JP5255783B2 - Resist composition for color filter, method for producing the same, and color filter using the same - Google Patents
Resist composition for color filter, method for producing the same, and color filter using the same Download PDFInfo
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- JP5255783B2 JP5255783B2 JP2007140149A JP2007140149A JP5255783B2 JP 5255783 B2 JP5255783 B2 JP 5255783B2 JP 2007140149 A JP2007140149 A JP 2007140149A JP 2007140149 A JP2007140149 A JP 2007140149A JP 5255783 B2 JP5255783 B2 JP 5255783B2
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- component
- acid
- color filter
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- black
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ATLNSQIIANHCSQ-UHFFFAOYSA-N bicyclo[2.2.1]heptane-1,2,2,3-tetracarboxylic acid cycloheptane-1,1,2,2-tetracarboxylic acid Chemical compound C12(C(C(C(CC1)C2)C(=O)O)(C(=O)O)C(=O)O)C(=O)O.C2(C(CCCCC2)(C(=O)O)C(=O)O)(C(=O)O)C(=O)O ATLNSQIIANHCSQ-UHFFFAOYSA-N 0.000 description 1
- KYQRDNYMKKJUTH-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)CC1C2 KYQRDNYMKKJUTH-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- CNASVLXXMGAQGK-UHFFFAOYSA-N bis(3,5-dichloro-4-hydroxyphenyl)methanone Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1C(=O)C1=CC(Cl)=C(O)C(Cl)=C1 CNASVLXXMGAQGK-UHFFFAOYSA-N 0.000 description 1
- JWAPUVVSOVJCJB-UHFFFAOYSA-N bis(4-hydroxy-3,5-dimethylphenyl)methanone Chemical compound CC1=C(O)C(C)=CC(C(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 JWAPUVVSOVJCJB-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- CCQPAEQGAVNNIA-UHFFFAOYSA-N cyclobutane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCC1 CCQPAEQGAVNNIA-UHFFFAOYSA-N 0.000 description 1
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- YZFOGXKZTWZVFN-UHFFFAOYSA-N cyclopentane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1 YZFOGXKZTWZVFN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- JNWGOCSTXJQFEP-UHFFFAOYSA-N hexane-1,1,1,2-tetracarboxylic acid Chemical compound CCCCC(C(O)=O)C(C(O)=O)(C(O)=O)C(O)=O JNWGOCSTXJQFEP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- MIVZUXGHPJSKRI-UHFFFAOYSA-N pentane-1,1,1,2-tetracarboxylic acid Chemical compound CCCC(C(O)=O)C(C(O)=O)(C(O)=O)C(O)=O MIVZUXGHPJSKRI-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明はカラーフィルター用レジスト組成物及びその製造方法並びにそれを用いたカラーフィルターに関し、詳しくは、カラーフィルター用のブラックレジストに適した感光性樹脂組成物の製造方法に関する。 The present invention relates to a color filter resist composition, a method for producing the same, and a color filter using the same, and more particularly to a method for producing a photosensitive resin composition suitable for a black resist for a color filter.
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。パターンサイズはカラーフィルターの用途並びにそれぞれの色により異なるが赤、緑、青の画素は100μm以下へ、ブラックマトリックスは10μm以下へ細線化され、これにともなって感光性樹脂材料には高い寸法精度が求められている。 A color liquid crystal display device includes a liquid crystal unit for controlling the amount of light transmitted or reflected and a color filter as components, and the method for producing the color filter is usually black on the surface of a transparent substrate such as glass or plastic sheet. Next, a method is used in which different colors of red, green, and blue are sequentially formed in a color pattern such as a stripe shape or a mosaic shape. The pattern size varies depending on the use of the color filter and each color, but red, green, and blue pixels are thinned to 100 μm or less, and the black matrix is thinned to 10 μm or less. With this, the photosensitive resin material has high dimensional accuracy. It has been demanded.
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、緑、青などの画素を今まで以上に高色純度化及び、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、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 influence the visibility of the color liquid crystal display device. In order to improve the visibility, that is, to obtain a clear image, the color filters such as red, green, and blue are used. It is necessary to achieve higher color purity of the pixel and higher light shielding with the black matrix than before, and it is necessary to add a colorant to the photosensitive resin composition in a larger amount than before.
しかし、着色剤の含有量が増加すると、カラーフィルター形成時、特にブラックレジスト膜では紫外線領域の光が塗膜深部にまで届きにくくなり、光硬化性組成物中の硬化不良によってパターンの密着不良や現像時のパターン剥がれ、エッジ形状のシャープ性損失が生じる問題が発生する。 However, when the content of the colorant is increased, it becomes difficult for light in the ultraviolet region to reach the deep part of the coating film when forming a color filter, particularly in a black resist film, and poor adhesion of the pattern due to poor curing in the photocurable composition. There arises a problem that pattern peeling occurs during development and sharpness loss of the edge shape occurs.
そこで、高濃度の着色剤が含まれる場合でも硬化不良が生じないように、高感度の光重合開始剤や重合度の高いアクリルモノマーを用いたりすることがある。しかしながら、現在の技術では光重合開始剤やアクリルモノマーについて高感度化が限界に来ているのが現状であり、ブラックマトリックスの高遮光を達成させることは非常に困難となっている。そのため、アルカリ可溶性樹脂について、高感度化を達成し、低露光量での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パターンを広い現像マージンで得ることが求められている。また、高濃度の着色剤を分散させるための分散剤についても、良好な現像溶解性と現像時の基板への高密着性が求められているが、それぞれトレードオフの関係を有するため、現状では充分なパターニング特性が得られていない。 Therefore, a highly sensitive photopolymerization initiator or an acrylic monomer having a high degree of polymerization may be used so that curing failure does not occur even when a high concentration of colorant is included. However, with the current technology, the photopolymerization initiator and the acrylic monomer are at the limit of increasing the sensitivity, and it is very difficult to achieve high light shielding of the black matrix. Therefore, it is required to achieve high sensitivity for alkali-soluble resins, and to obtain a pattern with good pattern dimensional stability, pattern adhesion, and pattern edge shape sharpness with a wide development margin. Yes. In addition, as for a dispersant for dispersing a high-concentration colorant, good development solubility and high adhesion to a substrate at the time of development are required. Sufficient patterning characteristics are not obtained.
特許文献１には、顔料濃度を高めて良好な色再現性を図りつつ感度低下を防止するために、高感度光重合開始剤としてハロメチルオキサジアゾール系化合物、ハロメチル-S-トリアジン系化合物の使用例が開示されている。しかし、これらの化合物は酸素による反応阻害により表面平坦性低下は改善されるものの、パターン寸法精度の点では依然として満足すべき水準には達していない。また、特許文献２〜５などには高感度光重合開始剤として感光性樹脂組成物にオキシムエステル系の光重合開始剤を用いた例が開示されているが、併用されているアルカリ可溶性樹脂化合物の感度及び現像特性が十分でないため、高濃度の着色剤を含む感光性樹脂組成物では良好なパターン形成を行うことは困難である。 In Patent Document 1, halomethyloxadiazole compounds and halomethyl-S-triazine compounds are used as high-sensitivity photopolymerization initiators in order to prevent a decrease in sensitivity while increasing the pigment concentration and achieving good color reproducibility. An example of use is disclosed. However, although these compounds are improved in surface flatness due to reaction inhibition by oxygen, they still do not reach a satisfactory level in terms of pattern dimensional accuracy. Patent Documents 2 to 5 disclose examples in which an oxime ester-based photopolymerization initiator is used in a photosensitive resin composition as a high-sensitivity photopolymerization initiator. Therefore, it is difficult to form a good pattern with a photosensitive resin composition containing a high concentration of colorant.
また、上記特許文献６〜１１には、ビスフェノールフルオレン構造を有するカラーフィルター用感光性樹脂組成物の実施例が示されているが、高濃度顔料領域においては良好なパターン形成をおこなうための十分な感度や密着性及び保存安定性が得られていない。 Moreover, although the Example of the photosensitive resin composition for color filters which has a bisphenol fluorene structure is shown by the said patent documents 6-11, sufficient in order to perform a favorable pattern formation in a high concentration pigment area | region. Sensitivity, adhesion and storage stability are not obtained.
従って、本発明の目的は、上記の問題を解決し、高遮光を達成する高濃度の着色剤を含む領域において、高感度で高い密着性能、かつ保存安定性の高いカラーフィルター用レジスト組成物を提供することにある。また、ブラックマトリックス用レジスト用感光性樹脂組成物を提供することにある。また、他の目的は、アルカリ現像型感光性樹脂組成物を用いて形成した塗膜並びにカラーフィルターを提供するものである。 Accordingly, an object of the present invention is to provide a color filter resist composition that solves the above-described problems and has high sensitivity, high adhesion performance, and high storage stability in a region containing a high concentration of colorant that achieves high light shielding. It is to provide. Moreover, it is providing the photosensitive resin composition for resists for black matrices. Another object of the present invention is to provide a coating film and a color filter formed using an alkali developing type photosensitive resin composition.
