TW200424219A - Photosensitive resin composition using photopolymer - Google Patents
Photosensitive resin composition using photopolymer Download PDFInfo
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- TW200424219A TW200424219A TW092127353A TW92127353A TW200424219A TW 200424219 A TW200424219 A TW 200424219A TW 092127353 A TW092127353 A TW 092127353A TW 92127353 A TW92127353 A TW 92127353A TW 200424219 A TW200424219 A TW 200424219A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Abstract
Description
200424219 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） 【發明所屬之技術領域】 本發明是有關一種感光度高的顯像邊緣突出的投射、 反射、半投射型液晶顯示器的濾色鏡用的感光性樹脂組成。 5【先前技術】 以往形成液晶顯示器的濾色鏡的方法有染色方法、印 刷方法、附著方式、喷墨（Ink-jet)法、顏料分散法等，但是 近來採用分辨力測試圖及製作方法簡單的顏料分散法，這 種方式應用於手機、筆記型電腦、指示器、電視等的液晶 10 顯示器的製造。 但是隨著指示器、電視等的色彩再現率（NTSC對比 色濃度）比筆記型電腦的液晶顯示器高，顏料的含量越來 越多，這在實際生產過程中需要很高的曝光量，以致顯像 時對於顯像邊緣(margin)及態樣(pattern)的直線性將造成不 15 好的影響。 以往使用的感光樹脂合成物一般由1)溶解於鹼性水 溶液的黏合劑；2)至少包括2個以上烯烴雙鍵的交聯性單 體；3)顏料；4)光聚合引發劑；以及5)溶劑等所組成， 而根據需要，更可包含增強與基板的黏附力的增強劑、為 20 穩定保管而使用的穩定劑、提高顏料分散性的分散劑等添 加劑。這些感光樹脂合成物一般因光而產生的光聚合引發 劑的基，而與交聯性單體形成雙鍵結合，在顯像過程中阻 止對懸浮液的溶解能力。但是這種結構隨著顏料的增加和 濾色鏡厚度的薄膜化，作為矩陣的黏結劑及單體的含量隨 ΣΙ'續次頁（發明說明頁不敷使用時，請註記並使用續頁） -6- 200424219 發明說明 著減少，這在形成態樣中與懸浮液的反應性及形成邊緣等 方面被認為係不可忽略的問題。 為解決上述問題，日本特開平8-278630號、6-1938 號及5-339356號和韓國發明專利公開第1995-702313號中 5 提出了利用感光性聚合物的製造方法。但是使用這種利用 聚合物的方法，會降低保管穩定性，且因顯像後形成殘影 的情形比較多，需要對其進行改善，此外對溶劑的溶解性 能不如以往的丙烯酸黏結劑。 10 【發明内容】 為解決上述以往技術中存在的問題，本發明提供一種 光（UV)硬化能力突出、與丙烯酸黏結劑的相溶性突出的 感光性聚合物及其共聚物。 本發明的另一個目的是提供一種以少量的曝光量即能 15 夠達到顯像性能高、保管穩定性突出的利用上述感光性聚 合物的樹脂組成。 為達到上述目的，本發明提供如下以化學式la或化學 式lb所表示的宏聚體。 [化學式la]200424219 发明 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings) [Technical field to which the invention belongs] The present invention relates to a high-sensitivity developing edge It consists of a photosensitive resin for color filters of a projection, reflection, and semi-projection type liquid crystal display. 5 [Prior art] In the past, methods for forming a color filter for a liquid crystal display include a dyeing method, a printing method, an attachment method, an ink-jet method, and a pigment dispersion method. However, recently, a resolution test chart and a simple method for producing pigments have been used. The dispersion method is used in the manufacture of liquid crystal 10 displays such as mobile phones, notebook computers, indicators, and televisions. However, as the color reproduction rate (NTSC contrast color density) of indicators, televisions, etc. is higher than that of the liquid crystal display of a notebook computer, the content of pigment is increasing, which requires a high exposure in the actual production process, so that the image is developed. The linearity of the development margin and pattern will cause a bad influence. Photosensitive resin compositions used in the past generally consist of 1) a binder dissolved in an alkaline aqueous solution; 2) a crosslinkable monomer including at least two or more olefinic double bonds; 3) a pigment; 4) a photopolymerization initiator; and 5 ), A solvent, etc., and may further include additives such as a reinforcing agent for enhancing adhesion to the substrate, a stabilizer used for stable storage of 20, a dispersant for improving pigment dispersibility, and the like. These photosensitive resin compositions generally form a base of a photopolymerization initiator due to light, and form a double bond with a crosslinkable monomer to prevent the ability to dissolve the suspension during development. However, with the increase of the pigment and the thinning of the thickness of the color filter, the content of the binder and monomer as a matrix will follow the ΣΙ 'continuation page (when the invention description page is insufficient, please note and use the continuation page) -6 -200424219 The invention illustrates reduction, which is considered to be a problem that cannot be ignored in terms of reactivity with suspensions and formation of edges during formation. In order to solve the above problems, Japanese Patent Laid-Open Nos. 8-278630, 6-1938, and 5-339356, and Korean Invention Patent Publication No. 1995-7023135 have proposed a manufacturing method using a photosensitive polymer. However, the use of this polymer method reduces storage stability, and there are many cases where afterimages are formed, and it needs to be improved. In