass transition temperature is used in these photosensitive resin compositions, when the photosensitive layer is formed, the photosensitive resin composition is first mixed with toluene and ethyl cellosolve. , Uniformly dissolved or dispersed in an organic solvent such as methyl ethyl ketone or methylene chloride, and then coated and dried to form a photosensitive layer.
【００１０】そのため、厚膜になると、乾燥時に気泡が
発生したり、樹脂の流動が起こりやすく、均一な保護膜
形成は困難である。Therefore, when the film is thick, it is difficult to form a uniform protective film because bubbles are likely to be generated during the drying and the resin flows easily.
【００１１】特公昭５５―１２７０９７号公報、特開昭
４９―１０７０４８号公報等には、永久マスクとして使
用可能な無溶剤型の感光性樹脂組成物が提案されてい
る。JP-B-55-127097 and JP-A-49-107048 propose a solventless photosensitive resin composition that can be used as a permanent mask.
【００１２】しかし、これらの液状組成物は厚膜、高解
像度の保護膜形成には不向きである。However, these liquid compositions are not suitable for forming a thick film and a high-resolution protective film.
【００１３】すなわち、これらの液状組成物では、溶解
性に劣るエポキシアクリレート樹脂が用いられているた
め現像性に劣り、通常のエッチングおよびメッキ用フィ
ルム状感光材料（デュポン社製リストン、日立化成工業
フォテックなど）に使用されている１．１．１―トリク
ロロエタン等の難燃性現像液による厚膜、高解像度の画
像形成は困難であり、また感度も必ずしも十分でない。That is, in these liquid compositions, an epoxy acrylate resin having a poor solubility is used, so that the developability is poor, and a film-shaped photosensitive material for ordinary etching and plating (Liston manufactured by DuPont, Hitachi Chemical Co., Ltd. It is difficult to form a thick film with a flame-retardant developer such as 1.1.1-trichloroethane used in (1) and high resolution images, and the sensitivity is not always sufficient.
【００１４】また、フェノールノボラック型エポキシ樹
脂はクレゾールノボラック型エポキシ樹脂と同様の構造
を有し、耐熱性に優れてはいるものの、１．１．１―ト
リクロロエタンに対する溶解性が極めて低いため使用で
きない。Further, although the phenol novolac type epoxy resin has the same structure as the cresol novolac type epoxy resin and is excellent in heat resistance, it cannot be used because of its extremely low solubility in 1.1.1-trichloroethane.
【００１５】[0015]
【発明が解決しようとする課題】本発明の目的は、高耐
熱性、溶剤溶解性、感光性などを有する光学材料、各種
高分子材料の架橋剤などの機能性高分子材料となりうる
モノマー、およびポリマー成分として極めて有用なエポ
キシアクリレート樹脂を提供するものである。An object of the present invention is to provide an optical material having high heat resistance, solvent solubility, photosensitivity, etc., a monomer which can be a functional polymer material such as a crosslinking agent for various polymer materials, and The present invention provides an epoxy acrylate resin which is extremely useful as a polymer component.
【００１６】[0016]
【課題を解決するための手段】本発明は、式Ｉの構造を
有するエポキシアクリレート樹脂である。SUMMARY OF THE INVENTION The present invention is an epoxy acrylate resin having the structure of Formula I.
【００１７】[0017]
【化２】 [Chemical 2]
【００１８】（ただしＲはＨ又は低級アルキル基を示
し、Ｒ′はＨ又はＣＨ3を示す。ｎ＝０〜２０の整数で
ある。）(Wherein R represents H or a lower alkyl group, R'represents H or CH 3, and n = 0 to an integer of 20).
【００１９】このエポキシアクリレート樹脂は、例えば
式ＩＩＩで示される両末端がグリシジルエーテル化され
たエポキシ樹脂This epoxy acrylate resin is, for example, an epoxy resin represented by the formula III, in which both terminals are glycidyl etherified.
【００２０】[0020]
【化３】 [Chemical 3]
【００２１】を、エチルセロソルブアセテート等の溶媒
に溶かし、２―エチル―４―イミダゾールまたはトリエ
チルベンジルアンモニウム等を触媒として、１１０〜１
２０℃にてアクリル酸またはメタクリル酸と５〜８時間
反応させることにより得られる。Is dissolved in a solvent such as ethyl cellosolve acetate, and 110 to 1 using 2-ethyl-4-imidazole or triethylbenzylammonium as a catalyst.
