TWI384008B - A photosensitive resin and a photosensitive resin composition using the same - Google Patents
A photosensitive resin and a photosensitive resin composition using the same Download PDFInfo
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- 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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Description
本發明係關於一種具有芴骨架之感光性樹脂及使用此之感光性樹脂組成物，更詳而言之，係有關一種感光性樹脂組成物，其係具有各種之優異性質，可以低成本容易地製造之感光性樹脂及利用此之用以調製液晶顯示器或電子零件等的層間絕緣膜或保護膜(例如彩色濾光片、液晶顯示元件、積體電路元件、固體攝影元件等所使用之層間絕緣膜或保護膜)等。The present invention relates to a photosensitive resin having an anthracene skeleton and a photosensitive resin composition using the same, and more particularly to a photosensitive resin composition having various excellent properties and being easily and at low cost. The photosensitive resin to be produced and the interlayer insulating film or protective film (for example, a color filter, a liquid crystal display element, an integrated circuit element, a solid-state imaging element, etc.) used for modulating a liquid crystal display, an electronic component, etc. Membrane or protective film).
具有芴骨架之高分子化合物係已知具有高耐熱性、高透明性、高折射率、低線膨脹率等優異之物性。利用此特性，於分子中導入自由基聚合性之不飽和鍵構造(乙烯基)的具有芴骨架之高分子化合物，於光學用被覆劑、硬塗劑、抗反射膜、眼鏡透鏡、光纖、光導波管、全像術等之光學材料用途已進行研究。例如塑膠透鏡材料係已揭示一種於9,9-雙(4-羥基苯基)芴上使氯化(甲基)丙烯酸反應之化合物、或於9,9-雙(4-羥基苯基)芴上加成環氧乙烷或環氧丙烷後，使(甲基)丙烯酸反應之化合物作為主成分之共聚物(專利文獻1)。The polymer compound having an anthracene skeleton is known to have excellent physical properties such as high heat resistance, high transparency, high refractive index, and low linear expansion ratio. By using this property, a polymer compound having an anthracene skeleton having a radical polymerizable unsaturated bond structure (vinyl group) introduced into a molecule is used as an optical coating agent, a hard coating agent, an antireflection film, an eyeglass lens, an optical fiber, and a light guide. The use of optical materials such as wave tubes and holograms has been studied. For example, plastic lens materials have disclosed a compound which reacts chlorinated (meth)acrylic acid on 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-hydroxyphenyl)fluorene. A copolymer obtained by adding a compound reacted with (meth)acrylic acid as a main component after addition of ethylene oxide or propylene oxide (Patent Document 1).
但，於此專利文獻所揭示之化合物中係分子量低，構造亦柔軟，難謂具有充分的折射率，且交聯密度低，故有所謂硬化物強度低之缺點。However, the compound disclosed in this patent document has a low molecular weight and a soft structure, and it is difficult to say that it has a sufficient refractive index and a low crosslinking density, so that there is a disadvantage that the strength of the cured product is low.
又，具有芴骨架之高分子化合物係利用其耐熱性、耐藥品物優之特性，亦適用於液晶彩色濾光片或黑色矩陣、阻焊劑等之所謂光阻劑(專利文獻2及3)。In addition, the polymer compound having an anthracene skeleton is also suitable for a liquid crystal color filter, a so-called photoresist such as a black matrix or a solder resist, and the like, which is excellent in heat resistance and chemical resistance (Patent Documents 2 and 3).
依此等之技術所得到的感光性樹脂係可得到高的交聯密度，可得到強度、耐熱性、耐藥品性優異之硬化物，但因於其合成需要非常長時間，故成本高，難謂廣泛普及為目前之情況。又，起因於其製造方法而產生著色，故很難適用於要求透明性之光學零件，難謂充分活用芴骨架之特性。The photosensitive resin obtained by such a technique can obtain a high crosslinking density, and can obtain a cured product excellent in strength, heat resistance, and chemical resistance. However, since it takes a long time to synthesize it, the cost is high and it is difficult. It is said that it is widely used as the current situation. Moreover, since it is colored by the manufacturing method, it is difficult to apply to an optical component which requires transparency, and it is difficult to fully utilize the characteristics of the skeleton.
(專利文獻1)特開平4-325508公報(Patent Document 1) Japanese Patent Publication No. 4-325508
(專利文獻2)特許3673321公報(Patent Document 2) License 3673321 Bulletin
(專利文獻3)特開2007-264433公報(Patent Document 3) JP-A-2007-264433 Bulletin
(發明之揭示)(disclosure of the invention)
因此，尋求提供一種感光性樹脂，其係可容易地以低成本製造，容易調整交聯密度或酸價，同時芴骨架本來具有之具備高耐熱性、高透明性、高折射率及低線膨脹率等優異之特性者，本發明之課題在於提供一種如此之感光性樹脂及利用此之感光性樹脂組成物。Therefore, it is desired to provide a photosensitive resin which can be easily produced at a low cost and which is easy to adjust the crosslinking density or the acid value, and the ruthenium skeleton originally has high heat resistance, high transparency, high refractive index, and low linear expansion. An object of the present invention is to provide such a photosensitive resin and a photosensitive resin composition using the same.
有鑑於如此之實情，本發明人等係為解決上述課題，累積專心研究之結果，發現於特定之具有芴骨架的化合物與四元酸二酐反應所得到之高分子化合物上，加成特定之羧酸反應性(甲基)丙烯酸酯化合物所得到之感光性樹脂，係可以低成本容易地製造，可以高交聯密度得到高的強度，同時並顯示高耐熱性、高透明性、高折射率、低線膨脹率等之優異的特性，終完成本發明。In view of the facts, the inventors of the present invention have accumulated the results of intensive studies to solve the above problems, and found that the addition of a specific compound having a fluorene skeleton to a tetrabasic acid dianhydride has a specific addition. The photosensitive resin obtained by the carboxylic acid-reactive (meth) acrylate compound can be easily produced at a low cost, and can have high strength at a high crosslinking density, and exhibits high heat resistance, high transparency, and high refractive index. The excellent characteristics such as the low linear expansion ratio and the like are completed.
亦即，本發明之感光性樹脂，其係於以下述通式(1)所示之具有芴骨架的化合物、與四元酸二酐反應所得到的高分子化合物上，加成以下述通式(2)所示之羧酸反應性(甲基)丙烯酸酯化合物所得到者；
本發明之感光性樹脂，其特徵在於：含有上述感光性樹脂、與光聚合起始劑及/或光增感劑。The photosensitive resin of the present invention contains the photosensitive resin, a photopolymerization initiator, and/or a photosensitizer.
本發明之感光性樹脂係保存安定性高，可以低成本容易地製造，生產性亦優，具有高耐熱性、高透明性、高折射率及低線膨脹率等優異之特性者。又，使用此感光性樹脂之本發明的感光性樹脂組成物係可得到感度高且強度等優之硬化物。The photosensitive resin of the present invention has high storage stability, can be easily produced at low cost, and is excellent in productivity, and has excellent properties such as high heat resistance, high transparency, high refractive index, and low linear expansion ratio. Further, the photosensitive resin composition of the present invention using the photosensitive resin can obtain a cured product having high sensitivity and excellent strength.
構成本發明之感光性樹脂之高分子化合物，其係使以下述通式(1)所示之具有芴骨架的化合物及後述之四元酸二酐反應所得到者。The polymer compound constituting the photosensitive resin of the present invention is obtained by reacting a compound having an anthracene skeleton represented by the following formula (1) with a tetrabasic acid dianhydride described later.
在上述式(1)中，對應於以環Z1 及環Z2 所示之烴環的烴，為單環式或縮合多環式者，可舉例如苯等之單環式烴、縮合二環式烴(例如茚、萘等之C8~20 縮合二環式烴，宜為C10-16 縮合二環式烴)、縮合三環式烴(蒽、菲等)等之縮合2乃至4環式烴等。尤其在要求高的折射率、耐熱性之 用途中較佳的烴，可舉例如縮合多環式芳香族烴(萘、蒽等)，尤宜為萘。又，尤其要求高的溶解性、相溶性及低溶液黏度之用途中宜為苯。又，環Z1 及環Z2 分別為同一或相異之環，一般，亦可為相同之環。In the above formula (1), the hydrocarbon corresponding to the hydrocarbon ring represented by the ring Z 1 and the ring Z 2 is a monocyclic or condensed polycyclic ring, and examples thereof include a monocyclic hydrocarbon such as benzene, and a condensation second. cyclic hydrocarbons (such as indene, naphthalene, etc. the fused bicyclic C 8 ~ 20 hydrocarbon, is suitably C 10-16 condensed bicyclic hydrocarbon), tricyclic condensed hydrocarbons (anthracene, phenanthrene, etc.) and the like and condensed 2 4 Cyclic hydrocarbons, etc. Particularly preferred hydrocarbons for use in applications requiring high refractive index and heat resistance include, for example, condensed polycyclic aromatic hydrocarbons (naphthalene, anthracene, etc.), and particularly preferably naphthalene. Further, benzene is preferably used in applications requiring high solubility, compatibility, and low solution viscosity. Further, the ring Z 1 and the ring Z 2 are respectively the same or different rings, and generally, they may be the same ring.
又，在上述式(1)中，以R1a 及R1b 所示之取代基，並無特別限定，但一般為烷基。烷基可例示甲基、乙基、丙基、異丙基、丁基、第三丁基等之C1-6 烷基(C1-4 烷基，尤其甲基)等。基R1a 及R1b 亦可互異，亦可為相同。又，k1(或k2)為2以上時，基R1a (或R1b )在同一的苯環中，可為相異，亦可為相同。又，對於構成芴骨架之苯環的基R1a (或R1b )之結合位置(取代位置)並無特別限制定。較佳之取代數k1及k2或0或1，尤其為0。又，取代數k1及k2可為相異，但一般為同一。Further, in the above formula (1), the substituent represented by R 1a and R 1b is not particularly limited, but is generally an alkyl group. The alkyl group may, for example, be a C 1-6 alkyl group (C 1-4 alkyl group, especially methyl group) such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a tributyl group. The radicals R 1a and R 1b may also be different or may be the same. Further, when k1 (or k2) is 2 or more, the group R 1a (or R 1b ) may be different or may be the same in the same benzene ring. Further, the bonding position (substitution position) of the group R 1a (or R 1b ) constituting the benzene ring of the anthracene skeleton is not particularly limited. Preferably, the substitution numbers k1 and k2 or 0 or 1, especially 0. Further, the substitution numbers k1 and k2 may be different, but are generally the same.
