JP2020106755A - Photosensitive resin composition for light-shielding film and cured product of the same, and method for manufacturing color filter and touch panel using the cured product - Google Patents
Photosensitive resin composition for light-shielding film and cured product of the same, and method for manufacturing color filter and touch panel using the cured product Download PDFInfo
- Publication number
- JP2020106755A JP2020106755A JP2018247791A JP2018247791A JP2020106755A JP 2020106755 A JP2020106755 A JP 2020106755A JP 2018247791 A JP2018247791 A JP 2018247791A JP 2018247791 A JP2018247791 A JP 2018247791A JP 2020106755 A JP2020106755 A JP 2020106755A
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- Prior art keywords
- light
- component
- shielding film
- resin composition
- photosensitive resin
- 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.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 43
- -1 fluorene compound Chemical class 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000012860 organic pigment Substances 0.000 claims abstract description 11
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 6
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000006229 carbon black Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 27
- 239000011521 glass Substances 0.000 abstract description 24
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
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- 239000002904 solvent Substances 0.000 description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 15
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- 230000000052 comparative effect Effects 0.000 description 14
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- 238000011156 evaluation Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 10
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 10
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229930185605 Bisphenol Natural products 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
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- 238000002156 mixing Methods 0.000 description 7
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 206010040844 Skin exfoliation Diseases 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- CYIHFQGZMRVBPF-UHFFFAOYSA-N 9,9-bis(prop-2-enyl)fluorene Chemical compound C1=CC=C2C(CC=C)(CC=C)C3=CC=CC=C3C2=C1 CYIHFQGZMRVBPF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- OTTUOKHGDUPOCQ-UHFFFAOYSA-N [9,9-bis(prop-2-enyl)fluoren-2-yl]-(2-methylphenyl)methanone Chemical compound CC1=CC=CC=C1C(=O)C2=CC3=C(C=C2)C4=CC=CC=C4C3(CC=C)CC=C OTTUOKHGDUPOCQ-UHFFFAOYSA-N 0.000 description 3
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 3
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- 238000000206 photolithography Methods 0.000 description 3
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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Landscapes
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、遮光膜用感光性樹脂組成物、及びその硬化物に関し、詳しくは、透明基板上に微細な遮光膜を形成するのに適したアルカリ水溶液現像型の遮光膜用感光性樹脂組成物、及びその硬化物であり、硬化させて得た遮光膜は、カラーフィルター(CF)やタッチパネルを形成する際に好適に利用されるものである。 TECHNICAL FIELD The present invention relates to a photosensitive resin composition for a light-shielding film and a cured product thereof, and more specifically, an alkaline aqueous solution-developing photosensitive resin composition for a light-shielding film suitable for forming a fine light-shielding film on a transparent substrate. And a cured product thereof, and the light-shielding film obtained by curing is suitably used when forming a color filter (CF) or a touch panel.
カラー液晶表示装置は、光の透過量あるいは反射量を制御する液晶部とカラーフィルターとを構成要素とするが、そのカラーフィルターの製造方法は、通常、ガラス、プラスチックシート等の透明基板の表面に黒色のマトリックスを形成し、続いて、赤、緑、青の異なる色相を順次、ストライプ状あるいはモザイク状等の色パターンで形成する方法が用いられている。 A color liquid crystal display device has a liquid crystal part for controlling the amount of transmitted or reflected light and a color filter as constituent elements, and the method for manufacturing the color filter is usually a glass, a surface of a transparent substrate such as a plastic sheet. A method is used in which a black matrix is formed, and subsequently, different hues of red, green, and blue are sequentially formed in a stripe-shaped or mosaic-shaped color pattern.
ここ数年、液晶テレビ、液晶モニター、カラー液晶携帯電話など、あらゆる分野でカラー液晶表示装置が用いられてきた。カラーフィルターはカラー液晶表示装置の視認性を左右する重要な部材の一つであり、視認性の向上、すなわち、鮮明な画像を得るためには、カラーフィルターを構成する赤(R)、緑(G)、青(B)などの画素を今まで以上に高色純度化すると共に、ブラックマトリックスでは高遮光化を達成する必要があり、そのためには、感光性樹脂組成物に着色剤を従来よりも多量に添加しなければならない。 In recent years, color liquid crystal display devices have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. The color filter is one of the important members that affect the visibility of the color liquid crystal display device. In order to improve the visibility, that is, to obtain a clear image, the red (R), green ( G), blue (B), and other pixels need to have higher color purity than ever, and a black matrix needs to achieve high light shielding. For that purpose, a colorant is added to the photosensitive resin composition more than ever before. Must also be added in large amounts.
また近年では、スマートフォンなどの中小型パネル向けではFull High Definitionの解像度を得るための超高精細化(400 Pixel Per Inch以上)技術が必要とされ、高精細化は必須の技術トレンドとなっている。高精細化を達成するためには、赤、緑、青の各画素サイズを細かくする必要があるが、カラーフィルターの開口率(バックライト光が透過するRGB画素の面積割合)を落とさないことが高輝度化には必要であり、ブラックマトリックスの細線化も同時に求められている。すなわち、ブラックマトリックスの線幅は、従来では6〜8μmが主流であったが、最近では4〜5μmサイズが求められるようになっている。 In recent years, ultra-high definition (400 Pixel Per Inch or higher) technology to obtain Full High Definition resolution has been required for small and medium-sized panels such as smartphones, and high definition has become an essential technology trend. .. In order to achieve high definition, it is necessary to make each pixel size of red, green, and blue small, but the aperture ratio of the color filter (area ratio of RGB pixels through which the backlight light passes) cannot be reduced. It is necessary for high brightness, and thinning of the black matrix is also required. That is, the line width of the black matrix has conventionally been 6 to 8 μm, but recently, the line width has been required to be 4 to 5 μm.
また高輝度化のために、バックライト強度をアップする傾向があり、それに伴いブラックマトリックスからの光漏れを防止するため、RGBの周りにあるブラックマトリックスを高遮光化する必要がある。高遮光を確保するためにはブラックマトリックスの膜厚を厚くすれば良いが、膜厚を厚くすると、現像プロセスの影響を受け易くなり、マザーガラス面内におけるブラックマトリックスの線幅のばらつきが大きくなる。特に、4〜5μmの細線の場合は、線幅のばらつきは表示ムラの発生などの表示性能に与える影響が大きい。よって、出来るだけ薄い膜厚で目標とする遮光度を確保するため、単位膜厚当たりの遮光性を上げる必要がある。ところが、通常、樹脂組成物中の黒色顔料の含有量を多くするため、その結果、硬化性に寄与するバインダー樹脂やアクリレート成分等の配合割合が相対的に小さくなり、塗膜が十分に硬化しにくくなり、塗膜とガラス基板との密着性が低下して、剥がれ等が生じやすくなるという問題が生じる。 Further, the backlight intensity tends to be increased for higher brightness, and accordingly, in order to prevent light leakage from the black matrix, it is necessary to make the black matrix around RGB highly light-shielded. The thickness of the black matrix may be increased in order to secure high light shielding. However, if the thickness of the black matrix is increased, it is easily affected by the development process, and the variation of the line width of the black matrix in the mother glass surface becomes large. .. In particular, in the case of a thin line of 4 to 5 μm, variations in line width have a great influence on display performance such as occurrence of display unevenness. Therefore, it is necessary to improve the light blocking property per unit film thickness in order to secure the target light blocking degree with the thinnest possible film thickness. However, in general, since the content of the black pigment in the resin composition is increased, as a result, the blending ratio of the binder resin and the acrylate component that contribute to the curability becomes relatively small, and the coating film is sufficiently cured. It becomes difficult, and the adhesion between the coating film and the glass substrate is lowered, so that peeling or the like is likely to occur.
ところで、液晶パネルにおける耐久性試験(信頼性試験)として一般的にPCT(Pressure Cooker Test)が行われるが、この試験法は、温度121℃、湿度100%、気圧2atmという過酷な条件下に数時間液晶パネルを放置し、液晶パネルのカラーフィルター基板とTFT基板との間に封入された液晶もれの有無の確認を行うものである。ブラックマトリックスは赤、緑、青の各色間に存在し、コントラスト向上の役割の他、カラーフィルターの外枠遮光膜としての機能もあり、外枠遮光膜の一部はシール材を介し対向基板と貼り合わさっている。そのため、ブラックマトリックスにはPCTのような過酷な条件下においてもガラス基板との剥がれが生じないような高い密着強度も同時に要求される。特に、近年では、液晶パネルの視認性向上のため外枠遮光膜おいても高遮光化のニーズが高い。 By the way, a PCT (Pressure Cooker Test) is generally performed as a durability test (reliability test) in a liquid crystal panel, and this test method is performed under severe conditions such as a temperature of 121° C., a humidity of 100%, and an atmospheric pressure of 2 atm. The liquid crystal panel is allowed to stand for a period of time, and the presence or absence of leakage of liquid crystal enclosed between the color filter substrate and the TFT substrate of the liquid crystal panel is confirmed. The black matrix exists between each color of red, green, and blue, and in addition to the role of improving contrast, it also functions as the outer frame light-shielding film of the color filter. A part of the outer frame light-shielding film is connected to the counter substrate through the sealing material. Pasted together. Therefore, the black matrix is also required to have high adhesion strength so that the black matrix does not peel off from the glass substrate even under severe conditions such as PCT. In particular, in recent years, there is a strong need for high light shielding even for the outer frame light shielding film in order to improve the visibility of the liquid crystal panel.
また、スマートフォン、モバイルなどの中小型パネルに使用されるIPS(FFS)モードパネル向けのCFにおいては、ブラックマトリックスは高抵抗化が好ましく要求されている。遮光性を上げるため遮光成分を増やすと抵抗値が下がることから、細線化、高遮光、高密着性(高信頼性)、かつ、高抵抗化を確保することは非常に高い技術ハードルである。
ところで、樹脂ブラックマトリックス用遮光材(黒色色材)としては、一般にカーボンブラックが知られているが、カーボンブラックは電気抵抗が比較的低いため、表示装置の誤作動を引き起こす原因となる場合がある。特に広い視野角が得られるインプレーンスイッチング(IPS)方式の液晶表示装置においては、液晶層面内方向に電界を加えるため、ブラックマトリックスの抵抗値が低いと電界が正常に印加されず、液晶配向に乱れが生じて表示ムラの原因となる。
Further, in CF for IPS (FFS) mode panels used for small and medium-sized panels such as smartphones and mobiles, it is preferable that the black matrix has high resistance. Since increasing the light-shielding component to increase the light-shielding property lowers the resistance value, it is a very high technical hurdle to secure thin lines, high light-shielding, high adhesion (high reliability) and high resistance.
By the way, although carbon black is generally known as a light-shielding material (black color material) for a resin black matrix, since carbon black has a relatively low electric resistance, it may cause a malfunction of the display device. .. Particularly, in an in-plane switching (IPS) type liquid crystal display device that can obtain a wide viewing angle, an electric field is applied in the in-plane direction of the liquid crystal layer, so if the resistance value of the black matrix is low, the electric field is not normally applied, and the liquid crystal orientation is Disturbance occurs and causes display unevenness.
そこで、カーボンブラックを用いてブラックマトリックスの電気抵抗を大きくする方法として、カーボンブラックの表面に樹脂を被覆する技術(特許文献1参照)が適用されてきたが、高抵抗にするために樹脂被覆量を増やすと、光パターンニング性を十分に保持した上で実現できる遮光度に限界があり、要求されるレベルの高遮光、高抵抗を実現することが困難になってきた。そこで、比較的高抵抗で高遮光が実現できる特定のチタン窒化物粒子を遮光材として用いる技術(特許文献2参照)が開発されているが、光パターニング性や保存安定性が不足することが懸念される。 Therefore, as a method of increasing the electrical resistance of the black matrix using carbon black, a technique of coating the surface of carbon black with a resin has been applied (see Patent Document 1). However, if the value is increased, there is a limit to the degree of light shielding that can be realized while sufficiently maintaining the optical patterning property, and it has become difficult to achieve the required high light shielding and high resistance. Therefore, although a technique (see Patent Document 2) using specific titanium nitride particles capable of realizing relatively high resistance and high light shielding as a light shielding material has been developed, there is concern that the photopatterning property and storage stability may be insufficient. To be done.
このように、様々な要求特性を満たすブラックマトリックスに対するニーズが高まる中で、具体的には、遮光材の含有割合が多く光硬化が困難な感光性樹脂組成物において、低露光量にてパターン寸法安定性、パターン密着性、パターンのエッジ形状のシャープ性が良好な細線パターンを広い現像マージンで得ること、および、高遮光、好ましくは高抵抗も具備し、PCTなどの耐久性試験においてもガラス基板との密着性の高い(高信頼性)、品質の良好なブラックマトリクスおよび外枠遮光膜を形成することが求められている。なお、カラーフィルター外枠遮光膜と同様な目的で、タッチパネルにおける外枠等に遮光膜を形成する要望も高まっている。 As described above, as the need for a black matrix satisfying various required characteristics increases, specifically, in a photosensitive resin composition containing a large amount of a light-shielding material and difficult to be photocured, the pattern size is reduced at a low exposure amount. A glass substrate capable of obtaining a fine line pattern having excellent stability, pattern adhesion, and sharpness of the edge shape of the pattern with a wide development margin, and also having high light shielding, preferably high resistance, even in a durability test such as PCT. It is required to form a black matrix and an outer frame light-shielding film having high adhesion (high reliability) with good quality. There is an increasing demand for forming a light-shielding film on the outer frame or the like of the touch panel for the same purpose as that of the outer frame light-shielding film for the color filter.