It is obtained by reacting with acrylic acid or methacrylic acid at 20 ° C. for 5 to 8 hours.
【００２２】得られたエポキシアクリレート樹脂は仕込
んだエポキシ樹脂の分子量により異なるが、すべて粘着
性のある半固体か固体である。The obtained epoxy acrylate resin is a semi-solid or a solid having stickiness, although it depends on the molecular weight of the charged epoxy resin.
【００２３】そして、この溶液を用いて塗布する場合
は、そのまま液状で使用するか、または適当量の溶媒を
用いて希釈して使用するとよい。When coating using this solution, it may be used as it is in a liquid state or may be diluted with an appropriate amount of solvent before use.
【００２４】この時用いる溶媒としては、低沸点溶媒と
してアセトン、酢酸エチル、テトラヒドロフラン、ジオ
キサン、クロロホルム、四塩化水素などがあり、この
他、エチルセロソルブアセテート、Ｎ，Ｎ―ジメチルホ
ルムアミド、Ｎ―メチルピロリドンにも容易に溶解す
る。As the solvent used at this time, there are acetone, ethyl acetate, tetrahydrofuran, dioxane, chloroform, hydrogen tetrachloride, etc. as a low boiling point solvent. In addition to this, ethyl cellosolve acetate, N, N-dimethylformamide, N-methylpyrrolidone. It also dissolves easily.
【００２５】本発明において、式Ｉ中に存在する二価ア
ルコール（ジオール）成分は、一般に次式で示されるジ
オール類に由来するものである。In the present invention, the dihydric alcohol (diol) component present in formula I is generally derived from diols represented by the following formula.
【００２６】[0026]
【化４】 [Chemical 4]
【００２７】ここで、Ｒは水素もしくはメチル基、エチ
ル基等の低級アルキル基である。これらのジオール成分
は原料として用いられるジオール類によるものであり、
このようなジオール成分を与えるジオール類としては、
９，９―ビス（４―ヒドロキシフェニル）フルオレン、
９，９―ビス（３―メチル―４―ヒドロキシフェニル）
フルオレンおよび９，９―ビス（３―エチル―４―ヒド
ロキシフェニル）フルオレン等が挙げられる。Here, R is hydrogen or a lower alkyl group such as a methyl group or an ethyl group. These diol components are due to the diols used as raw materials,
Examples of diols that give such diol components include:
9,9-bis (4-hydroxyphenyl) fluorene,
9,9-bis (3-methyl-4-hydroxyphenyl)
Examples thereof include fluorene and 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene.
【００２８】また、式ＩＩＩのエポキシ樹脂の製造方法
は、一般のエポキシ樹脂の合成法と同様であり、例え
ば、前記の式ＩＶのジオール成分を適当量のエピクロロ
ヒドリンに加熱溶解して重合させる。The method for producing the epoxy resin of the formula III is the same as the method for synthesizing a general epoxy resin. For example, the diol component of the above formula IV is heated and dissolved in an appropriate amount of epichlorohydrin for polymerization. Let
【００２９】そして、このエポキシ樹脂末端に付加させ
るアクリレート成分としては、光重合可能なアクリル
酸、メタクリル酸等を挙げることができる。また、この
付加反応のとき熱重合禁止剤としてハイドロキノン、ｐ
―メチルキノリン、フェノチアジンなどを樹脂分に対し
て数ｐｐｍ加えるとよい。Examples of the acrylate component added to the terminal of the epoxy resin include photopolymerizable acrylic acid and methacrylic acid. In addition, at the time of this addition reaction, hydroquinone, p
-Adding several ppm of methylquinoline, phenothiazine, etc. to the resin component is recommended.
【００３０】このエポキシアクリレート樹脂は、フォト
レジストの現像溶剤の主成分である１．１．１―トリク
ロロエタンへの溶解性が良く、現像時間が大幅に短縮さ
れる。This epoxy acrylate resin has good solubility in 1.1.1-trichloroethane, which is the main component of the photoresist developing solvent, and the developing time is greatly shortened.