取代成環Z1 及環Z2 之取代基R2a 及R2b 可舉例如烷基(甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基等之C1-20 烷基，宜為C1-8 烷基、更宜為C1-6 烷基等)、環烷基(環戊基、環己基等之C5~10 環烷基、宜為C5-8 環烷基、更宜為C5-6 環烷基等)、芳基〔苯基、烷基苯基(甲基苯基(甲苯基)、二甲基苯基(二甲苯基)等)等之C6-10 芳基、宜為C6-8 芳基、尤宜苯基等〕、芳烷基(苯甲基、苯乙基等之C6-10 芳基-C1-4 烷基等)等之烴基；烷氧基(甲氧基等之C1-4 烷氧基等)；醯基(乙醯基等之C1-6 醯基等)；烷氧基羰基(甲氧基羰基等之C1-4 烷氧基羰基等)；鹵原子(氟原子、氯原子等)；硝基；氰基等。The substituents R 2a and R 2b substituted with the ring Z 1 and the ring Z 2 may, for example, be an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group, tert-butyl group or the like). C 1-20 alkyl, preferably C 1-8 alkyl, more preferably C 1-6 alkyl, etc., cycloalkyl (cyclopentyl, cyclohexyl, etc. C 5-10 cycloalkyl, preferably C 5-8 cycloalkyl, more preferably C 5-6 cycloalkyl, etc.), aryl [phenyl, alkylphenyl (methylphenyl (tolyl), dimethylphenyl (xylyl) C6-10 aryl, etc., preferably C 6-8 aryl, especially phenyl, etc., aralkyl (benzyl, phenethyl, etc. C 6-10 aryl-C 1 a hydrocarbon group such as -4 alkyl group or the like; an alkoxy group (such as a C 1-4 alkoxy group such as a methoxy group); a fluorenyl group (such as a C 1-6 fluorenyl group such as an ethenyl group); an alkoxycarbonyl group; (C 1-4 alkoxycarbonyl group such as a methoxycarbonyl group; etc.); a halogen atom (a fluorine atom, a chlorine atom or the like); a nitro group; a cyano group;
較佳之取代基R2a (或R2b )係烷基(C1-6 烷基)、環烷基(C5-8 環烷基)、芳基(C6-10 芳基)、芳烷基(C6-8 -C1-2 烷基)，尤其，宜為C1-4 烷基、C1-4 烷氧基、C6-8 芳基。取代基R2a (或R2b )可單獨或組合2種以上而取代成苯環。又，基R2a 及R2b 亦可互相相同或相異，但一般為同一。又，m1(或m2)為2以上時，基R2a (或R2b )在同一的烴環中，可為相異，亦可為同一。Preferred substituents R 2a (or R 2b ) are alkyl (C 1-6 alkyl), cycloalkyl (C 5-8 cycloalkyl), aryl (C 6-10 aryl), aralkyl (C 6-8 -C 1-2 alkyl), in particular, preferably C 1-4 alkyl, C 1-4 alkoxy, C 6-8 aryl. The substituent R 2a (or R 2b ) may be substituted with two or more kinds alone or in combination with a benzene ring. Further, the radicals R 2a and R 2b may be the same or different from each other, but are generally the same. Further, when m1 (or m2) is 2 or more, the group R 2a (or R 2b ) may be different or may be the same in the same hydrocarbon ring.
又，取代基R2a (或R2b )之取代位置並無特別限定，而依照羥基或羥基(聚)烷撐基氧基(以下，有時總稱為含有羥基之基)的取代位置，可於構成酚骨架之苯基的2~6位(例如，2位、5位、2,5-位等)取代。Further, the substitution position of the substituent R 2a (or R 2b ) is not particularly limited, and may be a substitution position according to a hydroxyl group or a hydroxy (poly)alkyleneoxy group (hereinafter, collectively referred to as a group having a hydroxyl group). The 2 to 6 positions (for example, the 2, 5, 2, 5, etc.) of the phenyl group constituting the phenol skeleton are substituted.
取代基R2a 及R2b 之取代數m1及m2係亦依含有羥基之基的取代數，但宜為0~2，更宜為0~1(尤其0)。又，取代數m1及m2亦可為相異，但一般常為相同。The substitution numbers m1 and m2 of the substituents R 2a and R 2b are also based on the number of substitutions of the hydroxyl group-containing group, but are preferably 0 to 2, more preferably 0 to 1 (especially 0). Further, the substitution numbers m1 and m2 may be different, but are generally the same.
以含有羥基之基的R3a 及R3b 所示的取代基為氫或甲基。又，R3a 及R3b 可互相同一亦可相異，但一般為同一。The substituent represented by R 3a and R 3b having a hydroxyl group is hydrogen or a methyl group. Further, R 3a and R 3b may be the same or different from each other, but are generally the same.
(聚)烷撐基氧基的加成數n1及n2係同一或相異，可從0~10之範圍選擇，宜為0~8(例如1~8)，更宜為0~6(例如1~6)，尤宜為0~4(例如1~4)左右。又，n1與n2之和(n1+n2)，可從0~20之範圍選擇，宜為0~16(例如2~12)，更宜為0~12(例如2~12)，尤宜為0~8(例如2~8)左右。又，n1(或n2)為2以上時，(聚)烷撐基氧基係亦可以同一之烷氧基所構成，亦可異種的烷氧基(例如乙氧基與環氧丙烷基)混在一起而構成，但一般常以同一之烷氧基所構成。The number of additions of (poly)alkyleneoxy groups n1 and n2 are the same or different, and can be selected from the range of 0 to 10, preferably 0 to 8 (for example, 1 to 8), more preferably 0 to 6 (for example, 1) ~6), especially about 0~4 (for example, 1~4). Moreover, the sum of n1 and n2 (n1+n2) can be selected from the range of 0 to 20, preferably 0 to 16 (for example, 2 to 12), more preferably 0 to 12 (for example, 2 to 12), and particularly preferably 0~8 (for example, 2~8). Further, when n1 (or n2) is 2 or more, the (poly)alkyleneoxy group may be composed of the same alkoxy group, or a different alkoxy group (for example, an ethoxy group and an oxypropylene group) may be mixed. They are composed together, but they are usually composed of the same alkoxy group.
含有羥基之基的取代數p1及p2為0~4之範圍，宜為1~4，尤宜為1~2。但，環Z1 及環Z2 為單環式烴環時，p1及p2為1~3，環Z1 及環Z2 為縮合多環式烴時，含於環Z1 之p1的和及含於環Z2 之p2的和分別為1以上。又，p1與p2之和(p1+p2)宜為2~8，更宜為2~4。尤其硬化物之交聯密度要求之用途中p1及p2宜為2乃至3。又，取代數p1及p2亦可為相異，但一般常為同一。含有羥基之基之取代位置並無特別限定，而依照p1(或p2)之數目，可從芴之9位取代的苯基之2~6位選擇，p1(或p2)為2時，例如亦可為3,4-位、3,5-位等。一個之含有羥基之基一般亦可於4位取代。The substitution number p1 and p2 of the hydroxyl group-containing group are in the range of 0 to 4, preferably 1 to 4, and particularly preferably 1 to 2. However, when ring Z 1 and ring Z 2 are monocyclic hydrocarbon rings, p1 and p2 are 1 to 3, and when ring Z 1 and ring Z 2 are condensed polycyclic hydrocarbons, the sum of p1 contained in ring Z 1 and The sum of p2 contained in the ring Z 2 is 1 or more, respectively. Further, the sum of p1 and p2 (p1+p2) is preferably 2 to 8, more preferably 2 to 4. In particular, the use of p1 and p2 in the use of the crosslink density of the cured product is preferably 2 or 3. Further, the substitution numbers p1 and p2 may be different, but are generally the same. The substitution position of the hydroxyl group-containing group is not particularly limited, and depending on the number of p1 (or p2), it can be selected from the 2 to 6 positions of the phenyl group substituted at the 9-position of the fluorene, and when p1 (or p2) is 2, for example, It can be 3, 4-position, 3, 5-position, etc. A hydroxyl group-containing group can also be substituted at the 4-position.
又，構成同一之酚骨架的複數含有羥基之基係可為同一，亦可為相異。例如，複數之含有羥基之基係(i)可以n1=0(n2=0)之羥基單獨(但，p1及p2為2時除外)構成，(ii)亦可以n1=0(n2=0)之羥基與n1≠0(n2≠0)之羥基(聚)烷氧基(2-羥基乙氧基等)構成，(iii)可以n1≠0(n2≠0)之同一的羥基(聚)烷氧基單獨構成，(iv)亦可以n1≠0(n2≠0)之相異的羥基(聚)烷氧基[例如，2-羥基乙氧基與2-(2-羥基乙氧基)乙氧基]構成。Further, the plurality of hydroxyl group-containing groups constituting the same phenol skeleton may be the same or different. For example, a plurality of hydroxyl group-containing groups (i) may be composed of a hydroxyl group of n1 = 0 (n2 = 0) alone (except when p1 and p2 are 2), and (ii) may also be n1 = 0 (n2 = 0). The hydroxyl group is composed of a hydroxyl group (poly) alkoxy group (2-hydroxyethoxy group) of n1≠0 (n2≠0), and (iii) a hydroxyl group (poly) alkane which may be the same as n1≠0(n2≠0) The oxy group is composed singly, and (iv) may also be a different hydroxy (poly) alkoxy group of n1 ≠ 0 (n2 ≠ 0) [for example, 2-hydroxyethoxy group and 2-(2-hydroxyethoxy group) Oxy] constitutes.
在上述通式(1)之具有芴骨架的化合物中，要求特別高的折射率、耐熱性之用途中，宜為以下述通式(3)所示之構造者。Among the compounds having an anthracene skeleton of the above formula (1), those having a particularly high refractive index and heat resistance are preferably those having a structure represented by the following formula (3).
R1a 及R1b 、R2a 及R2b 、R3a 及R3b 、k1及k2、m1及m2、n1及n2係與前述相同。又，R6a 及R6b 係對應於前述R2a 及R2b 、m3及m4係對應於前述m1及m2、n3及n4係對應於前述n1及n2，具有相同的意義。p1及p2係與前述相同，但宜為1~4。p3及p4係與前述p1及p2對應，宜為0~3。R 1a and R 1b , R 2a and R 2b , R 3a and R 3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above. Further, R 6a and R 6b correspond to the above-mentioned R 2a and R 2b , and m3 and m4 have the same meanings corresponding to the above m1 and m2, n3 and n4 corresponding to the above n1 and n2. The p1 and p2 systems are the same as described above, but are preferably 1 to 4. The p3 and p4 lines correspond to the above p1 and p2, and are preferably 0 to 3.