そこで、例えば、特許文献3〜4には、高感度光重合開始剤としてオキシムエステルフルオレン系の化合物を含有するブラックマトリックス用感光性樹脂組成物が提案されている。ところが、低露光量にてパターン寸法安定性に優れ、パターン密着性、パターンのエッジ形状のシャープ性が良好な細線パターンを広い現像マージンで得る点で十分な性能を示すのは困難であり、また、高遮光かつ高抵抗と特性を満たす組成物に関する記載とか、PCTなどの耐久性試験における密着性を示す組成物に関する具体的な記載はない。 Therefore, for example, Patent Documents 3 to 4 propose a photosensitive resin composition for a black matrix containing an oxime ester fluorene compound as a high-sensitivity photopolymerization initiator. However, it is difficult to show sufficient performance in obtaining a fine line pattern with a wide development margin, which has excellent pattern dimensional stability at a low exposure amount, pattern adhesion, and sharpness of the edge shape of the pattern. There is no description about a composition that satisfies the requirements of high light-shielding and high resistance, or a specific description about a composition that exhibits adhesion in a durability test such as PCT.
本発明は、上記問題点に鑑みてなされたものであり、その目的とするところは、感光性樹脂組成物において、高精細、高遮光を維持しつつ、例えば5μmといった細線を形成した場合にも現像密着性を十分に確保し、ガラス基板との密着性にも優れ、更に高抵抗特性も具備することが可能であるブラックマトリックスを形成することができる、遮光膜用感光性樹脂組成物を提供することにある。本発明はまた、当該感光性樹脂組成物を用い、フォトリソグラフィー法により形成した遮光膜パターン等の硬化物であり、さらには、当該硬化物を含むカラーフィルターやタッチパネルを提供することにある。 The present invention has been made in view of the above problems, and an object thereof is also to form a thin line of, for example, 5 μm in a photosensitive resin composition while maintaining high definition and high light shielding. Provided is a photosensitive resin composition for a light-shielding film, which is capable of forming a black matrix capable of ensuring sufficient development adhesion, excellent adhesion to a glass substrate, and having high resistance characteristics. To do. The present invention also provides a cured product such as a light-shielding film pattern formed by a photolithography method using the photosensitive resin composition, and further provides a color filter or a touch panel including the cured product.
本発明者らは前記の課題を解決すべく検討を行った結果、重合性不飽和基含有アルカリ可溶性樹脂、光重合性モノマー、光重合開始剤、及び遮光成分を含む感光性樹脂組成物のうち、特に光重合開始剤として、重合性基を有するオキシムエステルフルオレン系光重合開始剤を配合することにより、高精細、高遮光、ガラス基板との高密着性を維持しつつ、細線の形成においても現像密着性を十分に確保することができ、更に、遮光成分として、光学濃度が4/μmとして製膜した際に表面抵抗率を高くすることができるような特定の絶縁性遮光成分を配合することで高抵抗の遮光膜を形成することが可能であることを見出し、本発明を完成させた。
すなわち、本発明の要旨は次のとおりである。
As a result of studies conducted by the present inventors to solve the above problems, a polymerizable unsaturated group-containing alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a photosensitive resin composition containing a light-shielding component , Especially as a photopolymerization initiator, by blending an oxime ester fluorene-based photopolymerization initiator having a polymerizable group, high definition, high light shielding, while maintaining high adhesion with a glass substrate, even in the formation of fine lines A specific insulating light-shielding component capable of ensuring sufficient development adhesion and further increasing the surface resistivity when formed into a film with an optical density of 4/μm is added as a light-shielding component. As a result, they have found that it is possible to form a high-resistance light-shielding film, and have completed the present invention.
That is, the gist of the present invention is as follows.
〔1〕下記(A)〜(D)成分、
(A)1分子内に2個以上のエポキシ基を有するエポキシ化合物に不飽和基含有モノカルボン酸を反応させ、更に多価カルボン酸又はその酸無水物を反応させて得られる重合性不飽和基含有アルカリ可溶性樹脂、
(B)少なくとも1個のエチレン性不飽和結合を有する光重合性モノマー、
(C)フルオレン環の9位に重合性基を有するフルオレン系化合物を含有する光重合開始剤、及び
(D)黒色有機顔料、混色有機顔料及び無機顔料からなる群から選ばれた1以上の遮光成分
を必須成分として含む遮光膜用感光性樹脂組成物において、
(A)成分と(B)成分との重量割合(A)/(B)が、50/50〜90/10であり、(A)成分と(B)成分の合計100質量部に対して(C)成分を2〜30質量部含有し、且つ、組成物の全固形分に対して(D)成分を20〜80質量%含有することを特徴とする遮光膜用感光性樹脂組成物。
〔2〕前記〔1〕に記載の遮光膜用感光性樹脂組成物において、(C)成分が下記一般式(I)で表される化合物を含有する光重合開始剤であることを特徴とする遮光膜用感光性樹脂組成物。
〔3〕前記〔1〕又は〔2〕に記載の遮光膜用感光性樹脂組成物において、(D)成分が、光学濃度が4/μmとなるように製膜した膜の表面抵抗率を1×108Ω/□以上とする絶縁性遮光成分であることを特徴とする遮光膜用感光性樹脂組成物。
〔4〕(A)成分が下記一般式(II)で表される化合物と(メタ)アクリル酸との反応物に、更に多価カルボン酸又はその無水物と反応させて得られる重合性不飽和基含有アルカリ可溶性樹脂であることを特徴とする〔1〕〜〔3〕のいずれかに記載の遮光膜用感光性樹脂組成物。
〔5〕(C)成分が、下記式(III)で表される化合物を含有する光重合開始剤であることを特徴とする〔1〕〜〔4〕のいずれかに記載の遮光膜用感光性樹脂組成物。
〔7〕前記〔1〕〜〔6〕のいずれかに記載の遮光膜用感光性樹脂組成物を硬化させて形成したことを特徴とする塗膜。
〔8〕前記〔1〕〜〔6〕のいずれかに記載の遮光膜用感光性樹脂組成物により作製された遮光膜を透明基板上に備えてなるカラーフィルターの製造方法であって、当該遮光膜用感光性樹脂組成物を透明基板上に塗布、プリベークした後、紫外線露光装置による露光、アルカリ水溶液による現像、及びポストベークして遮光膜を作製することを特徴とするカラーフィルターの製造方法。
〔9〕前記〔1〕〜〔6〕のいずれかに記載の遮光膜用感光性樹脂組成物により作製された遮光膜を透明基板上に備えてなるタッチパネルの製造方法であって、当該遮光膜用感光性樹脂組成物を透明基板上に塗布、プリベークした後、紫外線露光装置による露光、アルカリ水溶液による現像、及びポストベークして遮光膜を作製することを特徴とするタッチパネルの製造方法。
[1] The following components (A) to (D),
(A) a polymerizable unsaturated group obtained by reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound having two or more epoxy groups in one molecule, and further reacting a polyvalent carboxylic acid or an acid anhydride thereof Containing alkali-soluble resin,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator containing a fluorene compound having a polymerizable group at the 9-position of the fluorene ring, and
(D) A photosensitive resin composition for a light-shielding film containing as an essential component one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and inorganic pigments,
The weight ratio (A)/(B) of the component (A) and the component (B) is 50/50 to 90/10, and (100) parts by weight of the total of the component (A) and the component (B) ( A photosensitive resin composition for a light-shielding film, which contains 2 to 30 parts by mass of the component C) and 20 to 80% by mass of the component (D) with respect to the total solid content of the composition.
[2] The photosensitive resin composition for a light shielding film as described in [1] above, wherein the component (C) is a photopolymerization initiator containing a compound represented by the following general formula (I): A photosensitive resin composition for a light shielding film.
[3] In the photosensitive resin composition for a light-shielding film according to the above [1] or [2], the component (D) has a surface resistivity of 1 when formed into a film having an optical density of 4/μm. A photosensitive resin composition for a light-shielding film, which is an insulating light-shielding component having a density of ×10 8 Ω/□ or more.
[4] Polymerizable unsaturation obtained by reacting the reaction product of the compound (A) represented by the following general formula (II) with (meth)acrylic acid with a polycarboxylic acid or an anhydride thereof. The photosensitive resin composition for a light-shielding film according to any one of [1] to [3], which is a group-containing alkali-soluble resin.
[5] The photosensitive material for a light-shielding film according to any one of [1] to [4], wherein the component (C) is a photopolymerization initiator containing a compound represented by the following formula (III). Resin composition.
[7] A coating film formed by curing the photosensitive resin composition for a light-shielding film according to any one of [1] to [6] above.
[8] A method for producing a color filter, comprising a light-shielding film made of the photosensitive resin composition for light-shielding film according to any one of [1] to [6] above, which is provided on a transparent substrate. A method for producing a color filter, which comprises producing a light-shielding film by applying a photosensitive resin composition for a film on a transparent substrate, pre-baking, exposing with an ultraviolet exposure device, developing with an alkaline aqueous solution, and post-baking.
[9] A method for manufacturing a touch panel, comprising a light-shielding film made of the photosensitive resin composition for light-shielding film according to any one of [1] to [6] above, on a transparent substrate, the light-shielding film A method for manufacturing a touch panel, comprising: applying a photosensitive resin composition for use on a transparent substrate, pre-baking, exposing with an ultraviolet exposure device, developing with an alkaline aqueous solution, and post-baking to form a light-shielding film.
本発明の遮光膜用感光性樹脂組成物は、高精細、高遮光を維持しつつ、例えば線幅が5μm程度の細線を形成した場合にも現像密着性を十分に確保することができ、しかも、ガラス基板との密着性にも優れ、高抵抗の遮光膜とすることも可能である。 The photosensitive resin composition for a light-shielding film of the present invention can sufficiently secure development adhesion even when a fine line having a line width of about 5 μm is formed while maintaining high definition and high light-shielding. Also, it is possible to form a high-resistance light-shielding film that has excellent adhesion to a glass substrate.
以下、本発明について詳細に説明する。
(A)成分の重合性不飽和基含有アルカリ可溶性樹脂としては、1分子内に2個以上のエポキシ基を有するエポキシ化合物に不飽和基含有モノカルボン酸を反応させ、更に多価カルボン酸又はその酸無水物を反応させて得られる重合性不飽和基含有アルカリ可溶性樹脂であれば特に制限なく用いることができ、好ましくは、ビスフェノール類から誘導される2個のグリシジルエーテル基を有する以下の一般式(II)のエポキシ化合物に、(メタ)アクリル酸(これは「アクリル酸及び/又はメタクリル酸」の意味である)を反応させ、得られたヒドロキシ基を有する化合物に多価カルボン酸又はその無水物を反応させて得られるエポキシ(メタ)アクリレート酸付加物であることがよい。ビスフェノール類から誘導されるエポキシ化合物とは、ビスフェノール類とエピハロヒドリンを反応させて得られるエポキシ化合物又はこれと同等物を意味する。(A)成分は、重合性不飽和二重結合とカルボキシル基とを併せ持つため、感光性樹脂組成物に優れた光硬化性、良現像性、パターニング特性を与え遮光膜の物性向上をもたらす。
Hereinafter, the present invention will be described in detail.
As the polymerizable unsaturated group-containing alkali-soluble resin as the component (A), an unsaturated group-containing monocarboxylic acid is reacted with an epoxy compound having two or more epoxy groups in one molecule, and a polyvalent carboxylic acid or Any polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting an acid anhydride can be used without particular limitation, and preferably has the following general formula having two glycidyl ether groups derived from bisphenols. The epoxy compound of (II) is reacted with (meth)acrylic acid (which means “acrylic acid and/or methacrylic acid”), and the obtained compound having a hydroxy group is added with a polyvalent carboxylic acid or an anhydride thereof. It may be an epoxy (meth)acrylate acid addition product obtained by reacting a product. The epoxy compound derived from bisphenols means an epoxy compound obtained by reacting bisphenols with epihalohydrin or an equivalent thereof. Since the component (A) has both a polymerizable unsaturated double bond and a carboxyl group, it imparts excellent photocurability, good developability and patterning characteristics to the photosensitive resin composition, and improves the physical properties of the light-shielding film.
この一般式(II)のエポキシ化合物はビスフェノール類から誘導され、まず不飽和基含有モノカルボン酸を反応させる。このエポキシ化合物と不飽和基含有モノカルボン酸との反応物に対して、多価カルボン酸又はその無水物として、(a)ジカルボン酸若しくはトリカルボン酸又はその酸無水物、及び(b)テトラカルボン酸又はその酸二無水物を反応させて重合性不飽和基含有アルカリ可溶性樹脂を得る。以下、一般式(II)の化合物を用いて(A)成分を得る場合について説明する。 The epoxy compound represented by the general formula (II) is derived from bisphenols and firstly reacted with an unsaturated group-containing monocarboxylic acid. For the reaction product of this epoxy compound and an unsaturated group-containing monocarboxylic acid, as a polyvalent carboxylic acid or its anhydride, (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid Alternatively, the acid dianhydride is reacted to obtain a polymerizable unsaturated group-containing alkali-soluble resin. Hereinafter, the case of obtaining the component (A) using the compound of the general formula (II) will be described.