【００３１】また、未露光部の現像液に対する溶解性が
良いので、例えば直径０．４ｍｍあるいは０．３ｍｍの
小径の穴に詰まったレジストも現像で除去することがで
きる。Further, since the unexposed portion has a good solubility in the developing solution, the resist clogged in the hole having a small diameter of 0.4 mm or 0.3 mm can be removed by the development.
【００３２】さらに本発明のエポキシアクリレート樹脂
は耐薬品性、耐熱性、難燃性に優れており、これをフォ
トレジストに適用することにより耐酸性、耐アルカリ
性、半田耐熱性、難燃性などに優れたレジストが得られ
る。Furthermore, the epoxy acrylate resin of the present invention is excellent in chemical resistance, heat resistance and flame retardancy. By applying this to photoresist, it is possible to obtain acid resistance, alkali resistance, solder heat resistance, flame resistance and the like. An excellent resist can be obtained.
【００３３】式Ｉに示すエポキシアクリレート樹脂は、
ｎ＝２０を越えると溶液の粘度が非常に上がり扱いにく
い。The epoxy acrylate resin of formula I is
When n = 20 is exceeded, the viscosity of the solution is so high that it is difficult to handle.
【００３４】また、同様の理由で９０重量％以下が適当
である。１５重量％未満では光硬化性および基材への密
着性が劣るおそれがある。For the same reason, 90% by weight or less is suitable. If it is less than 15% by weight, the photocurability and the adhesion to the substrate may be poor.
【００３５】このエポキシアクリレート樹脂は、用途に
よっては単独でも使用可能であるが、レジスト、保護膜
等の感光性樹脂として使用する場合は、他の樹脂、例え
ば、不飽和ポリエステル、多価アクリレート、多価エポ
キシ樹脂等と混合して用いることもできる。This epoxy acrylate resin can be used alone depending on the application, but when it is used as a photosensitive resin for resists, protective films, etc., other resins such as unsaturated polyester, polyvalent acrylate, It can also be used as a mixture with a valent epoxy resin or the like.
【００３６】[0036]
【実施例】以下、この発明の実施例について説明する。Embodiments of the present invention will be described below.
【００３７】まず、式ＩＩＩのエポキシ樹脂の製法につ
いて述べる。これは、通常の公知のエポキシ樹脂の合成
法と同様であり、本発明に用いたジオール類とエピクロ
ロヒドリンの塩基性触媒を用いた開環重合で合成でき、
仕込み比を変えることによってｎ数を制御し、目的物質
を得ることができる。なお、ｎ数はＧＰＣ測定によって
も同定することができる。First, a method for producing the epoxy resin of the formula III will be described. This is the same as a usual known synthetic method of epoxy resin, and can be synthesized by ring-opening polymerization using a basic catalyst of diols and epichlorohydrin used in the present invention,
By changing the charging ratio, the n number can be controlled and the target substance can be obtained. The n number can also be identified by GPC measurement.
【００３８】[0038]
【実施例１】式ＩＩＩのエポキシ樹脂（エポキシ当量２
３１／ｅｑｉｖ，ｎ＝０，Ｒ＝Ｈ）２３１ｇとエチルセ
ロソルブアセテート１００ｇを５００ｍｌ四ツ口フラス
コ中で１２０℃に加熱して完全溶解させ、次にトリエチ
ルベンジルアンモニウムクロライド４５０ｍｇ、フェノ
チアジン１００ｍｇ、アクリル酸７２．０ｇを加え、８
時間攪拌する。Example 1 Epoxy resin of formula III (epoxy equivalent 2
31 / eqiv, n = 0, R = H) 231 g and ethyl cellosolve acetate 100 g are heated to 120 ° C. in a 500 ml four-necked flask to completely dissolve them, and then triethylbenzylammonium chloride 450 mg, phenothiazine 100 mg, acrylic acid 72 Add 0.0 g, 8
Stir for hours.
【００３９】この酸価を測定し、２．０ｍｇＫＯＨ／ｇ
未満になるまで加熱攪拌を続ける。酸価が目標に達した
後、室温で放冷し、エポキシアクリレート樹脂（試料
１）を得た。さらにこれを、３０℃にて一昼夜減圧乾燥
し目的物を得た。The acid value was measured and 2.0 mgKOH / g
Continue heating and stirring until less than. After the acid value reached the target, the mixture was allowed to cool at room temperature to obtain an epoxy acrylate resin (Sample 1). Further, this was dried under reduced pressure at 30 ° C. for a whole day and night to obtain a target product.