具體上，可舉例如9,9-雙(羥基烷氧基萘基)芴類、9,9-雙(羥基聚烷氧基萘基)芴類等之前述通式(3)中p1+p2+p3+p4為2之化合物；9,9-雙(聚羥基烷氧基萘基)芴類、9,9-雙(聚羥基聚烷氧基萘基)芴類等之前述通式(3)中p1+p2+p3+p4為2之化合物等。Specific examples thereof include p1+p2 in the above formula (3) such as 9,9-bis(hydroxyalkoxynaphthalenyl)anthracene or 9,9-bis(hydroxypolyalkoxynaphthyl)anthracene. +p3+p4 is a compound of 2; 9,9-bis(polyhydroxyalkoxynaphthalenyl)anthracene, 9,9-bis(polyhydroxypolyalkoxynaphthyl)anthracene, etc. a compound in which p1+p2+p3+p4 is 2.
9,9-雙(羥基烷氧基萘基)芴類方面，可舉例如9,9-雙(羥基烷氧基萘基)芴[例如9,9-雙[6-(2-羥基乙氧基)-2-萘基]芴、9,9-雙[6-(2-羥基丙氧基)-2-萘基]芴、9,9-雙[5-(2-羥基乙氧基)-1-萘基]芴、9,9-雙[5-(2-羥基丙氧基)-1-萘基]芴等之9,9-雙(羥基C2-4 烷氧基萘基)芴等]等。The 9,9-bis(hydroxyalkoxynaphthyl) anthracene may, for example, be 9,9-bis(hydroxyalkoxynaphthyl)anthracene [e.g., 9,9-bis[6-(2-hydroxyethoxy) ,2-naphthyl]anthracene, 9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]anthracene, 9,9-bis[5-(2-hydroxyethoxy) 9,9-bis(hydroxy C 2-4 alkoxynaphthyl), such as 1-naphthyl]anthracene, 9,9-bis[5-(2-hydroxypropoxy)-1-naphthyl]anthracene芴, etc.].
9,9-雙(羥基聚烷氧基萘基)芴類方面，可舉例如9,9-雙(羥基二烷氧基萘基)芴[例如9,9-雙[6-(2-(2-羥基乙氧基)乙氧基)-2-萘基]芴、9,9-雙[6-(2-(2-羥基丙氧基)丙氧基)-2-萘基]芴、9,9-雙[5-(2-(2-羥基乙氧基)乙氧基)-1-萘基]芴、9,9-雙[5-(2-(2-羥基丙氧基)丙氧基)-1-萘基]芴等之9,9-雙(羥基C2-4 烷氧基萘基)芴等]等之9,9-雙(羥基二烷氧基萘基)芴類；對應於此等之化合物，在前述通式(3)中，n1、n2、n3、n4為3以上之化合物等。The 9,9-bis(hydroxypolyalkoxynaphthyl) anthracene may, for example, be 9,9-bis(hydroxydialkoxynaphthyl)anthracene [e.g., 9,9-bis[6-(2-( 2-hydroxyethoxy)ethoxy)-2-naphthyl]anthracene, 9,9-bis[6-(2-(2-hydroxypropoxy)propoxy)-2-naphthyl]anthracene, 9,9-bis[5-(2-(2-hydroxyethoxy)ethoxy)-1-naphthyl]anthracene, 9,9-bis[5-(2-(2-hydroxypropoxy)) 9,9-bis(hydroxydialkoxynaphthyl)anthracene of 9,9-bis(hydroxy C 2-4 alkoxynaphthyl)anthracene, etc. such as propoxy)-1-naphthyl]anthracene In the above formula (3), n1, n2, n3, and n4 are compounds of 3 or more.
9,9-雙(聚羥基烷氧基萘基)芴類方面，可舉例如對應於前述9,9-雙(羥基烷氧基萘基)芴類，p1+p2+p3+p4為2以上之化合物，可舉例如9,9--雙(二或三羥基烷氧基萘基)芴[例如9,9-雙[二(2-羥基乙氧基)-2-萘基]芴、9,9-雙[二(2-羥基丙氧基)-2-萘基]芴等之9,9-雙(二或三羥基C2-4 烷氧基萘基)芴等]等之9,9-雙(聚羥基烷氧基萘基)芴。Examples of the 9,9-bis(polyhydroxyalkoxynaphthyl) anthracene include, for example, the above-mentioned 9,9-bis(hydroxyalkoxynaphthyl) anthracene, and p1+p2+p3+p4 is 2 or more. The compound may, for example, be 9,9-bis(di or trihydroxyalkoxynaphthyl)anthracene [e.g., 9,9-bis[bis(2-hydroxyethoxy)-2-naphthyl]anthracene, 9 9,9-bis[di(2-hydroxypropoxy)-2-naphthyl]anthracene, etc. 9,9-bis(di or trihydroxy C 2-4 alkoxynaphthyl) anthracene, etc. 9-bis(polyhydroxyalkoxynaphthyl)anthracene.
9,9-雙(聚羥基聚烷氧基萘基)芴類方面，可舉例如對應於前述9,9-雙(羥基烷氧基萘基)芴類，n1、n2、n3、n4為2以上且p1+p2+p3+p4為2以上之化合物，可舉例如9,9-雙(二或三羥基二烷氧基萘基)芴[例如9,9-雙[二[2-(2-羥基乙氧基)乙氧基]-2-萘基]芴等之9,9-雙(二或三羥基二C2-4 烷氧基萘基)芴等]等之9,9-(二或三羥基二烷氧基萘基)芴類；對應於此等之化合物，在前述式(化3)中，n1、n2、n3、n4為3以上之化合物等。The 9,9-bis(polyhydroxy polyalkoxynaphthyl) anthracene may, for example, correspond to the above 9,9-bis(hydroxyalkoxynaphthyl) anthracene, and n1, n2, n3, and n4 are 2 The above compound in which p1+p2+p3+p4 is 2 or more may, for example, be 9,9-bis(di or trihydroxydialkoxynaphthyl)anthracene [e.g., 9,9-bis[di[2-(2) 9,9-(9,9-bis(di or trihydroxydiC 2-4 alkoxynaphthyl) anthracene, etc. of -hydroxyethoxy)ethoxy]-2-naphthyl]anthracene, etc. In the above formula (Chemical Formula 3), n1, n2, n3, and n4 are compounds of 3 or more, etc., in the above formula (Chemical Formula 3).
此等之中，宜為9,9-雙[6-(2-羥基乙氧基)-2-萘基]芴等。Among these, 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]anthracene or the like is preferable.
在上述通式(1)之具有芴骨架的化合物中，要求特別高的溶解性、相溶性及低溶液黏度之用途中，宜為以下述通式(4)所示之構造者。Among the compounds having an anthracene skeleton of the above formula (1), those having a particularly high solubility, compatibility, and low solution viscosity are preferably those having a structure represented by the following formula (4).
R1a 及R1b 、R2a 及R2b 、R3a 及R3b 、k1及k2、m1及m2、n1及n2係與前述相同。又，R7a 及R7b 係對應於前述R3a 及R3b ，具有相同的意義。p1及p2係與前述相同，宜為1~3。R 1a and R 1b , R 2a and R 2b , R 3a and R 3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above. Further, R 7a and R 7b have the same meanings in correspondence with R 3a and R 3b described above. The p1 and p2 systems are the same as described above, and are preferably 1 to 3.
以代表性的前述式(4)所示之化合物係含有9,9-雙(羥基烷氧基苯基)芴類(在前述通式(4)中n1=n2=1之化合物)、9,9-雙(羥基聚烷氧基二烷基苯基)芴類(在前述通式(4)中n1、n2分別為1以上之化合物)等。The compound represented by the above formula (4) contains 9,9-bis(hydroxyalkoxyphenyl)fluorene (a compound in which n1=n2=1 in the above formula (4)), 9, 9-bis(hydroxypolyalkoxydialkylphenyl)anthracene (a compound in which n1 and n2 are each 1 or more in the above formula (4)) and the like.
9,9-雙(羥基烷氧基苯基)芴類中例如9,9-雙(羥基烷氧基苯基)芴類{例如，9,9-雙[4-(2-羥基乙氧基)苯基]芴、9,9-雙[4-(2-羥基丙氧基)苯基]芴、9,9-雙[4-(2-羥基乙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基丙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基乙氧基)-3,5-二甲基苯基]芴、9,9-雙[4-(2-羥基乙氧基)苯氧基乙烷]芴、9,9-雙[4-(2-羥基丙氧基)苯氧基乙烷]芴、9,9-雙[4-(2-羥基乙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基丙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基乙氧基)-2,5-二甲基苯基]芴、9,9-雙[4-(2-羥基丙氧基)-2,5-二甲基苯基]芴、9,9-雙[4-(2-羥基乙氧基)-3,6-二甲基苯基]芴、9,9-雙[4-(2-羥基丙氧基)-2,6-二甲基苯基]芴、9,9-雙[4-(2-羥基乙氧基)-2,4-二甲基苯基]芴、9,9-雙[3-(2-羥基丙氧基)-2,4-二甲基苯基]芴、9,9-雙[4-(2-羥基乙氧基)-3,4-二甲基苯基]芴、9,9-雙[2-(2-羥基丙氧基)-3,4-二甲基苯基]芴等之9,9-雙(羥基烷氧基烷基苯基)芴、較佳係含有9,9-雙(2-羥基丙氧基-二C1-4 烷基苯基)芴等之9,9-雙(羥基分枝C3-4 烷氧基-二烷基苯基)芴類}。9,9-bis(hydroxyalkoxyphenyl)anthracene such as 9,9-bis(hydroxyalkoxyphenyl)anthracene {e.g., 9,9-bis[4-(2-hydroxyethoxy) Phenyl]fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl芴, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,5- Dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)phenoxyethane]anthracene, 9,9-bis[4-(2-hydroxypropoxy)phenoxy Iridium, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropoxy)-3 -methylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-2,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropane) Oxy)-2,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,6-dimethylphenyl]anthracene, 9,9-double [4-(2-hydroxypropoxy)-2,6-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-2,4-dimethylphenyl芴, 9,9-bis[3-(2-hydroxypropoxy)-2,4-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3 9,9-bis(hydroxyl), 4-dimethylphenyl]anthracene, 9,9-bis[2-(2-hydroxypropoxy)-3,4-dimethylphenyl]anthracene Alkoxyalkyl phenyl) fluorene, preferred system contains 9,9-bis (2-hydroxy-propoxy - two C 1-4 alkylphenyl) fluorene of 9,9-bis (hydroxy-branched C 3-4 alkoxy-dialkylphenyl) hydrazines}.
