JP6787125B2 - 硬化膜形成用樹脂組成物、硬化膜、導電性部材、及びマイグレーションの抑制方法 - Google Patents
硬化膜形成用樹脂組成物、硬化膜、導電性部材、及びマイグレーションの抑制方法 Download PDFInfo
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- JP6787125B2 JP6787125B2 JP2016535934A JP2016535934A JP6787125B2 JP 6787125 B2 JP6787125 B2 JP 6787125B2 JP 2016535934 A JP2016535934 A JP 2016535934A JP 2016535934 A JP2016535934 A JP 2016535934A JP 6787125 B2 JP6787125 B2 JP 6787125B2
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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- 229940005605 valeric acid Drugs 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3495—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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Description
1.電極及び/又は配線が形成された基材上に前記電極及び/又は配線と接するように形成された硬化膜を備える導電性部材における、前記硬化膜を形成するための樹脂組成物であって、
(A)重量平均分子量が5,000〜180,000である(メタ)アクリレートポリマー(ただし、側鎖にシラン構造を有するものを除く。)、
(B)ベンゾトリアゾール化合物からなるマイグレーション抑制剤兼イオントラップ剤、及び
(C)溶剤
を含有し、(B)ベンゾトリアゾール化合物が、(A)成分100質量部に対して0.1〜50質量部含まれることを特徴とする硬化膜形成用樹脂組成物。
2.更に、(D)シランカップリング剤を含有する1の硬化膜形成用樹脂組成物。
3.更に、(E)多官能(メタ)アクリレート化合物を含有する1又は2の硬化膜形成用樹脂組成物。
4.更に、(F)ラジカル重合開始剤を含有する3の硬化膜形成用樹脂組成物。
5.1〜4のいずれかの硬化膜形成用樹脂組成物を用いて形成された硬化膜。
6.電極及び/又は配線が形成された基材と、この基材上に前記電極及び/又は配線と接するように形成された5の硬化膜とを備える導電性部材。
7.電極及び/又は配線が形成された基材上に硬化膜形成用樹脂組成物から形成された硬化膜を有する構造体の前記電極及び/又は配線からのマイグレーションを抑制する方法であって、
前記硬化膜形成用樹脂組成物として、1〜4のいずれかの硬化膜形成用樹脂組成物を用いることを特徴とする方法。
8.電極及び/又は配線が形成された基材上に、(メタ)アクリレートポリマー及び溶剤を含有する樹脂組成物から形成された硬化膜を有する構造体の前記電極及び/又は配線からのマイグレーションを抑制する方法であって、
前記組成物中に、ベンゾトリアゾール化合物を添加することを特徴とする方法。
本発明の硬化膜形成用樹脂組成物は、(A)重量平均分子量が5,000〜200,000である(メタ)アクリレートポリマー、(B)ベンゾトリアゾール化合物からなるマイグレーション抑制剤兼イオントラップ剤、及び(C)溶剤を含有する。
本発明の組成物に含まれる(A)成分は、重量平均分子量が5,000〜200,000である(メタ)アクリレートポリマーである。(メタ)アクリレートポリマーとは、アクリレート化合物及びメタクリレート化合物から選ばれる少なくとも1種のモノマーから誘導されるモノマー単位を有する重合体である。ただし、本発明における(メタ)アクリレートポリマーは、保存安定性の観点から、側鎖にシラン構造を含むものではない。