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、顔料分散の際に使用する樹脂を特定のものとし、それらを分散剤とともに共分散させることにより、前記の問題点が解決されることを見出し、本発明を完成させた。 As a result of studies conducted by the present inventors to solve the above-mentioned problems, the above-mentioned problems are solved by making specific resins used for pigment dispersion and co-dispersing them with a dispersant. The present invention has been completed.
本発明は、下記(E1)〜(E4)成分、
(E1)黒色有機顔料、混色有機顔料及び遮光材の中から選ばれる少なくとも1種類の着色材、
(E2)分散剤、
(E3)光硬化性樹脂若しくは熱硬化性樹脂、
(E4)溶剤
からなる(E)顔料分散体をあらかじめ調製したのち、必須成分として下記(A)〜(D)成分、
(A)不飽和基含有アルカリ可溶性樹脂、
(B)エチレン性不飽和結合を有する光重合性モノマー、
(C)光重合開始剤、
(D)溶剤
と混合することを特徴とするカラーフィルター用レジスト組成物の製造方法である。
The present invention includes the following components (E1) to (E4),
(E1) at least one colorant selected from black organic pigments, mixed-color organic pigments and light-shielding materials,
(E2) dispersant,
(E3) a photocurable resin or a thermosetting resin,
(E4) After preparing a (E) pigment dispersion consisting of a solvent in advance, the following components (A) to (D) as essential components:
(A) an unsaturated group-containing alkali-soluble resin,
(B) a photopolymerizable monomer having an ethylenically unsaturated bond,
(C) a photopolymerization initiator,
(D) A method for producing a resist composition for a color filter, which comprises mixing with a solvent.
ここで、上記(E3)成分は、次の要件1)を満足する。
本発明のカラーフィルター用レジスト組成物は、要件1)に加えて、要件2)を満足することにより、更に優れた性能を示す。
Here, the component (E3) satisfies the following requirement 1).
The color filter resist composition of the present invention exhibits further excellent performance by satisfying the requirement 2) in addition to the requirement 1) .
1） (E3)成分の少なくとも1部が、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エポキシ化合物と（メタ）アクリル酸との反応物にa)ジ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、a/bのモル比が0.1〜10となる範囲で反応させて得られる下記一般式（I）
2） (A)成分の少なくとも1部が、上記一般式（I）で表される不飽和基含有アルカリ可溶性樹脂であること。
1) At least one part of component (E3) is a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid, and a) a dicarboxylic acid or its acid anhydride and b The following general formula (I) obtained by reacting tetracarboxylic acid or its acid dianhydride in a range where the molar ratio of a / b is 0.1-10
2) At least one part of the component (A) is an unsaturated group-containing alkali-soluble resin represented by the general formula (I).
また、本発明は上記のカラーフィルター用レジスト組成物からなることを特徴とするブラックレジスト用感光性樹脂組成物である。
更に、本発明は上記のブラックレジスト用感光性樹脂組成物を硬化させて形成した塗膜である。
また、本発明は上記のブラックレジスト用感光性樹脂組成物をアルカリ現像液で現像して得られるブラックマトリックスである。
更に、本発明は上記のブラックマトリックスが形成されてなるカラーフィルターである。
The present invention also provides a photosensitive resin composition for a black resist, comprising the above-described color filter resist composition.
Furthermore, this invention is the coating film formed by hardening | curing said photosensitive resin composition for black resists.
Moreover, this invention is a black matrix obtained by developing the photosensitive resin composition for black resists with an alkaline developer.
Furthermore, the present invention is a color filter formed with the above black matrix.
以下、本発明のカラーフィルター用レジスト組成物又はブラックレジスト用感光性樹脂組成物（以下、両者をレジスト組成物ともいう）について詳細に説明する。本発明のレジスト組成物は感光性樹脂組成物であり、アルカリ現像が可能である。 Hereinafter, the resist composition for a color filter or the photosensitive resin composition for a black resist of the present invention (hereinafter, both are also referred to as a resist composition) will be described in detail. The resist composition of the present invention is a photosensitive resin composition and can be alkali developed.
本発明のレジスト組成物は、必須成分として上記(A)〜(E)成分を含む。ここで、(A)成分は不飽和基含有アルカリ可溶性樹脂であり（以下、アルカリ可溶性樹脂という）、(B)成分はエチレン性不飽和結合を有する光重合性モノマー（以下、光重合性モノマーという）、(C)成分は光重合開始剤、(D)成分は溶剤、(E)成分は顔料分散体である。 The resist composition of the present invention contains the above components (A) to (E) as essential components. Here, the component (A) is an unsaturated group-containing alkali-soluble resin (hereinafter referred to as an alkali-soluble resin), and the component (B) is a photopolymerizable monomer having an ethylenically unsaturated bond (hereinafter referred to as a photopolymerizable monomer). ), (C) component is a photopolymerization initiator, (D) component is a solvent, and (E) component is a pigment dispersion.
（A）成分のアルカリ可溶性樹脂は、不飽和基を有するアルカリ可溶性樹脂であればよいが、（メタ）アクリル酸に由来する不飽和基を有し、a)ジカルボン酸又はその酸無水物（以下、ジカルボン酸類と略称することがある）及びb)テトラカルボン酸又はその酸二無水物（以下、テトラカルボン酸類と略称することがある）に由来する酸性基を有するアルカリ可溶性樹脂であることが好ましい。これらのアルカリ可溶性樹脂は、その１種又は２種以上を使用することができる。
なお、本明細書において、酸成分というときは、上記ジカルボン酸類、テトラカルボン酸類又は両方を意味し、（メタ）アクリル酸は、アクリル酸、メタクリル酸又は両方を意味する。
The alkali-soluble resin of component (A) may be an alkali-soluble resin having an unsaturated group, but has an unsaturated group derived from (meth) acrylic acid, and a) a dicarboxylic acid or an acid anhydride thereof And b) an alkali-soluble resin having an acidic group derived from a tetracarboxylic acid or an acid dianhydride thereof (hereinafter sometimes abbreviated as a tetracarboxylic acid). . One or more of these alkali-soluble resins can be used.
In the present specification, the acid component means the above dicarboxylic acids, tetracarboxylic acids or both, and (meth) acrylic acid means acrylic acid, methacrylic acid or both.
好適な(A)成分のアルカリ可溶性樹脂は、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エポキシ化合物に、（メタ）アクリル酸を反応させ、得られたヒドロキシ基を有する化合物に、多塩基酸であるジカルボン酸類とテトラカルボン酸類の少なくとも各1種類と反応させて得られたエポキシ（メタ）アクリレート酸付加物である。かかる（A）成分は、エチレン性不飽和二重結合とカルボキシル基とを併せ持つため、アルカリ現像型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、良好なブラックマトリックスが得られる。最も好ましいアルカリ可溶性樹脂としては、上記一般式（I）で表される樹脂がある。 A preferred alkali-soluble resin as component (A) is a compound obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid, resulting in a compound having a hydroxy group. It is an epoxy (meth) acrylate acid adduct obtained by reacting at least one of dicarboxylic acids and tetracarboxylic acids as basic acids. Since the component (A) has both an ethylenically unsaturated double bond and a carboxyl group, it gives an excellent photocurability, good developability, and patterning characteristics to the alkali development type photosensitive resin composition, and a good black matrix. Is obtained. The most preferred alkali-soluble resin is a resin represented by the above general formula (I).
かかるアルカリ可溶性樹脂は、好ましくは、一般式(II)で表されるエポキシ化合物から誘導される。このエポキシ化合物はビスフェノール類から誘導される。
一般式(II)において、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ａは、一般式（I）と同様の意味を有する。好ましいＲ1、Ｒ2、Ｒ3、Ｒ4は水素原子であり、好ましいAは9,9-フルオレニル基である。lは０〜１０の整数であるが、好ましくは０又は平均値として０〜２の範囲である。ここで、9,9-フルオレニル基は、下記式一般式(III)で表される基をいう。
好ましい(A)成分のアルカリ可溶性樹脂を与えるビスフェノール類としては、次のようなものが挙げられる。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）エーテル等。また、Aが9,9−フルオレニル基である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-3,5-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）フルオレン等も好ましく挙げられる。更には、4,4'-ビフェノール、3,3'-ビフェノール等も好ましく挙げられる。 Examples of the bisphenols that give the alkali-soluble resin as the preferred component (A) include the following. 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) hexafluoropropane, 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 and the like. In addition, 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-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc. are also preferred Can be mentioned. Furthermore, 4,4′-biphenol, 3,3′-biphenol and the like are also preferred.