9,9-雙(羥基聚烷氧基苯基)芴類中係n1、n2為2以上之化合物例如9,9-雙(羥基二烷氧基苯基)芴類{例如，9,9-雙[4-(2-羥基二乙氧基)苯基]芴、9,9-雙[4-(2-羥基二丙氧基)苯基]芴、9,9-雙[4-(2-羥基二乙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基二丙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基二乙氧基)-3,5-二甲基苯基]芴、9,9-雙[4-(2-羥基二乙氧基)苯氧基乙醇]芴、9,9-雙[4-(2-羥基二丙氧基)苯氧基乙醇]芴、9,9-雙[4-(2-羥基二乙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基二丙氧基)-3-甲基苯基]芴、9,9-雙[4-(2-羥基二乙氧基)-2,5-二甲基苯基]芴、9,9-雙[4-(2-羥基二丙氧基)-2,5-二甲基苯基]芴、9,9-雙[4-(2-羥基二乙氧基)-3,6-二甲基苯基]芴、9,9-雙[4-(2-羥基二丙氧基)-2,6-二甲基苯基]芴、9,9-雙[4-(2-羥基二乙氧基)-2,4-二甲基苯基]芴、9,9-雙[3-(2-羥基二丙氧基)-2,4-二甲基苯基]芴、9,9-雙[4-(2-羥基二乙氧基)-3,4-二甲基苯基]芴、9,9-雙[2-(2-羥基二丙氧基)-3,4-二甲基苯基]芴等之9,9-雙(羥基二烷氧基苯基)芴}。Among the 9,9-bis(hydroxypolyalkoxyphenyl)anthracenes, compounds in which n1 and n2 are 2 or more, such as 9,9-bis(hydroxydialkoxyphenyl)anthracene {e.g., 9,9- Bis[4-(2-hydroxydiethoxy)phenyl]anthracene, 9,9-bis[4-(2-hydroxydipropoxy)phenyl]anthracene, 9,9-bis[4-(2 -hydroxydiethoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxydipropoxy)-3-methylphenyl]anthracene, 9,9-bis[ 4-(2-hydroxydiethoxy)-3,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)phenoxyethanol]anthracene, 9, 9-bis[4-(2-hydroxydipropoxy)phenoxyethanol]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)-3-methylphenyl]anthracene, 9 ,9-bis[4-(2-hydroxydipropoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)-2,5-dimethyl Phenyl]fluorene, 9,9-bis[4-(2-hydroxydipropoxy)-2,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethyl) Oxy)-3,6-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydipropoxy)-2,6-dimethylphenyl]anthracene, 9,9- Bis[4-(2-hydroxydiethoxy)-2,4-dimethylphenyl]anthracene, 9,9-bis[3-(2-hydroxydipropoxy)-2,4-dimethyl Phenyl] ruthenium, 9,9-bis[4-(2-hydroxydiethoxy)-3,4-dimethyl 9,9-bis(hydroxydialkoxyphenyl) such as phenyl]anthracene, 9,9-bis[2-(2-hydroxydipropoxy)-3,4-dimethylphenyl]anthracene芴}.
此等之中宜為9,9-雙(羥基乙氧基苯基)芴、9,9-雙(羥基乙氧基-3-甲基苯基)芴、9,9-雙(羥基乙氧基-3,5-二甲基苯基)芴、9,9-雙(羥基乙氧基-2-苯氧基乙醇)芴等。Among these, 9,9-bis(hydroxyethoxyphenyl)anthracene, 9,9-bis(hydroxyethoxy-3-methylphenyl)anthracene, 9,9-bis(hydroxyethoxyl) Alkyl-3,5-dimethylphenyl)anthracene, 9,9-bis(hydroxyethoxy-2-phenoxyethanol)anthracene or the like.
構成本發明之感光性樹脂的以前述通式(1)所示之具有芴骨架的化合物，要求特別高的折射率、溶解性、相溶性及低溶液黏度之用途中，宜R2a 及R2b 為苯基。The compound having an anthracene skeleton represented by the above formula (1) constituting the photosensitive resin of the present invention is preferably R 2a and R 2b in applications requiring a particularly high refractive index, solubility, compatibility, and low solution viscosity. Is a phenyl group.
具體上，例如在以前述通式(4)所示之化合物中包含9,9-雙(羥基烷氧基芳基苯基)芴類(在前述通式(4)中n1=n2=1，R2a 、R2b 為苯基之化合物)、9,9-雙(羥基聚烷氧基芳基苯基)芴類(在前述通式(4)中n1+n2為2以上，R2a 、R2b 為苯基之化合物)。Specifically, for example, a 9,9-bis(hydroxyalkoxyarylphenyl)anthracene is contained in the compound represented by the above formula (4) (in the above formula (4), n1=n2=1, R 2a , R 2b is a compound of a phenyl group), 9,9-bis(hydroxypolyalkoxyarylphenyl)anthracene (in the above formula (4), n1+n2 is 2 or more, R 2a , R 2b is a compound of a phenyl group).
9,9-雙(羥基烷氧基芳基苯基)芴類係含有9,9-雙[4-(2-羥基乙氧基)-3-苯基苯基]芴、9,9-雙[4-(2-羥基丙氧基)-3-苯基苯基]芴、9,9-雙[4-(2-羥基丙氧基)-3-甲苯基苯基]芴等之9,9-雙(羥基烷氧基芳基苯基)芴、較佳係含有9,9-雙(2--羥基乙氧基芳基苯基)芴]等。9,9-bis(hydroxyalkoxyarylphenyl)indoles contain 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]anthracene, 9,9-double [4-(2-hydroxypropoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]anthracene, etc. 9-bis(hydroxyalkoxyarylphenyl)anthracene, preferably contains 9,9-bis(2-hydroxyethoxyphenylphenyl)anthracene or the like.
9,9-雙(羥基聚烷氧基芳基苯基)芴類係含有9,9-雙(羥基二烷氧基芳基苯基)芴類[例如9,9-雙{4-[2-(2-羥基乙氧基)乙氧基]-3-苯基苯基}芴等之9,9-雙(羥基二烷氧基芳基苯基)芴、較佳係含有9,9-雙[2-(2-羥基乙氧基)乙氧基芳基苯基]芴]等。9,9-bis(hydroxypolyalkoxyarylphenyl)indoles contain 9,9-bis(hydroxydialkoxyarylphenyl)anthracenes [eg 9,9-double {4-[2 9,9-bis(hydroxydialkoxyarylphenyl)anthracene, such as -(2-hydroxyethoxy)ethoxy]-3-phenylphenyl}anthracene, preferably contains 9,9- Bis[2-(2-hydroxyethoxy)ethoxyarylphenyl]anthracene].
此等之中宜為9,9-雙(羥基乙氧基芳基苯基)芴等。Among these, it is preferably 9,9-bis(hydroxyethoxyarylphenyl)anthracene or the like.
就與上述具有芴骨架之化合物反應的化合物而言，可使用四元酸二酐。For the compound which reacts with the above compound having an anthracene skeleton, a tetrabasic acid dianhydride can be used.
四元酸二酐具體上係可例示丁烷四羧酸二酐、戊烷四羧酸二酐、己烷四羧酸二酐、環丁烷四羧酸二酐、環戊烷四羧酸二酐、環己烷四羧酸二酐、環庚烷四羧酸二酐、降冰片烷四羧酸二酐、均苯四甲酸二酐、二苯甲酮四羧酸二酐、聯苯基四羧酸二酐、聯苯基醚四羧酸二酐、5-(2,5-二氧四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、4-(2,5-二氧四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸酐、萘-1,4,5,8-四羧酸二酐、4,4’-(六氟異亞丙基)二酞酸酐、3,4,9,10-苝四羧酸二酐、3,3’-4,4’-二苯基碸四羧酸二酐等，可使用此等之1種或2種以上。此等之中宜為均苯四甲酸二酐、5-(2,5-二氧四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、二苯甲酮四羧酸二酐、聯苯基四羧酸二酐。Specific examples of the tetrabasic acid dianhydride include butane tetracarboxylic dianhydride, pentane tetracarboxylic dianhydride, hexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic acid II. Anhydride, cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetra Carboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylate Anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylate Acid dianhydride, 4,4'-(hexafluoroisopropylidene) diacetic anhydride, 3,4,9,10-decane tetracarboxylic dianhydride, 3,3'-4,4'-diphenylanthracene For the tetracarboxylic dianhydride or the like, one type or two or more types may be used. Among these, pyromellitic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride.
可得到於上述具有芴骨架之化合物上使四元酸二酐加成反應而構成本發明之感光性樹脂的高分子化合物。在此加成反應中之四元酸二酐對具有芴骨架之化合物1莫耳之比率宜為0.5莫耳~1.5莫耳，更宜為0.65莫耳~1.25莫耳。四元酸二酐之比例未達0.5莫耳及超過1.5莫耳時，有時無法得到充分的分子量。A polymer compound which forms a photosensitive resin of the present invention by adding a tetrabasic acid dianhydride to the compound having an anthracene skeleton can be obtained. The ratio of the tetrabasic acid dianhydride to the compound 1 molar having an anthracene skeleton in this addition reaction is preferably from 0.5 mol to 1.5 mol, more preferably from 0.65 mol to 1.25 mol. When the ratio of the tetrabasic acid dianhydride is less than 0.5 mol and exceeds 1.5 mol, a sufficient molecular weight may not be obtained.
