TWI397769B - Alkali-soluble resin and method for producing the same, and a photosensitive resin composition, a hardened product and a color filter using an alkali-soluble resin - Google Patents
Alkali-soluble resin and method for producing the same, and a photosensitive resin composition, a hardened product and a color filter using an alkali-soluble resin Download PDFInfo
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- TWI397769B TWI397769B TW096139867A TW96139867A TWI397769B TW I397769 B TWI397769 B TW I397769B TW 096139867 A TW096139867 A TW 096139867A TW 96139867 A TW96139867 A TW 96139867A TW I397769 B TWI397769 B TW I397769B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Description
本發明係有關一種藉由照射紫外線或電子線予以硬化，且藉由鹼顯像處理形成圖型之鹼可溶性樹脂及其製造方法、以及使用該鹼可溶性樹脂之感光性樹脂組成物，更詳言之，係有關一種適合於製造彩色濾光片用光阻的感光性樹脂組成物，以及有關一種適合於形成該感光性樹脂組成物之鹼可溶性樹脂。The present invention relates to an alkali-soluble resin which is cured by irradiation with ultraviolet rays or electron beams, and which forms a pattern by alkali development treatment, a method for producing the same, and a photosensitive resin composition using the alkali-soluble resin, more specifically There is a photosensitive resin composition suitable for producing a photoresist for a color filter, and an alkali-soluble resin suitable for forming the photosensitive resin composition.
彩色液晶顯示裝置，係以控制光之透過量或反射量的液晶部與彩色濾光片為構成要素，惟其彩色濾光片之製造方法，通常使用在玻璃、塑膠片等透明基板之表面上形成黑色矩陣，然後，順序使紅色、綠色、藍色等不同的色相以條狀或格子狀等顏色圖型予以形成的方法。近數年來，在液晶電視、液晶螢幕、彩色液晶手機等領域中使用彩色液晶顯示裝置，彩色濾光片係為影響此等彩色液晶顯示裝置之視認性的重要構件之一。圖型大小係視彩色濾光片之用途及各顏色而不同，各以紅色、綠色、藍色之畫素為100μm~50μm以下，黑色矩陣為20μm~10μm以下予以細線化。因此，要求感光性樹脂組成物藉由高尺寸精度形成圖型。The color liquid crystal display device is composed of a liquid crystal portion and a color filter for controlling the amount of light transmitted or reflected, but the method for manufacturing the color filter is usually formed on the surface of a transparent substrate such as glass or plastic sheet. The black matrix is then formed by sequentially forming different hue such as red, green, and blue in a color pattern such as a strip or a grid. In recent years, color liquid crystal display devices have been used in the fields of liquid crystal televisions, liquid crystal screens, color liquid crystal mobile phones, and the like, and color filters are one of important components that affect the visibility of such color liquid crystal display devices. The size of the pattern varies depending on the use of the color filter and the color, and each of the pixels of red, green, and blue is 100 μm to 50 μm or less, and the black matrix is 20 μm to 10 μm or less. Therefore, the photosensitive resin composition is required to form a pattern by high dimensional accuracy.
一般而言，該用途之感光性樹脂組成物，係使用組合具有聚合性不飽和鍵之多官能光硬化性單體、鹼可溶性黏 合劑樹脂、及此等與光聚合引發劑之組成物。例如，於日本特開昭61-213213號公報(專利文獻1)或特開平1-152449號公報(專利文獻2)中例示，作為彩色濾光片用材料之應用，揭示以具有羧基之(甲基)丙烯酸或(甲基)丙烯酸酯、與馬來酸酐、與其他聚合性單體之共聚物作為黏合劑樹脂。然而，此處所揭示的共聚物，由於此等為無規共聚物，在光照射部分內或光未照射部分內會產生鹼溶解速度分布情形，顯像操作時之範圍狹窄，且不易製得銳角之圖型形狀或微細圖型。特別是含有高濃度之顏料時，曝光感度顯著降低，無法製得微細的負型圖型。另外，於日本特開平4-340965號公報(專利文獻3)中揭示，有關在一分子中具有聚合性不飽和雙鍵與羧基之鹼可溶性不飽和化合物，在形成彩色濾光片等之負型圖型時有效。具有鹼可溶性之分子，由於藉由光照射予以不溶化，故與上述組合黏合劑樹脂及多官能聚合性單體相比時，預測具有更高感度，惟此處所例示的化合物為在苯酚低聚物之羥基上任意加成有聚合性不飽和基之丙烯酸與酸酐者，該提案中由於分子組成之不均勻性，鹼溶解速度之分布廣泛，不易形成微細的負型圖型。In general, the photosensitive resin composition for this use is a combination of a polyfunctional photocurable monomer having a polymerizable unsaturated bond, and an alkali soluble adhesive. A mixture of a resin and a composition of the photopolymerization initiator. For example, JP-A-61-213213 (Patent Document 1) or JP-A-1-52449 (Patent Document 2) exemplifies the use of a material having a carboxyl group as a material for a color filter. Acrylic acid or (meth) acrylate, copolymer with maleic anhydride, and other polymerizable monomers as a binder resin. However, in the copolymer disclosed herein, since these are random copolymers, an alkali dissolution rate distribution is generated in the light-irradiated portion or the unirradiated portion, and the range of development operation is narrow, and it is difficult to obtain an acute angle. The shape of the figure or the fine pattern. In particular, when a pigment having a high concentration is contained, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained. Japanese Patent Publication No. 4-340965 (Patent Document 3) discloses an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule, and a negative type in forming a color filter or the like. Valid when the pattern is used. Since the alkali-soluble molecule is insolubilized by light irradiation, it is predicted to have higher sensitivity when compared with the above-mentioned combination binder resin and polyfunctional polymerizable monomer, but the compound exemplified herein is a phenol oligomer. In the case where the polymerizable unsaturated group-containing acrylic acid and an acid anhydride are arbitrarily added to the hydroxyl group, in the proposal, the alkali dissolution rate is widely distributed due to the non-uniformity of the molecular composition, and it is difficult to form a fine negative pattern.
此外，於日本特開平4-345673號公報(專利文獻4)、特開平4-345608號公報(專利文獻5)、特開平4-355450號公報(專利文獻6)及特開平4-363311號公報(專利文獻7)中揭示，使用具有雙酚芴構造之環氧基(甲基)丙烯酸酯與酸酐之反應生成物的液狀樹脂。然而，藉由此等所例示的樹脂 ，由於為環氧基(甲基)丙烯酸酯與酸酐之反應生成物，故分子量小。因此，化合物之感度低，無法形成微細的圖型。Japanese Laid-Open Patent Publication No. Hei-4-345673 (Patent Document 4), Japanese Laid-Open Patent Publication No. Hei-4-345608 (Patent Document 5), Japanese Patent Application Laid-Open No. Hei-4-355450 (Patent Document No. 6), and Japanese Patent Publication No. Hei-4-363311 (Patent Document 7) discloses a liquid resin using a reaction product of an epoxy group (meth) acrylate having a bisphenol fluorene structure and an acid anhydride. However, the resin exemplified by this Since it is a reaction product of an epoxy (meth) acrylate and an acid anhydride, a molecular weight is small. Therefore, the sensitivity of the compound is low, and a fine pattern cannot be formed.
另外，於日本特開平5-339356號公報(專利文獻8)、特開平5-146132號公報(專利文獻9)、及WO94/00801號手冊(專利文獻10)中，揭示藉由使二羥基丙基丙烯酸酯化合物與酸二酐共聚合之鹼顯像性不飽和樹脂組成物、或藉由使酸酐及酸二酐與二羥基丙基丙烯酸酯化合物共聚合之鹼顯像性不飽和樹脂組成物。此時，使酸二酐與二羥基丙基丙烯酸酯化合物進行共聚合，製得低聚物。然而，由於重複單位中之聚合性不飽和鍵結數一定，故無法提高交聯密度，且在高濃度顏料下不易形成細線圖型，尚有待改善之處。Japanese Patent Publication No. Hei 5-339356 (Patent Document 8), Japanese Patent Application Laid-Open No. Hei 5-146132 (Patent Document No. 9), and WO 94/00801 (Patent Document 10) disclose that dihydroxypropyl group is disclosed. A base-developing unsaturated resin composition in which a acrylate compound is copolymerized with an acid dianhydride, or a base-developing unsaturated resin composition obtained by copolymerizing an acid anhydride and an acid dianhydride with a dihydroxypropyl acrylate compound . At this time, the acid dianhydride and the dihydroxypropyl acrylate compound were copolymerized to obtain an oligomer. However, since the number of polymerizable unsaturated bonds in the repeating unit is constant, the crosslinking density cannot be increased, and it is difficult to form a fine line pattern under a high concentration of pigment, and there is still room for improvement.
此外，於日本特開平9-325494號公報(專利文獻11)中，使含有羧基之共聚物的分子量增加，進行鹼可溶性樹脂組成物之多官能化。然而，此時與上述專利文獻相同地，由於重複單位中之聚合性不飽和鍵結數一定，故無法提高交聯密度。In JP-A-H09-325494 (Patent Document 11), the molecular weight of the carboxyl group-containing copolymer is increased, and the alkali-soluble resin composition is polyfunctionalized. However, at this time, as in the above-mentioned patent documents, since the number of polymerizable unsaturated bonds in the repeating unit is constant, the crosslinking density cannot be increased.
[專利文獻1]特開昭61-213213號公報[Patent Document 1] JP-A-61-213213
[專利文獻2]特開平1-152449號公報[Patent Document 2] Japanese Patent Publication No. 1-152449
[專利文獻3]特開平4-340965號公報[Patent Document 3] JP-A-4-340965
[專利文獻4]特開平4-345673號公報[Patent Document 4] Japanese Patent Publication No. 4-345673
[專利文獻5]特開平4-345608號公報[Patent Document 5] JP-A-4-345608
[專利文獻6]特開平4-355450號公報[Patent Document 6] JP-A-4-355450
[專利文獻7]特開平4-363311號公報[Patent Document 7] JP-A-4-363311
[專利文獻8]特開平5-339356號公報[Patent Document 8] JP-A-H05-339356
[專利文獻9]特開平5-146132號公報[Patent Document 9] Japanese Patent Laid-Open No. Hei 5-146132
[專利文獻10]WO94/00801號手冊[Patent Document 10] WO94/00801 manual
[專利文獻11]特開平9-325494號公報[Patent Document 11] JP-A-9-325494
因此，本發明人等如上所述為解決習知感光性樹脂組成物之課題時，再三深入研究的結果，發現藉由使含有聚合性不飽和基之二醇化合物與酸二酐進行反應所得的含有羧基之共聚物，與含有聚合性不飽和鍵結基之環氧化合物進行反應，再與酸酐進行反應，製得適合於形成感光性樹脂組成物之鹼可溶性樹脂。其次，藉由使用該鹼可溶性樹脂，可控制對鹼顯像液之溶解性且提高交聯密度、硬化部與未硬化部對鹼顯像液之溶解度差變大，可形成完美的細線圖型，且以高密度製得顯像密接範圍廣泛的感光性樹脂組成物，遂而完成本發明。Therefore, the inventors of the present invention have found that by solving the problem of the conventional photosensitive resin composition, as described above, it has been found that a reaction of a diol compound containing a polymerizable unsaturated group with an acid dianhydride is carried out. The copolymer containing a carboxyl group is reacted with an epoxy compound containing a polymerizable unsaturated bond group, and then reacted with an acid anhydride to obtain an alkali-soluble resin suitable for forming a photosensitive resin composition. Next, by using the alkali-soluble resin, the solubility in the alkali developing solution can be controlled, the crosslinking density can be increased, and the difference in solubility between the hardened portion and the uncured portion to the alkali developing solution can be increased, and a perfect thin line pattern can be formed. Further, the present invention has been completed by producing a photosensitive resin composition having a wide range of development and adhesion in a high density.
因此，本發明之目的係以提供一種微細圖型之形成優異、適合作為高遮光或高彩彩色濾光片用材料之感光性樹脂組成物、及形成該感光性樹脂組成物之鹼可溶性樹脂。Accordingly, an object of the present invention is to provide a photosensitive resin composition which is excellent in formation of a fine pattern and which is suitable as a material for a high light-shielding or high-color color filter, and an alkali-soluble resin which forms the photosensitive resin composition.