addition, the solubility in solvents is not as good as conventional acrylic adhesives. [Summary of the Invention] In order to solve the problems existing in the above-mentioned prior art, the present invention provides a photosensitive polymer and a copolymer thereof having outstanding light (UV) curing ability and excellent compatibility with an acrylic adhesive. Another object of the present invention is to provide a resin composition using the above-mentioned photosensitive polymer, which can achieve high development performance and outstanding storage stability with a small amount of exposure. To achieve the above object, the present invention provides a macromer represented by the following chemical formula la or chemical formula lb. [Chemical formula la]
20 200424219 [化學式lb]20 200424219 [Chemical Formula lb]
發明說明_頁 上式中R1表示各個獨立的氫或者碳的數量為1〜2的烴 基； 5 R2表示被羥基取代或未被取代的碳的數量為1〜2的烴 基， 其中 a+b+c=卜 0.1<a<0.4, 0<b<0.5，0.1<c<0.5。 並且，本發明所提供之在濾色鏡用之感光型樹脂組 成，係為包含有： 10 1)以如下化學式la或化學式lb表示的宏聚體佔1〜30 重量百分比； 2) 至少包括2個以上烯烴雙鍵的交聯性單體佔5〜30 重量百分比； 3) 顏料佔10〜60重量百分比； 15 4)光聚合引發劑0.5〜5重量百分比； 5)溶劑佔20〜80重量百分比的一種濾色鏡用感光性樹 脂組成。 [化學式la] -8- 200424219Description of the Invention_ In the formula on the page, R1 represents each independent hydrogen or carbon group having 1 to 2 hydrocarbon groups; 5 R2 represents a hydrocarbon group having 1 to 2 carbon groups substituted or unsubstituted with hydroxyl groups, where a + b + c = Bu 0.1 < a < 0.4, 0 < b < 0.5, 0.1 < c < 0.5. In addition, the photosensitive resin composition for color filters provided by the present invention includes: 10 1) Macromers represented by the following chemical formula la or chemical formula lb account for 1 to 30 weight percent; 2) At least two or more 5 to 30 weight percent of crosslinkable monomers of olefin double bonds; 3) 10 to 60 weight percent of pigment; 15 4) 0.5 to 5 weight percent of photoinitiator; 5) 20 to 80 weight percent of solvent It consists of photosensitive resin for color filters. [Chemical Formula la] -8- 200424219
[化學式lb][Chemical formula lb]
發明說明續頁 上式中R1表示各個獨立的氫或者碳的數量為1〜2的烴 5 基； R2表示被羥基取代或未被取代的碳的數量為1〜2的烴 基， 其中 a+b+c=卜 0.1<a<0.4,0<b<0.5,0.1<c<0.5。 10 【實施方式】 以下對本發明進行更為詳細的說明。 本發明的特徵是，利用包含在光照下自行硬化的感光 性樹脂的上述化學式la或者化學式lb的宏聚體，提供一 種感光性高、顯像邊緣突出的投射、反射、半投射型液晶 15 顯示器的濾色鏡用的感光性樹脂組成（合成物）。 -9- 200424219 發明說明頁 在本發明的感光性樹脂合成物，1)上述化學式la或 化學式lb的宏聚體是溶於鹼性水溶液的樹脂，在溶劑中把 以下化學式2a或者2b所表示的感光性樹脂和酸基的烯烴 單體或不具有烯烴單體共聚而成。 [化學式2a]Description of the invention On the following page, in the formula, R1 represents each independent hydrogen or a hydrocarbon group having a carbon number of 1 to 2; R2 represents a hydrocarbon group having a carbon number of 1 to 2 substituted or unsubstituted by a hydroxyl group, where a + b + c = bu 0.1 < a < 0.4,0 < b < 0.5,0.1 < c < 0.5. [Embodiment] The present invention will be described in more detail below. The present invention is characterized in that it uses a macropolymer of the chemical formula 1a or the chemical formula 1b containing a photosensitive resin that hardens by itself under light to provide a projection, reflection, and semi-projection type liquid crystal display 15 with high sensitivity and prominent development edges. Composition (composite) of photosensitive resin for color filters. -9- 200424219 Description page of the invention In the photosensitive resin composition of the present invention, 1) The macromer of the chemical formula la or chemical formula lb is a resin soluble in an alkaline aqueous solution, and the following chemical formula 2a or 2b is expressed in a solvent. A photosensitive resin is copolymerized with an acid-based olefin monomer or an olefin monomer having no olefin monomer. [Chemical Formula 2a]
[化學式2b][Chemical Formula 2b]
上式中，R1表示各個獨立的氫或者碳的數量為1〜2的 10 烴基；In the above formula, R1 represents each independent hydrogen or carbon number of 1 to 10 hydrocarbon groups;