一般式(II)のエポキシ化合物を与えるビスフェノール類としては、ビス(4−ヒドロキシフェニル)ケトン、ビス(4−ヒドロキシ−3,5−ジメチルフェニル)ケトン、ビス(4−ヒドロキシ−3,5−ジクロロフェニル)ケトン、ビス(4−ヒドロキシフェニル)スルホン、ビス(4−ヒドロキシ−3,5−ジメチルフェニル)スルホン、ビス(4−ヒドロキシ−3,5−ジクロロフェニル)スルホン、ビス(4−ヒドロキシフェニル)ヘキサフルオロプロパン、ビス(4−ヒドロキシ−3,5−ジメチルフェニル)ヘキサフルオロプロパン、ビス(4−ヒドロキシ−3,5−ジクロロフェニル)ヘキサフルオロプロパン、ビス(4−ヒドロキシフェニル)ジメチルシラン、ビス(4−ヒドロキシ−3,5−ジメチルフェニル)ジメチルシラン、ビス(4−ヒドロキシ−3,5−ジクロロフェニル)ジメチルシラン、ビス(4−ヒドロキシフェニル)メタン、ビス(4−ヒドロキシ−3,5−ジクロロフェニル)メタン、ビス(4−ヒドロキシ−3,5−ジブロモフェニル)メタン、2,2−ビス(4−ヒドロキシフェニル)プロパン、2,2−ビス(4−ヒドロキシ−3,5−ジメチルフェニル)プロパン、2,2−ビス(4−ヒドロキシ−3,5−ジクロロフェニル)プロパン、2,2−ビス(4−ヒドロキシ−3−メチルフェニル)プロパン、2,2−ビス(4−ヒドロキシ−3− クロロフェニル)プロパン、ビス(4−ヒドロキシフェニル)エーテル、ビス(4−ヒドロキシ−3,5−ジメチルフェニル)エーテル、ビス(4−ヒドロキシ−3,5−ジクロロフェニル)エーテル、9,9−ビス(4−ヒドロキシフェニル)フルオレン、9,9−ビス(4−ヒドロキシ−3−メチルフェニル)フルオレン、9,9−ビス(4−ヒドロキシ−3−クロロフェニル)フルオレン、9, 9−ビス(4−ヒドロキシ−3−ブロモフェニル)フルオレン、9,9−ビス(4−ヒドロキシ−3−フルオロフェニル)フルオレン、9,9−ビス(4−ヒドロキシ−3−メトキシフェニル)フルオレン、9,9−ビス(4−ヒドロキシ−3,5−ジメチルフェニル)フルオレン、9,9−ビス(4−ヒドロキシ−3,5−ジクロロフェニル)フルオレン、9,9−ビス(4−ヒドロキシ−3,5−ジブロモフェニル)フルオレン、4,4'−ビフェノール、3,3'−ビフェノール等を挙げられる。この中でも、一般式(II)におけるXがフルオレン-9,9-ジイル基であるビスフェノール類を特に好ましく用いることができる。 Examples of the bisphenols giving the epoxy compound of the general formula (II) include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl). ) Ketone, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, bis(4-hydroxy-3,5-dichlorophenyl) sulfone, bis(4-hydroxyphenyl)hexafluoro Propane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy) -3,5-Dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis (4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2- Bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4 -Hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9, 9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9, 9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene , 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'- Biphenol etc. are mentioned. Among these, bisphenols in which X in the general formula (II) is a fluorene-9,9-diyl group can be particularly preferably used.
(A)のアルカリ可溶性樹脂を得るに当たって、好適には、上記ビスフェノール類とエピクロルヒドリンとを反応させて2個のグリシジルエーテル基を有するエポキシ化合物を得る。この反応の際には、一般にジグリシジルエーテル化合物のオリゴマー化を伴うため、一般式(II)のエポキシ化合物を得ることになる。lは通常は複数の値が混在するため平均値0〜10(整数とは限らない)となるが、好ましいlの平均値は0〜3である。lの値が上限値を超えると、当該エポキシ化合物使用して合成したアルカリ可溶性樹脂を用いた感光性樹脂組成物としたときに組成物の粘度が大きくなりすぎて塗工がうまく行かなくなったり、アルカリ可溶性を十分に付与できずアルカリ現像性が非常に悪くなったりする。 In obtaining the alkali-soluble resin (A), it is preferable to react the bisphenols with epichlorohydrin to obtain an epoxy compound having two glycidyl ether groups. In this reaction, since the diglycidyl ether compound is generally oligomerized, the epoxy compound of the general formula (II) is obtained. Since a plurality of values of l are usually mixed, the average value is 0 to 10 (not necessarily an integer), but the preferable average value of l is 0 to 3. When the value of l exceeds the upper limit, the viscosity of the composition becomes too large when the photosensitive resin composition is prepared by using the alkali-soluble resin synthesized by using the epoxy compound, and the coating may not be successful. Alkali solubility cannot be sufficiently imparted, and the alkali developability may be extremely deteriorated.
なお、本発明の重合性不飽和基含有アルカリ可溶性樹脂は、上記のようなビスフェノール類から誘導されるエポキシ化合物から得ることができるが、かかるエポキシ化合物以外でも、例えば、フェノールノボラック型エポキシ化合物や、クレゾールノボラック型エポキシ化合物等の2個以上のグリシジルエーテル基を有するエポキシ化合物から得られるものも使用することができる。 The polymerizable unsaturated group-containing alkali-soluble resin of the present invention can be obtained from an epoxy compound derived from the above bisphenols, but other than such an epoxy compound, for example, a phenol novolac type epoxy compound, Those obtained from epoxy compounds having two or more glycidyl ether groups such as cresol novolac type epoxy compounds can also be used.
次に、一般式(II)の化合物に対して、例えば不飽和基含有モノカルボン酸としてアクリル酸若しくはメタクリル酸又はこれらの両方を反応させ、これにより得られたヒドロキシ基を有する反応物に対して、多価カルボン酸又はその無水物として、(a)ジカルボン酸若しくはトリカルボン酸又はその酸無水物、及び(b)テトラカルボン酸又はその酸二無水物を反応させる。その際、(a)/(b)のモル比が0.01〜10となる範囲で反応させることが好ましい。この反応によりエポキシ(メタ)アクリレート酸付加物の構造を有する重合性不飽和基含有アルカリ可溶性樹脂を得る。 Next, the compound of the general formula (II) is reacted with, for example, acrylic acid or methacrylic acid as an unsaturated group-containing monocarboxylic acid or both of them, and a reaction product having a hydroxy group obtained thereby is reacted. As the polyvalent carboxylic acid or its anhydride, (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid or its dianhydride are reacted. At that time, it is preferable to carry out the reaction in the range of (a)/(b) molar ratio of 0.01 to 10. By this reaction, a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth)acrylate acid adduct is obtained.
エポキシ(メタ)アクリレート酸付加物に利用される(a)ジカルボン酸若しくはトリカルボン酸又はその酸無水物としては、鎖式炭化水素ジカルボン酸若しくはトリカルボン酸又はその酸無水物や脂環式ジカルボン酸若しくはトリカルボン酸又はその酸無水物、芳香族ジカルボン酸若しくはトリカルボン酸又はその酸無水物が使用される。ここで、鎖式炭化水素ジカルボン酸若しくはトリカルボン酸又はその酸無水物としては、例えば、コハク酸、アセチルコハク酸、マレイン酸、アジピン酸、イタコン酸、アゼライン酸、シトラリンゴ酸、マロン酸、グルタル酸、クエン酸、酒石酸、オキソグルタル酸、ピメリン酸、セバシン酸、スベリン酸、ジグリコール酸等の化合物があり、更には任意の置換基が導入されたジカルボン酸若しくはトリカルボン酸又はその酸無水物でもよい。また、脂環式ジカルボン酸若しくはトリカルボン酸又はその酸無水物としては、例えば、シクロブタンジカルボン酸、シクロペンタンジカルボン酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、ノルボルナンジカルボン酸等の化合物があり、更には任意の置換基が導入されたジカルボン酸若しくはトリカルボン酸又はその酸無水物でもよい。更に、芳香族ジカルボン酸若しくはトリカルボン酸又はその酸無水物としては、例えばフタル酸、イソフタル酸、トリメリット酸等の化合物があり、更には任意の置換基が導入されたジカルボン酸若しくはトリカルボン酸又はその酸無水物でもよい。 The (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride used in the epoxy (meth)acrylate acid adduct is a chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride or alicyclic dicarboxylic acid or tricarboxylic acid. Acids or acid anhydrides thereof, aromatic dicarboxylic acids or tricarboxylic acids or acid anhydrides thereof are used. Here, as the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an acid anhydride thereof, for example, succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, There are compounds such as citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and further, a dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein or an acid anhydride thereof may be used. Further, examples of the alicyclic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and further optional It may be a dicarboxylic acid or tricarboxylic acid in which the substituent is introduced or an acid anhydride thereof. Furthermore, examples of the aromatic dicarboxylic acid or tricarboxylic acid or acid anhydride thereof include compounds such as phthalic acid, isophthalic acid and trimellitic acid, and further, a dicarboxylic acid or tricarboxylic acid having any substituent introduced therein or its It may be an acid anhydride.
また、エポキシ(メタ)アクリレート酸付加物に利用される(b)テトラカルボン酸又はその酸二無水物としては、鎖式炭化水素テトラカルボン酸又はその酸二無水物や脂環式テトラカルボン酸又はその酸二無水物、又は、芳香族多価カルボン酸又はその酸二無水物が使用される。ここで、鎖式炭化水素テトラカルボン酸又はその酸二無水物としては、例えば、ブタンテトラカルボン酸、ペンタンテトラカルボン酸、ヘキサンテトラカルボン酸等があり、更には任意の置換基が導入されたテトラカルボン酸又はその酸二無水物でもよい。また、脂環式テトラカルボン酸又はその酸二無水物としては、例えば、シクロブタンテトラカルボン酸、シクロペンタンテトラカルボン酸、シクロヘキサンテトラカルボン酸、シクロへプタンテトラカルボン酸、ノルボルナンテトラカルボン酸等があり、更には任意の置換基の導入されたテトラカルボン酸又はその酸二無水物でもよい。更に、芳香族テトラカルボン酸やその酸二無水物としては、例えば、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、ビフェニルエーテルテトラカルボン酸又はその酸二無水物が挙げられ、更には任意の置換基の導入されたテトラカルボン酸又はその酸二無水物でもよい。 Further, as the (b) tetracarboxylic acid or its dianhydride used in the epoxy (meth) acrylate acid addition product, a chain hydrocarbon tetracarboxylic acid or its dianhydride or alicyclic tetracarboxylic acid or The acid dianhydride, the aromatic polycarboxylic acid or the acid dianhydride is used. Here, as the chain hydrocarbon tetracarboxylic acid or an acid dianhydride thereof, there are, for example, butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, etc., and tetra substituted with any substituent. It may be a carboxylic acid or its dianhydride. The alicyclic tetracarboxylic acid or its dianhydride, for example, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like, Further, it may be a tetracarboxylic acid having an arbitrary substituent introduced or its dianhydride. Further, examples of the aromatic tetracarboxylic acid and its acid dianhydride include, for example, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid or its acid dianhydride, and further any It may be a tetracarboxylic acid having a substituent introduced therein or its dianhydride.
エポキシ(メタ)アクリレート酸付加物に使用される(a)ジカルボン酸若しくはトリカルボン酸又はその酸無水物と(b)テトラカルボン酸又はその酸二無水物とのモル比(a)/(b)は、上述したように0.01〜10であるのが好ましい。モル比(a)/(b)が上記範囲を逸脱すると最適分子量が得られず、(A)を使用した感光性樹脂組成物において、アルカリ現像性、耐熱性、耐溶剤性、パターン形状等が劣化するので好ましくない。なお、モル比(a)/(b)が小さいほどアルカリ溶解性が大となり、分子量が大となる傾向がある。 The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its dianhydride used for the epoxy (meth)acrylate acid adduct is It is preferably 0.01 to 10 as described above. When the molar ratio (a)/(b) deviates from the above range, the optimum molecular weight cannot be obtained, and in the photosensitive resin composition using (A), alkali developability, heat resistance, solvent resistance, pattern shape, etc. It is not preferable because it deteriorates. The smaller the molar ratio (a)/(b), the higher the alkali solubility and the higher the molecular weight.
エポキシ(メタ)アクリレート酸付加物は、上述の工程により、既知の方法、例えば特開平8-278629号公報や特開2008-9401号公報等に記載の方法により製造することができる。先ず、一般式(I)のエポキシ化合物に不飽和基含有モノカルボン酸を反応させる方法としては、例えば、エポキシ化合物のエポキシ基と等モルの不飽和基含有モノカルボン酸を溶剤中に添加し、触媒(トリエチルベンジルアンモニウムクロライド、2,6-ジイソブチルフェノール等)の存在下、空気を吹き込みながら90〜120℃に加熱・攪拌して反応させるという方法がある。次に、反応生成物であるエポキシアクリレート化合物の水酸基に酸無水物を反応させる方法としては、エポキシアクリレート化合物と酸二無水物および酸一無水物の所定量を溶剤中に添加し、触媒(臭化テトラエチルアンモニウム、トリフェニルホスフィン等)の存在下、90〜130℃で加熱・攪拌して反応させるという方法がある。 The epoxy (meth)acrylate acid adduct can be produced by the above-mentioned steps by a known method, for example, the method described in JP-A-8-278629 or JP-A-2008-9401. First, as a method of reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (I), for example, an epoxy group of the epoxy compound and an equimolar unsaturated group-containing monocarboxylic acid are added to a solvent, In the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.), there is a method of reacting by heating and stirring at 90 to 120° C. while blowing air. Next, as a method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound which is a reaction product, a predetermined amount of an epoxy acrylate compound, an acid dianhydride and an acid monoanhydride is added to a solvent, and a catalyst (odor In the presence of tetraethylammonium chloride, triphenylphosphine, etc.), the reaction is performed by heating and stirring at 90 to 130° C.
