JP7049067B2 - 重合性組成物、ブラックマトリクス用感光性組成物及び硬化物 - Google Patents
重合性組成物、ブラックマトリクス用感光性組成物及び硬化物 Download PDFInfo
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- JP7049067B2 JP7049067B2 JP2017093779A JP2017093779A JP7049067B2 JP 7049067 B2 JP7049067 B2 JP 7049067B2 JP 2017093779 A JP2017093779 A JP 2017093779A JP 2017093779 A JP2017093779 A JP 2017093779A JP 7049067 B2 JP7049067 B2 JP 7049067B2
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
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- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
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- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical group C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
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- 125000001425 triazolyl group Chemical group 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
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- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
上記カラーフィルタ用着色性組成物において顔料を用いる場合、着色性組成物を調製する際には顔料を予め樹脂や分散媒に分散させた顔料分散液を作成することが一般的である。
デンドリマー構造、ハイパーブランチ構造及びポリグリセリン由来の構造からなる群より選ばれる一つ以上構造を有するエチレン性不飽和化合物(A)、着色剤(B)、上記エチレン性不飽和化合物(A)を除くアルカリ現像性化合物(C)、及び重合開始剤(D)を含有する重合性組成物。
着色剤(B)が黒色顔料である[1]に記載の重合性組成物。
アルカリ現像性化合物(C)が、下記一般式(I)で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物と、多塩基酸無水物とのエステル化反応により得られる構造を有する不飽和化合物である[1]又は[2]に記載の重合性組成物。
Mで表される炭素原子数1~20の炭化水素基中の水素原子はハロゲン原子で置換される場合があり、
R1、R2、R3、R4、R5、R6、R7及びR8(以下、R1~R8とも記載)は、それぞれ独立に、水素原子、炭素原子数1~20の炭化水素基、又はハロゲン原子を表し、
R1~R8で表される基中のメチレン基は、不飽和結合、-O-又は-S-で置換される場合があり、
nは0~10の数であり、
n≧1の場合、複数存在するR1~R8及びMは、それぞれ、同一である場合もあり、異なる場合もある。)
R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34、R35、R36、R37及びR38(以下、R10~R38とも記載)は、それぞれ独立に、水素原子、炭素原子数1~20の炭化水素基、複素環を含有する炭素原子数2~20の基、又はハロゲン原子を表し、
R10~R38で表される基中のメチレン基は、不飽和結合、-O-又は-S-で置換される場合があり、
R10とR11、R11とR12、R12とR13、R13とR14、R22とR15、R15とR16、R16とR17、R30とR23、R23とR24、R24とR25、R38とR31、R31とR32、R32とR33、R34とR35、R35とR36及びR36とR37は結合して環を形成する場合があり、