當具有芴骨架之化合物與四元酸二酐之加成反應時亦可用觸媒。所使用之觸媒只要為可促進反應即可，無特別限制，但就一例而言係可舉例如吡啶、喹啉、咪唑、N,N-二甲基環己基胺、三乙胺、N-甲基嗎啉、N-乙基嗎啉、三乙二胺、N,N-二甲基苯胺、N,N-二甲基苯甲基胺、三(N,N-二甲基胺基甲基)酚、4-二甲基胺基吡啶、1,8-二偶氮雙環[5.4.0]-7-十一碳烯、1,5-二偶氮雙環[4.3.0]壬烯-5等之胺類、氯化四甲基銨、溴化四甲基銨、氯化三甲基苯甲基銨、氫氧化四甲基銨等之第4級銨化合物、三丁基磷、三苯基磷等及其等之混合物。又，所使用之觸媒的量亦無特別限定，但相對於具有芴骨架之化合物及四元酸二酐之合計100質量份宜為0.1~2.0質量份的範圍。若觸媒之量超過2.0質量份，有時對感光性樹脂之電特性或保存安定性出現不良影響。A catalyst may also be used when the compound having an anthracene skeleton is reacted with a tetrabasic acid dianhydride. The catalyst to be used is not particularly limited as long as it can promote the reaction, and examples thereof include pyridine, quinoline, imidazole, N,N-dimethylcyclohexylamine, triethylamine, and N-. Methylmorpholine, N-ethylmorpholine, triethylenediamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, tris(N,N-dimethylaminocarbamate Phenol, 4-dimethylaminopyridine, 1,8-diazobicyclo[5.4.0]-7-undecene, 1,5-diazobicyclo[4.3.0]nonene- a fourth-order ammonium compound such as amines, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, etc., tributylphosphorus, three a mixture of phenylphosphine and the like and the like. In addition, the amount of the catalyst to be used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass based on 100 parts by mass of the total of the compound having an anthracene skeleton and the tetrabasic acid dianhydride. When the amount of the catalyst exceeds 2.0 parts by mass, the electrical properties or storage stability of the photosensitive resin may be adversely affected.
又，加成反應時係就反應原料之溶解、黏度降低等之目的，亦可使用溶劑。溶劑之種類只要不阻礙反應即可，無特別限制，但就一例而言係可舉例如乙二醇二乙基醚、二乙二醇二甲基醚等之甘醇醚類、乙二醇單乙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯等之甘醇醚乙酸酯類、二丙二醇單乙基醚、丙二醇二甲基醚、二丙二醇二甲基醚、丙二醇二乙基醚、二丙二醇二乙基醚等之丙二醇醚類、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、二丙二醇單甲基醚乙酸酯、二丙二醇單乙基醚乙酸酯等之丙二醇醚乙酸酯類、丙酮、甲乙酮、甲基異丁基酮、環己酮等之酮類、醋酸乙酯、醋酸丁酯等之醋酸酯類、二甲基亞碸、N-甲基吡咯烷酮、二甲基甲醯胺、二甲基乙醯胺、及其等之混合物。Further, in the case of the addition reaction, a solvent may be used for the purpose of dissolution of the reaction raw material, reduction of viscosity, and the like. The type of the solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, and ethylene glycol singles. Glycol ether acetate such as ethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monoethyl ether, propylene glycol dimethyl Propylene glycol ethers such as ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl a propylene glycol ether acetate such as ether acetate or dipropylene glycol monoethyl ether acetate; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; ethyl acetate or butyl acetate; A mixture of acetates, dimethyl hydrazine, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like.
所使用之溶劑的量亦無特別限制，但相對於具有芴骨架之化合物與四元酸二酐之合計100質量份，宜為25~150質量份的範圍。未達25質量份有時黏度被充份降低。另外，超過150質量份時，反應物之濃度太低，有時反應速度降低。The amount of the solvent to be used is not particularly limited, but is preferably in the range of 25 to 150 parts by mass based on 100 parts by mass of the total of the compound having an anthracene skeleton and the tetrabasic acid dianhydride. When the amount is less than 25 parts by mass, the viscosity is sufficiently lowered. On the other hand, when it exceeds 150 parts by mass, the concentration of the reactant is too low, and the reaction rate may be lowered.
於具有芴骨架之化合物與四元酸二酐中依需要，添加溶劑或觸媒而加成反應，但當反應時宜進行加熱，藉加熱而原料溶解，反應速度亦被加速。加熱溫度係可依具有芴骨架之化合物與四元酸二酐之種類或使用之裝置而適當設定，但大概宜為60~220℃之範圍。更佳係90~160℃之範圍。若反應溫度低於60℃，有時至反應終了止耗費時間。另外，若反應溫度高於220℃，產生著色等之副反應，或酸酐進行閉環等之平衡，有時反應率會降低。In the case of a compound having an anthracene skeleton and a tetrabasic acid dianhydride, a solvent or a catalyst is added to form an addition reaction. However, when the reaction is carried out, heating is carried out, and the raw material is dissolved by heating, and the reaction rate is also accelerated. The heating temperature can be appropriately set depending on the type of the ruthenium skeleton compound and the tetrabasic acid dianhydride or the apparatus used, but it is preferably in the range of 60 to 220 °C. More preferably in the range of 90~160 °C. If the reaction temperature is lower than 60 ° C, it sometimes takes time until the end of the reaction. Further, when the reaction temperature is higher than 220 ° C, a side reaction such as coloring or the like, or an acid anhydride is balanced in a ring closure or the like, and the reaction rate may be lowered.
於如以上做法所得到之高分子化合物上使以下述通式(2)所示之羧酸反應性(甲基)丙烯酸酯化合物而得到本發明之感光性樹脂。The carboxylic acid-reactive (meth) acrylate compound represented by the following formula (2) is obtained from the polymer compound obtained by the above method to obtain the photosensitive resin of the present invention.
以前述通式(2)所示之羧酸反應性(甲基)丙烯酸酯具體上係可舉例如2-羥基乙基(甲基)丙烯酸酯縮水甘油基醚、2-羥基丙基(甲基)丙烯酸酯縮水甘油基醚、3-羥基丙基(甲基)丙烯酸酯縮水甘油基醚、4-羥基丁基(甲基)丙烯酸酯縮水甘油基醚、聚乙二醇-聚丙二醇(甲基)丙烯酸酯縮水甘油基醚等。The carboxylic acid-reactive (meth) acrylate represented by the above formula (2) may specifically be, for example, 2-hydroxyethyl (meth) acrylate glycidyl ether or 2-hydroxypropyl (methyl) Acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, polyethylene glycol-polypropylene glycol (methyl ) Acrylate glycidyl ether and the like.
使如此之羧酸反應性(甲基)丙烯酸酯化合物對上述高 分子化合物加成反應。本發明之感光性樹脂中的羧酸反應性(甲基)丙烯酸酯化合物之比例係亦依用途而異，很難一概而言，使用於光硬化性塗佈劑或光學材料時，亦可感光性樹脂之酸價加成至0止。另外，適用於鹼顯像性之用途時，宜樹脂固形分之酸價在於30~150 mgKOH/g的範圍進行調整。若酸價低於30 mgKOH/g，有時顯像速度降低而無法得到必須的圖型。另外，酸價高於150 mgKOH/g時，有時成為顯像過剩而圖型易剝離，電氣特性等亦降低。又，在本發明中，樹脂固形分之酸價為依據JIS-K0070之測定值。Making such a carboxylic acid-reactive (meth) acrylate compound high above Molecular compound addition reaction. The ratio of the carboxylic acid-reactive (meth) acrylate compound in the photosensitive resin of the present invention varies depending on the application, and it is difficult to use it in a photocurable coating agent or an optical material. The acid value of the resin is added to zero. Further, when it is suitable for use in alkali development, the acid value of the resin solid content should be adjusted in the range of 30 to 150 mgKOH/g. If the acid value is less than 30 mgKOH/g, the development speed may be lowered and the necessary pattern may not be obtained. Further, when the acid value is higher than 150 mgKOH/g, the image may be excessively formed, the pattern may be easily peeled off, and electrical characteristics and the like may be lowered. Further, in the present invention, the acid value of the resin solid content is a value measured in accordance with JIS-K0070.
在上述高分子化合物與羧酸反應性(甲基)丙烯酸酯化合物之反應中係就促進反應之目的，亦可使用觸媒。觸媒之種類係依羧酸反應性(甲基)丙烯酸酯化合物之種類而異，故很難一概而言，就一例而言係可舉例如吡啶、喹啉、咪唑、N,N-二甲基環己基胺、三乙胺、N-甲基嗎啉、N-乙基嗎啉、三乙二胺、N,N-二甲基苯胺、N,N-二甲基苯甲基胺、三(N,N-二甲基胺基甲基)酚、4-二甲基胺基吡啶、1,8-二偶氮雙環[5.4.0]-7-十一碳烯、1,5-二偶氮雙環[4.3.0]壬烯-5等之胺類、氯化四甲基銨、溴化四甲基銨、氯化三甲基苯甲基銨、氫氧化四甲基銨等之第4級銨化合物、三丁基磷、三苯基磷等及其等之混合物。In the reaction between the above polymer compound and a carboxylic acid-reactive (meth) acrylate compound, a catalyst may be used for the purpose of promoting the reaction. The type of the catalyst varies depending on the type of the carboxylic acid-reactive (meth) acrylate compound, and therefore it is difficult to cite, for example, pyridine, quinoline, imidazole, N,N-dimethyl. Cyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, three (N,N-Dimethylaminomethyl)phenol, 4-dimethylaminopyridine, 1,8-diazobicyclo[5.4.0]-7-undecene, 1,5-di An amine such as azobiscyclo[4.3.0]nonene-5, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, etc. A mixture of a quaternary ammonium compound, tributylphosphine, triphenylphosphine, etc., and the like.
又，所使用之觸媒的量亦無特別限定，但相對於前述具有芴骨架之化合物100質量份宜為0.1~2.0質量份的範圍。若觸媒之量太多，有時對感光性樹脂之電特性或保存安定性出現不良影響。In addition, the amount of the catalyst to be used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass based on 100 parts by mass of the compound having an anthracene skeleton. If the amount of the catalyst is too large, the electrical properties or storage stability of the photosensitive resin may be adversely affected.