(A)成分は、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の他に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も２個のグリシジルエーテル基を有する化合物を有意に含むものであれば使用することができる。また、ビスフェノール類をグリシジルエーテル化する際に、オリゴマー単位が混入することになるが、式(II)におけるｌの平均値が０〜１０、好ましくは０〜２の範囲であれば、本樹脂組成物の性能には問題はない。 The component (A) can be obtained from an epoxy compound derived from bisphenols as described above. In addition to such an epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, etc. are also two glycidyl ethers. Any compound containing a group-containing compound can be used. In addition, when bisphenols are glycidyl etherified, oligomer units are mixed. If the average value of l in formula (II) is in the range of 0 to 10, preferably 0 to 2, this resin composition There is no problem in the performance of things.
このようなエポキシ化合物と（メタ）アクリル酸との反応は、エポキシ化合物1モルに対し、約2モルの（メタ）アクリル酸を使用して行うが、かかる反応は前記特許文献６〜１１等で公知である。この反応で得られる反応物は、前記特許文献等に記載されている他、後記式(V)で表されるようなエポキシ（メタ）アクリレート化合物である。 The reaction between such an epoxy compound and (meth) acrylic acid is carried out using about 2 moles of (meth) acrylic acid with respect to 1 mole of the epoxy compound. It is known. The reaction product obtained by this reaction is an epoxy (meth) acrylate compound represented by the following formula (V) as well as described in the above-mentioned patent documents.
エポキシ化合物と（メタ）アクリル酸との反応で得られた反応物と、酸成分を反応させて（A)成分のアルカリ可溶性樹脂を得る。酸成分としては、エポキシ（メタ）アクリレート化合物分子中のヒドロキシ基と反応し得るa)ジカルボン酸類とb)テトラカルボン酸類が使用される。 The reaction product obtained by the reaction between the epoxy compound and (meth) acrylic acid is reacted with the acid component to obtain an alkali-soluble resin as the component (A). As the acid component, a) dicarboxylic acids and b) tetracarboxylic acids that can react with the hydroxy group in the epoxy (meth) acrylate compound molecule are used.
ここで、a)ジカルボン酸類としては、鎖式炭化水素ジカルボン酸又はその酸無水物や脂環式ジカルボン酸又はその酸無水物、芳香族ジカルボン酸やその酸無水物が使用される。
鎖式炭化水素ジ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の導入されたジカルボン酸類又はその酸無水物でもよい。
また、脂環式ジカルボン酸又はその酸無水物としては、例えば、ヘキサヒドロフタル酸、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、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の導入されたジカルボン酸類又はその酸無水物でもよい。
更に、芳香族ジカルボン酸やその酸無水物としては、例えばフタル酸、イソフタル酸等の化合物があり、更には任意の置換基の導入されたジカルボン酸類又はその酸無水物でもよい。
Here, as a) dicarboxylic acids, chain hydrocarbon dicarboxylic acid or its acid anhydride, alicyclic dicarboxylic acid or its acid anhydride, aromatic dicarboxylic acid or its acid anhydride is used.
Examples of the chain hydrocarbon dicarboxylic acid or its acid anhydride include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid. There are compounds such as acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like, and further dicarboxylic acids having an arbitrary substituent introduced therein or acid anhydrides thereof may be used.
Examples of the alicyclic dicarboxylic acid or its acid anhydride include compounds such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and any substituents introduced. Dicarboxylic acids or acid anhydrides thereof may be used.
Furthermore, examples of the aromatic dicarboxylic acid and its acid anhydride include compounds such as phthalic acid and isophthalic acid, and further dicarboxylic acids into which an arbitrary substituent is introduced or acid anhydrides thereof may be used.
また、b)テトラカルボン酸類としては、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、あるいは、芳香族多価カルボン酸あるいはその酸二無水物が使用される。
ここで、鎖状テトラカルボン酸又はその酸無水物としては、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、更には置換基の導入されたテトラカルボン酸類又はその酸無水物でもよい。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、更には置換基の導入されたテトラカルボン酸類又はその酸無水物でもよい。
更に、芳香族テトラカルボン酸やその酸無水物としては、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無水物が挙げられ、更には置換基の導入されたテトラカルボン酸類又はその酸無水物でもよい。
In addition, as b) tetracarboxylic acids, chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, or aromatic polyvalent carboxylic acid or its acid dianhydride Things are used.
Here, examples of the chain tetracarboxylic acid or its acid anhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and further, tetracarboxylic acids having a substituent introduced therein or acids thereof. An anhydride may be used. Examples of the alicyclic tetracarboxylic acid or its acid anhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid norbornanetetracarboxylic acid, and the like. It may be a tetracarboxylic acid having a substituent introduced therein or an acid anhydride thereof.
Furthermore, examples of the aromatic tetracarboxylic acid and acid anhydride thereof include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid anhydrides thereof, and further, substituents thereof. The introduced tetracarboxylic acids or acid anhydrides thereof may be used.
a)ジカルボン酸類とb)テトラカルボン酸類は、それぞれ1種以上を使用することができ、a)ジカルボン酸類とb)テトラカルボン酸類の使用割合は、a/bのモル比として0.1〜10となる範囲、好ましくは0.2〜1.0となる範囲である。この使用割合は、最適分子量、アルカリ現像性、光透過性、耐熱性、対溶剤性、パターン形状の効果に適した割合を選択することができるが、テトラカルボン酸類の使用割合が大き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。 One or more of a) dicarboxylic acids and b) tetracarboxylic acids can be used, respectively. The use ratio of a) dicarboxylic acids and b) tetracarboxylic acids is 0.1 to 10 as a molar ratio of a / b. The range is preferably 0.2 to 1.0. The use ratio can be selected as the optimum molecular weight, alkali developability, light transmittance, heat resistance, solvent resistance, and the pattern shape effect, but the higher the use ratio of tetracarboxylic acids, the higher the alkali solubility. Tend to be large and have a high molecular weight.
エポキシ化合物と（メタ）アクリル酸との反応で得られた反応物と、酸成分を反応させて（A）成分を製造する方法については、特に限定されるものでなく、前記特許文献６〜１１に記載のような公知の方法を採用することができる。
有利には、エポキシ（メタ）アクリレート化合物分子中のヒドロキシ基に対し等当量以上カルボキシ基となるように、且つ後記する酸価を示す量の酸成分を使用し、定量的に反応させることが望ましい。また、反応温度としては、90〜130℃、好ましくは95〜125℃である。
The method for producing the component (A) by reacting the reaction product obtained by the reaction between the epoxy compound and (meth) acrylic acid and the acid component is not particularly limited, and the above-mentioned Patent Documents 6 to 11 are not limited. A publicly known method as described in the above can be adopted.
Advantageously, it is desirable to carry out the reaction quantitatively by using an acid component in an amount that shows an acid value, which will be described later, so that the carboxy group is equal to or more equivalent to the hydroxy group in the epoxy (meth) acrylate compound molecule. . The reaction temperature is 90 to 130 ° C, preferably 95 to 125 ° C.
（A)成分を製造する方法の一例を9,9-ビス（4-ヒドロキシフェニル）フルオレンを出発原料とする場合について示せば、次のようである。
先ず、9,9-ビス（4-ヒドロキシフェニル）フルオレンとエピクロロヒドリンとを反応させて下記一般式(IV)で表されるビスフェノールフルオレン型エポキシ化合物を合成し、このビスフェノールフルオレン型エポキシ化合物とCH2＝CR5-COOHで表される（メタ）アクリル酸とを反応させて下記一般式（V）で表されるビスフェノールフルオレン型エポキシアクリレート樹脂を合成し、次いでプロピレングリコールモノメチル溶剤中でビスフェノールフルオレン型エポキシアクリレート樹脂と上記酸成分とを加熱下に反応させ、（A）成分である前記式（I）で表されるフルオレン型のアルカリ可溶性樹脂を得る。
An example of the method for producing the component (A) is as follows when 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material.
First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenolfluorene type epoxy compound represented by the following general formula (IV). A bisphenolfluorene type epoxy acrylate resin represented by the following general formula (V) was synthesized by reacting with (meth) acrylic acid represented by CH 2 = CR 5 -COOH, and then bisphenolfluorene in a propylene glycol monomethyl solvent. The epoxy acrylate resin and the acid component are reacted under heating to obtain a fluorene type alkali-soluble resin represented by the formula (I) as the component (A).
ここで、式(IV)及び(V)において、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5は、式（I）と同様な意味を有する。Aは9,9-フルオレニル基を示す。 Here, in the formulas (IV) and (V), R 1 , R 2 , R 3 , R 4 and R 5 have the same meaning as in the formula (I). A represents a 9,9-fluorenyl group.