上記式(a)、(b)、(c)及び(d)で表される基中の*は、結合手を表す。)
重合開始剤(D)が、下記一般式(II)で表される基を有する重合開始剤である[1]~[3]の何れか一に記載の重合性組成物。
R41及びR42で表される炭素原子数1~20の炭化水素基又はR41及びR42で表される複素環を含有する炭素原子数2~20の基の水素原子はハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基、炭素原子数1~20の炭化水素基又は複素環を含有する炭素原子数2~20の基で置換される場合があり、R41及びR42で表される炭素原子数1~20の炭化水素基又はR41及びR42で表される複素環を含有する炭素原子数2~20の基中のメチレン基は-O-、-CO-、-COO-、-OCO-、-NR43-、-NR43CO-、-S-、-CS-、-SO2-、-SCO-、-COS-、-OCS-又はCSO-で置換される場合もあり、
R43は、水素原子、炭素原子数1~20の炭化水素基を表し、
mは0又は1を表し、
式中の*は、結合手を表す。)
[1]~[4]の何れか一に記載の重合性組成物を含有するブラックマトリクス用感光性組成物。
[1]~[4]の何れか一に記載の重合性組成物を含有するブラックカラムスペーサー用感光性組成物。
[1]~[4]の何れか一に記載の重合性組成物、[5]に記載のブラックマトリクス用感光性組成物又は[6]に記載のブラックカラムスペーサー用感光性組成物を光照射又は加熱によって硬化させる、硬化物を製造する方法。
[1]~[4]の何れか一に記載の重合性組成物、[5]に記載のブラックカラムスペーサー用感光性組成物又は[6]に記載のブラックカラムスペーサー用感光性組成物の硬化物。
[8]に記載の硬化物を含有するディスプレイ表示装置。
本発明の重合性組成物はエチレン性不飽和化合物(A)を含有する。上記エチレン性不飽和化合物(A)は、デンドリマー構造、ハイパーブランチ構造及びポリグリセリン由来の構造からなる群より選ばれる一つ以上構造を有するエチレン性不飽和化合物を含有すればよく、種類等に特に制限されない。反応性が高いことから、エチレン性不飽和化合物(A)は、エチレン性不飽和基がアクリル基又はメタクリル基のものが好ましく、アクリル基のものが特に好ましい。
上記デンドリマー構造を有するエチレン性不飽和化合物(A)とは、上記デンドリマー構造の末端に重合性基としてエチレン性不飽和基、好ましくはアクリル基又はメタクリル基を有する化合物である。
上記デンドリマー構造を有するエチレン性不飽和化合物(A)におけるエチレン性不飽和基の数は、例えば、該エチレン性不飽和化合物(A)のヨウ素価を公知の方法で、重量平均分子量をGPCにより測定し、測定したヨウ素価及び重量平均分子量から、下記の計算式を用いて算出することができる。
(エチレン性不飽和基の数)=(ヨウ素価)/253.8×100/(重量平均分子量)
上記ハイパーブランチ構造を有するエチレン性不飽和化合物(A)とは、上記ハイパーブランチ構造の末端に重合性基としてエチレン性不飽和基、好ましくはアクリル基又はメタクリル基を有する化合物である。
上記ハイパーブランチ構造をエチレン性不飽和化合物(A)におけるエチレン性不飽和基の数は、例えば、該エチレン性不飽和化合物(A)のヨウ素価を公知の方法で、重量平均分子量をGPCにより測定し、測定したヨウ素価及び重量平均分子量から、下記の計算式を用いて算出することができる。
(エチレン性不飽和基の数)=(ヨウ素価)/253.8×100/(重量平均分子量)
上記ポリグリセリン由来の構造を有するエチレン性不飽和化合物(A)におけるエチレン性不飽和基の数は、例えば、該エチレン性不飽和化合物(A)のヨウ素価を公知の方法で、重量平均分子量をGPCにより測定し、測定したヨウ素価及び重量平均分子量から、下記の計算式を用いて算出することができる。
(エチレン性不飽和基の数)=(ヨウ素価)/253.8×100/(重量平均分子量)
例えば厚さ2~5μmの硬化物を形成する場合には、エチレン性不飽和化合物(A)の含有量は、特に限定されるものではないが、エチレン性不飽和化合物(A)、着色剤(B)、アルカリ現像性化合物(C)及び重合開始剤(D)の合計100質量部に対して、好ましくは、1~30質量部、より好ましくは、3~20質量部であり、更に好ましくは、5~15質量部である。
本発明の重合性組成物は着色剤(B)を含有する。