【００４０】以下に得られたエポキシアクリレート樹脂
の構造決定のための分析結果を示した。The analytical results for determining the structure of the obtained epoxy acrylate resin are shown below.
【００４１】融点 ４９〜５１℃ 1Ｈ―ＮＭＲ（溶媒：ＣＤＣｌ3、内部標準物質：ＴＭ
Ｓ）Melting point 49-51 ° C. 1 H-NMR (solvent: CDCl 3 , internal standard substance: TM
S)
【００４２】[0042]
【化５】 [Chemical 5]
【００４３】（ｎ＝０） 尚、この核磁気共鳴スペクトルを図１に示す。(N = 0) The nuclear magnetic resonance spectrum is shown in FIG.
【００４４】ＩＲ（ＫＢｒ錠剤） １７２０ｃｍ-1 （エステル基νc=O） １６００ｃｍ-1 （νc=c） ３０７０ｃｍ-1 （ベンゼン環ν C―H） また、この赤外線吸収スペクトルを図２に示す。IR (KBr tablet) 1720 cm-1 (Ester group νc = O) 1600 cm-1 (Νc = c) 3070 cm-1 (Benzene ring ν C-H) Moreover, this infrared absorption spectrum is shown in FIG.
【００４５】ＭＳ（ＥＩ ７０ｅＶ）、ｍ／ｎ＝６０
５．２９（ｍ+）MS (EI 70 eV), m / n = 60
5.29 (m + )
【００４６】＜感光性＞試料１に、増感剤としてミヒラ
ーケトン３重量％を混合溶解し、スピンコーターによ
り、乾燥膜厚が５０μｍになるようサンプルを作成し
た。<Photosensitivity> 3% by weight of Michler's ketone as a sensitizer was mixed and dissolved in Sample 1, and a sample was prepared by a spin coater so that the dry film thickness was 50 μm.
【００４７】そして次に、超高圧水銀灯を用いて露光し
た。このときの光量は、３００ｍｊ／ｃｍ2であった。Then, exposure was carried out using an ultra-high pressure mercury lamp. The amount of light at this time was 300 mj / cm 2 .
【００４８】＜耐熱性＞上記硬化膜の熱重量分析（Ｔ
Ｇ）を行なった。重量減少開始は２８０℃であった。
尚、データは図３に示した。<Heat Resistance> Thermogravimetric analysis (T
G) was performed. The onset of weight loss was 280 ° C.
The data are shown in FIG.
【００４９】＜光学的特性＞上記硬化膜の屈折率をアッ
ベ屈折率計にて測定した。屈折率１．６０５。<Optical Properties> The refractive index of the cured film was measured with an Abbe refractometer. Refractive index 1.605.
【００５０】これらの結果より、本発明のエポキシアク
リレート樹脂は高感度、高耐熱性、高屈折率を有してい
ることがわかる。From these results, it is understood that the epoxy acrylate resin of the present invention has high sensitivity, high heat resistance and high refractive index.
【００５１】[0051]
【実施例２】式ＩＩＩのエポキシ樹脂（エポキシ当量４
３４／ｅｑｉｖ，ｎ＝１，Ｒ＝Ｈ）４３４ｇとエチルセ
ロソルブアセテート１００ｇを５００ｍｌ四ツ口フラス
コ中で１２０℃に加熱して完全溶解させ、次にトリエチ
ルベンジルアンモニウムクロライド４５０ｍｇ、フェノ
チアジン１００ｍｇ、アクリル酸７２．０ｇを加えて同
様に酸価が２．０ｍｇＫＯＨ／ｇ未満になるまで加熱攪
拌を続ける。Example 2 Epoxy resin of formula III (epoxy equivalent 4
34 / eqiv, n = 1, R = H) 434 g and ethyl cellosolve acetate 100 g are heated to 120 ° C. in a 500 ml four-necked flask to completely dissolve them, and then triethylbenzylammonium chloride 450 mg, phenothiazine 100 mg, acrylic acid 72 Add 0.0 g and continue heating and stirring until the acid value becomes less than 2.0 mg KOH / g.