R2表示被羥基取代或未被取代的碳的數量為1〜2的烴 基； 上述化學式2a或化學式2b的感光性樹脂官能團的具 體例為，查耳酮(Chalcone)或肉桂酸(Cinnamate)樹脂。上述 15 化學式2a或化學式2b的含量最好是10〜50重量百分比。 上述具有烯烴酸基的單體有丙烯酸、甲基丙烯酸、衣 康酸、馬來酸、富馬酸、乙酸乙烯酯或者他們的酸酐形態， 或者2-乙氧基丙稀酸鄰苯二曱酸氫（2-acrylooxyethyl -10- 200424219 發明說明 hydrogenphthalate)、2-丙氧基丙稀酸鄰苯二甲酸氫 (2-acrylooxypropyl hydrogenphthalate)、2-丙氧基己基丙稀 酸鄰苯二曱酸氫(2-acrylooxypropylhexa hydrogenphthalate) 等。上述烯烴酸基單體的含量可望在10〜40重量百分比， 5 最好是在20〜30重量百分比。上述具有酸基的單體含量若 小於10重量百分比，存在降低感光性樹脂對鹼性懸浮液溶 液的溶解能力的傾向，若超過40重量百分比，會在鹼性懸 浮液顯像時發生態樣的脫落及剝落現象。 上述不具有酸性基的單體有異-丙烯酸丁酯、三級-丙烯 10 酸丁酯、丙烯酸月桂酯、丙烯酸烷基酯、十八烷基丙烯酸 S旨、丙烤酸環己醋、丙埽酸異冰片醋（is〇b〇rnyl acrylate)、 丙稀酸笨酯、2-羥基丙烯酸酯、三甲氧基丙烯酸丁酯、卡 比醇丙婦酸乙酯（ethylcarbitol aery late)、笨氧基丙烯酸乙 醋、4-羥基丙烯酸丁酯、苯氧基聚乙二醇丙烯酸酯、羥基 15 丙烯乙酯、2-羥基丙烯丙酯、2-乙氧基丙烯酸2-羥基鄰苯 二甲酸丙酯（2-acryloxyethyl 2-hydroxypropylphthalate)、2· 經基-3-笨氧基丙烯酸丙酯及其甲基丙稀酸酯類；3氟丙稀 酸乙酯、4-氟丙烯酸丙酯等的鹵系列化合物及其他們的甲 基丙稀酸酯類；像三乙矽氧烷丙烯酸乙酯包括矽氧烧基的 20丙烯酸鹽及其異丁烯酸鹽；苯乙烯、4-甲氧基苯乙烯等的 具有芳香烴的烯族等，或可以把上述單體單獨或者二種以 上混合使用。上述不具有單體的含量佔高分子組成中1〇〜8〇 重量百分比，最好是佔20〜70重量百分比。這些單體的含 量若不到10重量百分比，顯像工程中會降低與玻璃面的緊 -11- 200424219 發明說明 密結合性而增加態樣的剝落，降低形成態樣的直進性，若 超過80重量百分比會增加顯像時間。 溶解於本發明的鹼性水溶液的宏聚體的重量平均分子 量在10000〜80000，最好是在15000〜50000。上述宏聚體的 5 重量平均分子量超過80000會降低顯像時間、產生殘影， 重量平均分子量不到10000，會使顯影邊緣（development margin)消失。 上述化學式la或者化學式lb的宏聚體含量佔整個感 光性樹脂組成的5〜30重量百分比，且根據含量顯示感光度 10 和硬化程度的增加。上述宏聚體的含量不到1重量百分 比，形成的態樣的耐熱性及耐化學性會存在問題，超過30 重量百分比，會出現隨著固形粉增加黏度上升的問題。 在本發明的感光性樹脂合成物中至少具有2個以上的 烯烴雙鍵的交聯性單體有1，各丁二醇二丙烯酸酯、1，3-丁二 15 醇二丙烯酸酯、乙二醇二丙烯酸酯、季戊四醇四丙烯酸酯、 三乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、雙季戊四醇 二丙烯酸酯、山梨糖醇三丙烯酸酯、雙酚A二丙烯酸酯衍 生物、三羥曱基丙烷三丙烯酸酯、雙季戊四醇聚丙烯酸酯 及他們的甲基丙稀酸甲酯類。上述至少包括2個以上的烯 20 烴雙鍵的交聯性單體佔整個感光性樹脂合成物的5〜30重 量百分比，最好是5〜20重量百分比。上述交聯性單體的含 量不到5重量百分比，與感光性樹脂的低硬化度很難實現 態樣，超過30重量百分比會因高硬化度，顯像時會出現態 樣的剝落現象，態樣的直進性降低。 -12 - 200424219 發明說明_胃 在本發明的感光性樹脂合成物中的顏料可以使用有機 顏料或者無機顏料，這種有機㈣的具體例子冑CI顏料 黃83、C.L顏料黃150'CU.顏料黃138 C I顏料黃128、 C.I.顏料撥43、C.I.顏料紅177、CJ顏料紅2〇2 〇：1顏 料紅209、C.L顏料紅254、c丄顏料紅255、c丄顏料綠 7、〇丄顏料綠36、C丄顏料藍15、cj顏料藍i53、CI 顏料藍15:4、C.L顏料藍15:6、C I顏料紫23 cj顏料 黑l、c.l.顏料黑7等。無機顏料可以用氧化敛黑欽、 10 石反黑等。為了讓各種顏色組合’可以使用i種或2種以上 混合使用。上述顏料的含量佔整個感光性樹脂合成物含量 的10〜60重量百分比。 在本發明的光聚合引發劑可以採用三嗪系列化合物、 乙醯笨系列化合物、氧雜蒽酮系列化合物、苯偶姻系列化 合物、咪唑系列化合物所組成的族群中選擇丨種或以上。 15上述光聚合引發劑的具體例子有，2,4-雙-三氯甲基-6-P-甲 氧基苯乙烯基-s-三嗪、2-p-甲氧基苯乙烯基雙三氯甲基 三嗪、2,4-三氣甲基-6-三嗪、2,4-三氣甲基4-甲基萘基-6-三嗪、苯甲酮、p-(二乙氨基）笨甲酮、2,2-二氣_4_苯氧基 苯乙_、2,2-二乙氧基苯乙_、2,2-二丁氧基苯乙酮、2-經 20 基-2-曱基苯乙 _ (2-hydroxy-2-methylpropi〇phenone)、p-t-丁基三氯苯乙酮、2-甲基硫代二苯並π比喃酮 (2-methylthioxanthone)、2-異丁基硫代二苯並吡喃酮 (2-isobutylthioxanthone)、2-十二烷基硫代二苯並吡喃酮 (2-dodecylthioxanthone)、2,4-二甲基硫代二苯並吡喃酮 -13- 200424219 發明說明#賣Μ (2,4-dimethylthioxanthone)、2,4-二乙基硫代二苯並吼喃_ (2,4-diethylthioxanthone)、2,2-雙-2-氣苯 _4,5,4,5-四苯基-2-1， 2-二口米嗤（2,2-bis-2-cholorophenyl-4,5,4,5-tetraphenyl-2-l， 2-biimidazole)化合物等。 5 上述光聚合引發劑的含量佔感光性樹脂合成物的 0.5〜5重量百分比，最好是1〜2重量百分比。上述光聚合引 發劑的含量不到0.5重量百分比’因低感光度很難顯示正 常的態樣對態樣的直進性也不利，超過5重量百分比，會 導致保管穩定性發生問題，因高硬化度，在顯像時會加深 10 態樣的剝落現象，形成的態樣之外的部分容易產生殘影。 本發明的感光性樹脂合成物中’溶劑是按照溶解性、 顏料分散性、塗層性所選定，具體之例子有乙二醇一甲醚 醋酸鹽、丙二醇甲醚醋酸鹽、丙二醇甲醚醋酸鹽、丙二醇 一乙醚醋酸鹽、二乙二醇二甲醚、二乙二醇亞甲基二乙醚、 15 環己酮、3-甲氧基丙酸、3-乙氧基丙酸、3_乙氧基丙酸乙酯 等，可以把上述溶劑單獨或2種以上混合使用。上述溶劑 的含量佔整個感光性樹脂合成物含量的20〜80重量百分 比。 並且，本發明的感光性樹脂合成物可以包含為提高與 20顏料的分散性的分散劑或為提高畫層性能提高的添加劑， 例如，聚酯基分散劑、聚乙烯基分散劑、矽樹脂基表面活 性劑及氟基表面活性劑，其佔整個感光性樹脂合成物的 〇·〇1〜1重量百分比。 200424219 發明說明_頁 以下結合實施例對本發明進行更為詳細的說明，但不 表示本發明僅限於下述實施例。在下述實施例中，如沒有 另行說明，百分比及混合比表示重量百分比。 實施例1 5 1)溶解於鹼性水溶液的宏聚體，是由甲基丙稀酸苯酯 /甲基丙烯酸/羥基乙基丙烯酸肉桂酯的共聚物（在丙二醇甲 醚醋酸鹽溶液的溶解下共聚物比例為60/20/20，固形粉的 含量佔35重量百分比，重量平均分子量為30000的共聚物） 佔15重量百分比，2)至少包括2個以上烯烴雙鍵的宏聚 10 體，二異戊四醇丙烯酸己酯（dipentaerythritol hexaacrylate) 佔5重量百分比，3)顏料使用C.I·顏料紅254，佔40重 量百分比，4 )光聚合引發劑使用Irgacure369 ( Ciba Speciality Chemicals Ltd·製造）佔 1 重量百分比及 4, 4’-雙-二乙氨基苯曱佔1重量百分比，5)溶劑使用丙二醇曱醚醋 15 酸鹽佔28重量百分比及環己酮佔1〇重量百分比，把上述 原料混合製成液體狀態的感光性樹脂合成物。 實施例2 1 )溶解於鹼性水溶液的宏聚體，是由苯乙烯/曱基丙烯 酸/羥基丁基丙烯酸肉桂酯的共聚物（在丙二醇甲醚醋酸鹽 20 溶液的溶解下共聚物比例為60/20/20，固形粉的含量佔35 重量百分比，重量平均分子量為30000的共聚物）佔15重 量百分比，2)至少包括2個以上烯烴雙鍵的宏聚體，二異 戊四醇丙烯酸己酯佔5重量百分比，3)顏料使用C.I·顏料 黃138佔20重量百分比，4)光聚合引發劑使用Irgacure369 -15- 200424219 發明說明續頁 (Ciba Speciality Chemicals Ltd·製造）佔 1 重量百分比及 4, 4*-雙-二乙氨基苯甲酮佔1重量百分比，5)溶劑使用丙 二醇曱醚醋酸鹽佔18重量百分比及環己酮佔10重量百分 比，把上述原料混合製成液體狀態的感光性樹脂合成物。 5 實施例3 1 )溶解於鹼性水溶液的宏聚體，是由苯乙烯/甲基丙烯 酸/羥基丁基丙烯酸肉桂酯的共聚物（在丙二醇甲醚醋酸鹽 溶液的溶解下共聚物比例為50/25/25，固形粉的含量佔35 重量百分比，重量平均分子量為30000的共聚物）佔15重 10 量百分比，2)至少包括2個以上烯烴雙鍵的宏聚體，二異 戊四醇丙烯酸己酯佔5重量百分比，3)顏料使用C.I.顏料 藍15··6佔35重量百分比及C.I.顏料紫23佔5重量百分 比，4)光聚合引發劑使用 Irgacure369 ( Ciba Speciality Chemicals Ltd·製造）佔1重量百分比及4,4^雙-二乙氨基苯 15 甲酮佔1重量百分比，5)溶劑使用丙二醇甲醚醋酸鹽佔 28重量百分比及環己酮佔1〇重量百分比，把上述原料混 合製成液體狀態的感光性樹脂合成物。 實施例4 1)溶解於鹼性水溶液的宏聚體，是由甲基丙稀酸苯酯 20 /甲基丙烯酸/羥基苯基丙烯酸查耳酮酯的共聚物（在丙二醇 曱醚醋酸鹽溶液的溶解下共聚物比例為50/25/25,固形粉 的含量佔35重量百分比，重量平均分子量為30000的共聚 物）佔15重量百分比，2)至少包括2個以上烯烴雙鍵的 宏聚體，二異戊四醇丙烯酸己酯佔5重量百分比，3)顏料 -16- 200424219 發明說明續頁 使用碳黑（20%溶液）佔40重量百分比，4)光聚合引發劑 使用 Irgacure369(Ciba Speciality Chemicals Ltd·製造）佔 1 重量百分比及4,4f-雙-二乙氨基苯甲酮佔1重量百分比，5) 溶劑使用丙二醇甲醚醋酸鹽佔28重量百分比及環己酮佔 5 重量百分比，把上述原料混合製成液體狀態的感光性樹 脂合成物。 比較例1 與上述實施例2相同的組成和含量，但1)溶解於水溶 液黏結劑採用苯乙烯/甲基丙烯酸的共聚物（在丙二醇甲醚 10 醋酸鹽溶液的溶解下共聚物比例為70/30,固形粉的含量佔 35重量百分比，重量平均分子量為30000的共聚物）15重 量百分比，製造感光性樹脂合成物。 