本発明の組成物に含まれる(B)成分は、ベンゾトリアゾール化合物からなるマイグレーション抑制剤兼イオントラップ剤である。このようなベンゾトリアゾール化合物としては、ベンゾトリアゾール、4−メチルベンゾトリアゾール、5−メチルベンゾトリアゾール等の炭素数1〜3のアルキル基置換ベンゾトリアゾール誘導体が挙げられるが、中でも、5−メチルベンゾトリアゾールが好ましい。
本発明の組成物は、溶剤に溶解した溶液状態で用いられる。その際に使用する溶剤は、前記(A)及び(B)成分を溶解でき、更に後述の(D)〜(H)成分及びその他の添加剤を含有する場合はこれらも溶解できるものであれば、特に限定されない。
(D)シランカップリング剤、
(E)多官能(メタ)アクリレート化合物、
(F)ラジカル重合開始剤、
(G)重合禁止剤、
(H)ベンゾトリアゾール化合物以外のイオントラップ剤
等を含有してもよい。
本発明の組成物は、密着性を向上させる観点から、好ましくは、(D)成分としてシランカップリング剤を含有する。シランカップリング剤の好ましい一例としては、式(2)で表されるシラン化合物が挙げられる。
前記シランカップリング剤としては、市販品を使用し得る。
本発明の組成物は、硬度を改善する観点から、好ましくは、(E)成分として多官能(メタ)アクリレート化合物を含有する。多官能(メタ)アクリレート化合物とは、分子中に少なくとも3つの(メタ)アクリロキシ基を有する化合物のことであり、具体的には、多価アルコールと(メタ)アクリル酸とのエステルが挙げられる。また、1分子中の(メタ)アクリロキシ基の数は3〜6であり、好ましくは3又は4である。
本発明の組成物は、(E)成分の重合の開始又は促進の観点から、好ましくは、(F)成分としてラジカル重合開始剤を含有する。(E)成分は、高温で処理することによって自発的に重合するが、基板が変性する等高温硬化処理ができない場合、(F)成分を添加することによって低温硬化処理又は光硬化処理が可能となる。
本発明の組成物は、必要に応じて、(G)成分として重合禁止剤を含有することができる。前記重合禁止剤としては、例えば2,6−ジイソブチルフェノール、3,5−ジ−t−ブチルフェノール、3,5−ジ−t−ブチルクレゾール、ヒドロキノン、ヒドロキノンモノメチルエーテル、ピロガロール、t−ブチルカテコール、4−メトキシ−1−ナフトール等が挙げられる。
本発明の組成物は、(H)成分としてベンゾトリアゾール化合物以外のイオントラップ剤を含有することができる。このようなイオントラップ剤としては、例えば、N,N'−ビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニル]ヒドラジン(Irganox(登録商標)MD1024、BASF社製)、シュウ酸ビス(ベンジリデンヒドラジド)(Eastman Inhibitor OABH、イーストマンケミカル社製)等が挙げられる。
本発明の組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、更に界面活性剤、架橋剤、消泡剤、レオロジー調整剤、顔料、染料、保存安定剤、多価フェノールや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。
本発明の組成物の調製方法は、特に限定されない。一例としては、(A)成分を(C)溶剤に溶解し、この溶液に(B)成分を所定の割合で混合し、均一な溶液とする方法が挙げられる。また、この調製方法の適当な段階において、必要に応じて(D)〜(H)成分やその他の成分を更に添加して混合する調製方法が挙げられる。