本発明の重合性組成物に用いられる着色剤(B)としては、顔料及び染料を用いることができる。顔料及び染料としては、それぞれ、無機色材又は有機色材を用いることができ、これらを単独で又は2種以上を混合して用いることができる。ここで、顔料とは、後述の溶剤に不溶の着色剤を指し、無機又は有機色材の中でも溶剤に不溶であるもの、或いは無機又は有機染料をレーキ化したものも含まれる。
例えば厚さ1~3μmの硬化物を形成する場合には、着色剤(B)の含有量は、特に限定されるものではないが、アルカリ現像性化合物(C)100質量部に対して、好ましくは100~500質量部、より好ましくは150~400質量部であり、更に好ましくは200~350質量部である。
本発明の組成物はアルカリ現像性化合物(C)を含有する。
本発明に用いられるアルカリ現像性化合物(C)としては、親水性基を有し、アルカリ現像性を示すものであればよく、特に限定されず従来用いられているものを用いることができる。
上記親水性基としては、水酸基、チオール基、カルボキシル基、スルホ基、アミノ基、アミド基又はその塩等が挙げられ、水酸基及びカルボキシル基を有するアルカリ現像性化合物(C)はアルカリ現像性が高いため好ましい。
アルカリ現像性化合物(C)における親水性基の好ましい官能基当量(親水性基1当量を含む高分子化合物の質量)は、50~10000である。
アルカリ現像性化合物(C)の好ましい分子量は、1000~500000である。
ここで、酸価とは、JIS K 0050 及び JIS K 0211によるものである。
これらの中でも、上記一般式(I)で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物であるか、又は、該エポキシ付加化合物と多塩基酸無水物とのエステル化反応により得られる構造を有する不飽和化合物であるアルカリ現像性化合物が、重合性組成物の感度が高くなり、重合性組成物から得られる硬化物が弾性回復率に優れることから好ましい。
また、上記アルカリ現像性化合物は、不飽和基を0.2~1.0当量含有していることが好ましい。
上記式中のZで表される炭素原子数1~6のアルキレン基としては、上述した炭素原子数1~20のアルキレン基として例示したものの中の炭素原子数1~6のものを挙げることができる。
上記不飽和一塩基酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、桂皮酸、ソルビン酸及びヒドロキシエチルメタクリレート・マレート、ヒドロキシプロピルメタクリレート・マレート、ヒドロキシプロピルアクリレート・マレート及びジシクロペンタジエン・マレート等が挙げられる。
即ち、上記エポキシ付加化合物は、上記エポキシ化合物のエポキシ基1個に対し、上記不飽和一塩基酸のカルボキシル基が0.1~1.0個の比率となるように付加させるのが好ましく、また上記エチレン性不飽和化合物は、上記エポキシ付加物の水酸基1個に対し、上記多塩基酸無水物の酸無水物構造が0.1~1.0個となる比率となるようにするのが好ましい。
上記エポキシ化合物、上記不飽和一塩基酸及び上記多塩基酸無水物の反応は、常法に従って行なうことができる。
上記ビスフェノール型エポキシ化合物としては、上記一般式(I)で表されるエポキシ化合物を用いることができる他、例えば、水添ビスフェノール型エポキシ化合物等のビスフェノール型エポキシ化合物も用いることができる。
また上記グリシジルエーテル類としては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、1,8-オクタンジオールジグリシジルエーテル、1,10-デカンジオールジグリシジルエーテル、2,2-ジメチル-1,3-プロパンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、テトラエチレングリコールジグリシジルエーテル、ヘキサエチレングリコールジグリシジルエーテル、1,4-シクロヘキサンジメタノールジグリシジルエーテル、1,1,1-トリ(グリシジルオキシメチル)プロパン、1,1,1-トリ(グリシジルオキシメチル)エタン、1,1,1-トリ(グリシジルオキシメチル)メタン、1,1,1,1-テトラ(グリシジルオキシメチル)メタン等を用いることができる。