另外，本發明之另一目的係提供一種使用上述高感度感光性樹脂組成物所形成的被膜(硬化物)及彩色濾光片。Further, another object of the present invention is to provide a film (cured material) and a color filter formed using the above-described high-sensitivity photosensitive resin composition.
此外，本發明之另一目的係提供一種特別是即使添加高濃度之遮光性顏料時，微細圖型之形成優異、適合作為 高遮光或高彩彩色濾光片用黑色矩陣材料之黑色矩陣用感光性樹脂組成物。Further, another object of the present invention is to provide an excellent pattern formation of a fine pattern, particularly when a high concentration of a light-shielding pigment is added. The high light-shielding or high-color color filter is composed of a photosensitive resin composition for a black matrix of a black matrix material.
換言之，本發明之鹼可溶性樹脂，其特徵為以下述一般式(1)所示、在分子內具有羧酸殘基及聚合性不飽和基。
而且，本發明係為含有以(i)上述之鹼可溶性樹脂、(ii)至少具有1個以上乙烯性不飽和鍵之光聚合性單體、及(iii)光聚合引發劑為必須成份之感光性樹脂組成物。Further, the present invention is a photosensitive composition containing (i) the above alkali-soluble resin, (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as an essential component. Resin composition.
另外，本發明係為使上述感光性樹脂組成物予以硬化所得的硬化物，而且，藉由使上述感光性樹脂組成物被覆、硬化所得的硬化物所形成的彩色濾光片。In addition, the present invention is a cured product obtained by curing the photosensitive resin composition, and a color filter formed by coating and curing the cured resin composition.
此外，本發明之鹼可溶性樹脂的製造方法，其特徵為藉由使含有聚合性不飽和基之二醇化合物(A)與酸二酐(B)進行反應所得的具羧基之反應物，與至少含有1個以上聚 合性雙鍵、且含有1個環氧乙烷環之環氧乙烷化合物(C)進行反應，製得具有羥基之反應物，然後，使該具有羥基之反應物與酸酐(D)進行反應。Further, the method for producing an alkali-soluble resin of the present invention is characterized in that a reactant having a carboxyl group obtained by reacting a diol compound (A) containing a polymerizable unsaturated group with an acid dianhydride (B), and at least Contains more than one poly The oxirane compound (C) having a conjugated double bond and containing an oxirane ring is reacted to obtain a reactant having a hydroxyl group, and then reacting the reactant having a hydroxyl group with the acid anhydride (D) .
另外，本發明之黑色矩陣用感光性樹脂組成物，其特徵為含有
(i)以下述一般式(1)所示、在1分子內具有羧酸殘基及聚合性不飽和基之鹼可溶性樹脂，
(ii)至少具有1個以上乙烯性不飽和鍵之光聚合性單體，(iii)光聚合引發劑，以及(iv)遮光性顏料作為必須成分。(ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (iii) a photopolymerization initiator, and (iv) a light-shielding pigment as an essential component.
於下述中，詳細說明有關本發明。In the following, the present invention will be described in detail.
本發明之感光性樹脂組成物(亦包含黑色矩陣用感光性樹脂組成物。以下沒有特別的限制時，亦相同)，係為具有作為含以一般式(1)所示之鹼可溶性樹脂作為主成分的鹼顯像型光性樹脂組成物之性質的樹脂組成物。以一般式(1)所示之鹼可溶性樹脂，由於具有來自具(甲基)丙烯酸之二醇化合物的光聚合性不飽和基，故除具有游離基聚合性外，由於含有來自酸酐及酸二酐之酸性基，故具有鹼可溶性。The photosensitive resin composition of the present invention (including a photosensitive resin composition for a black matrix, which is also the same as the following is not particularly limited), and has an alkali-soluble resin represented by the general formula (1) as a main component. A resin composition of a nature of a component of an alkali-developing photosensitive resin composition. Since the alkali-soluble resin represented by the general formula (1) has a photopolymerizable unsaturated group derived from a diol compound having (meth)acrylic acid, it has a radical polymerizability and contains an acid anhydride and an acid The acid group of the anhydride has alkali solubility.
一般式(1)之鹼可溶性樹脂，係為藉由使由雙酚類所衍生的具有2個環氧丙醚基之環氧化合物與(甲基)丙烯酸進行反應所得的具有聚合性不飽和基之二醇化合物(A)及四羧酸或其酸二酐(B)進行反應所得的反應物，與含有聚 合性雙鍵之環氧乙烷化合物(C)進行反應，然後，與二羧酸或其酸酐(D)進行反應所得的含羧基之交互共聚物。一般式(1)之鹼可溶性樹脂，由於兼具有聚合性不飽和雙鍵與羧基，故鹼顯像型感光性樹脂組成物具有優異的光硬化性、優良的顯像性、圖型特性，且可提高保護膜、遮光膜、紅色、綠色、藍色之各畫素的物性。The alkali-soluble resin of the general formula (1) is a polymerizable unsaturated group obtained by reacting an epoxy compound having two glycidyl ether groups derived from a bisphenol with (meth)acrylic acid. a reaction product obtained by reacting a diol compound (A) and a tetracarboxylic acid or an acid dianhydride (B) thereof The carboxyl group-containing interactive copolymer obtained by reacting the oxirane compound (C) having a double bond and then reacting with a dicarboxylic acid or its anhydride (D). Since the alkali-soluble resin of the general formula (1) has both a polymerizable unsaturated double bond and a carboxyl group, the alkali-developing photosensitive resin composition has excellent photocurability, excellent developability, and pattern characteristics. Moreover, the physical properties of the protective film, the light shielding film, the red, green, and blue pixels can be improved.
詳細說明有關以一般式(1)所示之鹼可溶性樹脂之製造方法。首先，一般式(1)之鹼可溶性樹脂，係由使雙酚類所衍生的具有2個環氧丙醚基之環氧化合物、特別是較佳者以一般式(4)所示之環氧化合物與(甲基)丙烯酸進行反應所得的含聚合性不飽和基之二醇化合物(A)所衍生。
於上述一般式(4)中，R1
、R2
、R3
、及R4
係獨立表示氫原子、碳數1~5之烷基、鹵素原子或苯基；較佳者為氫原子、碳數1~5之烷基、或苯基；更佳者為氫原子。而且，X係表示-CO-、-SO2
-、-C(CF3
)2
-、-Si(CH3
)2
-、-CH2
-、-C(CH3
)2
-、-O-、9,9-亞芴基或直鍵結，以9,9-亞芴基較佳。此處，9,9-亞芴基係指以下述一般式(5)所示之基。
該環氧化合物與(甲基)丙烯酸之反應，可使用習知的方法，例如對1莫耳環氧化合物而言使用約2莫耳之(甲基)丙烯酸予以進行。以該反應所得的反應物，例如上述專利文獻6等所記載。以該反應所得的反應物，係為含有聚合性不飽和基之二醇化合物(A)，以下述一般式(6)所示之環氧基(甲基)丙烯酸酯化合物。
提供一般式(1)之鹼可溶性樹脂的較佳雙酚類，例如下述者。例如雙(4-羥基苯基)酮、雙(4-羥基-3,5-二甲基苯基)酮、雙(4-羥基-3,5-二氯苯基)酮、雙(4-羥基苯基)碸、雙(4-羥基-3,5-二甲基苯基)碸、雙(4-羥基-3,5-二氯苯基)碸、雙(4-羥基苯基)六氟丙烷、雙(4-羥基-3,5-二甲基苯基 )六氟丙烷、雙(4-羥基-3,5-二氯苯基)六氟丙烷、雙(4-羥基苯基)二甲基矽烷、雙(4-羥基-3,5-二甲基苯基)二甲基矽烷、雙(4-羥基-3,5-二氯苯基)二甲基矽烷、雙(4-羥基苯基)甲烷、雙(4-羥基-3,5-二氯苯基)甲烷、雙(4-羥基-3,5-二溴苯基)甲烷、2,2-雙(4-羥基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3-氯化苯基)丙烷、雙(4-羥基苯基)醚、雙(4-羥基-3,5-二甲基苯基)醚、雙(4-羥基-3,5-二氯苯基)醚等。而且，X為9,9-亞芴基之9,9-雙(4-羥基苯基)芴、9,9-雙(4-羥基-3-甲基苯基)芴、9,9-雙(4-羥基-3-氯化苯基)芴、9,9-雙(4-羥基-3-溴化苯基)芴、9,9-雙(4-羥基-3-氟化苯基)芴、9,9-雙(4-羥基-3,5-二甲基苯基)芴、9,9-雙(4-羥基-3,5-二氯苯基)芴、9,9-雙(4-羥基-3,5-二溴苯基)芴等較佳。另外，例如以4,4'-雙酚、3,3'-雙酚等較佳。Preferred bisphenols which provide the alkali-soluble resin of the general formula (1) are, for example, those described below. For example, bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis (4- Hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-dimethylphenyl)anthracene, bis(4-hydroxy-3,5-dichlorophenyl)anthracene, bis(4-hydroxyphenyl)hexa Fluoropropane, bis(4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethyloxane, bis(4-hydroxy-3,5-dimethyl Phenyl) dimethyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichloro Phenyl)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-hydroxyl) -3,5-dichlorophenyl)ether or the like. Moreover, X is 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-double (4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-brominated phenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorinated phenyl) Ruthenium, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene, 9,9-double (4-Hydroxy-3,5-dibromophenyl)anthracene or the like is preferred. Further, for example, 4,4'-bisphenol, 3,3'-bisphenol or the like is preferable.
一般式(1)之鹼可溶性樹脂，可由如上述雙酚類衍生的環氧化合物製得，除該環氧化合物外，只要是包含使用苯酚酚醛清漆型環氧化合物、或甲酚酚醛清漆型環氧化合物等具有2個環氧丙醚基之化合物者即可。而且，使雙酚類予以環氧丙醚化時，混入有以下述一般式(7)所示之低聚物單位，該一般式(7)中m之平均值為0~10，較佳者為0~2之範圍時，本樹脂組成物之性能不會有問題。
其次，說明藉由使含聚合性不飽和基之二醇化合物、四羧酸或其酸二酐、含聚合性不飽和基之環氧乙烷化合物、及二羧酸或其酸酐進行反應，製造以一般式(1)所示之本發明鹼可溶性樹脂的方法。本發明鹼可溶性樹脂之製造方法例，如下述反應式(I)所示。
有關上述反應式(I)，首先使上述環氧化合物與(甲基)丙烯酸進行反應所得的上述一般式(6)之環氧基(甲基)丙烯酸酯化合物[含有聚合性不飽和基之二醇化合物(A)]、與酸成份進行反應，製得以一般式(8)所示之化合物[具有羧基之反應物]。此時有關使用的溶劑、觸媒等之反應條件，沒有特別的限制，例如上述專利文獻11等詳細記載。而且，酸成份亦可使用與環氧基(甲基)丙烯酸酯化合物分子中之羥基反應所得的四羧酸二酐(B)。該酸成份不管是飽和或不飽和皆具有效果。其中，四羧酸二酐(B)係可使用飽和直鏈烴四羧酸之酸二酐或脂環式四羧酸之酸二酐、芳香族四羧酸之酸二酐等。With respect to the above reaction formula (I), the epoxy group (meth) acrylate compound of the above general formula (6) obtained by first reacting the above epoxy compound with (meth)acrylic acid [containing a polymerizable unsaturated group The alcohol compound (A)] is reacted with an acid component to obtain a compound represented by the general formula (8) [reactant having a carboxyl group]. In this case, the reaction conditions of the solvent, the catalyst, and the like to be used are not particularly limited, and are described in detail in, for example, Patent Document 11 and the like. Further, as the acid component, a tetracarboxylic dianhydride (B) obtained by reacting a hydroxyl group in a molecule of an epoxy (meth) acrylate compound can also be used. The acid component has an effect whether it is saturated or unsaturated. Among them, as the tetracarboxylic dianhydride (B), an acid dianhydride of a saturated linear hydrocarbon tetracarboxylic acid, an acid dianhydride of an alicyclic tetracarboxylic acid, an acid dianhydride of an aromatic tetracarboxylic acid, or the like can be used.
此處，飽和直鏈烴四羧酸之酸二酐例如丁烷四羧酸、戊烷四羧酸、己烷四羧酸之酸二酐等，另外，亦可為飽和環狀烴被取代的飽和環狀四羧酸之酸二酐。Here, the acid dianhydride of a saturated linear hydrocarbon tetracarboxylic acid, for example, butane tetracarboxylic acid, pentane tetracarboxylic acid, acid dianhydride of hexane tetracarboxylic acid, or the like, may be substituted with a saturated cyclic hydrocarbon. Saturated cyclic tetracarboxylic acid dianhydride.