又，使羧酸反應性(甲基)丙烯酸酯化合物反應時，係宜加入聚合抑制劑。若為抑制不飽和鍵之反應者，聚合抑制劑之種類並無特別限制，但就一例而言可舉例如氫醌、氫醌單甲基醚、第三丁基氫醌、第三丁基兒茶酚、N-甲基-N-亞硝基苯胺或N-亞硝基苯基羥基胺/銨鹽(和光純藥工業股份公司製：Q-1300)、N-亞硝基苯基羥基胺/鋁鹽(和光純藥工業股份公司製：Q-1301)、2,2,6,6-四甲基六氫吡啶-1-氧、4-羥基-2,2,6,6-四甲基六氫吡啶-1-氧等。尤宜N-亞硝基苯基羥基胺/鋁鹽、4-羥基-2,2,6,6-四甲基六氫吡啶-1-氧。聚合抑制劑之量係依其種類及反應條件而異，故很難一概而言，但相對於感光性樹脂全體宜為5~2000ppm之範圍。若少於此範圍，有時於製造中不飽和鍵會反應，產生凝膠化，若多於此範圍，有時感度降低，故不佳。Further, when a carboxylic acid reactive (meth) acrylate compound is reacted, it is preferred to add a polymerization inhibitor. The type of the polymerization inhibitor is not particularly limited as long as it is a reaction for suppressing the unsaturated bond, but examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, and thirteenth butyl. Camelliol, N-methyl-N-nitrosoaniline or N-nitrosophenylhydroxylamine/ammonium salt (made by Wako Pure Chemical Industries, Ltd.: Q-1300), N-nitrosophenylhydroxylamine /Aluminum salt (made by Wako Pure Chemical Industries Co., Ltd.: Q-1301), 2,2,6,6-tetramethylhexahydropyridine-1-oxo, 4-hydroxy-2,2,6,6-tetramethyl Hexahydropyridin-1-oxygen and the like. Particularly preferred is N-nitrosophenylhydroxylamine/aluminum salt, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo. The amount of the polymerization inhibitor varies depending on the type and reaction conditions, and therefore it is difficult to be generalized, but it is preferably in the range of 5 to 2,000 ppm with respect to the entire photosensitive resin. When the amount is less than this range, the unsaturated bond may react during production to cause gelation, and if it is more than this range, the sensitivity may be lowered, which is not preferable.
加成羧酸反應性(甲基)丙烯酸酯化合物時係宜以反應速度之提昇為目的而進行加熱。加熱溫度係可依羧酸反應性(甲基)丙烯酸酯化合物之種類或裝置而適當設定，但宜大約為60~150℃之範圍。若反應溫度低於60℃，有時至反應終了止耗費時間。另外，若反應溫度高於150℃，產生著色等之副反應，或不飽合鍵進行反應而引起凝膠化。In the case of adding a carboxylic acid-reactive (meth) acrylate compound, it is preferred to carry out heating for the purpose of improving the reaction rate. The heating temperature can be appropriately set depending on the type or device of the carboxylic acid reactive (meth) acrylate compound, but is preferably in the range of about 60 to 150 °C. If the reaction temperature is lower than 60 ° C, it sometimes takes time until the end of the reaction. Further, when the reaction temperature is higher than 150 ° C, a side reaction such as coloring or the like is caused, or a reaction is caused by a non-saturated bond to cause gelation.
如此做法所得到之本發明的感光性樹脂的分子量並無特別限定，但從塗膜強度、塗膜性或顯像性之觀點，宜為1000~200000，更宜為2500~50000。又，在本說明書中感光性樹脂之分子量係以實施例所記載之條件的GPC所得到的苯乙烯換算重量平均分子量。The molecular weight of the photosensitive resin of the present invention obtained in this manner is not particularly limited, but is preferably from 1,000 to 200,000, more preferably from 2,500 to 50,000, from the viewpoints of coating film strength, coating property, and development. In the present specification, the molecular weight of the photosensitive resin is a weight average molecular weight in terms of styrene obtained by GPC under the conditions described in the examples.
本發明之感光性樹脂係含有上述感光性樹脂、光聚合起始劑及/或光增感劑作為必須成分者。此光聚合起始劑及/或光增感劑係以溶解或分散於溶劑之狀態進行混合，或，亦可對於感光性樹脂化學結合。The photosensitive resin of the present invention contains the above-mentioned photosensitive resin, photopolymerization initiator, and/or photosensitizer as essential components. The photopolymerization initiator and/or the photosensitizer are mixed in a state of being dissolved or dispersed in a solvent, or may be chemically bonded to a photosensitive resin.
本發明所使用之光聚合起始劑及/或光增感劑係無特別限制，但可舉例如二苯甲酮、4-羥基二苯甲酮、雙-N,N-二甲基胺基二苯甲酮、雙-N,N-二乙基胺基二苯甲酮、4-甲氧基-4’-二甲基胺基二苯甲酮等之二苯甲酮類、硫雜蒽酮、2,4-二乙基硫雜蒽酮、異丙基硫雜蒽酮、氯硫雜蒽酮、異丙氧基氯硫雜蒽酮等之硫雜蒽酮類、乙基蒽醌、苯並蒽醌、胺基蒽醌、氯蒽醌、蒽醌-2-硫酸鹽、蒽醌-2,6-二磺酸鹽等之蒽醌類、乙醯苯類、苯偶因甲基醚、苯偶因乙基醚、苯偶因苯基醚等之苯偶因醚類、2,4,6-三鹵甲基三嗪類、1-羥基環己基苯基酮、2-(鄰-氯苯基)-4,5-二苯基咪唑偶體、2-(鄰-氯苯基)-4,5-二(間-甲氧基苯基)咪唑偶體、2-(鄰-氟苯基)-4,5-二苯基咪唑偶體、2-(鄰-甲氧基苯基)-4,5-二苯基咪唑偶體、2-(對-甲氧基苯基)-4,5-二苯基咪唑偶體、2,4-二(對-甲氧基苯基)-5-苯基咪唑偶體、2-(2,4-二甲氧基苯基)-4,5-二苯基咪唑偶體等之2,4,5-三芳基咪唑偶體類、苯甲基二甲基縮酮、2-苯甲基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、2-甲基-1-[4-(甲基硫)苯基]-2-嗎啉-1-丙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1,2-辛二酮、1-[4-(苯基硫)-,2-(鄰-苯甲醯基肟)]、菲醌、9,10-菲醌、甲基苯偶因、乙基苯偶因等苯偶因類、9-苯基吖嗪、1,7-雙(9,9’-吖嗪基)庚烷等、吖嗪衍生物、雙醯基磷氧化物，亦可使用此等之1種或2種以上。The photopolymerization initiator and/or the photosensitizer used in the present invention are not particularly limited, and examples thereof include benzophenone, 4-hydroxybenzophenone, and bis-N,N-dimethylamino group. Benzophenone, bis-N,N-diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. a thioxanthone such as a ketone, 2,4-diethylthianone, isopropyl thioxanthone, chlorothiazepine or isopropoxychlorothiazinone, ethyl hydrazine, Benzoquinone, aminoguanidine, chloranil, oxime-2-sulfate, ruthenium-2,6-disulfonate, oxime, acetophenone methyl ether a benzoin ether such as benzoin ethyl ether or benzoin phenyl ether, 2,4,6-trihalomethyltriazine, 1-hydroxycyclohexyl phenyl ketone, 2-(o- Chlorophenyl)-4,5-diphenylimidazolium, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole, 2-(o-fluoro Phenyl)-4,5-diphenylimidazolium, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium, 2-(p-methoxyphenyl)- 4,5-diphenylimidazolium couple, 2,4-di(p-methoxyphenyl)-5-phenylimidazolium couple, 2- 2,4,5-triarylimidazolium, etc., (2,4-dimethoxyphenyl)-4,5-diphenylimidazolium, benzyl dimethyl ketal, 2-benzene Methyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2 -morpholin-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy- 2-methyl-1-propan-1-one, 1,2-octanedione, 1-[4-(phenylsulfanyl)-,2-(o-benzhydrylhydrazine), phenanthrenequinone, 9 , 10-phenanthrene, methyl benzoin, ethyl benzoin and other benzoin, 9-phenylpyridazine, 1,7-bis(9,9'-pyridazinyl) heptane, etc. One or two or more kinds of these may be used as the azine derivative or the bis-indenyl phosphorus oxide.
於本發明之感光性樹脂中係亦可進一步添加促進劑。促進劑之例，可舉例如對-二甲基胺基安息香酸乙酯、對-二甲基胺基安息香酸異戊酯、N,N-二甲基乙醇胺、N-甲基二乙醇胺、三乙醇胺等。Further, an accelerator may be added to the photosensitive resin of the present invention. Examples of the accelerator include ethyl p-dimethylamino benzoate, isoamyl p-dimethylamino benzoate, N, N-dimethylethanolamine, N-methyldiethanolamine, and the like. Ethanolamine and the like.
於本發明之感光性樹脂組成物中係可進一步使用於分子中具有1個以上之不飽和基的聚合性單體(以下，有時僅稱「聚合性單體」)，藉此，可提升感度、耐藥品性、耐熱性及機械強度。又，就流動特性調節等之目的亦可添加聚合性單體。此聚合性單體若為於分子內具有不飽合鍵1個以上者，無特別限制而可使用，只要依適用之用途、目的而選擇適當者即可。例如聚乙二醇二(甲基)丙烯酸酯(乙烯基之數目為2~14者)、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷乙氧基三(甲基)丙烯酸酯、三羥甲基丙烷丙氧基三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯(丙烯基之數目為2~14者)、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、雙酚A聚氧乙烯二(甲基) 丙烯酸酯、雙酚A二氧乙烯二(甲基)丙烯酸酯、雙酚A三氧乙烯二(甲基)丙烯酸酯、雙酚A十氧乙烯二(甲基)丙烯酸酯、多元羧酸(酞酸酐等)與羥基及具有乙烯性不飽和基之化合物(β-羥基乙基(甲基)丙烯酸酯等)之酯化物、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己基酯等之(甲基)丙烯酸烷酯、乙二醇二縮水甘油基醚、二乙二醇二縮水甘油基醚、三乙二醇二縮水甘油基醚、四乙二醇二縮水甘油基醚、聚乙二醇二縮水甘油基醚、丙二醇二縮水甘油基醚、二丙二醇二縮水甘油基醚、三丙二醇二縮水甘油基醚、四丙二醇二縮水甘油基醚、聚丙二醇二縮水甘油基醚、山梨糖醇三縮水甘油基醚、甘油三縮水甘油基醚等之環氧基化合物的(甲基)丙烯酸加成物、馬來酸等之不飽和有機酸及其等之酸酐、N-甲基丙烯醯胺、N-乙基丙烯醯胺、N-異丙基丙烯醯胺、N-羥甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、N-異丙基甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、N,N-二乙基甲基丙烯醯胺等之丙烯醯胺類、苯乙烯、羥基苯乙烯等的苯乙烯類、N-乙烯基吡咯烷酮、N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基咪唑等，可使用此等之1種或2種以上。In the photosensitive resin composition of the present invention, a polymerizable monomer having one or more unsaturated groups in the molecule (hereinafter sometimes referred to as "polymerizable monomer") may be further used, thereby improving Sensitivity, chemical resistance, heat resistance and mechanical strength. Further, a polymerizable monomer may be added for the purpose of adjusting the flow characteristics and the like. When the polymerizable monomer has one or more unsaturated bonds in the molecule, it can be used without particular limitation, and may be appropriately selected according to the intended use and purpose. For example, polyethylene glycol di(meth)acrylate (the number of vinyl groups is 2 to 14), trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, Trimethylolpropane ethoxy tris(meth) acrylate, trimethylolpropane propoxy tri(meth) acrylate, tetramethylol methane tri(meth) acrylate, tetramethylol methane Tetra (meth) acrylate, polypropylene glycol di(meth) acrylate (the number of propylene groups is 2 to 14), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, double Phenol A polyoxyethylene di(methyl) Acrylate, bisphenol A dioxyethylene di(meth)acrylate, bisphenol A trioxyethylene di(meth)acrylate, bisphenol A decaoxyethylene di(meth)acrylate, polycarboxylic acid (酞An acid anhydride or the like, an esterified product of a hydroxyl group and a compound having an ethylenically unsaturated group (β-hydroxyethyl (meth) acrylate, etc.), methyl (meth) acrylate, ethyl (meth) acrylate, (A) (meth)acrylic acid alkyl ester such as butyl acrylate or 2-ethylhexyl (meth)acrylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol Diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, four a (meth)acrylic acid addition product of an epoxy compound such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether or glycerol triglycidyl ether, maleic acid, etc. Unsaturated organic acid and its anhydride, N-methyl acrylamide, N-ethyl acrylamide, N -isopropyl acrylamide, N-methylol acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-isopropyl methacrylamide, N- Methylol methacrylamide, N,N-dimethyl decylamine, N,N-diethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl A styrene amine such as methacrylamide or a styrene such as styrene or hydroxystyrene, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-ethylene One or two or more kinds of these may be used.