その他、フェノールノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールAノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物;3,4-エポキシ-6-メチルシクロヘキシルメチル-3,4-エポキシ-6-メチルシクロヘキサンカルボキシレート、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、1-エポキシエチル-3,4-エポキシシクロヘキサン等の脂環式エポキシ化合物;フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル類;テトラグリシジルジアミノジフェニルメタン、トリグリシジルP-アミノフェノール、N,N-ジグリシジルアニリン等のグリシジルアミン類;1,3-ジグリシジル-5,5-ジメチルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物;ジシクロペンタジエンジオキシド等のジオキシド化合物;ナフタレン型エポキシ化合物;トリフェニルメタン型エポキシ化合物;ジシクロペンタジエン型エポキシ化合物等を用いることもできる。
例えば厚さ2~5μmの硬化膜を形成する場合には、アルカリ現像性化合物(C)の含有量は、特に限定されるものではないが、エチレン性不飽和化合物(A)、着色剤(B)、アルカリ現像性化合物(C)及び重合開始剤(D)の合計100質量部に対して、好ましくは、5~50質量部、より好ましくは、10~40質量部であり、更に好ましくは、10~30質量部である。
本発明の重合性組成物は重合開始剤(D)を含有する。
本発明の重合性組成物に用いられる重合開始剤(D)としては、従来既知のラジカル重合開始剤を用いることが可能である。
R51及びR52は、それぞれ独立に、水素原子、ニトロ基、シアノ基、炭素原子数1~20のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は複素環を含有する炭素原子数2~20の基を表し、
X1は、酸素原子、硫黄原子、セレン原子、CR53R54、CO、NR55又はPR56を表し、
X2は、不存在、直接結合、炭素原子数1~20の炭化水素基、COを表し、
R53~R56は、それぞれ独立に、水素原子、炭素原子数1~20の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、R53~R56で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアン基、水酸基、カルボキシル基又は複素環基で置換される場合もあり、
R51~R56で表される基中のメチレン基は、酸素が隣り合わない条件で-O-に置換される場合もあり、
R51~R56は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成する場合もあり、
gは、0~4の数を表し、
hは、0~3の数を表す。)
本発明においては、X1が硫黄原子で、X2が不存在の場合、上記一般式(III)で表される化合物が上記化合物No.D1~8で表されるジフェニルスルフィド骨格を有したオキシムエステル系化合物となり、感度が良好な重合性組成物が得られる点で好ましい。
例えば厚さ2~5μmの硬化膜を形成する場合には、重合開始剤(D)の含有量は、特に限定されるものではないが、エチレン性不飽和化合物(A)、着色剤(B)、アルカリ現像性化合物(C)及び重合開始剤(D)の合計100質量部に対して、好ましくは、0.3~20質量部、より好ましくは、0.5~10質量部であり、より好ましくは3~8質量部である。
溶剤の含有量が上記範囲の場合、ハンドリング性(重合性組成物の粘度や濡れ性)、乾燥時のムラの低減及び液安定性(組成物に含まれる成分の析出や沈降を伴わない)に優れる重合性組成物並びに硬化物の厚さを適切にコントロールできることから好ましい。
エチレン性不飽和化合物は、単独で又は2種以上を混合して使用することができる。
好適な市販品としては、例えば、エポライト40E、1500NP、1600、80MF、4000及び3002(以上、共栄社化学製);アデカグリシロールED-503、ED-503D、ED-503G、ED-523T、ED-513、ED-501、ED-502、ED-509、ED-518、ED-529、アデカレジンEP-4000、EP-4005、EP-4080及びEP-4085(以上、ADEKA製);デナコールEX-201、EX-203、EX-211、EX-212、EX-221、EX-251、EX-252、EX-711、EX-721、デナコールEX-111、EX-121、EX-141、EX-142、EX-145、EX-146、EX-147、EX-171、EX-192