本発明の組成物を、電極及び/又は配線を有する基板(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;アルミニウム、モリブデン、クロム、銅、銀等の金属、銀ナノワイヤ等の金属ナノワイヤ、銀ナノ粒子、銅ナノ粒子等の金属ナノ粒子、ポリ(3,4−エチレンジオキシチオフェン)/ポリ(スチレンスルホン酸塩)(PEDOT/PSS)、グラフェン、カーボンナノチューブ等の導電性ポリマーが被覆された基板;ガラス基板;石英基板;ITO基板;ITOフィルム基板;TACフィルム、ポリエステルフィルム、アクリルフィルム、シクロオレフィン(COP)フィルム等の樹脂フィルム基板)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、スクリーン印刷、フレキソ印刷、グラビア印刷、オフセット印刷、グラビアオフセット印刷等の印刷法等によって塗布し、その後、ホットプレート又はオーブン等で予備乾燥(プリベーク)することにより、塗膜を形成することができる。本発明の組成物は、特にインクジェット塗布、スクリーン印刷、フレキソ印刷、グラビアオフセット印刷等の印刷法に適している。
・DEGMEA(ジエチレングリコールモノエチルエーテルアセテート)、MMA(メタクリル酸メチル)、MAA(メタクリル酸)、ST(スチレン):東京化成工業(株)製
・MAIB:2,2'−アゾビス(イソ酪酸)ジメチル、東京化成工業(株)製
・PET−30:ペンタエリスリトール(トリ/テトラ)アクリレート、日本化薬(株)製
・5−MBT:5−メチルベンゾトリアゾール、東京化成工業(株)製
・IRG184:光重合開始剤、BASF社製IRGACURE(登録商標)184
・APS:3−アミノプロピルトリエトキシシラン、信越化学工業(株)製LS-3150
・AGITAN771:消泡剤、MUNZING社製
・攪拌装置:(株)シンキー製あわとり練太郎ARE-310
[合成例1]
1,000mLの四つ口フラスコに、DEGMEA532.0gを入れ、窒素雰囲気下、70℃(内温)で攪拌しながら、そこにMMA280.0g、MAA30.1g、ST36.5g及びMAIB8.1gの混合液を2時間かけてゆっくり滴下した。滴下後、更に70℃で20時間反応させ、樹脂溶液P1を得た。なお、この樹脂溶液に含まれる樹脂((メタ)アクリレートポリマー)中のモノマー単位のモル比は、MMA単位:MAA単位:ST単位=80:10:10であって、そのMwは、約5万であった。
[実施例1]
200mLのプラスチック容器に、合成例1で得られた樹脂溶液P1を55.1g、PET−30を24.3g、IRG184を1.3g、5−MBTを1.3g、APSを0.02g、AGITAN771を0.03g、DEGMEAを17.9g入れ、これを攪拌装置に入れ、10分間、2,000rpmで攪拌し、ワニスを作製した。
200mLのプラスチック容器に、合成例1で得られた樹脂溶液P1を50.2g、PET−30を25.1g、IRG184を1.4g、5−MBTを0.68g、APSを0.03g、AGITAN771を0.03g、DEGMEAを22.6g入れ、これを攪拌装置に入れ、10分間、2,000rpmで攪拌し、ワニスを作製した。
200mLのプラスチック容器に、合成例1で得られた樹脂溶液P1を48.3g、PET−30を24.1g、IRG184を1.3g、5−MBTを2.62g、APSを0.02g、AGITAN771を0.03g、DEGMEAを23.7g入れ、これを攪拌装置に入れ、10分間、2,000rpmで攪拌し、ワニスを作製した。
200mLのプラスチック容器に、合成例1で得られた樹脂溶液P1を45.9g、PET−30を22.9g、IRG184を1.2g、5−MBTを5.00g、APSを0.02g、AGITAN771を0.03g、DEGMEAを25.0g入れ、これを攪拌装置に入れ、10分間、2,000rpmで攪拌し、ワニスを作製した。
200mLのプラスチック容器に、合成例1で得られた樹脂溶液P1を56.7g、PET−30を24.9g、IRG184を1.4g、APSを0.02g、AGITAN771を0.03g、DEGMEAを17.0g入れ、これを攪拌装置に入れ、10分間、2,000rpmで攪拌し、ワニスを作製した。
[光透過率測定用硬化膜の作製]
実施例1〜4及び比較例1のワニスを、それぞれガラス基板上にスピンコートにより塗布し、まず110℃で2分間プリベークを行った。次いでUV照射(800mJ/cm2)を行い、その後110℃で30分間ポストベークを行い、厚さ約5μmの硬化膜を作製した。得られた硬化膜について、下記方法によって鉛筆硬度、密着性、透明性の評価を行った。結果を表2に示す。