本発明のレジスト組成物は、上記(A)成分を樹脂成分の必須成分として含有する。ここで、樹脂成分とは、重合又は硬化させることにより樹脂となる成分をいい、樹脂（オリゴマーを含む）の他、モノマーも含む。(A)成分は、レジスト組成物の全固形分中15〜25wt％含まれることがよい。また、重量平均分子量（Mw）は、500〜10,000の間であることが好ましい。重量平均分子量（Mw）が500に満たないと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10,000を超えるとガラス基板への密着性が高くなりすぎてしまい、残渣やパターン部の残膜が残り易くなる。更に、(A)成分はその酸価が1〜200 KOHmg/gの範囲にあることが望ましい。この値が200 KOHmg/gを超えるとアルカリ現像液の浸透が早くなるため、剥離現像が起きる。なお、全固形分とは溶剤等の揮発分を含まず、重合又は硬化して固形分となるモノマー等を含む。 The resist composition of the present invention contains the component (A) as an essential component of the resin component. Here, the resin component refers to a component that becomes a resin by polymerization or curing, and includes a monomer in addition to a resin (including an oligomer). The component (A) is preferably contained in an amount of 15 to 25 wt% in the total solid content of the resist composition. The weight average molecular weight (Mw) is preferably between 500 and 10,000. If the weight average molecular weight (Mw) is less than 500, the pattern adhesion during development cannot be maintained and pattern peeling occurs. If the weight average molecular weight (Mw) exceeds 10,000, the adhesion to the glass substrate is high. As a result, the residue and the remaining film of the pattern portion are likely to remain. Furthermore, the component (A) preferably has an acid value in the range of 1 to 200 KOHmg / g. When this value exceeds 200 KOHmg / g, the permeation of the alkali developer is accelerated, and thus the peeling development occurs. The total solid content does not include a volatile component such as a solvent, but includes a monomer that is polymerized or cured to become a solid component.
(B)成分の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モノマーや、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、ジペンタエリスリトールヘキサ（メタ）アクリレート、グリセロール（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、これらの光重合性モノマーは、１種又は２種以上を使用することができる。なお、(B)成分の光重合性モノマーは遊離のカルボキシ基を有しない。 Examples of the photopolymerizable monomer of the component (B) include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (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, trimethylol Ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol (Meth) acrylic acid esters such as rutetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, and the like. These photopolymerizable monomers may be used alone or in combination. Can be used. The photopolymerizable monomer of component (B) does not have a free carboxy group.
(A)成分と(B)成分の配合割合は、重量比（A）/（B）で20/80〜90/10であることがよく、好ましくは40/60〜80/20である。(A)成分の配合割合が少ないと、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、パターンエッジががたつきシャープにならないといった問題が生じ、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も細ったり、パターンの欠落が生じや易くなるといった問題が生じる恐れがある。 The mixing ratio of the component (A) and the component (B) is preferably 20/80 to 90/10 in weight ratio (A) / (B), and preferably 40/60 to 80/20. When the blending ratio of the component (A) is small, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so the solubility in an alkali developer is lowered, and the pattern edge is scratched. When the problem of not being sharp and sharp occurs, the ratio of the photoreactive functional group in the resin is small and the formation of a crosslinked structure is insufficient, and the acid value in the resin component is too high, and the alkali in the exposed area Since the solubility in the developer is increased, there is a possibility that the formed pattern is narrower than the target line width or the pattern is easily lost.
(C)成分の光重合開始剤としては、1種類以上の開始剤を用いることができる。なお、本発明でいう光重合開始剤は増感剤を含む意味で使用される。
使用可能な光重合開始剤としては例えば、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チアゾール化合物類、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R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、トリエタノールアミン、トリエチルアミン等の第３級アミンなどが挙げられる。
As the photopolymerization initiator of component (C), one or more kinds of initiators can be used. In addition, the photoinitiator said by this invention is used by the meaning containing a sensitizer.
Usable photopolymerization initiators include, for example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-chlorophenyl) ) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2 -(o-methoxyphenyl)- Biimidazole compounds such as 4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl- Halomethylthiazole compounds such as 5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 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 (trichloroRmethyl) -1,3,5-triazine, 2- (4- Methoxystyryl) -4,6- (Trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halomethyl-S-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, O-acyloxime compounds such as 2-dione-2-oxime-o-acetate and 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate, benzyldimethyl ketal, thioxanthone, 2-chlorothio Xanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxone Organic compounds such as sulfur compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, etc. Products, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine.
(C)成分の光重合開始剤の使用量は、(A)及び(B)の各成分の合計100重量部を基準として2〜60重量部であることがよく、好ましくは10〜50重量部である。(C)成分の配合割合が少ないと、光重合の速度が遅くなって感度が低下し、一方、多過ぎると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がた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。 The amount of the photopolymerization initiator used as the component (C) is preferably 2 to 60 parts by weight, preferably 10 to 50 parts by weight based on the total of 100 parts by weight of the components (A) and (B). It is. When the blending ratio of the component (C) is small, the photopolymerization rate is slowed and the sensitivity is lowered.On the other hand, when the amount is too large, the sensitivity is too strong and the pattern line width becomes thicker than the pattern mask. On the other hand, there may be a problem that a faithful line width cannot be reproduced or the pattern edge is not rattling and sharp.
(D)成分の溶剤としては、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−若しくは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。 Examples of the solvent for component (D) 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, N -Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, 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 ethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Examples include acetic acid esters such as ethyl ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.
(E)成分の顔料分散体は、下記成分を含む。
(E1)黒色有機顔料、混色有機顔料及び遮光材の中から選ばれる少なくとも1種類の着色材（以下、着色材という）、
(E2)分散剤
(E3)光硬化性樹脂若しくは熱硬化性樹脂（以下、硬化性樹脂という）
(E4)溶剤
The pigment dispersion of component (E) includes the following components.
(E1) at least one colorant selected from black organic pigments, mixed color organic pigments and light-shielding materials (hereinafter referred to as colorants),
(E2) Dispersant
(E3) Photo-curing resin or thermosetting resin (hereinafter referred to as curable resin)
(E4) Solvent
(E)成分は、(E1)成分、(E2)成分、(E3)成分、(E4)成分及び必要により加えられる他の成分を混合し、ガラスビーズ、ジルコニアビーズ等のメディアを加えた後、ペイントコンディショナー、サンドグランダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー、超音波等等を単独もしくは複数組み合わせて分散処理されて得られるものであることが好ましい。この分散処理によって、顔料成分が微粒子化及び分散安定化されるため、レジスト組成物の遮光能力向上及び塗布特性の向上が図れる。 (E) component, (E1) component, (E2) component, (E3) component, (E4) component and other components added if necessary, after adding media such as glass beads, zirconia beads, A paint conditioner, a sand grounder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, an ultrasonic wave and the like are preferably obtained by being subjected to dispersion treatment alone or in combination. This dispersion treatment makes the pigment component fine particles and stabilizes the dispersion, so that the light shielding ability of the resist composition and the coating characteristics can be improved.
また、(E)成分は、まず(E2)成分と(E3)成分を最適な量の(E4)成分に溶解させ、その後(E1)成分を添加し、安定するまで分散を行うことがよい。 The component (E) is preferably dispersed until the components (E2) and (E3) are first dissolved in an optimal amount of the component (E4), and then the component (E1) is added and stabilized.
分散後の２次粒子径としては、(E1)成分、例えばカーボンブラックの分散粒径が５０〜２００ｎｍ、好ましくは８０〜１５０ｎｍとなるように調整するのが好ましい。ここでの分散粒径は、例えば公知のレーザードップラー式の粒度測定器で求めた平均の粒子径である。また分散液の粘度は、公知のコーンプレート型粘度形より求めたとき、分散液の液温２５℃で３．０〜１００．０ｍＰａ・ｓ、好ましくは３．０〜２０．０ｍＰａ・ｓに調整するのが好ましい。 The secondary particle diameter after dispersion is preferably adjusted so that the dispersed particle diameter of the component (E1), for example, carbon black, is 50 to 200 nm, preferably 80 to 150 nm. The dispersed particle diameter here is, for example, an average particle diameter obtained by a known laser Doppler type particle size measuring device. Further, the viscosity of the dispersion is adjusted to 3.0 to 100.0 mPa · s, preferably 3.0 to 20.0 mPa · s at a liquid temperature of 25 ° C. when calculated from a known cone plate type viscosity type. It is preferable to do this.
(E1)成分の着色材として使用される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少なくとも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。遮光材としては、カーボンブラック、酸化クロム、酸化鉄、チタンブラック、アニリンブラック、シアニンブラックを挙げることができる。着色材は、２種以上を適宜選択して用いることもできるが、特にカーボンブラックが、遮光性、表面平滑性、分散安定性、樹脂との相溶性が良好な点で好ましい。 Examples of the black organic pigment used as the colorant for the component (E1) include perylene black and cyanine black. Examples of mixed color organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like into a pseudo black color. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Two or more colorants can be appropriately selected and used, but carbon black is particularly preferable in terms of good light shielding properties, surface smoothness, dispersion stability, and compatibility with the resin.