及びEX-731(以上、ナガセケムテックス製);EHPE-3150、セロキサイド2021P、2081、2000及び3000(以上、ダイセル製);エピオールM、EH、L-41、SK、SB、TB及びOH(以上、日油製);エポライトM-1230及び100MF(以上、共栄社化学製);アロンオキセタンOXT-121、OXT-221、EXOH、POX、OXA、OXT-101、OXT-211及びOXT-212(以上、東亞合成製);エタナコールOXBP及びOXTP(以上、宇部興産製);2-ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル及び4-ヒドロキシブチルビニルエーテル(以上、丸善石油化学製);デナコールEX-121、EX-141、EX-142、EX-145、EX-146、EX-147、EX-201、EX-203、EX-711、EX-721、オンコートEX-1020、EX-1030、EX-1040、EX-1050、EX-1051、EX-1010、EX-1011及び1012(以上、ナガセケムテックス製);オグソールPG-100、EG-200、EG-210及びEG-250(以上、大阪ガスケミカル製);HP4032、HP4032D及びHP4700(以上、DIC製);ESN-475V(東都化成製);マープルーフG-0105SA及びG-0130SP(以上、日油製);エピクロンN-665及びHP-7200(以上、DIC製);EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S、XD-1000、NC-3000、EPPN-501H、EPPN-501HY、EPPN-502H及びNC-7000L(以上、日本化薬製)等が挙げられる。
また縮合反応終了後に、前記親水性溶媒に反応混合物を溶解し、水、n-ヘキサン及びn-ヘプタン等の沈殿剤に添加することにより、ノボラック樹脂を析出させ、析出物を分離し、加熱乾燥することにより回収することもできる。
上記潜在性添加剤としてはWO2014/021023号パンフレットに記載されているものを好ましく使うことができる。
上記アルカリ現像性化合物(C)と共に、上記有機重合体を用いることによって、硬化物の特性を改善することもできる。
有機重合体を使用する場合、その使用量は、上記アルカリ現像性化合物(C)100質量部に対して、好ましくは10~500質量部である。
また、これら無機化合物は、例えば、充填剤、反射防止剤、導電剤、安定剤、難燃剤、機械的強度向上剤、特殊波長吸収剤及び撥インク剤等としても好適に用いられる。
カップリング剤を添加することにより、硬化物と基材間の密着性を向上するので好ましい
上記マスクとしては、ハーフトーンマスク又はグレースケールマスク等の多階調マスクを用いることもできる。
MA100(三菱化学社製カーボンブラック)150g及びペルオキソ2硫酸ナトリウム脱イオン水溶液(濃度2.0N)3000mlを混合し、60℃で10時間撹拌した。ろ過し、得られたスラリーを水酸化ナトリウムで中和し、ダイアフィルトレーションにより処理し、得られた固体を75℃で一晩乾燥し、黒色粉末としてカーボンブラックNo.1を得た。
カーボンブラックNo.1を20g、重合性化合物No.1を2g、DISPERBYK-161(ビックケミー製、分散剤)を3g及びPGMEAを100g、それぞれ秤量して合わせ、ビーズミルにより処理して、カーボンブラック分散液No.1(固形分20%)を得た。
カーボンブラックとしてMA100(三菱化学社製)を20g、分散剤としてBYK161(ビックケミー(BYK)社製)12.5g(固形分濃度40質量%)、溶媒としてPGMEA92.5gを混合し、ビーズミルにより処理して、カーボンブラック分散液No.2(固形分20%)を調製した。
1,1-ビス〔4-(2,3-エポキシプロピルオキシ)フェニル〕インダンの184g、アクリル酸58g、2,6-ジ-tert-ブチル-p-クレゾール0.26g、テトラ-n-ブチルアンモニウムブロミド0.11g及びPGMEA105gを仕込み、120℃で16時間撹拌した。反応液を室温まで冷却し、PGMEA160g、ビフタル酸無水物59g及びテトラ-n-ブチルアンモニウムブロミド0.24gを加えて、120℃で4時間撹拌した。更に、テトラヒドロ無水フタル酸20gを加え、120℃で4時間、100℃で3時間、80℃で4時間、60℃で6時間、40℃で11時間撹拌した後、PGMEA128gを加えて、PGMEA溶液(固形分45質量%)としてアルカリ現像性化合物C-1を得た(Mw=5000、Mn=2100、酸価(固形分)92.7mgKOH/g)。アルカリ現像性化合物PGMEA溶液におけるアルカリ現像性化合物C-1の含有量は45質量%であった。