【００５２】酸価が目標に達した後、室温で放冷し、エ
ポキシアクリレート樹脂を得た。さらにこれを、５０℃
で一昼夜減圧乾燥して目的物を得た。After the acid value reached the target, the mixture was allowed to cool at room temperature to obtain an epoxy acrylate resin. Furthermore, this is 50 ℃
Then, the product was dried under reduced pressure for 24 hours to obtain the desired product.
【００５３】次に実施例１と同様にこの物質の構造決定
を行なった。Next, the structure of this substance was determined in the same manner as in Example 1.
【００５４】融点 １２１〜１２３℃ Melting point 121-123 ° C.
【００５５】尚、ｎ＝１〜２０の1Ｈ―ＮＭＲとＩＲス
ペクトルは、ｎ＝０の場合とほぼ同様で、ｎ数が大きく
なるにつれて1Ｈ―ＮＭＲについていえば、アクリル基
が持つプロトン（Ｈ）の積分比（５．３５―６．５０ｐ
ｐｍ）が全体に対して小さくなり、ＩＲでは、１７２０
ｃｍ-1、１６００ｃｍ-1の吸収強度が小さくなる。[0055] Incidentally, 1 H-NMR and IR spectra of n = 1 to 20 is substantially the same as in the case of n = 0, As for 1 H-NMR as the n number increases, protons having the acrylic group ( H) integral ratio (5.35-6.50p
pm) is smaller than the whole, and IR is 1720
cm -1, the absorption intensity of 1600 cm -1 is reduced.
【００５６】[0056]
【発明の効果】本発明は、高耐熱性、溶剤溶解性、感光
性に優れた新規なエポキシアクリレート樹脂であり、多
層化用絶縁膜、イメージセンサー用保護膜等の形成材
料、ソルダーレジスト、メッキレジスト、カラーフィル
ターの保護膜等として好適なものである。INDUSTRIAL APPLICABILITY The present invention is a novel epoxy acrylate resin having high heat resistance, solvent solubility, and photosensitivity. It is suitable as a protective film for resists and color filters.
【図１】核磁気共鳴スペクトル（1Ｈ―ＮＭＲ）の測定
結果を示すグラフである。FIG. 1 is a graph showing the measurement results of nuclear magnetic resonance spectrum ( 1 H-NMR).
【図２】赤外線吸収スペクトル（ＩＲ）の測定結果を示
すグラフである。FIG. 2 is a graph showing the measurement results of infrared absorption spectrum (IR).
【図３】熱重量分析（ＴＧ）の測定結果を示すグラフで
ある。FIG. 3 is a graph showing measurement results of thermogravimetric analysis (TG).
Claims (1)
ト樹脂 【化１】 （ただし、ＲはＨ又は低級アルキル基を示し、Ｒ′はＨ
又はＣＨ3を示す。ｎ＝０〜２０の整数である。）1. An epoxy acrylate resin represented by the following formula I: (However, R represents H or a lower alkyl group, and R'is H.
Or an CH 3. n is an integer of 0 to 20. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8376794A JPH0748424A (en) | 1989-10-06 | 1994-03-31 | Epoxyacrylate resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25994289 | 1989-10-06 | ||
| JP1-259942 | 1989-10-06 | ||
| JP8376794A JPH0748424A (en) | 1989-10-06 | 1994-03-31 | Epoxyacrylate resin |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1-323829A Division JPH0735426B2 (en) | 1989-10-06 | 1989-12-15 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0748424A true JPH0748424A (en) | 1995-02-21 |
Family
ID=26424800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8376794A Pending JPH0748424A (en) | 1989-10-06 | 1994-03-31 | Epoxyacrylate resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0748424A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6278153B1 (en) | 1998-10-19 | 2001-08-21 | Nec Corporation | Thin film capacitor formed in via |
| JP2002246744A (en) * | 2001-02-20 | 2002-08-30 | Nec Corp | Conductor-forming method, and multilayer wiring board manufacturing method using the same |
| KR100552914B1 (en) * | 1998-07-10 | 2006-06-28 | 제일모직주식회사 | Color resist resin composition |
| KR100655064B1 (en) * | 2005-05-27 | 2006-12-06 | 제일모직주식회사 | Hardmask composition having antireflective property |
| KR100671116B1 (en) * | 2005-07-28 | 2007-01-17 | 제일모직주식회사 | Hardmask composition having antireflective property |
| KR100671117B1 (en) * | 2005-07-28 | 2007-01-17 | 제일모직주식회사 | Hardmask composition having antireflective property |