具体的には三菱化学社製のカーボンブラック#2400、＃2350、#2300、#2200、#1000、#980、#970、#960、#950、#900、#850、MCF88、#650、MA600、MA7、MA8、MA11、MA100、MA220、MA230、IL30B、IL31B、IL7B、IL11B、IL52B、#4000、#4010、#55、#52、#50、#47、#45、#44、#40、#33、#32、#30、#20、#10、#5、CF9、#3050、#3150、#3250等。キャンカーブ社製のカーボンブラックサーマックスN990、N991、N907、N908、N990、N991、N908。旭カーボン社製のカーボンブラック旭#80、旭#70、旭＃70L、旭F−200、旭#66、旭#66HN、旭#60H、旭#60U、旭#60、旭#55、旭#50H、旭#51、旭#50U、旭#50、旭#35、旭#15、アサヒサーマル。デグサ社製のカーボンブラックColorBlack Fw200、ColorBlack Fw2、ColorBlack Fw2V、ColorBlack Fw1、ColorBlack Fw18、ColorBlack S170、ColorBlack S160、SpecialBlack6、SpecialBlack5、SpecialBlack4、SpecialBlack4A、SpecialBlack250、SpecialBlack350、PrintexU、PrintexV、Printex140U、Printex140V（すべて商品名）等が挙げられる。 Specifically, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # 650, MA600 manufactured by Mitsubishi Chemical Corporation , MA7, MA8, MA11, MA100, MA220, MA230, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, etc. Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal. Carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack350, PrintexU, PrintexV, Printex140U, Printex140V (all product names) ) And the like.
(E1)成分の着色剤の含有率は、(E1)/[(A)+(B)+(C)+(E')]×100で重量計算される(E1)成分含有率が40wt％以上となるように配合する。好ましくは45〜60 wt％、より好ましくは50〜55wt％の範囲である。ここで、(E')は（E）成分から(E4)成分を除いた成分である。上記計算式において、(E1)、(A)、(B)、(C)、(E')は、各成分の配合量（重量）である。(E1)成分含有率が低いと、遮光性が十分でなくなり、望ましいコントラストを得るためには膜厚を厚くしなければならなくなり、ブラックマトリックスの面平滑性が得にくい。反対に添加量が多すぎると、（E）成分の顔料分散体だけでなく、レジスト組成物の分散安定性が低下し、また、本来のバインダーとなる感光性樹脂の含有量も減少するため、良好な現像特性が得られなくなるという好ましくない問題が生じる恐れがある。 The content of the colorant of the (E1) component is (E1) / [(A) + (B) + (C) + (E ')] × 100. The weight content of the (E1) component is 40 wt%. It mix | blends so that it may become the above. Preferably it is 45-60 wt%, More preferably, it is the range of 50-55 wt%. Here, (E ′) is a component obtained by removing (E4) component from (E) component. In the above calculation formula, (E1), (A), (B), (C), and (E ′) are blending amounts (weight) of each component. When the content of the component (E1) is low, the light shielding property is not sufficient, and in order to obtain a desired contrast, the film thickness must be increased, and the surface smoothness of the black matrix is difficult to obtain. On the other hand, if the amount added is too large, not only the pigment dispersion of component (E), but also the dispersion stability of the resist composition is lowered, and the content of the photosensitive resin that is the original binder is also reduced. There is a possibility that an undesired problem that good development characteristics cannot be obtained may occur.
(E2)成分の分散剤は、(E1)成分の着色剤を顔料分散体として安定的に分散させる作用を有するものであればよく、例えば、各種高分子分散剤等の公知の分散剤を使用することができる。高分子分散剤の具体例としては、特に１級、２級若しくは３級アミノ基、ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環等の塩基性官能基を有する高分子分散剤が挙げられる。 The dispersant of the component (E2) may be any dispersant as long as it has an action of stably dispersing the colorant of the component (E1) as a pigment dispersion.For example, a known dispersant such as various polymer dispersants is used. can do. Specific examples of the polymer dispersant include polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups, nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine.
(E3)成分の硬化性樹脂は、少なくとも1種類の光硬化性樹脂若しくは熱硬化性樹脂を含む。(E3)成分の硬化性樹脂は、前述の分散剤と併用して、光硬化性樹脂若しくは熱硬化性樹脂を用いて分散剤と共分散させることができる。(E3)成分は酸性官能基を有するアクリル系樹脂であることがよく、好ましくは(A)成分と一部又は全部が同一であることがより効果的である。(E2)成分と(E3)成分を共分散させた場合、その添加量とともに、経時的な粘度安定性、線幅安定性が良好となり、また残渣低減、直線性改善、密着性向上などの効果が得られる。 The curable resin of component (E3) contains at least one photocurable resin or thermosetting resin. The curable resin of component (E3) can be co-dispersed with the dispersant using a photocurable resin or a thermosetting resin in combination with the aforementioned dispersant. The component (E3) is preferably an acrylic resin having an acidic functional group, and it is more effective that part or all of the component (E) is the same as the component (A). When (E2) component and (E3) component are co-dispersed, along with the added amount, viscosity stability over time and line width stability will be good, and effects such as residue reduction, linearity improvement, adhesion improvement etc. Is obtained.
(E4)成分の溶剤としては、（D）成分の溶剤と同一のものを使用することが望ましい。 As the solvent for the component (E4), it is desirable to use the same solvent as the solvent for the component (D).
本発明のレジスト組成物の製造では、上記(E)成分調製後、(A)成分、(B)成分、(C)成分、(D)成分及び必要により加えられる配合成分と混合させ、レジスト組成物とすることが望ましい。この混合は、均一に混合することができる方法であればよいが、攪拌や(E)成分調製に使用される分散装置等を使用して行うことができる。 In the production of the resist composition of the present invention, after the preparation of the above component (E), it is mixed with the component (A), the component (B), the component (C), the component (D) and a compounding component added as necessary, to obtain a resist composition. It is desirable to make it. This mixing may be performed by any method that allows uniform mixing, but can be performed by using a dispersing device or the like used for stirring and component (E) preparation.
また、本発明のレジスト組成物の製造においては、必要に応じて硬化促進剤、熱重合禁止剤、可塑剤、充填材、レベリング剤、消泡剤、分散剤用とは別の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、トリクレジル等を挙げることができ、充填材としては、グラスファイバー、シリカ、マイカ、アルミナ等を挙げることができ、また、消泡剤やレベリング剤としては、例えば、シリコン系、フッ素系、アクリル系の化合物を挙げることができる。 Further, in the production of the resist composition of the present invention, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant different from that for the dispersant, etc., as necessary. Additives can be blended. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and the like, and examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl, and the like. Can include glass fiber, silica, mica, alumina, and the like, and examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.
本発明のレジスト組成物は、本発明のレジスト組成物の製造方法によって得ることができる。また、本発明の顔料分散体は、上記（E）成分の製造方法によって得ることができる。この顔料分散体は、本発明のレジスト組成物の製造に有利に使用される。 The resist composition of the present invention can be obtained by the method for producing a resist composition of the present invention. Further, the pigment dispersion of the present invention can be obtained by the method for producing the component (E). This pigment dispersion is advantageously used in the production of the resist composition of the present invention.
本発明のレジスト組成物は、上記（A）〜（E）成分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）〜（E）成分が合計で70wt％以上、好ましくは80wt％、より好ましくは90wt％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、20〜90wt％の範囲が望ましい。 The resist composition of the present invention contains the components (A) to (E) as main components. In the solid content excluding the solvent (the solid content includes monomers that become solid content after curing), the total of components (A) to (E) is 70 wt% or more, preferably 80 wt%, more preferably 90 wt% or more It is desirable to include. The amount of solvent varies depending on the target viscosity, but is preferably in the range of 20 to 90 wt%.
本発明のレジスト組成物は、カラーフィルター用のレジスト、例えばインキ、遮光膜等として有用であるが、カラーフィルター用のブラックレジスト用感光性樹脂組成物（以下、ブラックレジスト組成物ともいう）に適する。 The resist composition of the present invention is useful as a resist for a color filter, for example, an ink, a light-shielding film, etc., but is suitable for a photosensitive resin composition for a black resist for a color filter (hereinafter also referred to as a black resist composition). .
本発明の塗膜は、例えば、上記ブラックレジスト組成物の溶液を、基板等に塗布し、乾燥し、光（紫外線、放射線等を含む）を照射し、これを硬化させることにより得られる。光が当たる部分と当たらない部分とを設けて、光が当たる部分だけを硬化させ、他の部分をアルカリ溶液で溶解させれば、所望のパターンの塗膜が得られる。 The coating film of the present invention can be obtained, for example, by applying the above black resist composition solution to a substrate or the like, drying it, irradiating it with light (including ultraviolet rays, radiation, etc.) and curing it. A coating film having a desired pattern can be obtained by providing a portion that is exposed to light and a portion not exposed to light, curing only the portion that is exposed to light, and dissolving the other portion with an alkaline solution.