本發明之感光性樹脂組成物中係就設計性、辨認性、及光阻劑等之防止光暈等之目的亦可添加著色劑。所添加之著色劑的種類係可依著色之目的而適當選擇，可舉例如酞菁系染料、蒽醌系染料、偶氮系染料、靛藍系染料、香豆素系染料、三苯基甲烷系染料、酞菁系顏料系染料、蒽醌系顏料系染料、偶氮系顏料、喹吖啶酮(Quinacridone)系顏料、香豆素系顏料、三苯基甲烷系顏料等，可使用此等之1種或2種以上。In the photosensitive resin composition of the present invention, a coloring agent may be added for the purpose of preventing halo or the like in terms of design, visibility, and photoresist. The type of the coloring agent to be added may be appropriately selected depending on the purpose of coloring, and examples thereof include a phthalocyanine dye, an anthraquinone dye, an azo dye, an indigo dye, a coumarin dye, and a triphenylmethane system. A dye, a phthalocyanine pigment dye, an anthraquinone pigment dye, an azo pigment, a quinacridone pigment, a coumarin pigment, a triphenylmethane pigment, or the like can be used. One or two or more.
本發明之感光性樹脂組成物係可形成混合有溶液或填充劑之糊劑的型態，因此，亦可含有溶劑。所使用之溶劑的種類並無特別限制，但就一例而言可舉例如水、乙二醇、二乙二醇、三乙二醇、四乙二醇等之乙二醇類、乙二醇單甲基醚、二乙二醇單甲基醚、乙二醇二乙基醚、二乙二醇二甲基醚等之甘醇醚類、乙二醇單乙基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯等之甘醇醚乙酸酯類、丙二醇、二丙二醇、三丙二醇等之丙二醇類、丙二醇單甲基醚、丙二醇單乙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、丙二醇二甲基醚、二丙二醇二甲基醚、丙二醇二乙基醚、二丙二醇二乙基醚等之丙二醇醚類、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、二丙二醇單甲基醚乙酸酯、二丙二醇單乙基醚乙酸酯等之丙二醇醚乙酸酯類、丙酮、甲乙酮、甲基異丁基酮、環己酮等之酮類、乳酸甲酯、乳酸乙酯等之乳酸酯類、醋酸乙酯、醋酸丁酯等之醋酸酯類、二甲基亞碸、N-甲基吡咯烷酮、二甲基甲醯胺、二甲基乙醯胺、及其等之混合物。The photosensitive resin composition of the present invention can form a paste in which a solution or a filler is mixed, and therefore may contain a solvent. The type of the solvent to be used is not particularly limited, and examples thereof include ethylene glycol such as water, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and ethylene glycol monomethyl. Glycol ethers such as ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetate such as monoethyl ether acetate or diethylene glycol monobutyl ether acetate; propylene glycol such as propylene glycol, dipropylene glycol or tripropylene glycol; propylene glycol monomethyl ether; propylene glycol monoethyl Ethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol ether, propylene glycol monomethyl Propylene glycol ether acetates such as phenyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketones and cyclohexanone, lactates such as methyl lactate and ethyl lactate, ethyl acetate and acetic acid Ester acetates, etc., dimethyl sulfoxide, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, etc. and mixtures thereof.
本發明之感光性樹脂組成物中係可進一步依需要調配聚合抑制劑、可塑劑、消泡劑、偶合劑等以往公知之成分。In the photosensitive resin composition of the present invention, a conventionally known component such as a polymerization inhibitor, a plasticizer, an antifoaming agent, or a coupling agent may be further blended as needed.
本發明之感光性樹脂組成物係可藉由依常用方法而混合上述必須成分及依需要之溶劑或其他之任意成分。The photosensitive resin composition of the present invention can be mixed with the above-mentioned essential components and optionally a solvent or any other optional component by a usual method.
使如以上做法所得到之本發明的感光性樹脂組成物用為光阻劑時，係以溶液或糊劑而被塗佈於基板上。塗佈方法並無特別限制，但可適用網版印刷、簾塗、刮塗、旋塗、噴塗、浸塗、模縫塗佈等。所塗佈之溶液或糊劑係介由特定之掩罩，以UV或電子束進行曝光。使用溶劑而塗佈時，亦可經由乾燥步驟。使所曝光之塗膜以濕式進行顯像，俾可形成圖型。顯像方法係噴塗式、槳式、浸漬式等任一者均可，但宜為殘渣很少之噴塗式。亦可依需要而照射超音波等。顯像液宜使用弱鹼性水。就顯像性補助之目的亦可添加有機溶劑、界面活性劑、消泡劑等。When the photosensitive resin composition of the present invention obtained as described above is used as a photoresist, it is applied onto a substrate by a solution or a paste. The coating method is not particularly limited, but may be applied to screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating, die coating, and the like. The applied solution or paste is exposed to UV or electron beam through a specific mask. When coating with a solvent, it is also possible to pass through a drying step. The exposed coating film is developed in a wet manner, and a crucible can be formed into a pattern. The development method may be any of spray type, paddle type, and immersion type, but it is preferably a spray type with few residues. Ultrasonic waves, etc. can also be irradiated as needed. It is advisable to use weakly alkaline water for the developer. An organic solvent, a surfactant, an antifoaming agent, etc. may be added for the purpose of imaging support.
以下，依實施例而詳細地說明本發明，但本發明係不受此等而任何限定。Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
於具備攪拌機與冷卻管之1000 ml的燒瓶中，置入均苯四甲酸二酐(Daicel公司製品：PMDA)64 g、9,9-雙[4-(2-羥基乙氧基)苯基]芴(大阪瓦斯化學公司製：BPEF)136 g、丙二醇單甲基醚乙酸酯134 g，在氮氣流下一邊攪拌一邊在155℃之油浴中加熱4小時。繼而，冷卻至120℃後，加入4-二甲基胺基吡啶1 g、4-羥基-2,2,6,6-四甲基六氫吡啶-1-氧(ADEKA公司製：Adekastab LA-7RD)0.04 g、4-羥丁基丙烯酸酯縮水甘油基醚(日本化成公司製品：4HBAGE)106 g，以120℃持續攪拌4小時。然後，冷卻至室溫，以不揮發成分成為50質量%之方式，加入丙二醇單甲基醚乙酸酯而得到淡黃色透明黏稠性之感光性樹脂(A1)溶液。In a 1000 ml flask equipped with a stirrer and a cooling tube, pyromellitic dianhydride (Daicel product: PMDA) 64 g, 9,9-bis[4-(2-hydroxyethoxy)phenyl] was placed. 136 g (BPEF, manufactured by Osaka Gas Chemical Co., Ltd.) and 134 g of propylene glycol monomethyl ether acetate were heated in an oil bath of 155 ° C for 4 hours while stirring under a nitrogen stream. Then, after cooling to 120 ° C, 1 g of 4-dimethylaminopyridine, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridin-1-oxyl (Adekastab LA-made by ADEKA) was added. 7RD) 0.04 g, 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) 106 g, and stirring was continued at 120 ° C for 4 hours. Thereafter, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 50% by mass to obtain a pale yellow transparent viscous photosensitive resin (A1) solution.
有關所得到之樹脂溶液，測定黏度、GPC之苯乙烯換算重量平均分子量及固形分酸價後，為黏度2900 mPa．s/25℃、以GPC所得到之苯乙烯換算重量平均分子量12523，固形分酸價為2.2 mgKOH/g。又，於黏度測定係使用東機產業股份公司製BM型黏度計。又，GPC的測定係於管柱使用Tosoh股份公司製TSKgel G7000HXL，TSKgel GMHXL 2根，TSKgel G2500HXL，以THF溶離液40℃，以0.5 ml/分鐘流速測定。酸價係依據JIS-K0070之中和滴定法而測定。For the obtained resin solution, the viscosity, the styrene-converted weight average molecular weight of GPC, and the solid acid value are measured, and the viscosity is 2900 mPa. The weight average molecular weight of s/25 ° C, obtained by GPC, was 12,523, and the solid acid value was 2.2 mgKOH/g. Further, a BM type viscometer manufactured by Toki Sangyo Co., Ltd. was used for the viscosity measurement. Further, the measurement of GPC was carried out by using TSKgel G7000HXL, TSKgel GMHXL 2, TSKgel G2500HXL manufactured by Tosoh Co., Ltd. in a column, and measuring at a flow rate of 0.5 ml/min with a THF solution at 40 ° C. The acid value was measured in accordance with JIS-K0070 and titration.