重合性不飽和基含有アルカリ可溶性樹脂(A)の重量平均分子量(Mw)については、2000〜50000の範囲であることが好ましく、2000〜7000の間であることがより好ましい。重量平均分子量(Mw)が2000に満たないとこの(A)成分を使用した感光性樹脂組成物の現像時のパターンの密着性が維持できず、パターン剥がれが生じ、また、重量平均分子量(Mw)が50000を超えると現像残渣や未露光部の残膜が残り易くなる。更に、この(A)成分は、その酸価が30〜200mgKOH/gの範囲であることが望ましい。この値が30mgKOH/gより小さいとこの(A)成分を使用した感光性樹脂組成物のアルカリ現像がうまくできないか、強アルカリ等の特殊な現像条件が必要となり、200mgKOH/gを超えるとこの(A)成分を使用した感光性樹脂組成物へのアルカリ現像液の浸透が早くなり過ぎ、剥離現像が起きるので、何れも好ましくない。なお、この(A)成分の重合性不飽和基含有アルカリ可溶性樹脂については、その1種のみを使用しても、2種以上の混合物を使用することもできる。 The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 2,000 to 50,000, more preferably in the range of 2,000 to 7,000. If the weight average molecular weight (Mw) is less than 2000, the pattern adhesion during development of the photosensitive resin composition using the component (A) cannot be maintained, pattern peeling occurs, and the weight average molecular weight (Mw) ) Is more than 50,000, development residues and residual films in unexposed areas tend to remain. Further, the component (A) preferably has an acid value in the range of 30 to 200 mgKOH/g. If this value is less than 30 mgKOH/g, the alkali development of the photosensitive resin composition using this component (A) may not be successful, or special developing conditions such as strong alkali are required, and if it exceeds 200 mgKOH/g, The alkali developer penetrates into the photosensitive resin composition containing the component A) too quickly and peeling development occurs, which is not preferable. As for the polymerizable unsaturated group-containing alkali-soluble resin as the component (A), only one kind thereof may be used or a mixture of two or more kinds may be used.
次に、(B)少なくとも1個のエチレン性不飽和結合を有する光重合性モノマーとしては、例えば、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート等の水酸基を有する(メタ)アクリル酸エステル類や、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、テトラメチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、グリセロール(メタ)アクリレート、ソルビトールペンタ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、又はジペンタエリスリトールヘキサ(メタ)アクリレート、ソルビトールヘキサ(メタ)アクリレート、フォスファゼンのアルキレンオキサイド変性ヘキサ(メタ)アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ(メタ)アクリレート等の(メタ)アクリル酸エステル類を挙げることができ、これらの1種又は2種以上を使用することができる。なお、(B)少なくとも1個のエチレン性不飽和結合を有する光重合性モノマーは遊離のカルボキシ基を有しない。 Next, (B) as the photopolymerizable monomer having at least one ethylenically unsaturated bond, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth) (Meth)acrylic acid esters having a hydroxyl group such as acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene Glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol tetra(meth)acrylate, glycerol(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene alkylene Examples thereof include (meth)acrylic acid esters such as oxide-modified hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and one or more of these can be used. The photopolymerizable monomer (B) having at least one ethylenically unsaturated bond does not have a free carboxy group.
これら(A)成分と(B)成分の配合割合は、重量比(A)/(B)で50/50〜90/10であり、好ましくは60/40〜80/20である。(A)成分の配合割合が50/50より少ないと、光硬化後の硬化物が脆くなり、また、未露光部において塗膜の酸価が低いためにアルカリ現像液に対する溶解性が低下し、パターンエッジがぎざつきシャープにならないといった問題が生じ、また、90/10よりも多いと、樹脂に占める光反応性官能基の割合が少なく架橋構造の形成が十分でなく、更に、樹脂成分における酸価度が高過ぎて、露光部におけるアルカリ現像液に対する溶解性が高くなることから、形成されたパターンが目標とする線幅より細ったり、パターンの欠落が生じや易くなったりするといった問題が生じる恐れがある。 The mixing ratio of these components (A) and (B) is 50/50 to 90/10, preferably 60/40 to 80/20 in terms of weight ratio (A)/(B). When the blending ratio of the component (A) is less than 50/50, the cured product after photocuring becomes brittle, and the acid value of the coating film in the unexposed area is low, resulting in a decrease in solubility in an alkali developing solution. There is a problem that the pattern edge is not sharp and sharp, and when it is more than 90/10, the proportion of the photoreactive functional group in the resin is small and the formation of the crosslinked structure is not sufficient. Since the valency is too high and the solubility in the exposed portion in the alkali developing solution becomes high, there arises a problem that the formed pattern becomes thinner than the target line width, or the pattern is apt to be missing. There is a fear.
また、(C)成分の光重合開始剤としては、フルオレン環の9位に重合性基を有するフルオレン系化合物を含有する光重合開始剤を用いる。このようにフルオレン環の9位に重合性基を有することにより、特に光重合開始剤の添加量が大きい際には加熱硬化時に光重合開始剤が揮散する量を抑制できる等の効果も期待されるため好ましい。好ましくは、以下の一般式(I)で表される化合物を含有し、紫外線光等の照射によりラジカル種を発生し、光重合性の化合物に付加してラジカル重合を開始させ、組成物を硬化させる。その中でもより好ましくは一般式(III)で表される1−[9,9−ジ(2−プロペニル)−7−ニトロフルオレン−2−イル]−(2−メチルフェニル)−メタノン オキシム−O−アセタートが高感度を達成可能である点で特に好ましい。一般式(I)の製造については、例えば特表2015-523318号公報にその製法の記載がある。 Further, as the photopolymerization initiator of the component (C), a photopolymerization initiator containing a fluorene compound having a polymerizable group at the 9-position of the fluorene ring is used. By thus having a polymerizable group at the 9-position of the fluorene ring, it is expected that the amount of the photopolymerization initiator volatilized during heat curing can be suppressed especially when the amount of the photopolymerization initiator added is large. Therefore, it is preferable. Preferably, it contains a compound represented by the following general formula (I), generates a radical species by irradiation with ultraviolet light or the like, initiates radical polymerization by adding to a photopolymerizable compound, and cures the composition. Let Among them, more preferably, 1-[9,9-di(2-propenyl)-7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime-O- represented by the general formula (III). Acetate is particularly preferable in that high sensitivity can be achieved. Regarding the production of the general formula (I), for example, the production method is described in Japanese Patent Publication No. 2015-523318.
また、本発明においては、一般式(I)で表される化合物を含有する光重合開始剤と共に、他の光重合開始剤若しくは増感剤を1種以上併用することができる。ここで、他の光重合開始剤若しくは増感剤としては、例えば、アセトフェノン、2,2−ジエトキシアセトフェノン、p−ジメチルアセトフェノン、p−ジメチルアミノプロピオフェノン、ジクロロアセトフェノン、トリクロロアセトフェノン、p−tert−ブチルアセトフェノン等のアセトフェノン類、ベンゾフェノン、2−クロロベンゾフェノン、p,p'-ビスジメチルアミノベンゾフェノン等のベンゾフェノン類、ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾインエーテル類、2-(o-クロロフェニル)-4,5-フェニルビイミダゾール、2-(o-クロロフェニル)-4,5-ジ(m-メトキシフェニル)ビイミダゾール、2-(o-フルオロフェニル)-4,5-ジフェニルビイミダゾール、2-(o-メトキシフェニル)-4,5-ジフェニルビイミダゾール、2,4,5-トリアリールビイミダゾール等のビイミダゾール系化合物類、2-トリクロロメチル−5−スチリル−1,3,4−オキサジアゾール、2−トリクロロメチル-5-(p-シアノスチリル)-1,3,4-オキサジアゾール、2-トリクロロメチル-5-(p-メトキシスチリル)-1,3,4-オキサジアゾール等のハロメチルジアゾール化合物類、2,4,6-トリス(トリクロロメチル)-1,3,5-トリアジン、2-メチル−4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-(4-クロロフェニル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-(4-メトキシフェニル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-(4-メトキシナフチル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-(4-メトキシスチリル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-(3,4,5-トリメトキシスチリル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン、2-(4-メチルチオスチリル)-4,6-ビス(トリクロロメチル)-1,3,5-トリアジン等のハロメチル−S−トリアジン系化合物類、1,2-オクタンジオン,1-[4-(フェニルチオ)フェニル]-,2-(o-ベンゾイルオキシム)、1-(4-フェニルスルファニルフェニル)ブタン-1,2-ジオン-2-オキシム-O-ベンゾアート、1-(4-メチルスルファニルフェニル)ブタン-1,2-ジオン-2-オキシム-O-アセタート、1-(4-メチルスルファニルフェニル)ブタン-1-オンオキシム-O-アセタート等のO-アシルオキシム系化合物類、ベンジルジメチルケタール、チオキサンソン、2-クロロチオキサンソン、2,4-ジエチルチオキサンソン、2-メチルチオキサンソン、2-イソプロピルチオキサンソン等のイオウ化合物、2-エチルアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン、2,3-ジフェニルアントラキノン等のアントラキノン類、アゾビスイソブチルニトリル、ベンゾイルパーオキサイド、クメンパーオキシド等の有機過酸化物、2-メルカプトベンゾイミダゾール、2-メルカプトベンゾオキサゾール、2-メルカプトベンゾチアゾール等のチオール化合物などが挙げられる。 Further, in the present invention, one or more kinds of other photopolymerization initiators or sensitizers can be used together with the photopolymerization initiator containing the compound represented by the general formula (I). Here, as other photopolymerization initiators or sensitizers, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert. -Acetophenones such as butylacetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p,p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5 -Diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl-5-styryl-1 ,3,4-Oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3 ,4-Oxadiazole and other halomethyldiazole compounds, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1 ,3,5-Triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3 ,5-Triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)- Halomethyl-S- such as 4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine Triazine compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), 1-(4 -Phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-( 4-methylsulfanylphenyl)butan-1-one oxime-O-acetate and other O-acyl oxime compounds, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthio Xanthones, sulfur compounds such as 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, Examples thereof include organic peroxides such as cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.
一般式(I)で表される化合物を含有する光重合開始剤を含めて、これらの光重合開始剤や増感剤は、その1種のみを単独で使用できるほか、2種以上を組み合わせて使用することもできる。組合せで使用する場合の好ましい組合せの例としては、一般式(I)の化合物を含有する光重合開始剤とチオール化合物との組合せを例示することができる。このようなチオール化合物としては、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、トリメチロールプロパントリス(3-メルカプトブチレート)、トリメチロールプロパントリス(3-メルカプトブチレート)、ペンタエリスリトールテトラキス(3-メルカプトブチレート)などを例示することができ、多官能のチオール化合物を用いることが好ましい。なお、このように光重合開始剤とチオール化合物を組合せる場合のチオール化合物の添加量は、(A)成分と(B)成分の合計100質量部を基準として1〜10質量部であることが好ましい。
また、それ自体では光重合開始剤や増感剤として作用しないが、組み合わせて用いることにより、光重合開始剤や増感剤の能力を増大させ得るような化合物を添加することもできる。そのような組み合わせに用いる化合物としては、例えば、ベンゾフェノンと組み合わせて使用すると効果のあるトリエタノールアミン、トリエチルアミン等の第3級アミンを挙げることができる。
These photopolymerization initiators and sensitizers including the photopolymerization initiator containing the compound represented by the general formula (I) can be used alone or in combination of two or more. It can also be used. Examples of preferable combinations when used in combination include a combination of a photopolymerization initiator containing a compound of the general formula (I) and a thiol compound. Examples of such thiol compounds are 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis. (3-mercaptobutyrate) and the like can be exemplified, and it is preferable to use a polyfunctional thiol compound. The amount of the thiol compound added when the photopolymerization initiator and the thiol compound are combined is 1 to 10 parts by mass based on 100 parts by mass of the total of the components (A) and (B). preferable.
Further, a compound which does not act as a photopolymerization initiator or a sensitizer by itself but which can increase the ability of the photopolymerization initiator or the sensitizer when used in combination can be added. Examples of compounds used in such a combination include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.
(C)成分の光重合開始剤の使用量は、(A)成分と(B)成分の合計100質量部を基準として2〜30質量部であり、好ましくは5〜25質量部、より好ましくは5〜20質量部である。(C)成分の配合割合が2質量部未満の場合には、光重合の速度が遅くなって、感度が低下し、一方、30質量部を超える場合には、感度が強すぎて、パターン線幅がパターンマスクに対して太った状態になり、マスクに対して忠実な線幅が再現できない、又は、パターンエッジがぎざつきシャープにならないといった問題が生じる恐れがある。(C)成分の光重合開始剤は、必須成分として一般式(I)で表される光重合開始剤を含むが、その量は他の(C)成分を加えない場合であっても、単独で光重合開始剤として有効に作用する量以上であることがよく、一般式(I)で表される光重合開始剤の量は(C)成分の全体量のうち、70〜100質量%であることが好ましい。 The amount of the photopolymerization initiator used as the component (C) is 2 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably 100 parts by mass of the component (A) and the component (B). 5 to 20 parts by mass. When the compounding ratio of the component (C) is less than 2 parts by mass, the photopolymerization rate becomes slow and the sensitivity decreases, while when it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line There is a possibility that the width becomes thicker than the pattern mask, a line width faithful to the mask cannot be reproduced, or the pattern edge is not sharp and sharp. The photopolymerization initiator of the component (C) contains a photopolymerization initiator represented by the general formula (I) as an essential component, but the amount thereof is independent even if the other component (C) is not added. The amount of the photopolymerization initiator represented by the general formula (I) is preferably 70 to 100% by mass based on the total amount of the component (C). It is preferable to have.