次に、本発明のブラックレジスト組成物を用いたカラーフィルターの製造法について説明する。まず、基板の表面上に、ブラックレジスト組成物を基板に塗布して、画素を形成する部分を区画するように遮光層（ブラックマトリクス）を形成する。次に、この基板上に、例えば赤色の顔料が分散された液状の感光性樹脂組成物（インキ）を塗布したのち、プレベークを行って溶剤を蒸発させ、塗膜を形成する。次いで、この塗膜にフォトマスクを介して露光したのち、アルカリ性現像液を用いて現像して、塗膜の未露光部を溶解除去し、その後ポストベークすることにより、赤色の画素パターンが所定の配列で配置された画素アレイを形成する。その後、緑色又は青色の顔料が分散されたインキを用い、前記と同様にして、各液状組成物の塗布、プリベーク、露光、現像及びポストベークを行って、緑色の画素アレイ及び青色の画素アレイを同一基板上に順次形成することにより、赤色、緑色及び青色の三原色の画素アレイが基板上に配置し、更に、この上に保護膜として、着色剤を含まない感光性樹脂の液状組成物を前記と同様にして、塗布、プリベーク、露光、現像及びポストベークを行って、保護膜が形成されたカラーフィルターを得る。 Next, a method for producing a color filter using the black resist composition of the present invention will be described. First, on the surface of the substrate, a black resist composition is applied to the substrate, and a light-shielding layer (black matrix) is formed so as to partition a portion for forming a pixel. Next, after applying a liquid photosensitive resin composition (ink) in which, for example, a red pigment is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, after exposing the coating film through a photomask, development using an alkaline developer is performed to dissolve and remove the unexposed portion of the coating film, and then post-baking to form a predetermined red pixel pattern. A pixel array arranged in an array is formed. Thereafter, using the ink in which the green or blue pigment is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above to obtain the green pixel array and the blue pixel array. By sequentially forming on the same substrate, a pixel array of three primary colors of red, green and blue is disposed on the substrate, and further, a liquid composition of a photosensitive resin not containing a colorant is formed thereon as a protective film. In the same manner as above, coating, pre-baking, exposure, development, and post-baking are performed to obtain a color filter on which a protective film is formed.
本発明のレジスト組成物又はブラックレジスト組成物の液状組成物を基板に塗布する際には、公知の溶液浸漬法、スプレー法の他、ローラーコーター、ランドコーター、スリットコーターやスピンコーター、スクリーン印刷法又はインクジェット印刷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（プリベーク）ことにより、被膜が形成される。プリベークはオーブン、ホットプレート等による加熱、真空乾燥又はこれらの組み合わせることによって行われる。プリ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80〜120℃の温度で1〜10分間行われる。 When applying the liquid composition of the resist composition or black resist composition of the present invention to the substrate, in addition to the known solution dipping method and spray method, roller coater, land coater, slit coater, spin coater, screen printing method Alternatively, any method such as an ink jet printing method can be adopted. After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate or the like, vacuum drying, or a combination thereof. The heating temperature and the heating time in the pre-baking are appropriately selected according to the solvent used, and for example, the heating is performed at a temperature of 80 to 120 ° C. for 1 to 10 minutes.
カラーフィルターを作製する際にレジスト組成物を露光、硬化させるために使用される放射線としては、例えば、可視光線、紫外線、遠紫外線、電子線、Ｘ線等を使用することができるが、波長が250〜450nmの範囲にある放射線が好ましい。次に、アルカリ現像するが、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0.05〜10重量％含有する弱アルカリ性水溶液を用いて20〜30℃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。なお、アルカリ現像後は、通常、水洗する。現像処理法としては、シャワー現像法、スプレー現像法、ディップ（浸漬）現像法、パドル（液盛り）現像法等を適用することができる。現像条件は、常温で10〜120秒が好ましい。 As the radiation used for exposing and curing the resist composition when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, and the like can be used. Radiation in the range of 250-450 nm is preferred. Next, although alkali development is performed, examples of the developer suitable for alkali development include aqueous solutions of alkali metal and alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, and the like. It is better to develop at a temperature of 20-30 ° C using a weakly alkaline aqueous solution containing 0.05-10% by weight of carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, etc. It can be used to form a fine image precisely. In addition, it is usually washed with water after alkali development. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 10 to 120 seconds at room temperature.
このようにして現像した後、180〜250℃の温度及び20〜100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塗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塗膜は、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 as described above, a heat treatment (post-bake) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned coating 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 coating film of this invention is formed through each process by the above photolithography method.
画素及びブラックマトリックスを備えたカラーフィルターを形成する際に使用される基板としては、例えば、ガラス、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、金等の透明電極が蒸着あるいはパターニングされたもの等が用いられる。また、これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。 As a substrate used when forming a color filter having pixels and a black matrix, for example, a transparent electrode such as ITO or gold on glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) is used. A vapor-deposited or patterned material is used. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
本発明のブラックマトリックスは、上記ブラックレジストを使用して、上記のように塗布、乾燥、露光、現像することにより得ることができる。本発明のカラーフィルターは、このブラックマトリックス上にカラーインキを使用して、上記のように塗布、乾燥、露光、現像の工程を繰り返すことにより得ることができる。 The black matrix of the present invention can be obtained by coating, drying, exposing and developing as described above using the above black resist. The color filter of the present invention can be obtained by using the color ink on the black matrix and repeating the steps of coating, drying, exposure and development as described above.
本発明のカラーフィルター用レジスト組成物は、現像特性及び基板密着性の優れた細線パターンの形成を可能とし、これをカラーフィルターに適用すると、高遮光性で高信頼性を持つブラックマトリックスを作成することが可能となる。したがって、カラー液晶表示装置、カラーファクシミリ、イメージセンサー等の各種の多色表示体や光学機器等に使用されるインク、及びブラックマトリックスを有するカラーフィルターや、テレビ、ビデオモニターあるいはコンピューターのディスプレー等に好適に使用することができる。 The resist composition for a color filter of the present invention enables formation of a fine line pattern having excellent development characteristics and substrate adhesion, and when applied to a color filter, creates a black matrix having high light shielding properties and high reliability. It becomes possible. Therefore, it is suitable for various multicolor displays such as color liquid crystal display devices, color facsimiles, and image sensors, inks used for optical devices, etc., color filters having a black matrix, televisions, video monitors, computer displays, etc. Can be used for
以下、合成例、実施例、比較例により、本発明を更に詳細に説明する。なお、以下の合成例における樹脂の評価は、断りのない限り以下の通りである。
固形分濃度：樹脂溶液を160℃にて2hr加熱して求めた。
酸価：1/10N−KOHエタノ−ル(50％)水溶液で滴定して求めた。
分子量：GPCにより求めた。この分子量は、未反応原料を除いた(A)成分のポリスチレン換算の重量平均分子量(Mw)である。
Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples, and comparative examples. In addition, evaluation of resin in the following synthesis examples is as follows unless otherwise noted.
Solid content concentration: Obtained by heating the resin solution at 160 ° C. for 2 hours.
Acid value: Determined by titration with 1/10 N-KOH ethanol (50%) aqueous solution.
Molecular weight: determined by GPC. This molecular weight is the weight average molecular weight (Mw) in terms of polystyrene of the component (A) excluding unreacted raw materials.
また、合成例で使用する略号は次のとおりである。
FHPA：フルオレンビスフェノール型エポキシ樹脂とアクリル酸との等当量反応物（新日鐵化学社製、ASF-400の溶液：固形分濃度50wt％、固形分換算の酸価1.3mgKOH/g、エポキシ当量21300）
ODPA：4,4'-オキシジフタル酸二無水物
SA：無水琥珀酸
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.
FHPA: Equivalent reaction product of fluorene bisphenol type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid content concentration 50wt%, solid content converted acid value 1.3mgKOH / g, epoxy equivalent 21300 )
ODPA: 4,4'-oxydiphthalic dianhydride
SA: Succinic 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FHPAのPGMEA溶液222.13 g（1当量）と、ODPA 42.45 g（0.75当量）、SA 9.18 g（0.5当量）、PGMEA 25.73 g及びTPP 0.47g（0.01当量）を仕込み、120〜130℃に加熱下に2hr撹拌し、更に80〜90℃にて6hrの加熱撹拌を行って、アルカリ可溶性樹脂溶液(A)-2を合成した。得られた樹脂溶液の固形分は55wt%、酸価（固形分換算）は150mgKOH/g、GPC分析によるMwは10,000であった。
Synthesis example 1
In a 500 ml four-necked flask equipped with a reflux condenser, 222.13 g (1 equivalent) of FHPA PGMEA solution, 42.45 g (0.75 equivalent) of ODPA, 9.18 g (0.5 equivalent) of SA, 25.73 g of PGMEA and 0.47 g of TPP (0.01 equivalent) ) And stirred for 2 hours while heating at 120 to 130 ° C., and further heated and stirred for 6 hours at 80 to 90 ° C. to synthesize an alkali-soluble resin solution (A) -2. The obtained resin solution had a solid content of 55 wt%, an acid value (in terms of solid content) of 150 mgKOH / g, and a Mw of 10,000 by GPC analysis.