而且，脂環式四羧酸之酸二酐例如環丁烷四羧酸、環戊烷四羧酸、環己烷四羧酸、環庚烷四羧酸、原菠烷四羧酸之酸二酐等，另外，亦可為飽和烴被取代的脂環式四羧酸之酸二酐。而且，芳香族四羧酸之酸二酐例如均苯四甲酸、二苯甲酮四羧酸、聯苯四羧酸、聯苯醚四羧酸、二苯 基碸四羧酸之酸二酐等。本發明之酸二酐以聯苯四羧酸、二苯甲酮四羧酸、聯苯醚四羧酸之酸二酐較佳，更佳者為聯苯四羧酸、聯苯醚四羧酸之酸二酐。此等酸二酐亦可2種以上併用。Further, an acid dianhydride of an alicyclic tetracarboxylic acid such as a cyclobutane tetracarboxylic acid, a cyclopentane tetracarboxylic acid, a cyclohexanetetracarboxylic acid, a cycloheptanetetracarboxylic acid, or an acid of a raw spinel tetracarboxylic acid An anhydride or the like may be an acid dianhydride of an alicyclic tetracarboxylic acid in which a saturated hydrocarbon is substituted. Further, an acid dianhydride of an aromatic tetracarboxylic acid such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl Based on tetracarboxylic acid dianhydride and the like. The acid dianhydride of the present invention is preferably an acid dianhydride of biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid or diphenyl ether tetracarboxylic acid, more preferably biphenyltetracarboxylic acid or diphenyl ether tetracarboxylic acid. Acid dianhydride. These acid dianhydrides may be used in combination of two or more kinds.
有關使環氧基(甲基)丙烯酸酯化合物與酸成分進行反應，製造以一般式(8)所示之化合物的方法，沒有特別的限制，可採用上述專利文獻11記載的習知方法。較佳者在以一般式(8)所示化合物之末端為羥基下，以一般式(6)所示具有聚合性不飽和基之二醇化合物(A)與酸二酐(B)之莫耳比[(B)/(A)]為50莫耳%以上、未達100莫耳%，定量進行反應較佳。莫耳比未達50莫耳%時，恐會有未反應環氧基(甲基)丙烯酸酯化合物之含量增大，鹼可溶性樹脂組成物之經時安定性降低的情形。另外，莫耳比為100莫耳%以上時，恐會使以一般式(8)所示化合物之末端變為酸酐，且未反應酸二酐之含有量增大，繼後的使環氧乙烷化合物進行反應時產生副反應。此外，反應溫度係以在90~130℃下加入原料予以均勻溶解且進行反應，然後，在40~80℃下進行反應及熟成較佳。The method of producing the compound represented by the general formula (8) by reacting an epoxy group (meth) acrylate compound with an acid component is not particularly limited, and the conventional method described in the above Patent Document 11 can be employed. Preferably, the diol compound (A) having a polymerizable unsaturated group represented by the general formula (6) and the dianhydride of the acid dianhydride (B) are obtained by using a terminal of the compound represented by the general formula (8) as a hydroxyl group. The ratio [[B)/(A)] is 50 mol% or more and less than 100 mol%, and the reaction is quantitatively carried out. When the molar ratio is less than 50% by mole, the content of the unreacted epoxy (meth) acrylate compound may increase, and the stability of the alkali-soluble resin composition may decrease. Further, when the molar ratio is 100 mol% or more, the terminal of the compound represented by the general formula (8) may be changed to an acid anhydride, and the content of the unreacted acid dianhydride may increase, followed by the epoxy group B. A side reaction occurs when the alkane compound undergoes a reaction. Further, the reaction temperature is uniformly dissolved and reacted by adding a raw material at 90 to 130 ° C, and then the reaction is carried out at 40 to 80 ° C and ripening is preferred.
然後，使以上述一般式(8)所示化合物與環氧乙烷化合物(C)進行反應，製得以一般式(9)所示化合物[具有羥基之反應物]。環氧乙烷化合物係為含有1個以上聚合性雙鍵，且含有1個環氧乙烷環之化合物，例如環氧丙基(甲基)丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯環氧丙醚、3,4-環氧基環己基甲基丙烯酸酯等。Then, the compound represented by the above formula (8) and the oxirane compound (C) are reacted to obtain a compound represented by the general formula (9) [reactant having a hydroxyl group]. The oxirane compound is a compound containing one or more polymerizable double bonds and containing one oxirane ring, such as a glycidyl (meth) acrylate or a 4-hydroxybutyl (meth) acrylate. Ester glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like.
有關以一般式(9)所示之化合物的製造方法，沒有特別的限制、可使用羧酸與環氧基化合物之加成反應時的一般反應條件。而且，可參考上述之專利文獻11記載的藉由環氧化合物與(甲基)丙烯酸進行反應，製造環氧基(甲基)丙烯酸酯化合物之方法。使以一般式(9)所示之化合物予以合成時之反應溫度，以40~120℃之範圍較佳、以40~90℃更佳。以一般式(9)所示之化合物合成時，使環氧乙烷化合物(C)之莫耳比，對以上述一般式(8)所示之化合物進行反應時所使用的酸二酐(B)而言、以莫耳比[(C)/(B)]為160~220莫耳%較佳。莫耳比未達160莫耳%時，由於藉由存在有未反應羧酸，部分來自以一般式(9)所示化合物中之酸二酐的酯鍵形成半酯時，恐會因酸酐之再生反應而導致分子量降低的情形。另外，莫耳比大於220莫耳%時，恐會因來自未反應環氧乙烷化合物之副反應等，引起以一般式(1)所示之鹼可溶性樹脂之經時變化。The method for producing the compound represented by the general formula (9) is not particularly limited, and general reaction conditions in the case of addition reaction of a carboxylic acid and an epoxy compound can be used. Further, a method of producing an epoxy (meth) acrylate compound by reacting an epoxy compound with (meth)acrylic acid described in Patent Document 11 above can be referred to. The reaction temperature at the time of synthesizing the compound represented by the general formula (9) is preferably in the range of 40 to 120 ° C, more preferably 40 to 90 ° C. When the compound represented by the general formula (9) is synthesized, the molar ratio of the oxirane compound (C) to the acid dianhydride (B) used in the reaction of the compound represented by the above general formula (8) is employed. In terms of Moh ratio [(C)/(B)], 160 to 220 mol% is preferable. When the molar ratio is less than 160 mol%, it may be caused by an acid anhydride due to the presence of an unreacted carboxylic acid and a partial ester derived from an ester bond of an acid dianhydride in the compound of the general formula (9). Regeneration reaction leads to a decrease in molecular weight. Further, when the molar ratio is more than 220 mol%, the alkali-soluble resin represented by the general formula (1) may be changed over time due to a side reaction or the like from the unreacted oxirane compound.
然後，使以上述一般式(9)所示之化合物的羥基與酸酐(D)進行反應，製得以一般式(10)所示之鹼可溶性樹脂。此處，酸酐(D)可使用飽和直鏈烴二羧酸之酸酐或飽和環狀烴二羧酸之酸酐、芳香族二羧酸之酸酐等。其中，可使用飽和直鏈烴二羧酸之酸酐等。其中，飽和直鏈烴二羧酸之酸酐例如琥珀酸、乙醯基琥珀酸、己二酸、壬二酸、檸康酸、丙二酸、戊二酸、檸檬酸、酒石酸、氧代戊二酸、庚二酸、癸二酸、辛二酸、二乙二醇酸等之酸酐，另外，亦可為烴基被取代的直鏈烴二羧酸酐。而且，飽合環狀 烴二羧酸之酸酐例如六氫苯二甲酸、環丁烷二羧酸、環戊烷二羧酸、原菠烷二羧酸、六氫偏苯三酸等之酸酐，此外，亦可為飽和烴被取代的脂環式二羧酸之酸酐。而且，不飽和二羧酸之酸酐例如馬來酸、衣康酸、苯二甲酸、四氫苯二甲酸、甲基原亞甲基四氫苯二甲酸、六氯內-甲烯基-四氫苯二甲酸、偏苯三酸之酸酐。於此等之中，酸酐(D)之較佳者為琥珀酸、衣康酸、四氫苯二甲酸、六氫偏苯三酸、苯二甲酸、偏苯三酸之酸酐，更佳者為琥珀酸、衣康酸、四氫苯二甲酸之酸酐。而且，以一般式(10)所示之鹼可溶性樹脂，不可說為以一般式(1)所示之鹼可溶性樹脂之一例。Then, the hydroxyl group of the compound represented by the above general formula (9) is reacted with an acid anhydride (D) to obtain an alkali-soluble resin represented by the general formula (10). Here, as the acid anhydride (D), an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid, an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid, an acid anhydride of an aromatic dicarboxylic acid, or the like can be used. Among them, an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid or the like can be used. Wherein the anhydride of a saturated linear hydrocarbon dicarboxylic acid such as succinic acid, acetyl succinic acid, adipic acid, sebacic acid, citraconic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxopentane An acid anhydride such as acid, pimelic acid, sebacic acid, suberic acid or diethylene glycol acid, or a linear hydrocarbon dicarboxylic acid anhydride in which a hydrocarbon group is substituted. Moreover, saturated ring An acid anhydride of a hydrocarbon dicarboxylic acid such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, raw spinane dicarboxylic acid, hexahydro trimellitic acid or the like, or may be saturated An anhydride of a hydrocarbon-substituted alicyclic dicarboxylic acid. Further, an anhydride of an unsaturated dicarboxylic acid such as maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl ortho-methylenetetrahydrophthalic acid, hexachloro-m-alkenyl-tetrahydrogen Anhydride of phthalic acid or trimellitic acid. Among these, the acid anhydride (D) is preferably an acid anhydride of succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid or trimellitic acid, and more preferably Anhydride of succinic acid, itaconic acid, and tetrahydrophthalic acid. Further, the alkali-soluble resin represented by the general formula (10) cannot be said to be an example of the alkali-soluble resin represented by the general formula (1).
使以一般式(9)所示化合物之羥基與酸酐(D)進行反應，使一般式(10)所示之化合物合成時的反應溫度，以20~120℃之範圍較佳，更佳者為40~90℃。使以一般式(10)所示化合物合成時之酸酐(D)的莫耳比，亦可對由上述具有聚合性不飽和基之二醇化合物(A)、酸二酐(B)及環氧乙烷化合物(C)之莫耳數(mol)所換算的式(2×((A)-(B))+(C))而言，即莫耳比[(D)/{2[(A)-(B)+(C)]}]為20~110莫耳%。酸酐之莫耳比，以調整以上述一般式(1)所示鹼可溶性樹脂之酸值為目的，可在上述範圍內任意改變。The reaction temperature at which the compound represented by the general formula (9) is reacted with the acid anhydride (D) to synthesize the compound represented by the general formula (10) is preferably in the range of 20 to 120 ° C, more preferably 40~90 °C. The molar ratio of the acid anhydride (D) when the compound represented by the general formula (10) is synthesized may also be the diol compound (A) having the polymerizable unsaturated group, the acid dianhydride (B), and the epoxy group. The formula (2 × ((A) - (B)) + (C)) converted by the molar number (mol) of the ethane compound (C), that is, the molar ratio [(D) / {2 [( A)-(B)+(C)]}] is 20 to 110 mol%. The molar ratio of the acid anhydride can be arbitrarily changed within the above range for the purpose of adjusting the acid value of the alkali-soluble resin represented by the above general formula (1).
有關製造一般式(1)之方法例，以9,9-雙(4-羥基苯基)芴為出發原料時，具體例如下所述。An example of the method for producing the general formula (1), which is based on 9,9-bis(4-hydroxyphenyl)fluorene, is specifically described below.