(D)成分は、黒色有機顔料、混色有機顔料又は無機顔料から選ばれる遮光成分であり、耐熱性、耐光性及び耐溶剤性に優れたものであるのがよい。ここで、黒色有機顔料としては、例えばペリレンブラック、シアニンブラック、アニリンブラック、ラクタムブラック等が挙げられる。混色有機顔料としては、赤、青、緑、紫、黄色、シアニン、マゼンタ等から選ばれる2種以上の顔料を混合して擬似黒色化されたものが挙げられる。無機顔料としては、カーボンブラック、酸化クロム、酸化鉄、チタンブラック等を挙げることができ、2種以上を適宜選択して用いることもできる。
このうち、遮光膜に高抵抗特性を具備させるために、好ましくは、光学濃度が4/μmとなるように製膜した膜の表面抵抗率(例えば、印可電圧10V時の表面抵抗率)を1×108Ω/□以上とするような絶縁性の高い遮光成分を用いることがよく、その代表的な例が絶縁性の表面処理を施したカーボンブラックである。表面処理カーボンブラックの例としては、特表H10−510861号公報に示されたジアゾニウム塩と反応させて置換アリール基等を表面に結合させたカーボンブラック、特開2001−207079号公報に示された表面に樹脂を被覆したカーボンブラック、再公表WO2013/129554公報に示された表面が染料で被覆されたカーボンブラックを例示することができるが、高抵抗化処理されたカーボンブラックで光学濃度が4/μmとなるように製膜した膜の表面抵抗率を1×108Ω/□以上とするものであれば、特に制限なく用いることができる。なお、光学濃度が4/μmとなるように製膜した膜の表面抵抗率は、1×1010Ω/□以上であることがより好ましく、1×1012Ω/□以上であることが特に好ましい。
The component (D) is a light-shielding component selected from black organic pigments, mixed color organic pigments or inorganic pigments, and preferably has excellent heat resistance, light resistance and solvent resistance. Here, examples of black organic pigments include perylene black, cyanine black, aniline black, and lactam black. Examples of the mixed color organic pigment include those obtained by mixing two or more kinds of pigments selected from red, blue, green, violet, yellow, cyanine, magenta and the like to be pseudo-blackened. Examples of the inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black, and the like, and two or more kinds may be appropriately selected and used.
Of these, in order to provide the light-shielding film with high resistance characteristics, it is preferable that the surface resistivity (for example, the surface resistivity at an applied voltage of 10 V) of the film formed to have an optical density of 4/μm. It is preferable to use a light-shielding component having a high insulating property such that the density is ×10 8 Ω/□ or more, and a typical example thereof is carbon black subjected to an insulating surface treatment. As an example of the surface-treated carbon black, carbon black in which a substituted aryl group or the like is bonded to the surface by reacting with a diazonium salt shown in Japanese Patent Publication No. H10-510861, is disclosed in JP 2001-207079 A. The carbon black whose surface is coated with a resin, and the carbon black whose surface is coated with a dye as shown in the republished WO 2013/129554 can be exemplified, but carbon black subjected to high resistance treatment has an optical density of 4/ Any film can be used without particular limitation as long as the film has a surface resistivity of 1×10 8 Ω/□ or more. The surface resistivity of the film was formed so that the optical concentration of 4 / [mu] m is more preferably 1 × 10 10 Ω / □ or more, and particularly not more 1 × 10 12 Ω / □ or more preferable.
そして、これらの遮光成分は、好ましくは、予め分散媒に分散させて遮光性分散液としたうえで、遮光膜用感光性樹脂組成物として配合するのがよい。ここで、分散媒としては、例えばプロピレングリコールモノメチルエーテルアセテート、3メトキシブチルアセテート等が挙げられる。遮光性分散液における(D)の遮光成分の配合割合については、本発明の組成物の全固形分に対して20〜80質量%、好ましくは40〜70質量%の範囲で用いられるのがよい。そのとき、アニリンブラック、シアニンブラック、ラクタムブラック等の有機顔料またはカーボンブラック等のカーボン系遮光成分を用いる場合は、40〜60質量%の範囲が特に好ましい。20質量%より少ないと、遮光性が十分でなくなる。80質量%を越えると、本来のバインダーとなる感光性樹脂の含有量が減少するため、現像特性を損なうと共に膜形成能が損なわれるという好ましくない問題が生じる。 Then, these light-shielding components are preferably dispersed in a dispersion medium in advance to prepare a light-shielding dispersion liquid, and then blended as a light-shielding film photosensitive resin composition. Here, examples of the dispersion medium include propylene glycol monomethyl ether acetate and 3 methoxybutyl acetate. The blending ratio of the light-shielding component (D) in the light-shielding dispersion liquid is 20 to 80% by mass, preferably 40 to 70% by mass, based on the total solid content of the composition of the present invention. .. At that time, when using an organic pigment such as aniline black, cyanine black, or lactam black, or a carbon-based light-shielding component such as carbon black, the range of 40 to 60 mass% is particularly preferable. When it is less than 20% by mass, the light-shielding property becomes insufficient. When it exceeds 80% by mass, the content of the photosensitive resin that serves as the original binder decreases, so that the development characteristics are impaired and the film forming ability is impaired, which is an undesirable problem.
本発明の遮光膜用感光性樹脂組成物においては、上記(A)〜(D)の他に溶剤を使用して粘度を調整することが好ましい。溶剤としては、例えば、メタノール、エタノール、n−プロパノール、イソプロパノール、エチレングリコール、プロピレングリコール等のアルコール類、α−もしくはβ−テルピネオール等のテルペン類等、アセトン、メチルエチルケトン、シクロヘキサノン、N−メチル−2−ピロリドン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、セロソルブ、メチルセロソルブ、エチルセロソルブ、カルビトール、メチルカルビトール、エチルカルビトール、ブチルカルビトール、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エチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類、酢酸エチル、酢酸ブチル、セロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の酢酸エステル類等が挙げられ、これらを用いて溶解、混合させることにより、均一な溶液状の組成物とすることができる。 In the photosensitive resin composition for a light-shielding film of the present invention, it is preferable to use a solvent in addition to the above (A) to (D) to adjust the viscosity. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-. Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol monomethyl ether, propylene. Glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve Acetates such as acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. can be mentioned. It can be a solution-like composition.
また、本発明の遮光膜用感光性樹脂組成物には、必要に応じて硬化促進剤、熱重合禁止剤および酸化防止剤、可塑剤、充填材、レベリング剤および消泡剤、カップリング剤、界面活性剤等の添加剤を配合することができる。熱重合禁止剤および酸化防止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロガロール、tert−ブチルカテコール、フェノチアジン等を挙げることができ、可塑剤としては、ジブチルフタレート、ジオクチルフタレート、リン酸トリクレジル等を挙げることができ、充填材としては、ガラスファイバー、シリカ、マイカ、アルミナ等を挙げることができ、レベリング剤や消泡剤としては、シリコーン系、フッ素系、アクリル系の化合物を挙げることができる。また、界面活性剤としてはフッ素系界面活性剤、シリコーン系界面活性剤等を挙げることができ、カップリング剤としては3−(グリシジルオキシ)プロピルトリメトキシシラン、3−イソシアナトプロピルトリエトキシシラン、3−ウレイドプロピルトリエトキシシラン等のシランカップリング剤を挙げることができる。 Further, the light-shielding film photosensitive resin composition of the present invention, if necessary, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent and a defoaming agent, a coupling agent, Additives such as surfactants can be added. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like, and examples of the plasticizer include dibutylphthalate, dioctylphthalate, tricresyl phosphate, and the like. Examples of the filler include glass fiber, silica, mica, alumina, and the like, and examples of the leveling agent and the defoaming agent include silicone-based, fluorine-based, and acrylic-based compounds. Further, examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant, and examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, A silane coupling agent such as 3-ureidopropyltriethoxysilane can be mentioned.
本発明の遮光膜用感光性樹脂組成物は、上記(A)〜(D)成分又はこれらと溶剤を主成分として含有する。溶剤を除いた固形分(固形分には硬化後に固形分となるモノマーを含む)中に、(A)〜(D)成分が合計で80質量%、好ましくは90質量%以上含むことが望ましい。溶剤の量は、目標とする粘度によって変化するが、感光性樹脂組成物中に70〜90質量%の範囲で含まれるようにするのがよい。 The photosensitive resin composition for a light shielding film of the present invention contains the above-mentioned components (A) to (D) or these and a solvent as main components. It is desirable that the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing) contains the components (A) to (D) in a total amount of 80% by mass, preferably 90% by mass or more. The amount of the solvent varies depending on the target viscosity, but it is preferable that the amount of the solvent be contained in the photosensitive resin composition in the range of 70 to 90% by mass.
本発明における遮光膜用感光性樹脂組成物は、例えばカラーフィルター遮光膜形成用の樹脂組成物として優れるものであり、遮光膜の形成方法としては、以下のようなフォトリソグラフィー法がある。先ず、感光性樹脂組成物を透明基板上に塗布し、次いで溶媒を乾燥させた(プレベーク)後、このようにして得られた被膜の上にフォトマスクをあて、紫外線を照射して露光部を硬化させ、更にアルカリ水溶液を用いて未露光部を溶出させる現像を行ってパターンを形成し、更に後硬化としてポストベーク(熱焼成)を行う方法が挙げられる。 The photosensitive resin composition for a light-shielding film in the present invention is excellent as a resin composition for forming a color filter light-shielding film, for example, and the following photolithography method can be used to form the light-shielding film. First, the photosensitive resin composition is applied on a transparent substrate, then the solvent is dried (prebaking), a photomask is applied to the coating film thus obtained, and ultraviolet rays are applied to expose the exposed portion. Examples include a method of curing, followed by development using an aqueous alkaline solution to elute unexposed areas to form a pattern, and post-baking (thermal baking) as post-curing.
感光性樹脂組成物を塗布する透明基板としては、ガラス基板のほか、透明フィルム(例えば、ポリカーボネート、ポリエチレンテレフタレート、ポリエーテルスルフォン等)上にITOや金などの透明電極が蒸着あるいはパターニングされたものなどが例示できる。透明基板上に感光性樹脂組成物の溶液を塗布する方法としては、公知の溶液浸漬法、スプレー法の他、ローラーコーター機、ランドコーター機、スリットコーター機やスピナー機を用いる方法等の何れの方法をも採用することができる。これらの方法によって、所望の厚さに塗布した後、溶剤を除去する(プレベーク)ことにより、被膜が形成される。プレベークはオーブン、ホットプレート等により加熱することによって行われる。プレベークにおける加熱温度及び加熱時間は使用する溶剤に応じて適宜選択され、例えば60〜110℃の温度で1〜3分間行われる。 As the transparent substrate to which the photosensitive resin composition is applied, in addition to a glass substrate, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone) on which transparent electrodes such as ITO and gold are vapor-deposited or patterned, etc. Can be illustrated. As a method for applying the solution of the photosensitive resin composition on the transparent substrate, any of known solution dipping method, spray method, roller coater machine, land coater machine, slit coater machine, spinner machine and the like can be used. The method can also be adopted. By these methods, after coating to a desired thickness, the solvent is removed (prebaking) to form a film. Prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected according to the solvent used, and for example, the heating is performed at a temperature of 60 to 110° C. for 1 to 3 minutes.
プレベーク後に行われる露光は、紫外線露光装置によって行なわれ、フォトマスクを介して露光することによりパターンに対応した部分のレジストのみを感光させる。露光装置及びその露光照射条件は適宜選択され、超高圧水銀灯、高圧水銀ランプ、メタルハライドランプ、遠紫外線灯等の光源を用いて露光を行い、塗膜中の感光性樹脂組成物を光硬化させる。 The exposure performed after the pre-baking is performed by an ultraviolet exposure device, and only the resist corresponding to the pattern is exposed by exposing through the photomask. The exposure apparatus and its exposure irradiation conditions are appropriately selected, and light exposure is performed using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and a far ultraviolet ray lamp, and the photosensitive resin composition in the coating film is photocured.
露光後のアルカリ現像は、露光されない部分のレジストを除去する目的で行われ、この現像によって所望のパターンが形成される。このアルカリ現像に適した現像液としては、例えばアルカリ金属やアルカリ土類金属の炭酸塩の水溶液、アルカリ金属の水酸化物の水溶液等を挙げることができるが、特に炭酸ナトリウム、炭酸カリウム、炭酸リチウム等の炭酸塩を0.05〜3質量%含有する弱アルカリ性水溶液を用いて23〜28℃の温度で現像するのがよく、市販の現像機や超音波洗浄機等を用いて微細な画像を精密に形成することができる。 The alkali development after exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for this alkali development include an aqueous solution of an alkali metal carbonate or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like, and particularly sodium carbonate, potassium carbonate, lithium carbonate. It is preferable to develop at a temperature of 23 to 28° C. using a weak alkaline aqueous solution containing 0.05 to 3 mass% of a carbonate such as, and a fine image can be obtained by using a commercially available developing machine or an ultrasonic cleaner. It can be precisely formed.