実施例、比較例のカラーフィルターの製造で用いた原料及び略号は以下の通りである。
成分(A)-I ： フルオレン骨格を有するエポキシアクリレートの酸無水物重縮合物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溶液（樹脂固形分濃度=56.5重量％、分子量Mw=3,500、酸価100mgKOH/g、新日鐵化学（株）製 商品名V259ME）
成分(A)-II ： 合成例１で得たアルカリ可溶性樹脂溶液(A)-2
成分(B) ： ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートとの混合物（日本化薬（株）製 商品名 DPHA）
成分(C) ： O-アシルオキシム系光重合開始剤（チバスペシャリティ製、イルガキュアOXE-02）
成分(D)： PGMEA
成分(E1)-I ： MA14（三菱化学社製）
成分(E1)-II ： Special Black 350 (デグサ社製)
成分(E2)：分散剤A：DisperK-182 変性アクリル系ブロック共重合体(アミン価13mgKOH/g、ビックケミー社製)
成分(E3)-I ：成分(A)-Iと同じ
成分(E3)-II ：成分(A)-II同じ
成分(E4) ： PGMEA
添加剤I ： 界面活性剤
添加剤II ： シランカップリング剤
The raw materials and abbreviations used in the production of the color filters of Examples and Comparative Examples are as follows.
Component (A) -I: Propylene glycol monomethyl ether acetate solution of acid anhydride polycondensate of epoxy acrylate having a fluorene skeleton (resin solid concentration = 56.5% by weight, molecular weight Mw = 3,500, acid value 100 mgKOH / g, Shinichi Sakai Chemical Co., Ltd. product name V259ME)
Component (A) -II: Alkali-soluble resin solution (A) -2 obtained in Synthesis Example 1
Component (B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name DPHA, manufactured by Nippon Kayaku Co., Ltd.)
Ingredient (C): O-acyloxime photopolymerization initiator (manufactured by Ciba Specialty, Irgacure OXE-02)
Ingredient (D): PGMEA
Ingredient (E1) -I: MA14 (Mitsubishi Chemical Corporation)
Ingredient (E1) -II: Special Black 350 (Degussa)
Ingredient (E2): Dispersant A: DisperK-182 Modified acrylic block copolymer (amine value 13 mgKOH / g, manufactured by BYK Chemie)
Component (E3) -I: Same as component (A) -I Component (E3) -II: Same component (A) -II Component (E4): PGMEA
Additive I: Surfactant additive II: Silane coupling agent
実施例１〜２６及び比較例１〜１０
上記配合成分を表１〜６に記載の重量割合で配合して、実施例１〜２６及び比較例１〜１０の樹脂組成物を調製した。
まず、表１〜６に記載の配合の(E2)成分と(E3)成分を(E4)成分に溶解させ、その後(E1)成分を添加し、メディアとして０．１ｍｍガラスビーズを使用したビーズミルを用いて、冷却水を循環して容器を冷却しながら室温で分散状態が安定するまで分散を行い、(E)顔料分散体を調製した。
次に、表１〜６記載の配合成分(A)、（B）、(C)、(D)及びその他の添加剤と先に調製した(E)顔料分散体を均一に混合し、感光性樹脂組成物（レジスト組成物）とした。
なお、表１〜６の順に、(E1)成分含有率は40wt％、45wt％、50 wt％、52 wt％、55 wt％、57 wt％である。
Examples 1-26 and Comparative Examples 1-10
The said compounding component was mix | blended in the weight ratio as described in Tables 1-6, and the resin composition of Examples 1-26 and Comparative Examples 1-10 was prepared.
First, dissolve the (E2) component and (E3) component of the formulation shown in Tables 1-6 in the (E4) component, then add the (E1) component, and use a bead mill using 0.1 mm glass beads as the media. Then, while cooling the vessel by circulating cooling water, dispersion was performed at room temperature until the dispersion state became stable, to prepare (E) a pigment dispersion.
Next, the components (A), (B), (C), (D) and other additives described in Tables 1 to 6 and the previously prepared (E) pigment dispersion were uniformly mixed to obtain photosensitivity. A resin composition (resist composition) was obtained.
In addition, in the order of Tables 1 to 6, the (E1) component content is 40 wt%, 45 wt%, 50 wt%, 52 wt%, 55 wt%, 57 wt%.
実施例及び比較例の配合成分を均一に混合して得た感光性樹脂組成物を、スピンコーターを用いて125ｍｍ×125ｍｍのガラス基板上にポストベーク後の膜厚が1.0μmとなるように塗布し、80℃で1分間プリベーク後、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。次に、この露光済み塗板を0.1％水酸化カリウム水溶液中、25℃にて60秒の0.1MPa圧シャワー現像及び0.5MPa圧のスプレー水洗を行い、塗膜の未露光部を除去し、現像性の評価をおこなった。その後、熱風乾燥機を用いて230℃で30分間熱ポストベークしてカラーフィルター用途膜を作成し、現像性評価及びパターン形状評価を行った。 The photosensitive resin composition obtained by uniformly mixing the blending components of Examples and Comparative Examples was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking was 1.0 μm. Then, after pre-baking at 80 ° C. for 1 minute, the photo-curing reaction of the photosensitive part was performed by irradiating with 10 mj / cm 2 of ultraviolet light with an ultra-high pressure mercury lamp with I-line illuminance of 30 mW / cm 2 . Next, this exposed coated plate is subjected to 0.1 MPa pressure shower development for 60 seconds at 25 ° C. in 0.1% potassium hydroxide aqueous solution and spray water washing at 0.5 MPa pressure to remove unexposed portions of the coating film, and developability Was evaluated. Thereafter, a film for color filter application was prepared by hot post-baking at 230 ° C. for 30 minutes using a hot air dryer, and developability evaluation and pattern shape evaluation were performed.
また、各実施例、比較例での樹脂組成物のブラック感光性樹脂組成物としての物性評価は以下のようにして行った。 Moreover, the physical-property evaluation as a black photosensitive resin composition of the resin composition in each Example and a comparative example was performed as follows.
＊膜厚：触針式段差形状測定装置（ケーエルエー・テンコール（株）製 商品名P-15）を用いて測定した。
＊10μm線幅減少率（線幅減少率）：製膜した塗膜を乾燥後露光し、アルカリ現像により10μm細線パターニングをおこない、線幅を測定。また、レジストを40℃で3日間保存した後、同様にパターニングをおこない、線幅を測定した時の線細りの状態を10μm線幅減少率として示した。その際の線幅の測定については、測長顕微鏡（（株）ニコン製 商品名XD-20）を用いて測定をおこなった。但し、10μｍ細線パターンが残らず、測定不可能なサンプルについては測定不可とした。
＊残渣：現像後のガラス基板上にカーボン由来の黒色異物が残存した場合を、残渣あり○とし、その量が比較的少ない場合を△、非常に多い場合を×とした。
＊直線性：10μm細線パターンについて、現像後の熱処理後、直線性が良好なものを○、良好だが一部欠けやフリンジ（ガタツキ）が生じているものを△、欠けやフリンジが多く、直線性が維持できていないものを×<不良>と評価した。
＊密着性：ポストベーク実施済みのパターン形成基板を、121℃、100％RH、2atm、24時間の条件下においてPCT（プレッシャー・クッカー）テストを実施後、20μmパターン部にセロハンテープを貼り付けピーリングテストを行うことでパターン密着性を評価した。
＊総合評価：○<良好>、△<やや良好>、×<不良>
評価結果を配合組成と共に表１から表６に示す。
* Film thickness: measured using a stylus type step shape measuring device (trade name P-15, manufactured by KLA-Tencor Corporation).
* 10 μm line width reduction rate (line width reduction rate): The film formed was dried and exposed, and 10 μm fine line patterning was performed by alkali development, and the line width was measured. Further, after the resist was stored at 40 ° C. for 3 days, patterning was performed in the same manner, and the line thinning state when the line width was measured was shown as a 10 μm line width reduction rate. In this case, the line width was measured using a length measuring microscope (trade name XD-20 manufactured by Nikon Corporation). However, measurement was not possible for samples that could not be measured because a 10 μm fine line pattern did not remain.
* Residue: The case where black foreign matter derived from carbon remained on the developed glass substrate was marked with ○, the case where the amount was relatively small, Δ, and the case where the amount was very large, x.
* Linearity: 10μm fine line pattern with good linearity after heat treatment after development, ◯ with good but partially chipped or fringed (backlash), with many chips and fringes, linearity Those that could not be maintained were evaluated as x <defect>.
* Adhesion: Post-baked pattern-formed substrate is subjected to PCT (pressure cooker) test under conditions of 121 ° C, 100% RH, 2atm, 24 hours, and then cellophane tape is applied to the 20μm pattern area for peeling. The pattern adhesion was evaluated by performing a test.
* Comprehensive evaluation: ○ <Good>, △ <Slightly good>, × <Bad>
The evaluation results are shown in Tables 1 to 6 together with the composition.