首先，使9,9-雙(4-羥基苯基)芴與環氧氯丙烷進行反應，使以下述一般式(11)所示之雙酚芴型環氧化合物合成
，且使該雙酚芴型環氧化合物與CH2
=CHR5
-COOH(R5
係與上述相同)所示之(甲基)丙烯酸進行反應，使以下述一般式(12)所示之雙酚芴型環氧基(甲基)丙烯酸酯樹脂合成。然後，該雙酚芴型環氧基(甲基)丙烯酸酯樹脂在丙二醇單甲醚乙酸酯等之溶劑中、加熱下，使酸二酐(B)、環氧乙烷化合物(C)、酸酐(D)順序進行反應，製得上述一般式(1)之鹼可溶性樹脂。
而且，本發明之感光性樹脂組成物，含有以上述一般式(1)之鹼可溶性樹脂作為樹脂成份之主成份。此處，樹脂成份係指藉由進行聚合或硬化形成樹脂之成份，除樹脂外，可含有低聚物、單體。此外，含有作為主成份時，係指一般式(1)之鹼可溶性樹脂在樹脂成份中含有30wt%以上 ，較佳者為50wt%以上，更佳者為60wt%以上。本發明之感光性樹脂組成物，亦可含有以一般式(1)所示之鹼可溶性樹脂作為必須成份，除一般式(1)之樹脂外之成份可為樹脂成份，亦可為溶劑或填充材料或著色劑等之非樹脂成份。Further, the photosensitive resin composition of the present invention contains the alkali-soluble resin of the above general formula (1) as a main component of the resin component. Here, the resin component means a component which forms a resin by polymerization or hardening, and may contain an oligomer or a monomer in addition to the resin. Further, when it contains a main component, it means that the alkali-soluble resin of the general formula (1) contains 30% by weight or more of the resin component. Preferably, it is 50% by weight or more, and more preferably 60% by weight or more. The photosensitive resin composition of the present invention may further contain an alkali-soluble resin represented by the general formula (1) as an essential component, and the component other than the resin of the general formula (1) may be a resin component, or may be a solvent or a filler. Non-resin component such as material or colorant.
為產生作為感光性樹脂組成物之特徵時，以含有下述(i)~(iii)成份作為必須成份較佳。換言之，含有(i)以上述一般式(1)所示之鹼可溶性樹脂、(ii)至少具有1個以上之乙烯性不飽和鍵的光聚合性單體、及(iii)光聚合引發劑作為必須成份。In order to produce a characteristic as a photosensitive resin composition, it is preferred to contain the following components (i) to (iii) as essential components. In other words, it contains (i) an alkali-soluble resin represented by the above general formula (1), (ii) a photopolymerizable monomer having at least one or more ethylenically unsaturated bonds, and (iii) a photopolymerization initiator; Must have ingredients.
另外，本發明之黑色矩陣用感光性樹脂組成物，含有以下述(i)、(ii)、(iii)及(iv)成份作為必須成份。換言之，含有(i)以一般式(1)所示之在一分子內具有羧酸基及聚合性不飽和基之鹼可溶性樹脂、(ii)至少具有1個以上之乙烯性不飽和鍵之光聚合性單體、(iii)光聚合引發劑、及(iv)遮光性顏料作為必須成份。Further, the photosensitive resin composition for a black matrix of the present invention contains the following components (i), (ii), (iii) and (iv) as essential components. In other words, it contains (i) an alkali-soluble resin having a carboxylic acid group and a polymerizable unsaturated group in one molecule as shown in the general formula (1), and (ii) light having at least one or more ethylenically unsaturated bonds. The polymerizable monomer, (iii) a photopolymerization initiator, and (iv) a light-shielding pigment are essential components.
其中，(ii)成份之至少具有1個以上乙烯性不飽和鍵的光聚合性單體，例如2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸等具有羥基之單體、或乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、四甲二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸 酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、丙三醇(甲基)丙烯酸酯等之(甲基)丙烯酸酯類。此等之化合物，可使用其中1種或2種以上。Wherein (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 a monomer having a hydroxyl group such as ethylhexyl (meth)acrylic acid, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or triethylene glycol di(meth)acrylic acid Ester, tetraethylene glycol di(meth)acrylate, tetramethyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tris(methyl) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylic acid (meth)acrylates such as esters, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate. One or two or more kinds of these compounds can be used.
有關此等(ii)成份與(i)以一般式(1)所示鹼可溶性樹脂之配合比例[(i)/(ii)]，以20/80~90/10為宜，較佳者為40/60~80/20。鹼可溶性樹脂之配合比例少時，光硬化後之硬化物變脆，且由於未曝光部上被膜之酸值低，故對鹼顯像液而言溶解性降低且會有圖型邊界不明顯的問題產生。反之，鹼可溶性樹脂之配合比例大於上述範圍時，樹脂中所佔有的光反應性官能基之比例變少時，交聯構造之形成變得不充分，且樹脂成份之酸值過高，曝光部對鹼顯像液而言溶解性變高，故所形成的圖型較目標之線寬更細，容易產生圖型缺陷的問題。The ratio of the components (ii) to (i) the alkali-soluble resin represented by the general formula (1) [(i)/(ii)] is preferably 20/80 to 90/10, preferably 40/60~80/20. When the blending ratio of the alkali-soluble resin is small, the cured product after photocuring becomes brittle, and since the acid value of the film on the unexposed portion is low, the solubility of the alkali developing solution is lowered and the pattern boundary is not conspicuous. The problem arises. On the other hand, when the blending ratio of the alkali-soluble resin is larger than the above range, when the proportion of the photoreactive functional group in the resin is small, the formation of the crosslinked structure is insufficient, and the acid value of the resin component is too high, and the exposed portion is exposed. Since the solubility of the alkali developing solution is high, the pattern formed is thinner than the target line width, and the pattern defect is liable to occur.
此外，成份(iii)之光聚合引發劑例如苯乙酮、2,2-二乙氧基苯乙酮、對-二甲基苯乙酮、對-二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對-第3-丁基苯乙酮等之苯乙酮類、二苯甲酮、2-氯二苯甲酮、p,p'-雙二甲基胺基二苯甲酮等之二苯甲酮類、苯甲基、苯偶因、苯偶因甲基***、苯偶因異丙醚、苯偶因異丁醚等之苯偶因醚類、2-(鄰-氯化苯基)-4,5-苯基二咪唑、2-(鄰-氯化苯基)-4,5-二(間-甲氧基苯基)二咪唑、2-(鄰-氟化苯基)-4,5-二苯基二咪唑、2-(鄰-甲氧基苯基)-4,5-二苯基二咪唑、2,4,5-三芳基二咪唑等之二咪唑系化合物類、2-三氯化甲基-5-苯乙烯 基-1,3,4-噁二唑、2-三氯化甲基-5-(對-氰基苯乙烯基)-1,3,4-噁二唑、2-三氯化甲基-5-(對-甲氧基苯乙烯基)-1,3,4-噁二唑等之鹵化甲基噻唑化合物類、2,4,6-參(三氯化甲基)-1,3,5-三嗪、2-甲基-4,6-雙(三氯甲基)-1,3,5-三嗪、2-苯基-4,6-雙(三氯化甲基)-1,3,5-三嗪、2-(4-氯化苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(3,4,5-三甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲基硫代苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪等之鹵化甲基-第2-三嗪系化合物類、1,2-辛二酮、1-[4-(苯基硫代)苯基]-1,2-(鄰-苯甲醯基肟)、1-(4-苯基磺醯基苯基)丁烷-1,2-二酮-2-肟-鄰-苯甲酸酯、1-(4-甲基磺醯基苯基)丁烷-1,2-二酮-2-肟-鄰-乙酸酯、1-(4-甲基磺醯基苯基)丁烷-1-酮肟-鄰-乙酸酯等之鄰-醯基肟系化合物類、苯甲基二甲基縮醛、噻噸酮、2-氯化噻噸酮、2,4-乙基噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等之硫化合物、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌等之蒽醌類、偶氮雙異丁腈、過氧化苯甲醯基、過氧化枯烯基等之有機過氧化物、2-巰基苯并咪唑、2-巰基苯并噁唑、2-巰基苯并噻唑等之硫醇化合物、三乙醇胺、三乙胺等之三級胺等。此等之光聚合引發劑，可使用1種或2種以上。Further, a photopolymerization initiator of the component (iii) such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichlorobenzene Acetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylamino group, such as ethyl ketone, trichloroacetophenone, p-butyl acetophenone Benzophenones such as benzophenones, benzophenones, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., 2- (o-chlorophenyl)-4,5-phenyldiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)diimidazole, 2-(ortho -fluorinated phenyl)-4,5-diphenyldiimidazole, 2-(o-methoxyphenyl)-4,5-diphenyldiimidazole, 2,4,5-triaryldiimidazole, etc. Diimidazole compounds, 2-trimethylmethyl-5-styrene Base-1,3,4-oxadiazole, 2-trimethylmethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trimethyl chloride- Halogenated methylthiazole compounds of 5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4,6-parade (methyltrichloride)-1,3, 5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trimethyl chloride)-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-trimethyl Oxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloro) Halogenated methyl-2-triazine-based compounds such as methyl)-1,3,5-triazine, 1,2-octanedione, 1-[4-(phenylthio)phenyl]- 1,2-(o-benzylidene fluorenyl), 1-(4-phenylsulfonylphenyl)butane-1,2-dione-2-indole-o-benzoate, 1- (4-methylsulfonylphenyl)butane-1,2-dione-2-indole-o-acetate, 1-(4-methylsulfonylphenyl)butan-1-one肟- - o-mercapto fluorene compounds such as acetate, benzyl dimethyl acetal, thioxanthone, 2-thioxanthone, 2,4-ethyl thioxanthone, 2-methyl a sulfur compound such as thioxanthone or 2-isopropylthioxanthone, 2-ethylhydrazine, octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylfluorene or the like Organic peroxides such as anthraquinone, azobisisobutyronitrile, benzammonium peroxide, cumenyl peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzoene A thiol compound such as thiazole, a tertiary amine such as triethanolamine or triethylamine, or the like. These photopolymerization initiators may be used alone or in combination of two or more.
(iii)成份之光聚合引發劑的使用量，以合計量100重 量份(i)以一般式(1)所示之鹼可溶性樹脂及(ii)光聚合性單體為基準，以2~50重量份為宜，以15~40重量份較佳。(ii)成分之光聚合引發劑的配合比例過少時，會有光聚合之速度變慢、感度降低情形。反之，過多時，恐會有感度過強、圖型線寬對圖型光罩而言變得過粗的狀態，對光罩而言無法使忠實的線寬再現，且圖型邊界不明顯的問題。而且，(iii)之光聚合引發劑亦包含併用光增感作用者，惟亦可不添加另外的光增感劑。(iii) The amount of photopolymerization initiator used in the component is 100 in total The amount of the component (i) is preferably 2 to 50 parts by weight, and preferably 15 to 40 parts by weight, based on the alkali-soluble resin represented by the general formula (1) and (ii) the photopolymerizable monomer. When the blending ratio of the photopolymerization initiator of the component (ii) is too small, the photopolymerization rate is slow and the sensitivity is lowered. On the other hand, when there is too much, there is a fear that the sensitivity is too strong, the line width of the pattern becomes too thick for the pattern mask, and the faithful line width cannot be reproduced for the mask, and the pattern boundary is not obvious. problem. Further, the photopolymerization initiator of (iii) also includes a photo-sensitizer, but may not be added with another photo-sensitizer.
另外，(iv)成份之遮光性顏料例如黑色有機顏料、混色有機顏料或遮光材料等。其中，黑色有機顏料例如苝黑、深藍黑等。混色有機顏料例如至少混合2種以上選自紅色、藍色、綠色、紫色、深藍色、品紅色等之顏料，予以類似黑色化者。遮光材料例如碳黑、氧化鉻、氧化鐵、鈦黑、苯胺黑、喹啉黑，可適當選擇2種以上，特別是碳黑，就遮光性、表面平滑性、分散安定性、與樹脂之相溶性良好而言較佳。Further, the light-shielding pigment of the component (iv) is, for example, a black organic pigment, a mixed color organic pigment or a light-shielding material. Among them, black organic pigments such as dark black, dark blue black, and the like. The mixed color organic pigment is mixed with at least two or more kinds of pigments selected from red, blue, green, purple, dark blue, magenta, and the like, and is similarly blackened. The light-shielding material such as carbon black, chromium oxide, iron oxide, titanium black, nigrosine, and quinoline black can be appropriately selected from two or more types, particularly carbon black, in terms of light blocking property, surface smoothness, dispersion stability, and phase with resin. It is preferred in terms of good solubility.