硬化膜の紫外可視吸収スペクトルを(株)島津製作所製UV-3100PCを用いて測定し、波長400nmにおける透過率を評価した。
JIS K 5400に準拠し、1,000g荷重で測定した。
クロスカット試験方法により評価した。まず、カッターガイドを用いて、硬化膜に100個の碁盤目を作成した。次に、当該碁盤目上にニチバン(株)製のセロハンテープを接着し、上から消しゴムで強く擦り、充分に密着させた。そして、次にセロハンテープをはがし、その際に、100個の碁盤目のうち、何個が剥離したかで評価を行った。
0B:66個以上が剥離
1B:36〜65個が剥離
2B:16〜35個が剥離
3B:6〜15個が剥離
4B:1〜5個が剥離
5B:剥離なし
図1のような銀パターン2をスパッタ蒸着によりガラス基板1上に作製した。実施例1〜4及び比較例1のワニスを、それぞれ当該銀パターン付きガラス基板上にスクリーン印刷法により塗布し、まず110℃で2分間プリベークを行った。次いで110℃で30分間ポストベークを行い、厚さ約5μmの硬化膜3を作製し、評価用サンプルを得た。硬化膜を形成した銀パターン基板の断面図を図2に示す。得られたサンプルについて、下記方法によって、耐マイグレーション評価を行なった。
評価用サンプルを温度60℃、相対湿度90%RHの条件下に置き、銀パターン両端部に陽極と陰極をつなぎパターン先端部に電界集中が起こるように5Vの電圧を15時間印加するという試験を行い、この試験によるマイグレーションの発生の有無を確認した。なお、マイグレーションが発生したか否かは、試験前後のパターンを顕微鏡で観察することで確認した。試験前後のパターンを図3〜5に示す。
2 銀パターン
3 硬化膜
Claims (9)
- 電極及び/又は配線が形成された基材上に前記電極及び/又は配線と接するように形成された硬化膜を備える導電性部材における、前記硬化膜を形成するための樹脂組成物であって、
(A)重量平均分子量が5,000〜180,000である(メタ)アクリレートポリマー(ただし、側鎖にシラン構造を有するものを除く。)、
(B)ベンゾトリアゾール化合物からなるマイグレーション抑制剤兼イオントラップ剤、
(C)溶剤、及び
(E)多官能(メタ)アクリレート化合物
を含有し、(B)ベンゾトリアゾール化合物が、(A)成分100質量部に対して0.1〜50質量部含まれることを特徴とする硬化膜形成用樹脂組成物。 - 更に、(D)シランカップリング剤を含有する請求項1記載の硬化膜形成用樹脂組成物。
- 更に、(F)ラジカル重合開始剤を含有する請求項1又は2記載の硬化膜形成用樹脂組成物。
- 請求項1〜3のいずれか1項記載の硬化膜形成用樹脂組成物を用いて形成された硬化膜。
- 電極及び/又は配線が形成された基材と、この基材上に前記電極及び/又は配線と接するように形成された請求項4記載の硬化膜とを備える導電性部材。
- 電極及び/又は配線が形成された基材上に硬化膜形成用樹脂組成物から形成された硬化膜を有する構造体の前記電極及び/又は配線からのマイグレーションを抑制する方法であって、
前記硬化膜形成用樹脂組成物として、請求項1〜3のいずれか1項記載の硬化膜形成用樹脂組成物を用いることを特徴とする方法。 - 電極及び/又は配線が形成された基材上に、(メタ)アクリレートポリマー、多官能(メタ)アクリレート化合物及び溶剤を含有する樹脂組成物から形成された硬化膜を有する構造体の前記電極及び/又は配線からのマイグレーションを抑制する方法であって、
前記組成物中に、ベンゾトリアゾール化合物を添加することを特徴とする方法。 - 前記(メタ)アクリレートポリマーが、重量平均分子量が5,000〜180,000である(メタ)アクリレートポリマー(ただし、側鎖にシラン構造を有するものを除く。)である請求項7記載の方法。
- 前記組成物が、更にラジカル重合開始剤を含有する請求項7又は8記載の方法。
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