(E1)成分含有率が40wt％のときは、総合評価は全てが良好な結果○となった。45wt％のときは、比較例では現像性や直線性に影響が発生し、総合評価は△となったが、実施例では全てが良好な結果○となった。50wt％のときは、比較例では現像性や直線性に影響が発生し、総合評価は×となったが、実施例では残渣や直線性に影響が出始めたが密着性が良好であったため、総合評価は良好○となった。 When the (E1) component content was 40 wt%, the overall evaluation was a good result. When it was 45 wt%, the developability and linearity were affected in the comparative example, and the overall evaluation was Δ, but in the example, all were good results ○. When it was 50 wt%, the developability and linearity were affected in the comparative example, and the overall evaluation was x, but in the examples, the residue and linearity began to be affected, but the adhesion was good. The overall evaluation was good.
52wt％のときは、比較例では現像後に10μm細線パターンが得られず、総合評価は評価不可となったが、分散剤(E2)と(E3)の両者を使用した実施例では、E3の割合が高い実施例１６〜１８では良好な結果○となり、E3の割合が低い実施例１９〜２０は残渣の評価が×、直線性、密着性の評価が△であったため、総合評価は△となった。55 wt％及び57 wt％のときは、比較例では現像後に10μm細線パターンが得られず、総合評価は測定不可となったが、(E2)と(E3)の両者を使用した実施例では総合評価は△となった。 In the case of 52 wt%, a 10 μm fine line pattern was not obtained after development in the comparative example, and the comprehensive evaluation was impossible, but in the example using both the dispersants (E2) and (E3), the ratio of E3 In Examples 16 to 18 with high values, good results were obtained, and in Examples 19 to 20 with a low E3 ratio, the evaluation of the residue was x, and the evaluation of linearity and adhesion was Δ, so the overall evaluation was Δ. It was. In the case of 55 wt% and 57 wt%, in the comparative example, a 10 μm fine line pattern was not obtained after development, and the comprehensive evaluation was impossible to measure, but in the examples using both (E2) and (E3) Evaluation was △.
以上の結果より、(E1)成分含有率が40wt％では分散剤を(E3)に置き換え共分散させても大きな効果は現れないが、45wt%以上になるとその共分散の効果が現れ、残渣、直線性及び細線の密着性に効果をもたらすことが判る。また、レジストについて述べると40℃、3日の経時後の安定性は分散剤単独の時よりも、(E3)が含有されている方が高く、10μm細線の線細りの度合いも低いことが判った。 From the above results, when the content of component (E1) is 40 wt%, no significant effect appears even if the dispersant is replaced with (E3) and co-dispersed, but when it exceeds 45 wt%, the effect of the co-dispersion appears, residue, It turns out that it has an effect on the linearity and the adhesion of the fine wires. In addition, when describing the resist, it was found that the stability after 3 days at 40 ° C. is higher when (E3) is contained and the degree of thinning of the 10 μm fine wire is lower than when the dispersant alone. It was.
Claims (8)
(E1)黒色有機顔料、混色有機顔料及び遮光材の中から選ばれる少なくとも1種類の着色材、
(E2)分散剤、
(E3)光硬化性樹脂若しくは熱硬化性樹脂、
(E4)溶剤
からなる(E)顔料分散体をあらかじめ調製したのち、必須成分として下記(A)〜(D)成分、
(A)不飽和基含有アルカリ可溶性樹脂、
(B)エチレン性不飽和結合を有する光重合性モノマー、
(C)光重合開始剤、
(D)溶剤
を含む配合成分と、(E)顔料分散体を混合すること、及び上記(E3)成分の少なくとも1部が、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エポキシ化合物と（メタ）アクリル酸との反応物にa)ジ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、a/bのモル比が0.1〜10となる範囲で反応させて得られる下記一般式（I）
(E1) at least one colorant selected from black organic pigments, mixed-color organic pigments and light-shielding materials,
(E2) dispersant,
(E3) a photocurable resin or a thermosetting resin,
(E4) After preparing a (E) pigment dispersion consisting of a solvent in advance, the following components (A) to (D) as essential components:
(A) an unsaturated group-containing alkali-soluble resin,
(B) a photopolymerizable monomer having an ethylenically unsaturated bond,
(C) a photopolymerization initiator,
(D) a compounding component containing a solvent, (E) mixing the pigment dispersion , and an epoxy compound in which at least one part of the (E3) component has two glycidyl ether groups derived from bisphenols; (A) Dicarboxylic acid or its acid anhydride and b) tetracarboxylic acid or its acid dianhydride are reacted with the reaction product with (meth) acrylic acid in a range where the molar ratio of a / b is 0.1 to 10. The following general formula (I)
(E1)/[(A)+(B)+(C)+(E')]×100
（ただし、(E')は（E）成分から(E4)成分を除いた成分であり、上記計算式において(E1)、(A)、(B)、(C)、(E')は、各成分の配合量（重量）を表す。）
で計算される(E1)成分含有率が40wt%以上であることを特徴とする請求項１記載のカラーフィルター用レジスト組成物の製造方法。 (E3) component is an acrylic polymer having an acidic functional group, and the following calculation formula
(E1) / [(A) + (B) + (C) + (E ')] × 100
(However, (E ') is a component obtained by removing (E4) component from (E) component, and (E1), (A), (B), (C), (E') in the above formula is (Represents the amount (weight) of each component)
The method for producing a resist composition for a color filter according to claim 1, wherein the content of the component (E1) calculated by the formula (1) is 40 wt% or more.
(E1)黒色有機顔料、混色有機顔料及び遮光材の中から選ばれる少なくとも1種類の着色材、(E1) at least one colorant selected from black organic pigments, mixed-color organic pigments and light-shielding materials,
(E2)分散剤、(E2) dispersant,
(E3)光硬化性樹脂若しくは熱硬化性樹脂、(E3) a photocurable resin or a thermosetting resin,
(E4)溶剤(E4) Solvent
からなるあらかじめ調製された(E)顔料分散体と、必須成分として下記(A)〜(D)成分、(E) pigment dispersion prepared in advance, and the following components (A) to (D) as essential components:
(A)不飽和基含有アルカリ可溶性樹脂、(A) an unsaturated group-containing alkali-soluble resin,
(B)エチレン性不飽和結合を有する光重合性モノマー、(B) a photopolymerizable monomer having an ethylenically unsaturated bond,
(C)光重合開始剤、(C) a photopolymerization initiator,
(D)溶剤(D) Solvent
を含む配合成分とが混合されてなること、及び上記(E3)成分の少なくとも1部が、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エポキシ化合物と（メタ）アクリル酸との反応物にa)ジ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、a/bのモル比が0.1〜10となる範囲で反応させて得られる下記一般式（I）And a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid, wherein at least one part of the component (E3) is mixed And a) a dicarboxylic acid or an acid anhydride thereof and b) a tetracarboxylic acid or an acid dianhydride thereof in the range where the molar ratio of a / b is 0.1 to 10, and the following general formula (I)
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| KR20130132322A (en) * | 2012-05-25 | 2013-12-04 | 주식회사 엘지화학 | Photosensitive resin composition, pattern formed by using the same and display panel comprising the same |
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| TWI485167B (en) * | 2013-08-29 | 2015-05-21 | Chi Mei Corp | Alkali-solutable resin, photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus |
| JP6455007B2 (en) * | 2013-08-29 | 2019-01-23 | 日鉄ケミカル＆マテリアル株式会社 | Gate insulating film, organic thin film transistor, and organic thin film transistor manufacturing method |
| JP6455008B2 (en) * | 2013-08-29 | 2019-01-23 | 日鉄ケミカル＆マテリアル株式会社 | Gate insulating film, organic thin film transistor, and organic thin film transistor manufacturing method |
| JP6307237B2 (en) * | 2013-09-30 | 2018-04-04 | 新日鉄住金化学株式会社 | Black photosensitive resin composition and cured film thereof, and color filter and touch panel having the cured film |
| JP6708367B2 (en) * | 2014-03-31 | 2020-06-10 | 日鉄ケミカル＆マテリアル株式会社 | Photosensitive resin composition for light-shielding film, light-shielding film and color filter obtained by curing the same |
| JP6463018B2 (en) | 2014-07-11 | 2019-01-30 | 日鉄ケミカル＆マテリアル株式会社 | Method for producing photosensitive resin composition for color filter and photosensitive resin composition for color filter |
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| JP3287661B2 (en) * | 1993-08-30 | 2002-06-04 | 新日本製鐵株式会社 | Thermosetting resin composition, cured product thereof, and image forming material |
| JPH08278630A (en) * | 1995-04-07 | 1996-10-22 | Nippon Steel Chem Co Ltd | Ink for color filter excellent in storage stability and color filter formed by using the ink |
| JPH09133806A (en) * | 1995-11-08 | 1997-05-20 | Dainippon Printing Co Ltd | Hologram color filter and its production |
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