現像後、好ましくは180〜250℃の温度及び20〜60分の条件で熱処理(ポストベーク)が行われる。このポストベークは、パターニングされた遮光膜と基板との密着性を高めるため等の目的で行われる。これはプリベークと同様に、オーブン、ホットプレート等により加熱することによって行われる。本発明のパターニングされた遮光膜は、以上のフォトリソグラフィー法による各工程を経て形成される。 After the development, heat treatment (post-baking) is preferably performed at a temperature of 180 to 250° C. for 20 to 60 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate or the like as in the pre-baking. The patterned light-shielding film of the present invention is formed through the above steps of the photolithography method.
本発明の遮光膜用感光性樹脂組成物は、上述したように、露光、アルカリ現像等の操作によって微細なパターンを形成するのに適している。また、本発明の遮光膜用感光性樹脂組成物は、コーティング材として好適に用いることができ、特に液晶の表示装置あるいは撮影素子に使われるカラーフィルター用インキとして好適であり、これにより形成された遮光膜はカラーフィルター、液晶プロジェクション用のブラックマトリックス、遮光膜、タッチパネル用遮光膜等として有用である。 The photosensitive resin composition for a light-shielding film of the present invention is suitable for forming a fine pattern by operations such as exposure and alkali development, as described above. The photosensitive resin composition for a light-shielding film of the present invention can be preferably used as a coating material, and is particularly suitable as an ink for a color filter used in a liquid crystal display device or a photographing element, and formed by this. The light-shielding film is useful as a color filter, a black matrix for liquid crystal projection, a light-shielding film, a light-shielding film for a touch panel, etc.
以下、実施例及び比較例に基づいて、本発明の実施形態を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.
先ず、本発明の(A)重合性不飽和基含有アルカリ可溶性樹脂の合成例1を示す。合成例における樹脂の評価は、以下の通りに行った。 First, Synthesis Example 1 of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention will be shown. Evaluation of the resin in the synthesis example was performed as follows.
[固形分濃度]
合成例中で得られた樹脂溶液1gをガラスフィルター〔重量:W0(g)〕に含浸させて秤量し〔W1(g)〕、160℃にて2hr加熱した後の重量〔W2(g)〕から次式より求めた。
固形分濃度(重量%)=100×(W2−W0)/(W1−W0)
[Solid content concentration]
1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W 0 (g)] and weighed [W 1 (g)], and the weight after heating at 160° C. for 2 hours [W 2 ( g)] from the following equation.
Solid content concentration (% by weight)=100×(W 2 −W 0 )/(W 1 −W 0 ).
[酸価]
樹脂溶液をジオキサンに溶解させ、電位差滴定装置〔平沼製作所(株)製 商品名COM-1600〕を用いて1/10N−KOH水溶液で滴定して求めた。
[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator [trade name COM-1600 manufactured by Hiranuma Seisakusho Co., Ltd.].
[分子量]
ゲルパーミュエーションクロマトグラフィー(GPC)[東ソー(株)製商品名HLC-8220GPC、溶媒:テトラヒドロフラン、カラム:TSKgelSuperH-2000(2本)+TSKgelSuperH-3000(1本)+TSKgelSuperH-4000(1本)+TSKgelSuper-H5000(1本)〔東ソー(株)製〕、温度:40℃、速度:0.6ml/min]にて測定し、標準ポリスチレン〔東ソー(株)製PS−オリゴマーキット〕換算値として重量平均分子量(Mw)を求めた。
[Molecular weight]
Gel permeation chromatography (GPC) [trade name: HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper- H5000 (one) [manufactured by Tosoh Corp.], temperature: 40° C., speed: 0.6 ml/min], and measured as standard polystyrene [PS-Oligomer Kit manufactured by Tosoh Corp.] weight average molecular weight ( Mw).
また、合成例で使用する略号は次のとおりである。
BPFE:9,9-ビス(4-ヒドロキシフェニル)フルオレンとクロロメチルオキシランとの反応物。一般式(II)の化合物において、Xがフルオレン-9,9-ジイル基、R6及びR7が水素の化合物。
BPDA:3,3',4,4'-ビフェニルテトラカルボン酸二無水物
THPA:1,2,3,6-テトラヒドロフタル酸無水物
TPP:トリフェニルホスフィン
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
The abbreviations used in the synthesis examples are as follows.
BPFE: A reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. The compound of the general formula (II), wherein X is a fluorene-9,9-diyl group, and R 6 and R 7 are hydrogen.
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate
[合成例1]
還留冷却器付き500ml四つ口フラスコ中に、BPFE 78.63g(0.17mol)、アクリル酸24.50g(0.34mol)、TPP 0.45g、及びPGMEA 114gを仕込み、100〜105℃の加熱下で12hr撹拌し、反応生成物を得た。
次いで、得られた反応生成物にBPDA 25.01g(0.085mol)及びTHPA 12.93g(0.085mol)を仕込み、120〜125℃の加熱下で6hr撹拌し、重合性不飽和基含有アルカリ可溶性樹脂溶液(A)-1を得た。得られた樹脂溶液の固形分濃度は55.8wt%であり、酸価(固形分換算)は103mgKOH/gであり、GPC分析によるMwは2600であった。
[Synthesis example 1]
Into a 500 ml four-necked flask equipped with a reflux condenser, BPFE 78.63g (0.17mol), acrylic acid 24.50g (0.34mol), TPP 0.45g, and PGMEA 114g were charged and stirred under heating at 100 to 105°C for 12 hours. And a reaction product was obtained.
Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were added to the obtained reaction product, and the mixture was stirred for 6 hours under heating at 120 to 125° C. to give a polymerizable unsaturated group-containing alkali-soluble resin solution ( A)-1 was obtained. The solid content concentration of the obtained resin solution was 55.8 wt%, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw by GPC analysis was 2,600.
[比較合成例1]
窒素導入管及び還流管付き1000ml四つ口フラスコ中にメタクリル酸51.65g(0.60mol)、メタクリル酸メチル38.44g(0.38mol)、メタクリル酸シクロヘキシル36.33g(0.22mol)、AIBN5.91g、及びDMDG368gを仕込み、80〜85℃で窒素気流下、8hr撹拌して重合させた。更に、フラスコ内にメタクリル酸グリシジル39.23g(0.28mol)、TPP1.44g、2,6-ジ−tert−ブチル−p−クレゾール0.055gを仕込み、80〜85℃で16hr撹拌し、重合性不飽和基含有アルカリ可溶性樹脂溶液(A)-2を得た。得られた重合性不飽和基含有アルカリ可溶性樹脂の固形分濃度は32質量%、酸価(固形分換算)は110mgKOH/g、GPC分析によるMwは18080であった。
[Comparative Synthesis Example 1]
Methacrylic acid 51.65 g (0.60 mol), methyl methacrylate 38.44 g (0.38 mol), cyclohexyl methacrylate 36.33 g (0.22 mol), AIBN 5.91 g, and DMDG 368 g in a 1000 ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube. After charging, the mixture was polymerized by stirring at 80 to 85°C under a nitrogen stream for 8 hours. Furthermore, 39.23 g (0.28 mol) of glycidyl methacrylate, 1.44 g of TPP, and 0.055 g of 2,6-di-tert-butyl-p-cresol were charged into the flask, and the mixture was stirred at 80 to 85° C. for 16 hours to be polymerizable unsaturated. A group-containing alkali-soluble resin solution (A)-2 was obtained. The polymerizable unsaturated group-containing alkali-soluble resin thus obtained had a solid content concentration of 32% by mass, an acid value (in terms of solid content) of 110 mgKOH/g, and an Mw by GPC analysis of 18080.
[合成例2]
(C)成分として、前記の式(III)で表される化合物の合成例を示す。
[Synthesis example 2]
As the component (C), a synthesis example of the compound represented by the formula (III) is shown.
<STEP1>
反応容器に、テトラヒドロフラン(THF)250質量部、および、カリウムtert−ブトキシド(KTB)42.2質量部を仕込み、フルオレン25.0質量部を添加した。次いで、反応容器に、3−ブロモ−1−プロペン40.0質量部を滴下した。この液を40℃に加熱し、3時間攪拌した。次いで、この液を室温まで冷却し、酢酸エチル、および、水を注入して、油層を分離し、水洗を2回繰り返した。次いで、油層を無水硫酸マグネシウムにて乾燥した後、無水硫酸マグネシウムを濾別し、この濾過液を濃縮して、9,9−ジ(2−プロペニル)−フルオレン37.0質量部を得た。
<STEP1>
250 parts by mass of tetrahydrofuran (THF) and 42.2 parts by mass of potassium tert-butoxide (KTB) were charged into a reaction vessel, and 25.0 parts by mass of fluorene was added. Next, 40.0 parts by mass of 3-bromo-1-propene was added dropwise to the reaction vessel. This solution was heated to 40° C. and stirred for 3 hours. Next, this liquid was cooled to room temperature, ethyl acetate and water were injected, the oil layer was separated, and washing with water was repeated twice. Then, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to obtain 37.0 parts by mass of 9,9-di(2-propenyl)-fluorene.
<STEP2>
得られた9,9−ジ(2−プロペニル)−フルオレン36.3質量部と、塩化メチレン370質量部と、塩化アルミニウム29.5質量部とを反応容器に仕込み、攪拌した。この液を10℃に冷却し、o−トルオイルクロライド22.8質量部を滴下し、さらに4時間攪拌した。10℃以下に冷却した370質量部の水に、この反応液を注入して、油層を分離し、炭酸カリウム水溶液にて洗浄した。次いで、油層を無水硫酸マグネシウムにて乾燥した後、無水硫酸マグネシウムを濾別し、濾過液を濃縮することで、9,9−ジ(2−プロペニル)−フルオレンの2位にo−トリオイル基を導入した1−[9,9−ジ(2−プロペニル)−フルオレン−2−イル]−(2−メチルフェニル)−メタノン(化合物1−A)50.6質量部を得た。
<STEP2>
The obtained 9,9-di(2-propenyl)-fluorene (36.3 parts by mass), methylene chloride (370 parts by mass) and aluminum chloride (29.5 parts by mass) were charged into a reaction vessel and stirred. This liquid was cooled to 10° C., 22.8 parts by mass of o-toluoyl chloride was added dropwise, and the mixture was further stirred for 4 hours. The reaction solution was poured into 370 parts by mass of water cooled to 10° C. or lower, the oil layer was separated, and washed with an aqueous potassium carbonate solution. Then, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to form an o-trioil group at the 2-position of 9,9-di(2-propenyl)-fluorene. 50.6 parts by mass of 1-[9,9-di(2-propenyl)-fluoren-2-yl]-(2-methylphenyl)-methanone (Compound 1-A) introduced were obtained.
<STEP3>
得られた化合物1−A 50.0質量部と酢酸500質量部とを反応容器に仕込み、発煙硝酸11.3質量部を滴下し、この液を80℃に加熱した。この反応液に濃硫酸13.7質量部を滴下し、80℃で3時間攪拌した。攪拌後、室温まで冷却し、水、酢酸エチルを注入し油層を分離し、水、炭酸カリウム水溶液にて洗浄を繰り返した。次いで、油層を無水硫酸マグネシウムにて乾燥した後、無水硫酸マグネシウムを濾別し、濾過液を濃縮した。得られた油状物をシリカゲルカラムクロマトグラフィーにより単離精製し、化合物1−Aのフルオレン骨格の7位にニトロ基を導入した1−[9,9−ジ(2−プロペニル)−7−ニトロフルオレン−2−イル]−(2−メチルフェニル)−メタノン(化合物1−B)33.4質量部を得た。
<STEP3>
50.0 parts by mass of the obtained compound 1-A and 500 parts by mass of acetic acid were charged into a reaction vessel, 11.3 parts by mass of fuming nitric acid was added dropwise, and this liquid was heated to 80°C. 13.7 parts by mass of concentrated sulfuric acid was added dropwise to this reaction solution, and the mixture was stirred at 80° C. for 3 hours. After stirring, the mixture was cooled to room temperature, water and ethyl acetate were injected, the oil layer was separated, and washing with water and an aqueous potassium carbonate solution was repeated. Then, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated. The obtained oily substance was isolated and purified by silica gel column chromatography, and 1-[9,9-di(2-propenyl)-7-nitrofluorene in which a nitro group was introduced at the 7-position of the fluorene skeleton of compound 1-A. -2-yl]-(2-methylphenyl)-methanone (Compound 1-B) was obtained in an amount of 33.4 parts by mass.
<STEP4>
得られた化合物1−B 30.0質量部と、プロピレングリコールモノメチルエーテル(PGME) 90質量部と、ピリジン 35質量部とを反応容器に仕込み攪拌した。次いで、ヒドロキシルアミン塩酸塩 30.5質量部を添加し、140℃に加熱し、4時間攪拌した。この反応液を室温まで冷却し、水、酢酸エチルを注入し油層を分離し、再度、水、希塩酸、塩化ナトリウム水溶液にて洗浄した。次いで、油層を無水硫酸マグネシウムにて乾燥した後、無水硫酸マグネシウムを濾別し、濾過液を濃縮することで化合物1−Bをオキシム化した1−[9,9−ジ(2−プロペニル)−7−ニトロフルオレン−2−イル]−(2−メチルフェニル)−メタノンオキシム(化合物1−C) 27.7質量部を得た。
<STEP4>
30.0 parts by mass of the obtained compound 1-B, 90 parts by mass of propylene glycol monomethyl ether (PGME), and 35 parts by mass of pyridine were charged into a reaction vessel and stirred. Then, 30.5 parts by mass of hydroxylamine hydrochloride was added, and the mixture was heated to 140° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were injected, the oil layer was separated, and washed again with water, dilute hydrochloric acid and an aqueous sodium chloride solution. Then, the oil layer was dried over anhydrous magnesium sulfate, anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to oxime compound 1-B 1-[9,9-di(2-propenyl)- 77.7 parts by mass of 7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime (Compound 1-C) was obtained.