比較例2 與上述實施例4相同的組成和含量，但1)溶解於水溶 15 液黏結劑採用t-丙烯酸丁酯/曱基丙烯酸/水凝膠（2-羥基乙 基甲基丙歸酸鹽（2-hydroxyethylmethacrylate，HEMA))的 共聚物（在丙二醇甲醚醋酸鹽溶液的溶解下共聚物比例為 60/20/20，固形粉的含量佔35重量百分比，重量平均分子 量為30000的共聚物）15重量百分比，製造感光性樹脂合 20 成物。 特性比較 對上述實施例1至4的包含有感光性樹脂的合成物和 沒有包含感光性樹脂的比較例1至2的合成物進行顯像特 性及態樣的直進性的評價。 -17- 200424219 發明說明$賣;Μ 1)顯像特性評價 把上述通過實施例和比較例所得到的感光性合成物放 到玻璃面上旋塗方式塗層，塗層厚度為2μιη，80°C的溫度 條件下在加熱板上乾燥2分鐘獲得塗層膜。 5 然後把遮光模設置在上述膜上之後，利用放出200nmR2 represents a hydrocarbon group having 1 to 2 carbon atoms substituted or unsubstituted. Specific examples of the photosensitive resin functional group of the above Chemical Formula 2a or Chemical Formula 2b are Chalcone or Cinnamate resin. The content of the above 15 chemical formula 2a or 2b is preferably 10 to 50% by weight. The monomers having an olefinic acid group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetate or their anhydride forms, or 2-ethoxyacrylic acid phthalic acid Hydrogen (2-acrylooxyethyl -10- 200424219 Description of the invention, hydrogenphthalate), 2-acrylooxypropyl hydrogen phthalate, 2-propoxyhexyl propionic acid phthalate ( 2-acrylooxypropylhexa hydrogenphthalate). The content of the olefinic acid-based monomer is expected to be 10 to 40 weight percent, and 5 is preferably 20 to 30 weight percent. If the content of the monomer having an acid group is less than 10% by weight, the solubility of the photosensitive resin in the alkaline suspension solution tends to decrease. If it exceeds 40% by weight, the appearance of the alkaline suspension will appear during development. Shedding and peeling. The monomers having no acidic group include iso-butyl acrylate, tertiary-propylene 10-butyl acrylate, lauryl acrylate, alkyl acrylate, octadecyl acrylic acid, cyclohexanyl acrylate, and propionate. Isobornyl acrylate, isopropyl acrylate, 2-hydroxy acrylate, trimethoxybutyl acrylate, ethylcarbitol aery late, ethyl oxyacrylic acid Ethyl acetate, 4-hydroxy butyl acrylate, phenoxy polyethylene glycol acrylate, hydroxy 15 propylene ethyl, 2-hydroxy propylene propyl, 2-ethoxy acrylate 2-hydroxy phthalate (2 -acryloxyethyl 2-hydroxypropylphthalate), 2 · Ethyl-3-benzyloxypropyl acrylate and its methyl acrylates; halogen series compounds such as ethyl 3fluoropropionate and 4-fluoropropyl acrylate; and Their methyl methacrylates; like triethoxyethyl acrylate, including 20 acrylates and their methacrylates; styrene, 4-methoxystyrene and other aromatic hydrocarbons The olefins may be used alone or in combination of two or more kinds. The content of the non-monomer described above accounts for 10 to 80 weight percent in the polymer composition, and preferably 20 to 70 weight percent. If the content of these monomers is less than 10% by weight, the tightness with the glass surface will be reduced in the development process. 11-200424219 Description of the invention The close bonding will increase the peeling of the appearance and reduce the straightness of formation. If it exceeds 80, Weight percent increases development time. The weight average molecular weight of the macromer dissolved in the alkaline aqueous solution of the present invention is 10,000 to 80,000, preferably 15,000 to 50,000. When the macromer has a weight average molecular weight of more than 80,000, the development time is reduced, and afterimages are generated. When the weight average molecular weight is less than 10,000, the development margin disappears. The content of the macromer of the chemical formula 1a or the chemical formula 1b accounts for 5 to 30% by weight of the entire photosensitive resin composition, and an increase in the sensitivity 10 and the degree of hardening is shown according to the content. The content of the macropolymer is less than 1% by weight, and there is a problem in the heat resistance and chemical resistance of the formed state. If it exceeds 30% by weight, the viscosity rises with the increase of the solid powder. The crosslinkable monomer having at least two olefinic double bonds in the photosensitive resin composition of the present invention includes 1, each of butanediol diacrylate, 1,3-butanediol 15 and diethylene glycol. Alcohol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trihydroxy Fluorenyl propane triacrylate, dipentaerythritol polyacrylate and their methyl methacrylates. The above-mentioned crosslinkable monomer including at least