| US7271536B2 (en) | 2004-08-04 | 2007-09-18 | Fuji Electric Holdings Co., Ltd. | Organic EL panel |
| JP2008111138A (en) * | 2008-01-31 | 2008-05-15 | Osaka Gas Co Ltd | Fluorene-containing resin |
| US8741539B2 (en) | 2010-12-17 | 2014-06-03 | Cheil Industries, Inc. | Hardmask composition, method of forming a pattern using the same, and semiconductor integrated circuit device including the pattern |
| JP2016169257A (en) * | 2015-03-11 | 2016-09-23 | 大阪ガスケミカル株式会社 | Phenoxy (meth) acrylate, and method for the production thereof and use thereof |
| JP2018087284A (en) * | 2016-11-29 | 2018-06-07 | 大阪ガスケミカル株式会社 | Active energy ray-curable composition for optical articles, and optical article prepared therewith |
| KR20190008914A (en) | 2016-07-28 | 2019-01-25 | 쇼와 덴코 가부시키가이샤 | Epoxy (meth) acrylate compounds and curing compositions containing them |
| DE10392604B4 (en) | 2002-05-23 | 2023-03-09 | Global Oled Technology Llc | Organic EL display |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03106918A (en) * | 1989-09-19 | 1991-05-07 | Nitto Denko Corp | Ultraviolet-curable resin composition |
-
1994
- 1994-03-31 JP JP8376794A patent/JPH0748424A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03106918A (en) * | 1989-09-19 | 1991-05-07 | Nitto Denko Corp | Ultraviolet-curable resin composition |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100552914B1 (en) * | 1998-07-10 | 2006-06-28 | 제일모직주식회사 | Color resist resin composition |
| US6278153B1 (en) | 1998-10-19 | 2001-08-21 | Nec Corporation | Thin film capacitor formed in via |
| JP2002246744A (en) * | 2001-02-20 | 2002-08-30 | Nec Corp | Conductor-forming method, and multilayer wiring board manufacturing method using the same |
| DE10392604B4 (en) | 2002-05-23 | 2023-03-09 | Global Oled Technology Llc | Organic EL display |
| US7271536B2 (en) | 2004-08-04 | 2007-09-18 | Fuji Electric Holdings Co., Ltd. | Organic EL panel |
| KR100655064B1 (en) * | 2005-05-27 | 2006-12-06 | 제일모직주식회사 | Hardmask composition having antireflective property |
| KR100671117B1 (en) * | 2005-07-28 | 2007-01-17 | 제일모직주식회사 | Hardmask composition having antireflective property |
| KR100671116B1 (en) * | 2005-07-28 | 2007-01-17 | 제일모직주식회사 | Hardmask composition having antireflective property |
| JP2008111138A (en) * | 2008-01-31 | 2008-05-15 | Osaka Gas Co Ltd | Fluorene-containing resin |
| US8741539B2 (en) | 2010-12-17 | 2014-06-03 | Cheil Industries, Inc. | Hardmask composition, method of forming a pattern using the same, and semiconductor integrated circuit device including the pattern |
| JP2016169257A (en) * | 2015-03-11 | 2016-09-23 | 大阪ガスケミカル株式会社 | Phenoxy (meth) acrylate, and method for the production thereof and use thereof |
| KR20190008914A (en) | 2016-07-28 | 2019-01-25 | 쇼와 덴코 가부시키가이샤 | Epoxy (meth) acrylate compounds and curing compositions containing them |
| US10851199B2 (en) | 2016-07-28 | 2020-12-01 | Showa Denko K. K. | Epoxy (meth) acrylate compound and curable composition containing same |
| TWI732008B (en) * | 2016-07-28 | 2021-07-01 | 日商昭和電工股份有限公司 | Epoxy(metha)acrylate compounds and curable composition having epoxy(metha)acrylate compounds |
| JP2018087284A (en) * | 2016-11-29 | 2018-06-07 | 大阪ガスケミカル株式会社 | Active energy ray-curable composition for optical articles, and optical article prepared therewith |
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