9,9-ビス(4-グリシジルオキシフェニル)フルオレン75.0g、アクリル酸23.8g、2,6-ジ-t-ブチル-p-クレゾール0.273g、テトラブチルアンモニウムクロリド0.585g、及びPGMEA65.9gを仕込み、90℃で1時間、100℃で1時間、110℃ で1時間及び120℃ で14時間撹拌した。室温まで冷却し、無水コハク酸25.9g、テトラブチルアンモニウムクロリド0.427g、及びPGMEA1.37gを加えて、100℃で5時間撹拌した。更に、9,9-ビス(4-グリシジルオキシフェニル)フルオレン30.0g、2,6-ジ-t-ブチル-p-クレゾール0.269g、及びPGMEA1.50gを加えて、90℃で90分、120℃ で4時間撹拌後、PGMEA122.2gを加えて、PGMEA溶液(固形分45%)として目的物であるアルカリ現像性化合物C-2を得た(Mw=4190、Mn=2170,酸価(固形分)52mg・KOH/g)。アルカリ現像性化合物PGMEA溶液におけるアルカリ現像性化合物C-2の含有量は45質量%であった。
[表1]及び[表2]の配合に従って各成分を混合し、重合性組成物(実施例1~7及び比較例1~2)を得た。尚、表中の配合の数値は質量部を表す。
また、表中の各成分の符号は、下記の成分を表す。
A-1 ビスコート1000
(デンドリックアクリレート、10~15官能、重量平均分子量1840;大阪有機化学社製)
A-2 A-HBR-5
(デンドリックアクリレート、10~15官能、重量平均分子量1830;新中村化学社製)
A-3 A-PG5027E
(ポリグリセリンアクリレート、9官能、重量平均分子量2200;新中村化学社製)
A-4 A-PG5054E
(ポリグリセリンアクリレート、9官能、重量平均分子量3400;新中村化学社製)
A’-5 M450
(ペンタエリスリトールテトラアクリレート、4官能、東亜合成社製)
A’-6 DPHA
(ジペンタエリスリトールヘキサアクリレート、6官能、日本化薬社製)
B-1 カーボンブラック分散液No.1 (酸化処理CBブラック)
B-2 カーボンブラック分散液No.2 (酸価処理なしCBブラック)C-1 アルカリ現像性化合物PGMEA溶液C-1
C-2 アルカリ現像性化合物PGMEA溶液C-2
D-1 化合物No.D9
D-2 化合物No.D10
E-1 PGMEA
F-1 KBM-403(アルコキシシランカップリング剤;信越化学社製)
実施例1~7及び比較例1~2の重合性組成物の感度並びに得られる硬化物について、遮光性(OD値)、シール強度の評価を、下記の手順で行った。結果を[表1]及び[表2]に併記する。
基板上に上記重合性組成物又は比較重合性組成物をスピンコート(300rpm、7秒間)し乾燥させた後、100℃で100秒間プリベークを行った。所定のマスクを用い、光源として超高圧水銀ランプを用いて40mJ/cm2(365nmセンサーで測定)露光後、0.04%KOH水溶液に23℃で30秒間浸漬して現像し、良く水洗した。水洗乾燥後、230℃で30分間ベークを行った。パターンが定着したものをAとし、パターンが定着しなかったものをBとした。
ガラス基板上に上記重合性組成物及び上記比較重合性組成物をスピンコート(300rpm、7秒間)し乾燥させた後、90℃で100秒間プリベークを行った。光源として超高圧水銀ランプを用いて露光後した後、230℃で30分間ベークして硬化物を作成した。得られた膜のOD値を、マクベス透過濃度計を用いて測定し、該OD値をポストベイク後の膜厚で割って、膜厚あたりのOD値を算出した。
膜厚あたりのOD値が3.0以上の硬化物はBMとして使用することができ、膜厚あたりのOD値が3.5以上の硬化物はBMとして好ましく使用することができ、膜厚あたりのOD値が4.0以上の硬化物はBMとして特に好まし使用できる。膜厚あたりのOD値が1.0未満の硬化物はBMとして使用できない。
ガラス基板に6mmx3.5mmの面積で熱硬化接着剤(シール剤:三井化学社製XN-21S)を塗布し、基板Aを作成し、次いで別のガラス基板に上記重合性組成物を塗布し、230℃、1時間熱硬化して作成した樹脂製ブラックマトリックス層のあるガラス基板Bを作成した。得られたガラス基板Aの熱硬化性接着剤塗布面とガラス基板Bの樹脂製ブラックマトリックス層形成面を貼りあわせ、150℃、2時間加熱しガラス基板Aとガラス基板Bを接着させた。