two olefinic hydrocarbon double bonds accounts for 5 to 30 weight percent of the entire photosensitive resin composition, and preferably 5 to 20 weight percent. The content of the above-mentioned crosslinkable monomer is less than 5 weight percent, and it is difficult to achieve a low degree of curing with the photosensitive resin. If it exceeds 30 weight percent, the phenomenon of peeling will occur during development due to the high degree of curing. Such straightness is reduced. -12-200424219 Description of the invention _ Stomach The organic resin or inorganic pigment can be used as the pigment in the photosensitive resin composition of the present invention. Specific examples of this organic ㈣ CI Pigment Yellow 83, CL Pigment Yellow 150'CU. Pigment Yellow 138 CI Pigment Yellow 128, CI Pigment Dial 43, CI Pigment Red 177, CJ Pigment Red 2 0 2 0: 1 Pigment Red 209, CL Pigment Red 254, C 丄 Pigment Red 255, C 丄 Pigment Green 7, 丄 Pigment Green 36. C 丄 pigment blue 15, cj pigment blue i53, CI pigment blue 15: 4, CL pigment blue 15: 6, CI pigment purple 23, cj pigment black 1, cl pigment black 7, and the like. Inorganic pigments can be blackened with oxidation, 10 stone anti-black and so on. In order to make various color combinations', i kinds or two or more kinds can be used in combination. The content of the above pigments is 10 to 60% by weight based on the entire content of the photosensitive resin composition. The photopolymerization initiator of the present invention may be selected from the group consisting of triazine series compounds, acetophenone series compounds, xanthone series compounds, benzoin series compounds, and imidazole series compounds. 15 Specific examples of the photopolymerization initiator include 2,4-bis-trichloromethyl-6-P-methoxystyryl-s-triazine and 2-p-methoxystyrylbistrizine Chloromethyltriazine, 2,4-trifluoromethyl-6-triazine, 2,4-trifluoromethyl 4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino ) Benzophenone, 2,2-digas_4_phenoxyacetophenone_, 2,2-diethoxyphenethene_, 2,2-dibutoxyacetophenone, 2-mer 20 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, 2-methylthioxanthone, 2-methylthioxanthone, 2 -2-isobutylthioxanthone, 2-dodecylthioxanthone, 2,4-dimethylthiodibenzo Pyranone-13- 200424219 Description of the invention # 卖 Ｍ (2,4-dimethylthioxanthone), 2,4-diethylthioxanthone (2,4-diethylthioxanthone), 2,2-bis-2 -Gasbenzene_4,5,4,5-tetraphenyl-2-1, 2-tetraphenyl-2- (2,2-bis-2-cholorophenyl-4,5,4,5-tetraphenyl-2-l , 2-biimidazole) compounds. 5 The content of the photopolymerization initiator is 0.5 to 5 weight percent of the photosensitive resin composition, and preferably 1 to 2 weight percent. The content of the above-mentioned photopolymerization initiator is less than 0.5% by weight. 'It is difficult to show normal appearance due to low sensitivity. The straightness of the appearance is also unfavorable. If it exceeds 5% by weight, it may cause storage stability problems and high hardening. During the development, the peeling phenomenon of 10 aspects will be deepened, and the part other than the formation will easily cause afterimages. The solvent in the photosensitive resin composition of the present invention is selected based on solubility, pigment dispersibility, and coating properties. Specific examples include ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, and propylene glycol methyl ether acetate. , Propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methylene diethyl ether, 15 cyclohexanone, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Ethyl propionate, etc., may be used alone or as a mixture of two or more of these solvents. The content of the above-mentioned solvent accounts for 20 to 80% by weight of the entire photosensitive resin composition. In addition, the photosensitive resin composition of the present invention may include a dispersant for improving dispersibility with 20 pigments or an additive for improving performance of a paint layer, for example, a polyester-based dispersant, a polyethylene-based dispersant, and a silicone resin-based dispersant. The surfactant and the fluorine-based surfactant account for 0.001 to 1 weight percent of the entire photosensitive resin composition. 