(iv)成份之遮光性顏料，視其所需可與分散劑同時使用。該分散劑例如陽離子系、陰離子系、非離子系、兩性、矽系、氟系等之界面活性劑。界面活性劑之具體例如聚氧化乙烯月桂醚、聚氧化乙烯硬脂醚等之聚氧化乙烯烷醚類等。(iv)成份之遮光性顏料的使用量，對總量100重量份以一般式(1)所示之鹼可溶性樹脂及(ii)成分而言為30~280重量份、較佳者為50~230重量份之範圍。較此等之範圍更少時，遮光性變得不充分，為製得企求的遮光率時， 膜厚必須變厚，不易製得彩色濾光片之面平滑性。反之，過多時，會產生黑色矩陣用感光性樹脂組成物之分散安定性降低，且為減少原有的黏合劑之感光性樹脂的含量時，會損害顯像特性且損害膜形成機能之不為企求的問題。(iv) The light-blocking pigment of the component may be used together with the dispersing agent as needed. The dispersing agent is, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, an anthraquinone system or a fluorine compound. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether. (iv) The amount of the light-shielding pigment used as a component is 30 to 280 parts by weight, preferably 50%, based on 100 parts by weight of the alkali-soluble resin represented by the general formula (1) and (ii) the component. A range of 230 parts by weight. When the range is less than this, the light-shielding property becomes insufficient, and in order to obtain the desired light-shielding ratio, The film thickness must be thick, and it is difficult to obtain the smoothness of the surface of the color filter. On the other hand, when the amount is too large, the dispersion stability of the photosensitive resin composition for the black matrix is lowered, and when the content of the photosensitive resin of the original binder is reduced, the development characteristics are impaired and the film formation function is impaired. The question of seeking.
含有以(i)成份之以一般式(1)所示之鹼可溶性樹脂、(ii)成份之光聚合性單體、及(iii)成份之光聚合引發劑作為必須成份之感光性樹脂組成物，於彩色濾光片油墨、保護膜等之彩色濾光片用材料等極為有用。此外，含有以(i)成份之以一般式(1)所示之鹼可溶性樹脂、(ii)成份之光聚合性單體、(iii)成份之光聚合引發劑及(iv)成份之遮光性顏料作為必須成份之黑色矩陣用感光性樹脂組成物，作為彩色濾光片用黑色矩陣材料極為有用。而且，視其所需亦可溶解於溶劑中，且配合各種添加劑使用。A photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1), a photopolymerizable monomer of the component (ii), and a photopolymerization initiator of the component (iii) as an essential component It is extremely useful for materials for color filters such as color filter inks and protective films. Further, the photo-polymerizable monomer having the (i) component represented by the general formula (1), the photopolymerizable monomer of the component (ii), the photopolymerization initiator of the component (iii), and the (iv) component are contained. The pigment is a photosensitive resin composition for a black matrix which is an essential component, and is extremely useful as a black matrix material for a color filter. Further, it may be dissolved in a solvent as needed, and used in combination with various additives.
於彩色濾光片用等中使用本發明之感光性樹脂組成物時，除上述各成份外，以使用溶劑較佳。溶劑例如甲醇、乙醇、正丙醇、異丙醇、乙二醇、丙二醇等之醇類、α-或β-萜烯醇等之萜烯類等、丙酮、甲基乙酮、環己酮、N-甲基-2-吡咯烷酮等之酮類、甲苯、二甲苯、四甲基苯等之芳香族烴類、溶纖劑、甲基溶纖劑、乙基溶纖劑、卡必醇、甲基卡必醇、乙基卡必醇、丁基卡必醇、丙二醇單甲醚、丙二醇單***、二丙二醇單甲醚、二丙二醇單***、三乙二醇單甲醚、三乙二醇單***等之乙二醇醚等之乙二醇醚類、醋酸乙酯、醋酸丁酯、溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、乙基卡必醇 乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等之醋酸酯類等，藉由使用此等予以溶解、混合，可形成均勻的溶液狀組成物。When the photosensitive resin composition of the present invention is used for a color filter or the like, a solvent is preferably used in addition to the above components. The solvent is, for example, an alcohol such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol or propylene glycol, a terpene such as α- or β-nonenol, acetone, methyl ethyl ketone or cyclohexanone. Ketones such as N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, and A Kikabi alcohol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol single Glycol ethers such as diethyl ether and the like, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol B Acid ester, ethyl carbitol Acetate such as acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., can be dissolved and mixed by using these to form a uniform solution. Composition.
此外，本發明之感光性樹脂組成物中，視其所需可配合硬化促進劑、熱聚合禁止劑、可塑劑、填充材料、溶劑、水平劑、消泡劑等之添加劑。其中，熱聚合禁止劑例如氫醌、氫醌單甲醚、焦培酚、第3-丁基兒茶酚、吩噻嗪等。可塑劑例如二丁基苯二甲酸酯、二辛基苯二甲酸酯、三甲酚等。填充材料例如石墨棒、二氧化矽、雲母、氧化鋁等。而且，消泡劑或水平劑例如矽系、氟系、丙烯酸系之化合物。Further, in the photosensitive resin composition of the present invention, an additive such as a hardening accelerator, a thermal polymerization inhibiting agent, a plasticizer, a filler, a solvent, a leveling agent, an antifoaming agent or the like may be blended as needed. Among them, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrophenol, 3-butyl catechol, phenothiazine and the like. Plasticizers such as dibutyl phthalate, dioctyl phthalate, cresol, and the like. Filling materials such as graphite rods, cerium oxide, mica, alumina, and the like. Further, the antifoaming agent or the leveling agent is, for example, a lanthanide, fluorine-based or acrylic compound.
本發明之感光性樹脂組成物，除溶劑外之固形份(固形份係包含硬化後形成固形份之單體)中，以含有合計量為70wt%以上(較佳者為80wt%以上、更佳者為90wt%以上)之以一般式(1)所示鹼可溶性樹脂、(ii)光聚合性單體及(iii)光聚合引發劑、視其所需所加入的(iv)遮光性顏料為宜。溶劑之量係視目標之黏度予以變化，對全體量而言以20~80wt%之範圍為宜。以本發明之感光性樹脂組成物作為彩色濾光片用時，適合於保護膜用途及黑色矩陣用途。In the photosensitive resin composition of the present invention, the solid content other than the solvent (the solid portion includes the monomer which forms a solid component after curing) is contained in a total amount of 70% by weight or more (preferably 80% by weight or more, more preferably (90% by weight or more) of the alkali-soluble resin represented by the general formula (1), (ii) a photopolymerizable monomer, and (iii) a photopolymerization initiator, and (iv) a light-shielding pigment added as required should. The amount of the solvent varies depending on the viscosity of the target, and is preferably in the range of 20 to 80% by weight based on the total amount. When the photosensitive resin composition of the present invention is used as a color filter, it is suitable for use as a protective film and a black matrix.
本發明之被膜(硬化物)，例如藉由在基板上等被覆上述感光性樹脂組成物之溶液且予以乾燥，照射光(包含紫外線、放射線等)，使該物進行硬化、製得。設置光照射的部分與光未照射的部分，僅使光照射的部分進行硬化，使其他部分以鹼溶液進行溶解時，可製得企求的圖型被膜 。The film (cured material) of the present invention is obtained by, for example, coating a solution of the photosensitive resin composition on a substrate, drying it, and irradiating light (including ultraviolet rays, radiation, or the like) to cure the material. When the portion irradiated with light and the portion not irradiated with light are provided, only the portion irradiated with the light is hardened, and when the other portion is dissolved in the alkali solution, the desired pattern film can be obtained. .
其次，說明有關使用感光性樹脂組成物之彩色濾光片的製造方法。首先，在基板之表面上被覆感光性樹脂組成物後，進行預烘烤處理以使溶劑蒸發，形成被膜。然後，在該被膜上經由光罩予以曝光後，使用鹼性顯像液進行顯像，溶解除去被膜之未曝光部分，然後，藉由後烘烤處理，製得分畫有形成畫素的部分所形成的黑色矩陣。在該基板上例如被覆分散有紅色顏料之感光性樹脂組成物的液狀組成物後，進行預烘烤以使溶劑蒸發，形成被膜。然後，在該被膜上經由光罩予以曝光後，使用鹼性顯像液進行顯像，且溶解除去被膜之未曝光部分，然後，藉由進行後烘烤處理，形成以所定配列所配置有紅色畫素圖型之畫素列。然後，使用分散有綠色或藍色顏料的感光性樹脂組成物之液狀組成物，與上述相同地，藉由進行各液狀組成物之被覆、預烘烤、曝光、顯像及後烘烤處理，在同一基板上順序形成綠色畫素列及藍色畫素列，在基板上配置紅色、綠色及藍色等三原色之畫素列，另外與上述相同地於其上進行各液狀組成物之被覆、預烘烤、曝光、顯像及後烘烤處理作為保護膜，製得形成有保護膜之彩色濾光片。Next, a method of producing a color filter using a photosensitive resin composition will be described. First, after coating the photosensitive resin composition on the surface of the substrate, a prebaking treatment is performed to evaporate the solvent to form a film. Then, after exposure on the film through a photomask, development is performed using an alkaline developing solution, and the unexposed portion of the film is dissolved and removed, and then the portion where the pixels are formed by the post-baking treatment is obtained. The black matrix formed. On the substrate, for example, a liquid composition in which a photosensitive resin composition of a red pigment is dispersed is coated, and then pre-baked to evaporate the solvent to form a film. Then, after exposure on the film through a photomask, development is performed using an alkaline developing solution, and the unexposed portion of the film is dissolved and removed, and then post-baking treatment is performed to form red arranged in a predetermined arrangement. The prime picture of the pictogram. Then, using a liquid composition of a photosensitive resin composition in which a green or blue pigment is dispersed, coating, prebaking, exposure, development, and post-baking of each liquid composition are carried out in the same manner as described above. In the process, a green pixel sequence and a blue pixel sequence are sequentially formed on the same substrate, and a pixel sequence of three primary colors such as red, green, and blue is disposed on the substrate, and each liquid composition is performed thereon in the same manner as described above. The coating, prebaking, exposure, development, and post-baking treatment are used as a protective film to obtain a color filter formed with a protective film.
在基板上被覆感光性樹脂組成物時，除習知的溶液浸漬法、噴霧法外，可採用使用滾筒被覆機、溢料被覆機或旋轉機之方法等任何方法。藉由此等方法被覆企求的厚度後，藉由除去溶劑(預烘烤處理)以形成被膜。預烘烤係藉由烤箱、熱板等予以加熱、真空乾燥或組合此等進行。預 烘烤處理之加熱溫度及加熱時間，係視使用的溶劑而定適當選擇，例如在80~120℃之溫度下進行1~10分鐘。When the photosensitive resin composition is coated on the substrate, any method such as a roll coating machine, a flash coating machine, or a rotary machine may be employed in addition to the conventional solution dipping method and spraying method. After the desired thickness is coated by such a method, the solvent is removed (prebaking treatment) to form a film. The prebaking is carried out by heating, vacuum drying or a combination of an oven, a hot plate or the like. Pre The heating temperature and the heating time of the baking treatment are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 120 ° C for 1 to 10 minutes.
製作彩色濾光片時所使用的放射線，例如可使用可視光線、紫外線、遠紫外線、電子線、X光等，以波長為250~450nm範圍的放射線較佳。而且，適合於該鹼顯像處理之顯像液，例如鹼金屬或鹼土類金屬之碳酸鹽水溶液、鹼金屬之氫氧化物水溶液等，特別是可使用含有0.05~10重量%碳酸鈉、碳酸鉀、碳酸鋰等碳酸鹽之弱鹼性水溶液，在20~30℃之溫度下予以顯像較佳，使用市售的顯像機或超音波洗淨機等，精密地形成微細影像。而且，於鹼顯像處理後，通常進行水洗。顯像處理法可使用沖洗顯像法、噴霧顯像法、浸漬顯像法、起泡(盛液)顯像法等。顯像條件以在常溫下10~120秒較佳。For the radiation used for producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength of 250 to 450 nm is preferable. Further, a developing solution suitable for the alkali development treatment, for example, an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, or the like, in particular, 0.05 to 10% by weight of sodium carbonate or potassium carbonate can be used. A weakly alkaline aqueous solution of a carbonate such as lithium carbonate is preferably imaged at a temperature of 20 to 30 ° C, and a fine image is precisely formed using a commercially available developing machine or an ultrasonic cleaner. Further, after the alkali development treatment, water washing is usually carried out. As the development processing method, a rinsing development method, a spray development method, an immersion development method, a foaming (liquid) development method, or the like can be used. The developing condition is preferably 10 to 120 seconds at normal temperature.