<STEP5>
得られた化合物1−C 25.0質量部、酢酸エチル 125質量部を反応容器に仕込み、無水酢酸 13.8質量部を滴下し、室温にて5時間攪拌した。この反応液に水、酢酸エチルを注入し油層を分離し、炭酸カリウム水溶液、塩化ナトリウム水溶液にて洗浄した。次いで、油層を無水硫酸マグネシウムにて乾燥し、無水硫酸マグネシウムを濾別し、濾過液を濃縮した。得られた生成物を酢酸エチル/ヘキサンにて再結晶化を行い、式(III)の化合物である1−[9,9−ジ(2−プロペニル)−7−ニトロフルオレン−2−イル]−(2−メチルフェニル)−メタノン オキシム−O−アセタート(化合物1)を17.2質量部得た。
<STEP5>
25.0 parts by mass of the obtained compound 1-C and 125 parts by mass of ethyl acetate were charged into a reaction vessel, 13.8 parts by mass of acetic anhydride were added dropwise, and the mixture was stirred at room temperature for 5 hours. Water and ethyl acetate were poured into this reaction solution, the oil layer was separated, and washed with an aqueous potassium carbonate solution and an aqueous sodium chloride solution. Next, the oil layer was dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated. The resulting product was recrystallized from ethyl acetate/hexane to give the compound of formula (III), 1-[9,9-di(2-propenyl)-7-nitrofluoren-2-yl]-. 17.2 parts by mass of (2-methylphenyl)-methanone oxime-O-acetate (Compound 1) was obtained.
[比較合成例2]
合成例2において、STEP1で3−ブロモ−1−プロペンの代わりにn−ブチルブロマイドを用いた以外は、合成例2と同様の各反応STEPを経ることにより、1−[9,9−ジ(n−ブチル)−7−ニトロフルオレン−2−イル]−(2−メチルフェニル)−メタノン オキシム−O−アセタート(化合物2)を得た。
[Comparative Synthesis Example 2]
1-[9,9-di(Synthesis Example 2) is the same as Synthesis Example 2 except that n-butyl bromide is used in place of 3-bromo-1-propene in STEP 1. n-Butyl)-7-nitrofluoren-2-yl]-(2-methylphenyl)-methanone oxime-O-acetate (Compound 2) was obtained.
[比較合成例3]
合成例2において、STEP1で3−ブロモ−1−プロペンの代わりにn−プロピルブロマイドを用い、また、STEP2でo−トルオイルクロライドの代わりにアセチルクロライドを用いた以外は、合成例2と同様の各反応STEPを経ることにより、エタノン,1−[9,9−ジn−プロピル−7−ニトロフルオレン−2−イル]−O−アセチルオキシム(化合物3)を得た。
[Comparative Synthesis Example 3]
Similar to Synthesis Example 2 except that in Synthesis Example 2, n-propyl bromide was used in place of 3-bromo-1-propene in STEP 1, and acetyl chloride was used in place of o-toluoyl chloride in STEP 2. By going through each reaction step, ethanone, 1-[9,9-di-n-propyl-7-nitrofluoren-2-yl]-O-acetyloxime (Compound 3) was obtained.
(実施例1〜4、比較例1〜4)
次に、感光性樹脂組成物及びその硬化物の製造に係る実施例及び比較例に基づいて、本発明を具体的に説明するが、本発明はこれらに限定されるものではない。ここで、以降の実施例及び比較例の感光性樹脂組成物及びその硬化物の製造で用いた原料及び略号は以下の通りである。
(Examples 1 to 4, Comparative Examples 1 to 4)
Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the production of a photosensitive resin composition and a cured product thereof, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions of the following Examples and Comparative Examples and cured products thereof are as follows.
(重合性不飽和基含有アルカリ可溶性樹脂)
(A)−1成分:上記合成例1で得られた重合性不飽和基含有アルカリ可溶性樹脂溶液
(A)−2成分:上記比較合成例1で得られた重合性不飽和基含有アルカリ可溶性樹脂溶液
(Polymerizable unsaturated group-containing alkali-soluble resin)
(A)-1 component: A polymerizable unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 1 above.
(A)-2 component: Polymerizable unsaturated group-containing alkali-soluble resin solution obtained in Comparative Synthesis Example 1 above
(光重合性モノマー)
(B)-1:ジペンタエリスリトールペンタアクリレートとヘキサアクリレートとの混合物(日本化薬(株)製 商品名DPHA)
(B)-2:ペンタエリスリトールトリアクリレートとテトラアクリレートとの混合物(東亜合成株式会社製、商品名M-450)
(Photopolymerizable monomer)
(B)-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.)
(B)-2: Mixture of pentaerythritol triacrylate and tetraacrylate (manufactured by Toagosei Co., Ltd., trade name M-450)
(光重合開始剤)
(C)-1:上記合成例2で得られた化合物1〔式(III)で表される化合物〕
(C)-2:上記比較合成例2で得られた化合物2
(C)-3:上記比較合成例3で得られた化合物3
(C)-4:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(0-アセチルオキシム)(BASFジャパン社製、製品名イルガキュアOXE02)
(Photopolymerization initiator)
(C)-1: Compound 1 obtained in Synthesis Example 2 above (compound represented by formula (III))
(C)-2: Compound 2 obtained in Comparative Synthesis Example 2 above
(C)-3: Compound 3 obtained in Comparative Synthesis Example 3 above
(C)-4: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(0-acetyloxime) (manufactured by BASF Japan Ltd., product name Irgacure OXE02)
(遮光成分分散体)
(D)-1:表面処理カーボンブラックAの濃度25.0質量%、高分子分散剤濃度4.0質量%のプロピレングリコールモノメチルエーテルアセテート分散液(固形分29.0%)
(D)-2:表面処理カーボンブラックBの濃度25.0質量%、高分子分散剤濃度3.8質量%のプロピレングリコールモノメチルエーテルアセテート分散液(固形分28.8%)
(D)-3:表面処理カーボンブラックCの濃度25.0質量%、高分子分散剤濃度5.0質量%のプロピレングリコールモノメチルエーテルアセテート分散液(固形分30.0%)
(Shading component dispersion)
(D)-1: Propylene glycol monomethyl ether acetate dispersion having a surface-treated carbon black A concentration of 25.0% by mass and a polymer dispersant concentration of 4.0% by mass (solid content 29.0%).
(D)-2: Propylene glycol monomethyl ether acetate dispersion having a surface-treated carbon black B concentration of 25.0% by mass and a polymer dispersant concentration of 3.8% by mass (solid content 28.8%).
(D)-3: Propylene glycol monomethyl ether acetate dispersion liquid having a surface-treated carbon black C concentration of 25.0% by mass and a polymer dispersant concentration of 5.0% by mass (solid content: 30.0%)
(シランカップリング剤)
(E):3−メルカプトプロピルトリメトキシシラン〔商品名:KBM-803:信越化学(株)製〕
(Silane coupling agent)
(E): 3-mercaptopropyltrimethoxysilane [trade name: KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.]
(チオール化合物)
(F):ペンタエリスリトール テトラキス(3-メルカプトブチレート)〔商品名:カレンズMT PE1:昭和電工(株)製〕
(Thiol compound)
(F): Pentaerythritol tetrakis (3-mercaptobutyrate) [Product name: Karenz MT PE1: Showa Denko KK]
(溶剤)
(G)-1:プロピレングリコールモノメチルエーテルアセテート(PGMEA)
(G)-2:シクロヘキサノン(ANON)
(solvent)
(G)-1: Propylene glycol monomethyl ether acetate (PGMEA)
(G)-2: Cyclohexanone (ANON)
(界面活性剤)
(H):BYK-330(ビックケミー社製)
(Surfactant)
(H): BYK-330 (manufactured by Big Chemie)
[遮光成分に関する評価]
<遮光成分の特性評価用組成物の調製>
樹脂溶液〔(A)−1成分〕、遮光成分分散体〔(D)−1成分〜(D)−3成分〕及び溶剤〔(G)−1成分〕を固形分濃度20%になるように混合して表面抵抗率測定用組成物を調製した。この際、光学濃度(OD)を測定しながら樹脂と遮光成分の比率を変えて、OD=4/μmの硬化膜を形成できる組成物を調製した。
[Evaluation of light-shielding components]
<Preparation of composition for evaluating characteristics of light-shielding component>
Resin solution [(A)-1 component], light-shielding component dispersion [(D)-1 component to (D)-3 component] and solvent [(G)-1 component] so that the solid content concentration is 20%. A composition for measuring surface resistivity was prepared by mixing. At this time, a composition capable of forming a cured film with OD=4/μm was prepared by changing the ratio of the resin and the light-shielding component while measuring the optical density (OD).
<光学濃度>
上記で得られた表面抵抗率測定用組成物を、厚さ1.2mmのガラス基板上にスピンコーターを用いて熱硬化処理後の膜厚が1.1μmとなるように塗布し、90℃で1分間プリベークした。その後、熱風乾燥機を用いて230℃で30分間加熱硬化処理を行い、組成物の硬化膜を得た。次に、得られた硬化膜の光学濃度はマクベス透過濃度計を用いて測定し、単位膜厚当たりの光学濃度で評価した。
<Optical density>
The composition for measuring surface resistivity obtained above was applied onto a glass substrate having a thickness of 1.2 mm by a spin coater so that the film thickness after heat curing treatment would be 1.1 μm, and at 90° C. Prebaked for 1 minute. After that, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the composition. Next, the optical density of the obtained cured film was measured using a Macbeth transmission densitometer and evaluated by the optical density per unit film thickness.
<表面抵抗率測定>
光学濃度を測定した硬化膜の表面抵抗率を、表面抵抗率測定器(三菱化学アナリテック社製ハイレスタUP)を用いて電圧10Vで測定した。
OD=4/μmの硬化膜を形成できる組成物について、組成物配合比率と測定結果を表1に示した。
<Surface resistivity measurement>
The surface resistivity of the cured film whose optical density was measured was measured at a voltage of 10 V using a surface resistivity meter (HIRESTA UP manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
Table 1 shows the composition ratios of the compositions and the measurement results for the compositions capable of forming a cured film with OD=4/μm.
上記の配合成分を表2に示す割合で配合して、実施例1〜4及び比較例1〜4の感光性樹脂組成物を調製した。 The above-mentioned components were mixed in the proportions shown in Table 2 to prepare the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4.
[評価]
実施例1〜4および比較例1〜4の遮光膜用感光性樹脂組成物を用いて、以下に記す評価を行った。これらの評価結果を表3に示す。
[Evaluation]
Using the photosensitive resin compositions for light-shielding films of Examples 1 to 4 and Comparative Examples 1 to 4, the following evaluations were performed. The results of these evaluations are shown in Table 3.
<現像特性(パターン線幅・パターン直線性)の評価>
上記で得られた各遮光膜用感光性樹脂組成物を、スピンコーターを用いて125mm×125mmのガラス基板(コーニング1737)上にポストベーク後の膜厚が1.1μmとなるように塗布し、90℃で1分間プリベークした。その後、露光ギャップを100μmに調整し、乾燥塗膜の上に、5μmのネガ型フォトマスクを被せ、フォトマスクの上に短波長カットフィルター〔型番LU0350、朝日分光(株)社製(340nm以下の水銀ランプ波長をカット)〕を乗せて、i線照度30mW/cm2の超高圧水銀ランプで80mJ/cm2の紫外線を照射し、感光部分の光硬化反応を行った。
<Evaluation of development characteristics (pattern line width/pattern linearity)>
Each of the light-shielding film photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, Prebaked at 90° C. for 1 minute. After that, the exposure gap was adjusted to 100 μm, a 5 μm negative photomask was covered on the dry coating film, and a short-wavelength cut filter [Model LU0350, manufactured by Asahi Spectroscopy Co., Ltd. (340 nm or less The wavelength of the mercury lamp was cut)), and an ultraviolet ray of 80 mJ/cm 2 was irradiated with an ultrahigh pressure mercury lamp having an i-line illuminance of 30 mW/cm 2 to carry out a photocuring reaction on the photosensitive portion.
次に、この露光済み塗板を25℃、0.08%水酸化カリウム水溶液中、1kgf/cm2のシャワー現像圧にて、パターンが現れ始める現像時間(ブレイクタイム=BT)から、+10秒、+15秒の現像後、5kgf/cm2圧のスプレー水洗を行い、塗膜の未露光部を除去してガラス基板上に画素パターンを形成し、その後、熱風乾燥機を用いて230℃、30分間熱ポストベークした後の5μm線のマスク幅に対する線幅、パターン直線性及を評価した。現像時間80秒を過ぎてもパターン像が現れない場合は現像不可とした。なお、各評価方法は次のとおりである。 Next, the exposed coated plate was subjected to a shower development pressure of 1 kgf/cm 2 in a 0.08% potassium hydroxide aqueous solution at 25° C., from the development time (break time=BT) at which a pattern began to appear, +10 seconds, +15. After development for 2 seconds, spray washing with 5 kgf/cm 2 pressure is performed to remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate, and then heat at 230° C. for 30 minutes using a hot air dryer. After the post-baking, the line width with respect to the mask width of the 5 μm line and the pattern linearity were evaluated. When the pattern image did not appear even after the development time of 80 seconds, it was determined that development was impossible. The evaluation methods are as follows.