200424219 Description of the invention_page The following describes the present invention in more detail with reference to the examples, but it does not mean that the present invention is limited to the following examples. In the following examples, percentages and mixing ratios represent weight percentages unless otherwise specified. Example 1 5 1) A macromer dissolved in an alkaline aqueous solution, which is a copolymer of phenyl methacrylate / methacrylic acid / cinnamo hydroxyethyl acrylate (under the dissolution of propylene glycol methyl ether acetate solution) The copolymer ratio is 60/20/20, the solid powder content is 35 weight percent, the copolymer with a weight average molecular weight of 30,000) is 15 weight percent, 2) the macropolymer 10 includes at least 2 olefinic double bonds, Dipentaerythritol hexaacrylate is 5 weight percent, 3) CI · Pigment Red 254 is used as the pigment, 40% by weight, 4) Irgacure369 (made by Ciba Speciality Chemicals Ltd.) is used as the photopolymerization initiator, and 1 weight is used Percentage and 4, 4'-bis-diethylaminophenylhydrazone accounted for 1% by weight, 5) propylene glycol ether ether vinegar 15 acid salt accounted for 28% by weight and cyclohexanone accounted for 10% by weight, the above raw materials were mixed and prepared Liquid resin composition. Example 2 1) The macromer dissolved in an alkaline aqueous solution is a copolymer of styrene / fluorenyl acrylic acid / hydroxybutyl cinnamyl acrylate (the proportion of the copolymer after dissolution of the propylene glycol methyl ether acetate 20 solution is 60 / 20/20, the solid powder content is 35 weight percent, the copolymer with a weight average molecular weight of 30,000) accounts for 15 weight percent, 2) the macropolymer including at least two olefinic double bonds, Ester accounts for 5 weight percent, 3) CI · Pigment Yellow 138 accounts for 20 weight percent, 4) Photopolymerization initiator uses Irgacure369 -15- 200424219 Description of the invention Continuation sheet (Ciba Speciality Chemicals Ltd.) accounts for 1 weight percent and 4 , 4 * -bis-diethylaminobenzophenone accounts for 1% by weight, 5) the solvent uses propylene glycol ether ether acetate 18% by weight and cyclohexanone 10% by weight, and the above raw materials are mixed to form a liquid state of light sensitivity Resin composition. 5 Example 3 1) The macromer dissolved in an alkaline aqueous solution is a copolymer of styrene / methacrylic acid / cinnamo hydroxybutyl acrylate (the proportion of the copolymer after dissolution of the propylene glycol methyl ether acetate solution is 50 / 25/25, the solid powder content is 35 weight percent, the copolymer with a weight average molecular weight of 30,000) accounts for 15 weight and 10 weight percent, 2) the macropolymer including at least 2 olefinic double bonds, diisopentyl alcohol Hexyl acrylate accounts for 5% by weight, 3) CI Pigment Blue 15 ·· 6 accounts for 35% by weight and CI Pigment Violet 23 accounts for 5% by weight, 4) Photopolymerization initiator uses Irgacure369 (manufactured by Ciba Speciality Chemicals Ltd.) 1% by weight and 4,4 ^ bis-diethylaminobenzene 15 ketone 1% by weight, 5) the solvent uses propylene glycol methyl ether acetate 28% by weight and cyclohexanone 10% by weight, the above raw materials are mixed to prepare A photosensitive resin composition in a liquid state. Example 4 1) A macromer dissolved in an alkaline aqueous solution is a copolymer of phenyl methacrylate 20 / methacrylic acid / chalcone hydroxyphenyl acrylate (in a solution of propylene glycol ether ether acetate) The proportion of the copolymer under dissolution is 50/25/25, the content of solid powder accounts for 35 weight percent, and the copolymer with a weight average molecular weight of 30,000) accounts for 15 weight percent; Hexyl acrylate diisopentaerythritol 5% by weight, 3) Pigment-16- 200424219 Description of the invention Continuation sheet uses carbon black (20% solution) 40% by weight, 4) Photopolymerization initiator uses Irgacure369 (Ciba Speciality Chemicals Ltd · Manufacturing) 1% by weight and 4,4f-bis-diethylaminobenzophenone 1% by weight, 5) Solvent using propylene glycol methyl ether acetate 28% by weight and cyclohexanone 5% by weight. They are mixed to form a liquid photosensitive resin composition. Comparative Example 1 Same composition and content as in Example 2 