於該顯像後，在180~250℃之溫度及20~100分鐘之條件下進行熱處理(後烘烤處理)。該後烘烤處理係以提高經圖型化的被膜與基板之密接性為目的時予以進行。此係與預烘烤處理相同地，藉由烤箱、熱板等進行加熱予以進行。本發明經圖型化的被膜，藉由上述微影術、經由各製程所形成。After the development, heat treatment (post-baking treatment) is performed at a temperature of 180 to 250 ° C and a temperature of 20 to 100 minutes. This post-baking treatment is performed for the purpose of improving the adhesion between the patterned film and the substrate. This is carried out by heating in an oven, a hot plate or the like in the same manner as the prebaking treatment. The patterned film of the present invention is formed by each of the processes by the above-described lithography.
於形成具備畫素及/或黑色矩陣之彩色濾光片時所使用的基板，例如玻璃、透明薄膜(如聚碳酸酯、聚對苯二甲酸乙二酯、聚醚碸等)等。而且，視其所需亦可實施賦予透明電極層、藉由矽烷偶合劑等之藥品處理、電漿處理、離子薄層被覆處理、濺射處理、氣相反應法、真空蒸鍍 處理等之適當的前處理。A substrate used for forming a color filter having a pixel and/or a black matrix, such as glass, a transparent film (such as polycarbonate, polyethylene terephthalate, polyether oxime, etc.). Further, depending on the necessity, a transparent electrode layer, a drug treatment by a decane coupling agent, a plasma treatment, an ion thin layer coating treatment, a sputtering treatment, a gas phase reaction method, and a vacuum evaporation method may be performed. Proper pre-processing such as processing.
本發明之感光性樹脂組成物，由於含有以一般式(1)所示之鹼可溶性樹脂，與習知者相比時，對鹼顯像液而言溶解性高，且由於在一分子內之乙烯性不飽和鍵基數很多，故硬化後之交聯密度高。換言之，由於紫外線或電子線照射後之硬化部與未硬化部對鹼顯像液而言溶解度差大，故即使為薄膜或高著色劑濃度時，仍可形成微細圖型。因此，本發明之感光性樹脂組成物適合於形成彩色濾光片，特別是適合作為彩色濾光片保護膜材料及黑色矩陣形成用材料。而且，該所得的彩色濾光片，例如於透過型、反射型或半透過型彩色液晶顯示裝置、彩色攝影管元件、彩色感應器等極為有用。The photosensitive resin composition of the present invention contains an alkali-soluble resin represented by the general formula (1), and has higher solubility in an alkali developing solution than in a conventional one, and is in a molecule. Since the number of ethylenically unsaturated bond groups is large, the crosslinking density after hardening is high. In other words, since the hardened portion and the uncured portion after irradiation with ultraviolet rays or electron beams have a large difference in solubility to the alkali developing solution, a fine pattern can be formed even when the film or the high colorant concentration is used. Therefore, the photosensitive resin composition of the present invention is suitable for forming a color filter, and is particularly suitable as a color filter protective film material and a black matrix forming material. Further, the obtained color filter is extremely useful, for example, in a transmissive, reflective or transflective color liquid crystal display device, a color photographic tube element, a color sensor, or the like.
於下述中，以實施例及比較例為基準，更詳細地說明本發明。而且，本發明不受此等實施例及比較例限制其範圍。此外，於下述之實施例中樹脂之評估，在沒有特別限制時如下述進行。In the following, the present invention will be described in more detail on the basis of examples and comparative examples. Further, the present invention is not limited by the scope of the embodiments and the comparative examples. Further, the evaluation of the resin in the following examples was carried out as follows without particular limitation.
在彩色濾光片[重量：W0 (g)]中含浸1g之實施例(包含比較例)中所得的樹脂溶液(亦包含反應生成物或鹼可溶性 樹脂)且予以稱重[W1 (g)]，在160℃下加熱2小時後之重量[W2 (g)]，藉由下式求取。The color filter [Weight: W 0 (g)] was impregnated with 1 g of the resin solution (including the reaction product or the alkali-soluble resin) obtained in the example (including the comparative example) and weighed [W 1 (g) )], the weight [W 2 (g)] after heating at 160 ° C for 2 hours was obtained by the following formula.
固形份濃度(重量%)=100×(W2 -W0 )/(W1 -W0 )Solid concentration (% by weight) = 100 × (W 2 - W 0 ) / (W 1 - W 0 )
使樹脂溶液溶解於二噁烷中，以酚酞作為指示劑，以1/10N-KOH水溶液進行滴定求取。The resin solution was dissolved in dioxane, and phenolphthalein was used as an indicator and titrated with a 1/10 N-KOH aqueous solution.
以四氫呋喃作為展開溶劑，以凝膠滲透色層分析法(GPC)，作為標準聚苯乙烯換算值求取重量平均分子量(Mw)之值。Using tetrahydrofuran as a developing solvent, the value of the weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.
而且，實施例中使用的簡稱如下所述。Moreover, the abbreviations used in the examples are as follows.
FHPA：雙酚芴型環氧樹脂與丙烯酸之等當量反應物(新日鐵化學公司製、ASF-400溶液：固形份濃度50wt%、固形份換算之酸值1.28mgKOH/g)FHPA: Equivalent reactant of bisphenol quinone type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid content concentration 50wt%, solid value conversion acid value 1.28mgKOH/g)
FHPPA：雙(苯基苯酚)芴型環氧樹脂與丙烯酸之等當量反應物(50wt%PGMEA溶液、固形份換算之酸值7.51mgKOH/g)FHPPA: an equivalent reaction of bis(phenylphenol) oxime epoxy resin with acrylic acid (50 wt% PGMEA solution, acid value in terms of solid content 7.51 mg KOH/g)
BisA-GEA：雙酚A二環氧丙醚與丙烯酸之當量反應物(50wt%PGMEA溶液、固形份換算之酸值1.72mgKOH/g)BisA-GEA: equivalent reaction of bisphenol A diglycidyl ether with acrylic acid (50 wt% PGMEA solution, acid value in solid content: 1.72 mg KOH/g)
BDPA:3,3',4,4'-聯苯四羧酸二酐BDPA: 3,3',4,4'-biphenyltetracarboxylic dianhydride
BTDA:3,3',4,4'-二苯甲酮四羧酸二酐BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride
ODPA:3,3',4,4'-氧化二苯基四羧酸二酐ODPA: 3,3',4,4'-diphenyltetracarboxylic dianhydride
CHDA:3,3',4,4'-氧化二苯基四羧酸二酐CHDA: 3,3',4,4'-diphenyltetracarboxylic dianhydride
THPA:1,2,3,6-四氫苯二甲酸酐THPA: 1,2,3,6-tetrahydrophthalic anhydride
HHPA：六氫苯二甲酸酐HHPA: hexahydrophthalic anhydride
GMA：甲基丙烯酸環氧丙酯GMA: glycidyl methacrylate
HBAGE：4-羥基苯基丙烯酸酯環氧丙醚HBAGE: 4-hydroxyphenyl acrylate glycidyl ether
TEAB：溴化四乙銨TEAB: Tetraethylammonium bromide
TPP：三苯基膦TPP: triphenylphosphine
PGMEA：丙二醇單甲醚乙酸酯PGMEA: propylene glycol monomethyl ether acetate
[實施例1][Example 1]
在1000ml附有回流冷卻器之四口燒瓶中加入600.00g(0.49莫耳)FHPA[(A)成份]之50%PGMEA溶液、72.75g(0.247莫耳)BPDA[(B)成份]、39.56g之PGMEA、及1.30g之TPP，在120~125℃下加熱，進行攪拌2小時，另外在70~75℃下進行6小時之加熱攪拌處理，製得反應生成物(a)。所得的反應生成物(a)之固形份濃度為52.4wt%、樹脂之酸值(固形份換算)為78.0mgKOH/g、及藉由GPC分析之重量平均分子量(Mw)為3400。In a 1000 ml four-necked flask equipped with a reflux cooler, 600.00 g (0.49 mol) of FHPA [(A) component] 50% PGMEA solution, 72.75 g (0.247 mol) BPDA [(B) component], 39.56 g were added. The PGMEA and the 1.30 g of TPP were heated at 120 to 125 ° C for 2 hours, and further heated and stirred at 70 to 75 ° C for 6 hours to obtain a reaction product (a). The solid content concentration of the obtained reaction product (a) was 52.4% by weight, the acid value of the resin (calculated as solid content) was 78.0 mgKOH/g, and the weight average molecular weight (Mw) by GPC analysis was 3,400.
然後，在該反應生成物中加入73.92g(0.52莫耳)GMA[(C)成份]，在80℃下進行攪拌8小時予以反應。另外，在燒瓶內加入156.71g(1.03莫耳)THPA[(D成份]，在80℃下進行攪拌7小時，合成鹼可溶性樹脂(1)-1。所得的 鹼可溶性樹脂之固形份濃度為62.0wt%，酸值(固形份換算)為111.8mgKOH/g，藉由GPC分析之Mw為3700。而且，合成實施例1之鹼可溶性樹脂(1)-1時所使用的(A)~(D)成份名及配合比例、以及所得的鹼可溶性樹脂(1)-1脂重量平均分子量及酸值皆如表1所示(有關下述之實施例及參考例亦相同)。Then, 73.92 g (0.52 mol) of GMA [(C) component] was added to the reaction product, and the mixture was stirred at 80 ° C for 8 hours to carry out a reaction. Further, 156.71 g (1.03 mol) of THPA [(D component]) was added to the flask, and the mixture was stirred at 80 ° C for 7 hours to synthesize an alkali-soluble resin (1)-1. The solid content of the alkali-soluble resin was 62.0% by weight, the acid value (in terms of solid content) was 111.8 mgKOH/g, and the Mw by GPC analysis was 3,700. Further, the (A) to (D) component names and mixing ratios used in the synthesis of the alkali-soluble resin (1)-1 of Example 1, and the obtained alkali-soluble resin (1)-1 lipid weight average molecular weight and acid value All are shown in Table 1 (the same applies to the following examples and reference examples).
在1000ml附有回流冷卻器之四口燒瓶中加入600.00g(0.49莫耳)FHPA[(A)成份]之50%PGMEA溶液、96.02g(0.33莫耳)BPDA((B)成份)、4.36g之PGMEA、及1.02g之TEAB，在120~125℃下加熱下進行攪拌2小時，另外在60~65℃下進行8小時之加熱攪拌處理，製得反應生成物(b)。所得的反應生成物(b)之固形份濃度為57.8wt%，酸值(固形份換算)為91.6mgKOH/g，及藉由GPC分析之重量平均分子量(Mw)為8800。In a 1000 ml four-necked flask equipped with a reflux cooler, 600.00 g (0.49 mol) of FHPA [(A) component] 50% PGMEA solution, 96.02 g (0.33 mol) BPDA ((B) component), 4.36 g were added. The PGMEA and the 1.02 g of TEAB were stirred under heating at 120 to 125 ° C for 2 hours, and further heated and stirred at 60 to 65 ° C for 8 hours to obtain a reaction product (b). The solid content of the obtained reaction product (b) was 57.8 wt%, the acid value (in terms of solid content) was 91.6 mgKOH/g, and the weight average molecular weight (Mw) by GPC analysis was 8,800.
然後，在該反應生成物(b)中加入93.82g(0.66莫耳)GMA[(C)成份]，在80℃下進行攪拌24小時予以反應。另外，在燒瓶內加入153.67g(1.01莫耳)THPA[(D成份]、及153.67g之PGMEA，在80℃下進行攪拌24小時，合成鹼可溶性樹脂(1)-2。所得的鹼可溶性樹脂之固形份濃度為59.2wt%，酸值(固形份換算)為126.8mgKOH/g，藉由GPC分析之Mw為6800。Then, 93.82 g (0.66 mol) of GMA [(C) component] was added to the reaction product (b), and the mixture was stirred at 80 ° C for 24 hours to carry out a reaction. Further, 153.67 g (1.01 mol) of THPA [(D component) and 153.67 g of PGMEA was placed in a flask, and the mixture was stirred at 80 ° C for 24 hours to synthesize an alkali-soluble resin (1)-2. The obtained alkali-soluble resin The solid content concentration was 59.2% by weight, the acid value (calculated as solid content) was 126.8 mgKOH/g, and the Mw by GPC analysis was 6,800.