パターン線幅:測長顕微鏡(ニコン社製「XD−20」)を用いてマスク幅5μmのパターン線幅を測定した。
パターン直線性:ポストベーク後の5μmマスクパターンを顕微鏡観察し、基板に対する剥離やパターンエッジ部分のギザツキが認められないものを○、一部に認められるものを△、全体に渡って認められるものを×と評価した。
Pattern line width: A pattern line width with a mask width of 5 μm was measured using a length measuring microscope (“XD-20” manufactured by Nikon Corporation).
Pattern linearity: A 5 μm mask pattern after post-baking is observed under a microscope, and no peeling from the substrate or jagged edges of the pattern edge is observed, ◯, some are observed, and all are observed. It was evaluated as x.
<残膜感度の評価>
上記で得られた各遮光膜用感光性樹脂組成物を、スピンコーターを用いて125mm×125mmのガラス基板(コーニング1737)上にポストベーク後の膜厚が1.1μmとなるように塗布し、90℃で1分間プリベークした後の乾燥塗膜の膜厚を測定した。その後、乾燥塗膜の上に短波長カットフィルター〔型番LU0350、朝日分光(株)社製(340nm以下の水銀ランプ波長をカット)〕を乗せて、i線照度30mW/cm2の超高圧水銀ランプで10mJ/cm2の紫外線を照射し、感光部分の光硬化反応を行った。同様の手法で露光量の異なる塗布板を作製することにより、5mJ/cm2毎に10〜100mJ/cm2露光した露光済み塗布板を得た。
次に、この露光済み塗布板を25℃、0.08%水酸化カリウム水溶液中、1kgf/cm2のシャワー現像圧にて、パターンが現れ始める現像時間(ブレイクタイム=BT)+15秒の現像後、5kgf/cm2圧のスプレー水洗を行い、各露光量で作成した塗布膜の膜厚を測定する。膜厚が現像前の膜厚と比較して95%以上となる露光量を残膜感度とした。
<Evaluation of residual film sensitivity>
Each of the light-shielding film photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, The film thickness of the dried coating film after prebaking at 90° C. for 1 minute was measured. After that, a short-wavelength cut filter [Model No. LU0350, manufactured by Asahi Bunko Co., Ltd. (cuts the wavelength of the mercury lamp of 340 nm or less)] is placed on the dried coating film, and an ultrahigh-pressure mercury lamp with an i-line illuminance of 30 mW/cm 2 is placed. At 10 mJ/cm 2 to irradiate it with light, and the photocuring reaction of the photosensitive portion was carried out. By making coated plates having different exposure doses by the same method, exposed coated plates were exposed at 10 to 100 mJ/cm 2 every 5 mJ/cm 2 .
Next, the exposed coated plate was developed in a 0.08% potassium hydroxide aqueous solution at 25° C. under a shower developing pressure of 1 kgf/cm 2 and a developing time (break time=BT)+15 seconds after development was started. Spray washing with a pressure of 5 kgf/cm 2 is performed, and the film thickness of the coating film formed at each exposure amount is measured. The residual film sensitivity was defined as the exposure amount at which the film thickness was 95% or more compared to the film thickness before development.
<OD/μmの評価>
上記で得られた各遮光膜用感光性樹脂組成物を、スピンコーターを用いて125mm×125mmのガラス基板(コーニング1737)上にポストベーク後の膜厚が1.1μmとなるように塗布し、90℃で1分間プリベークした。その後、乾燥塗膜の上に、ネガ型フォトマスクを被せず、短波長カットフィルター〔型番LU0350、朝日分光(株)社製(340nm以下の水銀ランプ波長をカット)〕を乗せて、i線照度30mW/cm2の超高圧水銀ランプで80mJ/cm2の紫外線を照射し、感光部分の光硬化反応を行った。
<Evaluation of OD/μm>
The photosensitive resin composition for each light-shielding film obtained above was applied on a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, Prebaked at 90° C. for 1 minute. After that, a short wavelength cut filter [model number LU0350, manufactured by Asahi Bunko Co., Ltd. (cuts mercury lamp wavelength of 340 nm or less)] is placed on the dried coating film without covering with a negative photomask, and i-line illuminance Ultraviolet light of 80 mJ/cm 2 was irradiated with an ultra-high pressure mercury lamp of 30 mW/cm 2 to carry out a photocuring reaction on the photosensitive portion.
次に、この露光済み塗板を25℃、0.08%水酸化カリウム水溶液中、1kgf/cm2のシャワー現像圧にて、60秒の現像後、5kgf/cm2圧のスプレー水洗を行い、その後、熱風乾燥機を用いて230℃、30分間熱ポストベークした後、光照射部のODをマクベス透過濃度計を用いて評価した。さらに、光照射部の膜厚を測定し、OD値を膜厚で割った値をOD/μmとした。 Next, the exposed coated plate was developed in a 0.08% aqueous potassium hydroxide solution at 25° C. at a shower development pressure of 1 kgf/cm 2 for 60 seconds, and then spray washed with 5 kgf/cm 2 pressure. After hot post-baking at 230° C. for 30 minutes using a hot air dryer, the OD of the light irradiation part was evaluated using a Macbeth transmission densitometer. Further, the film thickness of the light irradiation portion was measured, and the value obtained by dividing the OD value by the film thickness was defined as OD/μm.
<密着性の評価>
上記で得られた各遮光膜用感光性樹脂組成物を、スピンコーターを用いて125mm×125mmのガラス基板(コーニング1737)上にポストベーク後の膜厚が1.1μmとなるように塗布し、90℃で1分間プリベークした。その後、ネガ型フォトマスクを用いずに塗膜の上に短波長カットフィルター〔型番 LU0350 朝日分光(株)社製(340nm以下の水銀ランプ波長をカット)〕を乗せて、i線照度30mW/cm2の超高圧水銀ランプで80mJ/cm2でベタ露光し、熱風乾燥機を用いて230℃、30分間熱ポストベークした。そして、上記で得られたポストベーク基板について、JISK6856−1994の3点折り曲げ密着試験方法に準じた評価法により、以下のようにしてシールガラス基板との密着強度を評価した。
<Adhesion evaluation>
Each of the light-shielding film photosensitive resin compositions obtained above was applied onto a 125 mm×125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking would be 1.1 μm, Prebaked at 90° C. for 1 minute. After that, a short-wavelength cut filter [model number LU0350 manufactured by Asahi Bunko Co., Ltd. (cuts a mercury lamp wavelength of 340 nm or less)] was placed on the coating film without using a negative photomask, and the i-line illuminance was 30 mW/cm. and solid exposed by 2 extra-high pressure mercury lamp at 80 mJ / cm 2, 230 ° C. using a hot air dryer to heat post-baked for 30 minutes. Then, the post-baked substrate obtained above was evaluated for adhesion strength with the seal glass substrate by the evaluation method according to the three-point bending adhesion test method of JIS K6856-1994 as follows.
上記のポストベーク基板、及び樹脂組成物を塗布してないガラス基板(コーニング1737)それぞれを20mm×63mmの短冊状に切断し、試験片を用意した。ポストベーク済の塗膜板と感光性樹脂組成物を塗布してないガラス基板とが一定の量のシール剤エポキシ系接着剤(ストラクトボンドXN−21s(三井化学製))を介して重ね合わせ幅が8mmになるように、双方の基板(試験片)を貼りあわせた。重ね合わせたときのシール剤エポキシ系接着剤の形が円形でかつ直径が約5mmである。その後、重ね合わせた試験片を90℃、20分のプリベーク、続いて、150℃、2時間ポストベークをそれぞれ実施し、三点折り曲げ試験片を作成した。さらに20mm×63mmの塗布していないガラス片同士も上記と同じ方法で張り合わせた比較試験用のサンプルを作成した。 Each of the above post-baked substrate and the glass substrate (Corning 1737) not coated with the resin composition was cut into a strip of 20 mm×63 mm to prepare a test piece. A post-baked coating plate and a glass substrate not coated with the photosensitive resin composition are overlapped with a certain amount of a sealant epoxy adhesive (Structbond XN-21s (manufactured by Mitsui Chemicals)) Both substrates (test pieces) were bonded together so that the thickness was 8 mm. The shape of the sealant epoxy adhesive when superposed is circular and the diameter is about 5 mm. After that, the laminated test pieces were prebaked at 90° C. for 20 minutes, and then post-baked at 150° C. for 2 hours to form three-point bent test pieces. Further, 20 mm×63 mm uncoated glass pieces were also laminated in the same manner as above to prepare a sample for a comparative test.
上記で得られた試験片において、重ね合わせ部位が中心となるよう、塗布板と対向基板(塗布無し基板)、又は塗布していない比較試験用のガラス基板を2点の支持体で支え(2点の支持体の長さは3cm)、重ね合わせ部の真上から真下に向かってオリエンテック社製「UCT−100」を用いて1mm/分の速度で加重をかけていき、剥離面の観察とそのときの加重を読み取り、シール剤エポキシ系接着剤の塗布面積で割り、単位面積当たりの加重を密着強度とした。また、121℃、100%RH、2atm、及び5時間の条件下においてPCT(プレッシャー・クッカー・テスト)を実施した後、同様の密着強度テストを実施し、PCT前後での密着強度を評価した。PCT前後におけるレジストを塗布していないガラス同士の密着強度をそれぞれ100としたときの、各組成の密着強度を相対値として示した。PCT前後において60以上を○、60未満を×とした。 In the test piece obtained above, the coated plate and the counter substrate (non-coated substrate) or the uncoated glass substrate for the comparative test are supported by two supports so that the overlapping portion is centered (2 The length of the support at the point is 3 cm), and the weight is applied at a speed of 1 mm/minute from just above the overlay to just below it using "UCT-100" manufactured by Orientec Co., and the peeled surface is observed. Then, the weight at that time was read, divided by the application area of the sealant epoxy adhesive, and the weight per unit area was taken as the adhesion strength. Further, after performing PCT (pressure cooker test) under the conditions of 121° C., 100% RH, 2 atm, and 5 hours, the same adhesion strength test was performed to evaluate the adhesion strength before and after PCT. The adhesion strength of each composition is shown as a relative value, where the adhesion strength between the glasses not coated with the resist before and after PCT is 100. Before and after PCT, 60 or more was evaluated as ◯, and less than 60 was evaluated as x.
<体積抵抗率>
上記で得られた各遮光膜用感光性樹脂組成物を、Cr蒸着された厚さ1.2mmのガラス基板上の電極を除いた部分にスピンコーターを用いて熱硬化処理後の膜厚が3.5μmとなるように塗布し、90℃で1分間プリベークした。その後、熱風乾燥機を用いて230℃、30分間加熱硬化処理を行い、感光性樹脂組成物の硬化膜を得た。その後、硬化膜上にアルミニウム電極を形成して体積抵抗率測定用基板を作成した。次に、エレクトロメーター(ケースレー社製、「6517A型」)を用いて、印加電圧1Vから10Vにおける体積抵抗率を測定した。1Vステップで各印加電圧で60秒ずつ電圧保持する条件で測定し、1V、5Vおよび10V印加時の体積抵抗率を表3に示した。
<Volume resistivity>
Each of the light-shielding film photosensitive resin compositions obtained above had a thickness of 3 after heat curing using a spin coater on a portion of the 1.2-mm thick Cr-deposited glass substrate excluding the electrodes. It was applied so as to have a thickness of 0.5 μm, and prebaked at 90° C. for 1 minute. After that, heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer to obtain a cured film of the photosensitive resin composition. Then, an aluminum electrode was formed on the cured film to prepare a substrate for measuring volume resistivity. Next, the volume resistivity at an applied voltage of 1V to 10V was measured using an electrometer (“6517A type” manufactured by Keithley). The volume resistivity was measured under the condition that the voltage was held for 60 seconds at each applied voltage in 1 V steps, and the volume resistivity when 1 V, 5 V and 10 V was applied are shown in Table 3.
Claims (9)
(A)1分子内に2個以上のエポキシ基を有するエポキシ化合物に不飽和基含有モノカルボン酸を反応させ、更に多価カルボン酸又はその酸無水物を反応させて得られる重合性不飽和基含有アルカリ可溶性樹脂、
(B)少なくとも1個のエチレン性不飽和結合を有する光重合性モノマー、
(C)フルオレン環の9位に重合性基を有するフルオレン系化合物を含有する光重合開始剤、及び
(D)黒色有機顔料、混色有機顔料及び無機顔料からなる群から選ばれた1以上の遮光成分
を必須成分として含む遮光膜用感光性樹脂組成物において、
(A)成分と(B)成分との重量割合(A)/(B)が、50/50〜90/10であり、(A)成分と(B)成分の合計100質量部に対して(C)成分を2〜30質量部含有し、且つ、組成物の全固形分に対して(D)成分を20〜80質量%含有することを特徴とする遮光膜用感光性樹脂組成物。 The following (A) ~ (D) components,
(A) a polymerizable unsaturated group obtained by reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound having two or more epoxy groups in one molecule, and further reacting a polyvalent carboxylic acid or an acid anhydride thereof Containing alkali-soluble resin,
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator containing a fluorene compound having a polymerizable group at the 9-position of the fluorene ring, and
(D) A photosensitive resin composition for a light-shielding film, which contains as an essential component one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and inorganic pigments,
The weight ratio (A)/(B) of the component (A) and the component (B) is 50/50 to 90/10, and (100) parts by weight of the total of the component (A) and the component (B) ( A photosensitive resin composition for a light-shielding film, which contains 2 to 30 parts by mass of the component C) and 20 to 80% by mass of the component (D) with respect to the total solid content of the composition.
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