above, but 1) A styrene / methacrylic acid copolymer was used for dissolving in an aqueous solution binder (the ratio of the copolymer after dissolution of propylene glycol methyl ether 10 acetate solution was 70 / 30. The solid powder content is 35 weight percent, and the copolymer having a weight average molecular weight of 30,000) is 15 weight percent, and a photosensitive resin composition is manufactured. Comparative Example 2 Same composition and content as in Example 4 above, but 1) dissolved in water 15 liquid binder using t-butyl acrylate / fluorenyl acrylic acid / hydrogel (2-hydroxyethyl methylpropionate) (2-hydroxyethylmethacrylate, HEMA)) copolymer (copolymer ratio of 60/20/20 after dissolution of propylene glycol methyl ether acetate solution, solid powder content of 35 weight percent, copolymer with weight average molecular weight of 30,000) 15% by weight to produce a photosensitive resin composite. Comparison of characteristics The compositions containing the photosensitive resin of Examples 1 to 4 and the compositions of Comparative Examples 1 to 2 not containing the photosensitive resin were evaluated for development characteristics and straightness of appearance. -17- 200424219 Description of the invention $ Sell; M 1) Evaluation of development characteristics The photosensitive composition obtained by the above examples and comparative examples was placed on a glass surface by a spin coating method, and the coating thickness was 2 μm, 80 °. The coating film was obtained by drying on a hot plate under a temperature condition of C for 2 minutes. 5 After setting the light-shielding mode on the film, use 200nm
至400nm波長的超高壓水銀燈，以365nm為基準下曝光一 定時間使其成為200mj/cm2,利用KOH顯像液（東進 SemiChem株式會社製造，DCD-260CF)通過空心光錐進行 顯像。通過顯像的微態樣的程度和態樣末端部分的直進性 10 評價了顯像性能，實驗結果如下表1所述，下表1中〇表 示態樣末端部分的直進性的優秀、△表示直進性的不佳、 X表示態樣被顯像液所清除掉。 表1An ultra-high pressure mercury lamp with a wavelength of 400 nm was exposed at a time of 365 nm to make it 200 mj / cm2, and developed using a KOH imaging solution (manufactured by Tojin SemiChem Co., Ltd., DCD-260CF) with a hollow light cone. The imaging performance was evaluated based on the extent of the microscopic image developed and the straightness of the end portion of the image. The experimental results are shown in Table 1 below. In the following table, 0 indicates the excellent straightness of the end portion of the sample, and △ indicates Poor straightness, X indicates that the appearance was removed by the developer. Table 1
實施例 實施例 實施例 實施例 比較例 比較例 1 2 3 4 1 2 態樣幅 100 〇 〇 〇 〇 Δ Δ 度（μπι) 50 〇 〇 〇 〇 X X 20 〇 〇 〇 〇 X X 察看上表，本發明的實施例1至4在低曝光量顯示出 15 優秀的顯像效果，但比較例1至2中顯像性極其不佳。 2)保管穩定性的評價 通過上述實施例所製造的感光性樹脂，80°C的溫度條 件下在密閉的加熱爐裏10天内以2日為間隔拿出後測試塗 層後的厚度及顯像評價ΙΟΟμπι圖形成型後態樣的直進性， -18- 200424219 發明說明$賣頁 實驗結果如下表2所示。下表2中〇表示初期沒有狀態變 化的情況，△表示塗層後厚度有變化，但顯像後態樣的直 進性良好的情況，X表示塗層後其厚度有變化，態樣的直 進性變壞的情況。 5 表2 實施例1 實施例2 實施例3 實施例4 態樣幅 度（μπι) 2曰 〇 〇 〇 〇 4曰 〇 〇 〇 〇 6曰 〇 〇 〇 〇 8曰 〇 〇 〇 〇 10曰 〇 Δ 〇 △ 察看上表2,本發明的實施例1至4顯示其保管穩定性 優秀。EXAMPLES EXAMPLES EXAMPLES EXAMPLES COMPARATIVE EXAMPLES COMPARATIVE EXAMPLES 1 2 3 4 12 2 Dimensions of 100 000 00 Δ Δ Degrees (μπι) 50 000 00XX 20 00 00XX Take a look at the above table, the present invention Examples 1 to 4 exhibited excellent developing effects at a low exposure, but Comparative Examples 1 to 2 had extremely poor developability. 2) Evaluation of storage stability The photosensitive resin manufactured in the above example was tested at a temperature of 80 ° C in a closed heating furnace for 10 days after taking it out at intervals of 2 days to measure the thickness and development of the coating. Assess the linearity of the appearance of the 100μm pattern after forming, -18- 200424219 Description of the invention The results of the experiment of selling pages are shown in Table 2 below. In Table 2 below, 0 indicates that there is no state change at the initial stage, △ indicates that the thickness changes after coating, but the straightness of the appearance after development is good, and X indicates that the thickness changes after coating, and the straightness of appearance Worsening situation. 5 Table 2 Example 1 Example 2 Example 3 Example 4 Amplitude of appearance (μπι) 2 〇 〇 〇 〇 4 〇 〇 〇 〇 〇 〇 〇 0 〇 〇 〇 〇 〇 10 〇 〇 Δ 〇 〇 △ Looking at Table 2 above, Examples 1 to 4 of the present invention show excellent storage stability.