在500ml附有回流冷卻器之四口燒瓶中加入200.0g以上述實施例2所得的反應生成物(b)與13.36g(0.094莫耳)GMA[(C)成份]，在80℃下進行攪拌24小時，另外在燒瓶內加入28.91g(0.19莫耳)THPA[(D成份]及28.91g之PGMEA，在80℃下進行攪拌24小時，合成鹼可溶性樹脂(1)-3。所得的鹼可溶性樹脂之固形份濃度為59.2wt%，酸值(固形份換算)為100.3mgKOH/g，藉由GPC分析之Mw為6700。200.0 g of the reaction product (b) obtained in the above Example 2 and 13.36 g (0.094 mol) of GMA [(C) component] were placed in a 500 ml four-necked flask equipped with a reflux condenser, and stirred at 80 ° C. After 24 hours, 28.91 g (0.19 mol) of THPA [(D component] and 28.91 g of PGMEA was added to the flask, and the mixture was stirred at 80 ° C for 24 hours to synthesize the alkali-soluble resin (1)-3. The alkali solubility obtained. The solid content of the resin was 59.2% by weight, the acid value (in terms of solid content) was 100.3 mgKOH/g, and the Mw by GPC analysis was 6,700.
在500ml附有回流冷卻器之四口燒瓶中加入200.0g以上述實施例2所得的反應生成物(b)與27.01g(0.19莫耳)GMA[(C)成份]，在80℃下攪拌24小時，另外在燒瓶內加入12.78g(0.084莫耳)THPA[(D成份]及12.78g之PGMEA，在80℃下進行攪拌24小時，合成鹼可溶性樹脂(1)-4。所得的鹼可溶性樹脂之固形份濃度為60.5wt%，酸值(固形份換算)為32.5mgKOH/g，藉由GPC分析之Mw為6400。200.0 g of the reaction product (b) obtained in the above Example 2 and 27.01 g (0.19 mol) of GMA [(C) component] were placed in a 500 ml four-necked flask equipped with a reflux condenser, and stirred at 80 ° C. In an hour, 12.78 g (0.084 mol) of THPA [(D component] and 12.78 g of PGMEA was added to the flask, and the mixture was stirred at 80 ° C for 24 hours to synthesize an alkali-soluble resin (1)-4. The obtained alkali-soluble resin The solid content concentration was 60.5 wt%, the acid value (in terms of solid content) was 32.5 mgKOH/g, and the Mw by GPC analysis was 6,400.
使至少部分以實施例2所使用的(A)~(D)成分以下述表1記載的原料取代，換言之，使實施例2之FHPA、BPDA、THPA或GMA以表1記載的原料取代外，與實施例2相同地進行反應，製得鹼可溶性樹脂(1)-5~(1)-14。At least part of the components (A) to (D) used in Example 2 were replaced with the materials described in Table 1 below, in other words, the FHPA, BPDA, THPA or GMA of Example 2 was replaced with the materials described in Table 1. The reaction was carried out in the same manner as in Example 2 to obtain an alkali-soluble resin (1)-5~(1)-14.
除使上述實施例1之THPA[(D)成份]之添加量改為118.68(0.78莫耳)外，與實施例1相同地進行反應，製得鹼可溶性樹脂(1)-15。The alkali-soluble resin (1)-15 was obtained in the same manner as in Example 1 except that the amount of THPA [(D) component] in the above Example 1 was changed to 118.68 (0.78 mol).
在500ml附有回流冷卻器之四口燒瓶中加入206.26g(0.17莫耳)FHPA之50%PGMEA溶液、0.085莫耳BPDA、0.085莫耳THPA、26.0g之PGMEA、及0.45g之TPP，在120~125℃下加熱進行攪拌6小時，製得樹脂(參考)-1。所得的鹼可溶性樹脂之固形份濃度為55.6wt%，酸值(固形份換算)為103.0mgKOH/g，藉由GPC分析之Mw為2600。In a 500 ml four-necked flask equipped with a reflux cooler, 206.26 g (0.17 mol) of FHPA 50% PGMEA solution, 0.085 mol BPDA, 0.085 mol THPA, 26.0 g PGMEA, and 0.45 g TPP were added at 120 The mixture was heated and heated at ~125 ° C for 6 hours to obtain a resin (reference)-1. The solid content of the obtained alkali-soluble resin was 55.6 wt%, the acid value (in terms of solid content) was 103.0 mgKOH/g, and the Mw by GPC analysis was 2,600.
在1000ml附有回流冷卻器之四口燒瓶中加入600.00g(0.49莫耳)FHPA之50%PGMEA溶液、96.02g(0.33莫耳)BPDA、4.36g之PGMEA、及1.02g之TEAB，在120~125℃下加熱進行攪拌2小時，另外在60~65℃下進行加熱攪拌8小時，製得樹脂(參考)-2。所得的鹼可溶性樹脂之固形份濃度為58.5wt%，酸值(固形份換算)為91.0mgKOH/g，藉由GPC分析之Mw為8600。
其次，以製造彩色濾光片時之實施例及比較例為基準，具體地說明本發明。而且，本發明不受此等所限制。此處，製造實施例及必較例之彩色濾光片所使用的原料及簡稱，如下所述。Next, the present invention will be specifically described on the basis of the examples and comparative examples in the case of producing a color filter. Moreover, the invention is not limited by these. Here, the raw materials and abbreviations used in the production of the color filters of the examples and the comparative examples are as follows.
(1)成分：(1)-1~(1)-4、(參考)-1及(參考)-2：上述實施例1~4及參考例1及2所得的鹼可溶性樹脂，(ii)-1成分：二季戊四醇六丙烯酸酯(1) Ingredients: (1)-1 to (1)-4, (Reference)-1, and (Reference)-2: the alkali-soluble resins obtained in the above Examples 1 to 4 and Reference Examples 1 and 2, (ii) -1 component: dipentaerythritol hexaacrylate
(iii)-1成分：肟酯系光聚合引發劑(千葉特殊化學製、衣魯卡奇亞(譯音)OXE01)(iii)-1 component: oxime ester photopolymerization initiator (Chiba Special Chemicals, 衣鲁卡奇亚(音音) OXE01)
(iii)-2成分：米烯酮(光增感劑)(iii)-2 ingredient: minoenketone (photosensitizer)
(v)成分：四甲基聯苯型環氧樹脂(v) Component: tetramethylbiphenyl type epoxy resin
溶劑：溶纖劑乙酸酯Solvent: cellosolve acetate
藉由使上述配合成份[(1)、(ii)、(iii)及(v)]以表2所示比例配合，調製使用上述實施例1~4及參考例1~2所得的鹼可溶性樹脂之感光性樹脂組成物。
使使用上述實施例1~4、及參考例1~2所得的鹼可溶性樹脂之感光性樹脂組成物使用旋轉被覆器，在 125mm×125mm之玻璃基板上進行後烘烤處理後之膜厚為2μm下予以被覆，在90℃下進行預烘烤2分鐘後，作成被覆板。然後，以500W/cm2 之高壓水銀燈經由圖型光罩照射波長365nm之照度10mW/cm2 的紫外線10秒，進行感光部分之光硬化反應。其次，使該曝光完成的被覆板在1wt%碳酸鈉水溶液中、在25℃下視認企求的圖型後，另外進行20秒顯像及水洗，除去被覆之未曝光部分。然後，使用熱風乾燥機，在230℃下進行加熱乾燥處理30分鐘，製得試驗用彩色濾光片。評估實施例16~19、及比較例1~2之試驗用彩色濾光片的顯像性、顯像密接性等。具體而言，有關所得的試料，評估被膜之乾燥性、對鹼水溶液之顯像性、曝光感度、被膜硬度、與基板之密接性、耐熱性、耐藥品性。結果如表3所示。而且，各種物性數據以下述條件測定。The photosensitive resin composition using the alkali-soluble resin obtained in the above Examples 1 to 4 and Reference Examples 1 and 2 was subjected to post-baking treatment on a glass substrate of 125 mm × 125 mm using a spin coater to have a film thickness of 2 μm. After coating, it was pre-baked at 90 ° C for 2 minutes, and then a coated board was prepared. Then, an ultraviolet ray having an illuminance of 10 mW/cm 2 having a wavelength of 365 nm was irradiated with a high-pressure mercury lamp of 500 W/cm 2 through a pattern mask for 10 seconds to carry out a photohardening reaction of the photosensitive portion. Next, the coated plate having the exposure was visually observed at 25 ° C in a 1 wt% aqueous sodium carbonate solution, and then developed for 20 seconds and washed with water to remove the unexposed portion of the coating. Then, heat drying treatment was carried out at 230 ° C for 30 minutes using a hot air dryer to obtain a test color filter. The development properties, development adhesion, and the like of the test color filters of Examples 16 to 19 and Comparative Examples 1 and 2 were evaluated. Specifically, the obtained sample was evaluated for the drying property of the film, the developability to an aqueous alkali solution, the exposure sensitivity, the film hardness, the adhesion to the substrate, the heat resistance, and the chemical resistance. The results are shown in Table 3. Further, various physical property data were measured under the following conditions.
被膜之乾燥性以JIS-K5400為基準予以評估。評估基準如下所述。The dryness of the film was evaluated based on JIS-K5400. The evaluation criteria are as follows.
○：全部沒有皺摺者○: All without wrinkles
△：稍有皺摺者△: slightly wrinkled
×：有顯著皺摺者×: There are significant wrinkles
在1重量%碳酸鈉水溶液中、25℃下使圖型顯像後，浸 漬20秒進行顯像。顯像後，以目視評估擴大40倍殘存的樹脂。評估基準如下所述。Dip in a 1% by weight sodium carbonate aqueous solution at 25 ° C, dip The stain was imaged for 20 seconds. After the development, the resin remaining 40 times larger was visually evaluated. The evaluation criteria are as follows.
○：顯像性良好者(在玻璃上完全沒有光阻殘留者)○: Those with good imaging properties (no photoresist residue on the glass)
△：顯像性稍微不佳者(在玻璃上稍有光阻殘留者)△: The developer is slightly inferior (there is a slight photoresist residue on the glass)
×：顯像性不佳者(在玻璃上有些許光阻殘留者)×: Those with poor imaging properties (some photoresist residues on the glass)
使具有10μm細線圖型之曝光光罩密接於被膜上，使用500W高壓水銀燈以100J/cm2 之光量照射。然後，對鹼水溶液而言顯像性1重量%碳酸鈉水溶液中、25℃下進行圖型顯像後，再浸漬20秒以進行顯像處理。顯像後，評估所形成的細線圖型之線寬(該評估法係於高感度愈高時線寬預粗)。The exposure mask having a fine line pattern of 10 μm was adhered to the film, and irradiated with a light amount of 100 J/cm 2 using a 500 W high pressure mercury lamp. Then, in a developing aqueous solution of 1% by weight of sodium carbonate in an aqueous alkali solution, pattern development was carried out at 25 ° C, and then immersed for 20 seconds to carry out development processing. After the development, the line width of the formed thin line pattern is evaluated (the evaluation method is such that the line width is pre-rough when the high sensitivity is higher).
於曝光顯像後，使在230℃下進行加熱30分鐘之被覆的硬度，以JIS-K5400之試驗法為基準，使用鉛筆硬度試驗機施加1kg荷重時，以被膜沒有受到刮傷的最高硬度表示。使用的鉛筆為「三菱高單位」。After the exposure development, the hardness of the coating which was heated at 230 ° C for 30 minutes was expressed by the highest hardness of the film without being scratched by applying a load of 1 kg using a pencil hardness tester based on the test method of JIS-K5400. . The pencil used is "Mitsubishi High Unit".
於曝光顯像後，在230℃下進行加熱30分鐘之被膜上作成至少100個棋盤格子進行交叉切割，然後，使用膠帶(註冊商標)進行剝離試驗，藉由目視評估棋盤格子之剝離 狀態。評估基準係如下所述。After exposure development, at least 100 checkerboard grids were formed on the film which were heated at 230 ° C for 30 minutes for cross-cutting, and then a peel test was performed using a tape (registered trademark) to visually evaluate the peeling of the checkerboard grid. status. The evaluation criteria are as follows.
○：全部沒有剝離者○: All are not stripped
×：有少許剝離者×: There is a little peeler
始於曝光顯像後，使230℃下進行加熱30分鐘之被膜，在250℃下、置於烤箱中3小時，評估被膜之狀態。評估基準如下所述。After the exposure development, the film was heated at 230 ° C for 30 minutes, and placed in an oven at 250 ° C for 3 hours to evaluate the state of the film. The evaluation criteria are as follows.