このサンプルについて島津製EZ-Graphにて3点支持曲げ試験を実施し、シール強度を測定した。
Claims (8)
- デンドリマー構造及びポリグリセリン由来の構造からなる群より選ばれる一つ以上構造を有するエチレン性不飽和化合物(A)、着色剤(B)、上記エチレン性不飽和化合物(A)を除くアルカリ現像性化合物(C)、及び重合開始剤(D)を含有し、アルカリ現像性化合物(C)が、下記一般式(I)で表されるエポキシ化合物に不飽和一塩基酸を付加させた構造を有するエポキシ付加化合物と、多塩基酸無水物とのエステル化反応により得られる構造を有する不飽和化合物であり、上記エチレン性不飽和化合物(A)の含有量が、該エチレン性不飽和化合物(A)、着色剤(B)、アルカリ現像性化合物(C)及び重合開始剤(D)の合計100質量部に対して、1~20質量部である、重合性組成物。
(式中、Mは下記式(b)、又は(c)で表される群から選ばれる置換基を表し、
Mで表される炭素原子数1~20の炭化水素基中の水素原子はハロゲン原子で置換される場合があり、
R1、R2、R3、R4、R5、R6、R7及びR8(以下、R1~R8とも記載)は、それぞれ独立に、水素原子、炭素原子数1~20の炭化水素基、又はハロゲン原子を表し、
R1~R8で表される基中のメチレン基は、不飽和結合、-O-又は-S-で置換される場合があり、
nは0~10の数であり、
n≧1の場合、複数存在するR1~R8及びMは、それぞれ、同一である場合もあり、異なる場合もある。)
(式中、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29及びR30(以下、R15~R30とも記載)は、それぞれ独立に、水素原子、炭素原子数1~20の炭化水素基、複素環を含有する炭素原子数2~20の基、又はハロゲン原子を表し、
R15~R30で表される基中のメチレン基は、不飽和結合、-O-又は-S-で置換される場合があり、
R22とR15、R15とR16、R16とR17、R30とR23、R23とR24、R24とR25は結合して環を形成する場合があり、
上記式(b)及び(c)で表される基中の*は、結合手を表す。) - 着色剤(B)が黒色顔料である請求項1に記載の重合性組成物。
- 重合開始剤(D)が、下記一般式(II)で表される基を有する重合開始剤である請求項1又は2に記載の重合性組成物。
(式中、R41及びR42は、それぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数1~20の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R41及びR42で表される炭素原子数1~20の炭化水素基又はR41及びR42で表される複素環を含有する炭素原子数2~20の基の水素原子はハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基、炭素原子数1~20の炭化水素基又は複素環を含有する炭素原子数2~20の基で置換される場合があり、R41及びR42で表される炭素原子数1~20の炭化水素基又はR41及びR42で表される複素環を含有する炭素原子数2~20の基中のメチレン基は-O-、-CO-、-COO-、-OCO-、-NR43-、-NR43CO-、-S-、-CS-、-SO2-、-SCO-、-COS-、-OCS-又はCSO-で置換される場合もあり、
R43は、水素原子、炭素原子数1~20の炭化水素基を表し、
mは0又は1を表し、
式中の*は、結合手を表す。) - 請求項1~3の何れか一項に記載の重合性組成物を含有するブラックマトリクス用感光性組成物。
- 請求項1~3の何れか一項に記載の重合性組成物を含有するブラックカラムスペーサー用感光性組成物。
- 請求項1~3の何れか一項に記載の重合性組成物、請求項4に記載のブラックマトリクス用感光性組成物又は請求項5に記載のブラックカラムスペーサー用感光性組成物を光照射又は加熱によって硬化させる、硬化物を製造する方法。
- 請求項1~3の何れか一項に記載の重合性組成物、請求項4に記載のブラックカラムスペーサー用感光性組成物又は請求項5に記載のブラックカラムスペーサー用感光性組成物の硬化物。
- 請求項7に記載の硬化物を含有するディスプレイ表示装置。
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