如上所述，本發明的感光性樹脂合成物使用了可以通 過光照自行進行交鍵的感光性樹脂基的樹脂，可以在包含 10 高濃度顏料或者使用黑顏料等的顯像性能不佳的情況下， 可以在低曝光量下顯示出優秀的顯像性能，其保管穩定性 優秀，可以在包括濾色鏡的LCD製造工程中有效運用。 -19-As described above, the photosensitive resin composition of the present invention uses a photosensitive resin-based resin capable of self-crosslinking by irradiation with light. It can be used in the case of poor development performance including 10 high-concentration pigments or the use of black pigments. It can show excellent developing performance under low exposure, its storage stability is excellent, and it can be effectively used in LCD manufacturing processes including color filters. -19-
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| KR10-2002-0060604A KR100481014B1 (en) | 2002-10-04 | 2002-10-04 | Photosensitive resin composition using photopolymer |
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| JP (1) | JP2004124096A (en) |
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| KR100468398B1 (en) * | 2002-10-22 | 2005-01-27 | 엘지전선 주식회사 | Polyacrylate polymers composition for photoinduced liquid crystal alignment through co-polymerization, preparation method of the film for photoinduced liquid crystal thereby and the liguid crystal cell using the film |
| JP4601267B2 (en) * | 2003-06-20 | 2010-12-22 | 東洋インキ製造株式会社 | Photosensitive black composition, black matrix substrate and color filter using the same |
| JP4864375B2 (en) * | 2004-08-09 | 2012-02-01 | ドンジン セミケム カンパニー リミテッド | Photosensitive resin composition for spacer, spacer and liquid crystal display element |
| JP4677262B2 (en) * | 2005-03-24 | 2011-04-27 | 東洋インキ製造株式会社 | Photocurable coloring composition and color filter formed using the same |
| JP4887486B2 (en) * | 2005-11-08 | 2012-02-29 | 国立大学法人東京工業大学 | Chalcone analog |
| KR101306153B1 (en) * | 2006-08-25 | 2013-09-10 | 주식회사 동진쎄미켐 | Photosensitive resin composition |
| JP5487368B2 (en) * | 2008-11-17 | 2014-05-07 | 地方独立行政法人大阪府立産業技術総合研究所 | Photoresist composition |
| JP2010271729A (en) * | 2010-07-05 | 2010-12-02 | Toyo Ink Mfg Co Ltd | Photocurable colored composition and color filter formed using the same |
| KR101443757B1 (en) | 2010-11-08 | 2014-09-25 | 제일모직 주식회사 | Photosensitive resin composition for color filter and color filter using same |
| WO2013031736A1 (en) * | 2011-08-30 | 2013-03-07 | 旭硝子株式会社 | Negative photosensitive resin composition, partition wall, black matrix and optical element |
| KR101674990B1 (en) | 2012-12-07 | 2016-11-10 | 제일모직 주식회사 | Photosensitive resin composition for color filter, and color filter using the same |
| KR20150029921A (en) * | 2013-09-11 | 2015-03-19 | 동우 화인켐 주식회사 | A colored photosensitive resin composition for forming the frontal light-shielding layer of a display device |
| KR20200092131A (en) | 2019-01-24 | 2020-08-03 | 전백원 | Frying pan handle automatic assembly device |
| CN112812347B (en) * | 2021-02-23 | 2022-08-30 | 新纶新材料股份有限公司 | Optical thin film material, preparation method thereof and polarizer |
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| JPS55118911A (en) * | 1979-03-06 | 1980-09-12 | Agency Of Ind Science & Technol | Photosensitive resin composition |
| JPS6036503A (en) * | 1983-08-10 | 1985-02-25 | Agency Of Ind Science & Technol | Photosensitive resin |
| JPH0745533B2 (en) * | 1986-02-19 | 1995-05-17 | 新技術事業団 | Photosensitive resin and method for producing the same |
| JPS63254443A (en) * | 1987-04-13 | 1988-10-21 | Fuji Photo Film Co Ltd | Photosensitive composition |
| JPH06194515A (en) * | 1992-12-25 | 1994-07-15 | Hitachi Ltd | Photosensitive resin for forming color filter |
| US5641594A (en) * | 1993-12-27 | 1997-06-24 | Hoechst Japan Limited | Colored, photosensitive resin composition |
| 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 |
| JP3730318B2 (en) * | 1996-05-31 | 2006-01-05 | 日本合成化学工業株式会社 | Photosensitive resin composition and laminate using the same |
| JPH1010315A (en) * | 1996-06-27 | 1998-01-16 | Hitachi Chem Co Ltd | Photosensitive film for color filters and production of color filters by using the same |
| US6433118B1 (en) * | 1998-10-15 | 2002-08-13 | Mitsui Chemicals, Inc. | Copolymer, a manufacturing process therefor and a solution containing thereof |
| DE60020762T2 (en) * | 1999-02-25 | 2006-05-04 | Dai Nippon Printing Co., Ltd. | Photosensitive resin composition, color filter and copolymer resin suitable therefor |
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| KR20040031227A (en) | 2004-04-13 |
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| CN100334506C (en) | 2007-08-29 |
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