○：被膜之外觀沒有異常現象○: There is no abnormality in the appearance of the film.
×：被膜之外觀有破裂、剝離、著色情形×: The appearance of the film is broken, peeled, and colored.
於曝光顯像後，使在230℃下進行加熱30分鐘的被膜，在下述藥品中以下述條件浸漬，且評估浸漬後之外觀及密接性。After the exposure and development, the film which was heated at 230 ° C for 30 minutes was immersed in the following chemicals under the following conditions, and the appearance and adhesion after immersion were evaluated.
耐酸性試驗：5%HCl中24小時Acid resistance test: 24 hours in 5% HCl
耐鹼性試驗1:5%NaOH中浸漬24小時Alkali resistance test 1: immersion in 5% NaOH for 24 hours
耐鹼性試驗2:4%KOH中、50℃下浸漬10分鐘Alkali resistance test 2: 4% KOH, immersed for 10 minutes at 50 ° C
耐鹼性試驗3:1%NaOH中、80℃下浸漬5分鐘Alkali resistance test 3: 1% NaOH, immersed for 5 minutes at 80 ° C
耐溶劑性試驗1:NMP中、40℃下浸漬10分鐘Solvent resistance test 1: immersion in NMP for 10 minutes at 40 ° C
耐溶劑性試驗2:NMP中、80℃下浸漬5分鐘Solvent resistance test 2: immersion in NMP at 80 ° C for 5 minutes
(注)NMP:N-甲基-吡咯烷酮
由上述表3之結果可知，實施例16~19、特別是實施例16及17與比較例相比時，顯像性、密接性優異。換言之，紫外線或電子線照射後硬化部與未硬化部對顯像液而言溶解度差大，且藉由在一分子內之乙烯性不飽和鍵結基數增加，可提供具有良好顯像性、高密接性之硬化膜。As is clear from the results of the above Table 3, in Examples 16 to 19, particularly in Examples 16 and 17, compared with the comparative examples, the developing property and the adhesion were excellent. In other words, after the ultraviolet or electron beam irradiation, the hardened portion and the uncured portion have a large difference in solubility to the developing liquid, and the number of ethylenically unsaturated bonding groups in one molecule is increased to provide good development and high visibility. Adhesive hardened film.
其次，於製造黑色矩陣時，以實施例及比較例為基準具體地說明本發明，惟本發明不受此等所限制。此處，製造下述之實施例及比較例之黑色矩陣時所使用的原料及簡稱如下所述。Next, in the case of producing a black matrix, the present invention will be specifically described on the basis of the examples and comparative examples, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the black matrix of the following examples and comparative examples are as follows.
(i)-1成分：以上述實施例1所得的鹼可溶性樹脂(i)-1 component: the alkali-soluble resin obtained in the above Example 1
(i)-2成分：以上述實施例15所得的鹼可溶性樹脂(i)-2 component: the alkali-soluble resin obtained in the above Example 15
(i)-3成分：以上述實施例2所得的鹼可溶性樹脂(i)-3 component: the alkali-soluble resin obtained in the above Example 2
(i)-4成分：以上述參考例1所得的鹼可溶性樹脂(i)-4 component: the alkali-soluble resin obtained in the above Reference Example 1
(i)-5成分：以上述參考例2所得的鹼可溶性樹脂(i)-5 component: the alkali-soluble resin obtained in the above Reference Example 2
(ii)-2成分：三羥甲基丙烷三丙烯酸酯(ii)-2 component: trimethylolpropane triacrylate
(iii)-3成分：肟酯系光聚合引發劑(千葉特殊化學製、衣魯卡奇亞OXE02)(iii) -3 component: oxime ester photopolymerization initiator (Chiba Special Chemicals, 衣鲁卡奇亚 OXE02)
(iii)-4成分：二苯甲酮系光聚合引發劑(千葉特殊化學製、衣魯卡奇亞369)(iii) -4 component: benzophenone-based photopolymerization initiator (Chiba Special Chemicals, 衣鲁卡奇亚369)
(iv)-1成分：顏料濃度20.0%、總固形份24%之碳分散體(平均粒徑100~130nm)(iv)-1 component: a carbon dispersion having a pigment concentration of 20.0% and a total solid content of 24% (average particle diameter: 100 to 130 nm)
(iv)-2成分：顏料濃度20.0%、總固形份29%之碳分散體(平均粒徑100~150nm)(iv)-2 component: carbon dispersion having a pigment concentration of 20.0% and a total solid content of 29% (average particle diameter: 100 to 150 nm)
溶劑-1：丙二醇單甲醚乙酸酯Solvent-1: Propylene glycol monomethyl ether acetate
溶劑-2：環己酮Solvent-2: cyclohexanone
添加劑-1：矽烷偶合劑(東雷拉克寧古(譯音)製SH-6040)Additive-1: decane coupling agent (SH-6040 made by East Relacn Ninggu)
使上述配合成分以表4所示之比例配合，調製實施例20~25及比較例3~6之黑色光阻用感光性樹脂組成物。而且，表4中之數值全部以重量份表示。
使表4所示之黑色光阻用感光性樹脂組成物使用旋轉被覆器，在125mm×125mm之玻璃基板上進行後烘烤處理後之膜厚為0.9~1.0μm下予以被覆，且在80℃下進行預烘烤處理1分鐘，作成被覆板。然後，以500W/cm2 之高壓水銀燈照射波長365nm之照度100mJ/cm2 的紫外線，進行感光部分之光硬化反應。其次，使該曝光完成的被覆板在0.04wt%氫氧化鉀水溶液或0.5wt%碳酸鈉水溶液中，進行24℃沖洗顯像處理使圖型顯像後，再進行顯像處理30秒，然後，進行噴霧水洗處理，除去被膜之未曝光部分。其次，使用熱風乾燥機、在230℃下進行加熱乾燥處理30分鐘，製得實施例20~25、及比較例3~6之彩色濾光片。The photosensitive resin composition for black photoresist shown in Table 4 was coated with a spin coater after being post-baking on a glass substrate of 125 mm × 125 mm, and the film thickness was 0.9 to 1.0 μm, and it was coated at 80 ° C. The prebaking treatment was carried out for 1 minute to prepare a coated board. Then, ultraviolet rays having an illuminance of 100 mJ/cm 2 at a wavelength of 365 nm were irradiated with a high-pressure mercury lamp of 500 W/cm 2 to carry out a photohardening reaction of the photosensitive portion. Next, the exposed coated plate is subjected to a 24° C. rinse development process in a 0.04 wt% potassium hydroxide aqueous solution or a 0.5 wt% sodium carbonate aqueous solution to develop a pattern, and then subjected to development treatment for 30 seconds, and then, A spray water washing treatment was performed to remove the unexposed portion of the film. Next, heat drying treatment was carried out at 230 ° C for 30 minutes using a hot air dryer to obtain color filters of Examples 20 to 25 and Comparative Examples 3 to 6.
有關上述所得的實施例20~25、及比較例3~6之彩色濾光片，顯像性及顯像範圍等之評估結果如表5所示。此等之評估方法如下所述。The evaluation results of the color filters of Examples 20 to 25 and Comparative Examples 3 to 6 obtained as described above, the development properties, the development range, and the like are shown in Table 5. The evaluation methods for these are as follows.
使用觸針式段差形狀測定裝置(肯耶魯耶．迪克魯(譯音)(股)製商品名P-10)進行測定。The measurement was carried out using a stylus type step shape measuring device (trade name P-10 manufactured by Kenyer Rue Dekru).
記錄鹼顯像時、看見全部圖型時所需要的時間，顯像時間大於120秒時仍不見圖型時為×。When the alkali image is recorded, the time required to see all the patterns is × when the imaging time is more than 120 seconds and the image is still not visible.
使以10μm圖型光罩予以曝光的部分進行顯像時，記錄自看見圖型至維持圖型部分為10±1μm之時間。圖型部分之線寬係使用測長顯微鏡((股)理光(譯音)製商品名XD-20)進行測定。When the portion exposed by the 10 μm pattern mask was developed, the time from the view pattern to the maintenance pattern portion of 10 ± 1 μm was recorded. The line width of the pattern portion was measured using a length measuring microscope (trade name: XD-20, manufactured by Ricoh).
使顯像後之圖型使用掃描型電子顯微鏡((股)KEYENCE製商品名VE-780)進行觀察，圖型之截面形狀維持正錐形者為○，為倒錐形或產生剝離情形時為×。The pattern after development was observed using a scanning electron microscope (trade name: VE-780, manufactured by KEYENCE), and the cross-sectional shape of the pattern was maintained at a forward taper of ○, which was a reverse taper or a peeling condition. ×.
有關顯像後之10μm線，以上述測長顯微鏡評估圖型部分之直線性或有無干涉紋等。此處，直線性佳、沒有產生干涉紋者為○(佳)，產生干涉紋且直線性不佳者為×(不佳)。僅限各項目皆極佳時，評估為◎。Regarding the 10 μm line after development, the linearity of the pattern portion or the presence or absence of interference lines was evaluated by the above-described length measuring microscope. Here, the linearity is good, the interference pattern is not produced as ○ (good), the interference pattern is generated, and the linearity is not good (x is not good). Only when each item is excellent, the evaluation is ◎.
使用光學濃度計(大塚電子股份有限公司製)進行測定。
由上述表5之結果可知，實施例20~25之彩色濾光片，各性能皆優異，特別是實施例23~25之黑色矩陣與比較例5及6相比時，顯像性及密接性優異，即使減低光聚合引發劑之使用量時，可形成細線圖型。換言之，紫外線或電子線照射後硬化部與未硬化部對顯像液而言溶解度差大，且藉由在一分子內之乙烯性不飽和鍵結基數增加，可提供具有良好顯像性、高密接性之硬化膜。As is apparent from the results of the above Table 5, the color filters of Examples 20 to 25 were excellent in performance, and in particular, the development and adhesion of the black matrix of Examples 23 to 25 compared with Comparative Examples 5 and 6. Excellent, even when the amount of the photopolymerization initiator used is reduced, a fine line pattern can be formed. In other words, after the ultraviolet or electron beam irradiation, the hardened portion and the uncured portion have a large difference in solubility to the developing liquid, and the number of ethylenically unsaturated bonding groups in one molecule is increased to provide good development and high visibility. Adhesive hardened film.
本發明之感光性樹脂組成物與習知者相比時，對鹼顯像液而言溶解性高，且由於在一分子內之乙烯性不飽和鍵結基數很多，硬化後之交聯密度高。換言之，由於紫外線或電子線照射後硬化部與未硬化部對顯像液而言溶解度差變大，即使為薄膜或高著色劑濃度，仍可形成微細圖型。因此，本發明之感光性樹脂組成物，可適合使用於彩色液晶顯示裝置、彩色傳真機、影像感應器等之各種多色顯示體、或光學機器等所使用的彩色濾光片用之著色油墨、及藉由此等所形成的具有黑色矩陣之彩色濾光片、或電視、錄放影機、或電腦之顯示裝置等。特別是適合作為彩色濾光片保護膜材料及黑色矩陣形成用材料。而且，該所得的彩色濾光片例如於透過型、反射型或半透過型彩色液晶顯示裝置、彩色攝影管元件、彩色感應器等極為有用。When the photosensitive resin composition of the present invention is compared with a conventional one, the solubility in the alkali developing solution is high, and since the number of ethylenically unsaturated bonding groups in one molecule is large, the crosslinking density after hardening is high. . In other words, since the difference in solubility between the hardened portion and the uncured portion after the irradiation of the ultraviolet ray or the electron beam is large, even if it is a film or a high colorant concentration, a fine pattern can be formed. Therefore, the photosensitive resin composition of the present invention can be suitably used for various color control inks such as color liquid crystal display devices, color facsimile machines, and image sensors, or color filters for color filters used in optical devices and the like. And a color filter having a black matrix formed by the like, or a display device such as a television, a video recorder, or a computer. In particular, it is suitable as a color filter protective film material and a black matrix forming material. Further, the obtained color filter is extremely useful, for example, in a transmissive, reflective or transflective color liquid crystal display device, a color photographic tube element, a color sensor, and the like.
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| JP6482176B2 (en) * | 2013-03-21 | 2019-03-13 | 日鉄ケミカル＆マテリアル株式会社 | Photosensitive resin composition for insulating film and cured product |
| TWI477539B (en) * | 2014-02-13 | 2015-03-21 | Chi Mei Corp | Alkali-solutable resin, photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus |
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