於具備攪拌機與冷卻管之1000 ml的燒瓶中，置入聯苯基四羧酸二酐(宇部興產公司製品：BPDA)72 g、9,9-雙[4-(2-羥基乙氧基)苯基]芴(大阪瓦斯化學公司製：BPEF)128 g、4-二甲基胺基吡啶1g、丙二醇單甲基醚乙酸酯134g，在氮氣流下一邊攪拌一邊在155℃之油浴中加熱4小時。繼而，冷卻至120℃後，加入4-羥基-2,2,6,6-四甲基六氫吡啶-1-氧(ADEKA公司製：Adekastab LA-7RD)0.04 g、4-羥丁基丙烯酸酯縮水甘油基醚(日本化成公司製品：4HBAGE)84g，以120℃攪拌4小時。然後，冷卻至室溫，以不揮發成分成為50質量%之方式，加入丙二醇單甲基醚乙酸酯而得到淡黃色透明黏稠性之感光性樹脂(A2)溶液。有關所得到之樹脂溶液，測定黏度、GPC之苯乙烯換算重量平均分子量及固形分酸價後，為黏度4200mPa．s/25℃、以GPC所得到之苯乙烯換算重量平均分子量7243，固形分酸價為2.5 mgKOH/g。In a 1000 ml flask equipped with a stirrer and a cooling tube, biphenyltetracarboxylic dianhydride (product of Ube Industries Co., Ltd.: BPDA) 72 g, 9,9-bis[4-(2-hydroxyethoxy) was placed. ) phenyl] hydrazine (manufactured by Osaka Gas Chemical Co., Ltd.: BPEF) 128 g, 1-dimethylaminopyridine 1 g, propylene glycol monomethyl ether acetate 134 g, and stirred in a 155 ° C oil bath under a nitrogen stream Heat for 4 hours. Then, after cooling to 120 ° C, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo (Adekastab LA-7RD, manufactured by Adeka Co., Ltd.) was added in an amount of 0.04 g, 4-hydroxybutylacrylic acid. 84 g of ester glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) was stirred at 120 ° C for 4 hours. Then, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 50% by mass to obtain a pale yellow transparent viscous photosensitive resin (A2) solution. The viscosity of the resin solution obtained after determining the viscosity, GPC styrene-converted weight average molecular weight and solid acid value, the viscosity is 4200 mPa. The weight average molecular weight of 74.3 in terms of styrene in terms of GPC obtained at s/25 ° C, and the solid acid value was 2.5 mg KOH/g.
依據特開平9-325008號公報記載之合成例1，得到感光性樹脂(A3)。According to Synthesis Example 1 described in JP-A-9-325008, a photosensitive resin (A3) was obtained.
使用實施例1~2及比較例1之感光性樹脂，以表1之組成製作感光性組成物。此感光性組成物於1.1mm厚之鈉玻璃基板以條棒塗佈機塗佈成乾燥膜厚6μm，以80℃之溫風乾燥機乾燥10分鐘後，冷卻至室溫。繼而，以超高壓水銀燈UV照射機，照射積算光量300 mJ/cm2 之紫外線。對於此硬化塗膜，依據JIS-K5400，實施鉛筆硬度及百格剝離試驗，評估塗膜之強度。Using the photosensitive resins of Examples 1 and 2 and Comparative Example 1, a photosensitive composition was produced in the composition of Table 1. The photosensitive composition was applied to a 1.1 mm-thick soda glass substrate by a bar coater to a dry film thickness of 6 μm, and dried in a warm air dryer at 80 ° C for 10 minutes, and then cooled to room temperature. Then, an ultraviolet light having an integrated light amount of 300 mJ/cm 2 was irradiated with an ultrahigh pressure mercury lamp UV irradiator. With respect to this hardened coating film, the pencil hardness and the hundred-bar peeling test were carried out in accordance with JIS-K5400, and the strength of the coating film was evaluated.
使用比較例1之感光性樹脂的感光性組成物係因為低分子量，塗膜形成能力弱，若不施加其他之樹脂成分，無法評估。使用實施例1~2之感光性樹脂的感光性組成物係可得到平滑的膜，硬度、密著性均良好。The photosensitive composition using the photosensitive resin of Comparative Example 1 was weak in coating film formation ability due to low molecular weight, and could not be evaluated unless other resin components were applied. Using the photosensitive composition of the photosensitive resin of Examples 1-2, a smooth film was obtained, and hardness and adhesiveness were favorable.
於具備攪拌機與冷卻管之1000 ml的燒瓶中，置入均苯四甲酸二酐(Daicel公司製品：PMDA)76 g、9,9-雙[4-(2-羥基乙氧基)苯基]芴(大阪瓦斯化學公司製：BPEF)124 g、丙二醇單甲基醚乙酸酯134g，在氮氣流下一邊攪拌一邊在155℃之油浴中加熱4小時。繼而，冷卻至120℃後，加入4-二甲基胺基吡啶1 g、4-羥基-2,2,6,6-四甲基六氫吡啶-1-氧(ADEKA公司製：Adekastab LA-7RD)0.04 g、4-羥丁基丙烯酸酯縮水甘油基醚(日本化成公司製品：4HBAGE)106g，以120℃攪拌2小時。然後，冷卻至室溫，以不揮發成分成為50重量%之方式，加入丙二醇單甲基醚乙酸酯而得到淡黃色透明黏稠性之感光性樹脂(A4)溶液。In a 1000 ml flask equipped with a stirrer and a cooling tube, pyromellitic dianhydride (Daicel product: PMDA) 76 g, 9,9-bis[4-(2-hydroxyethoxy)phenyl] was placed. 124 g of hydrazine (manufactured by Osaka Gas Chemical Co., Ltd.: BPEF) and 134 g of propylene glycol monomethyl ether acetate were heated in an oil bath of 155 ° C for 4 hours while stirring under a nitrogen stream. Then, after cooling to 120 ° C, 1 g of 4-dimethylaminopyridine, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridin-1-oxyl (Adekastab LA-made by ADEKA) was added. 7RD) 0.04 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) 106 g, and stirred at 120 ° C for 2 hours. Thereafter, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so as to have a nonvolatile content of 50% by weight to obtain a pale yellow transparent viscous photosensitive resin (A4) solution.
有關所得到之樹脂溶液，測定黏度、GPC之苯乙烯換算重量平均分子量及固形分酸價後，為黏度4800mPa．s/25℃、以GPC所得到之苯乙烯換算重量平均分子量23169，固形分酸價為75.2 mgKOH/g。The viscosity of the obtained resin solution was measured after the viscosity, GPC styrene-converted weight average molecular weight and solid acid value, and the viscosity was 4800 mPa. The weight average molecular weight of styrene was 23,169 at s/25 ° C, and the solid acid value was 75.2 mg KOH/g.
於具備攪拌機與冷卻管之1000 ml的燒瓶中，置入聯苯基四羧酸二酐(宇部興產公司製品：BPDA)90g、9,9-雙[4-(2-羥基乙氧基)苯基]芴(大阪瓦斯化學公司製：BPEF)110g、丙二醇單甲基醚乙酸酯134g、4-二甲基胺基吡啶1g，在氮氣流下一邊攪拌一邊在155℃之油浴中加熱4小時。繼而，冷卻至120℃後，加入4-羥基-2,2,6,6-四甲基六氫吡啶-1-氧(ADEKA公司製：Adekastab LA-7RD)0.04 g、4-羥丁基丙烯酸酯縮水甘油基醚(日本化成公司製品：4HBAGE)80g，以120℃攪拌2小時。然後，冷卻至室溫，以不揮發成分成為50質量%之方式，加入丙二醇單甲基醚乙酸酯而得到淡黃色透明黏稠性之感光性樹脂(A5)溶液。In a 1000 ml flask equipped with a stirrer and a cooling tube, biphenyltetracarboxylic dianhydride (product of Ube Industries Co., Ltd.: BPDA) 90 g, 9,9-bis[4-(2-hydroxyethoxy) was placed. 110 g of phenyl] hydrazine (manufactured by Osaka Gas Chemical Co., Ltd.: BPEF), 134 g of propylene glycol monomethyl ether acetate, and 1 g of 4-dimethylaminopyridine, and heated in an oil bath of 155 ° C while stirring under a nitrogen stream. hour. Then, after cooling to 120 ° C, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo (Adekastab LA-7RD, manufactured by Adeka Co., Ltd.) was added in an amount of 0.04 g, 4-hydroxybutylacrylic acid. 80 g of ester glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) was stirred at 120 ° C for 2 hours. Then, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 50% by mass to obtain a pale yellow transparent viscous photosensitive resin (A5) solution.
有關所得到之樹脂溶液，測定黏度、GPC之苯乙烯換算重量平均分子量及固形分酸價後，為黏度6600mPa．s/25℃、以GPC所得到之苯乙烯換算重量平均分子量18230，固形分酸價為71.6 mgKOH/g。The viscosity of the obtained resin solution was measured after the viscosity, GPC styrene-converted weight average molecular weight and solid acid value, and the viscosity was 6600 mPa. The weight average molecular weight of 1830, which is obtained by GPC, is s/25 ° C, and the solid content acid value is 71.6 mgKOH/g.
使用環氧基當量257之雙酚芴型環氧樹脂(大阪瓦斯化學公司製：BPFG)110g，依據特許第3813244號公報記載之合成例1及實施例1，得到感光性樹脂(A6)。於合成係需要20小時以上，相較於本發明之實施例1~4而生產性係明顯降低者。A photosensitive resin (A6) was obtained according to Synthesis Example 1 and Example 1 described in Japanese Patent No. 3813244, using 110 g of a bisphenol hydrazine type epoxy resin (BPFG, manufactured by Osaka Gas Chemical Co., Ltd.) having an epoxy group equivalent of 257. It takes more than 20 hours for the synthesis system to be significantly lower than the production systems of Examples 1-4 of the present invention.
使用環氧基當量257之雙酚芴型環氧樹脂(大阪瓦斯化學公司製：BPFG)110g，依據特許第3813244號公報記載之合成例1及實施例2，得到感光性樹脂(A7)。於合成係需要21小時以上，相較於本發明之實施例7及實施例8而生產性係明顯降低者。A photosensitive resin (A7) was obtained according to Synthesis Example 1 and Example 2 described in Japanese Patent No. 3813244, using 110 g of a bisphenol oxime type epoxy resin (BPFG, manufactured by Osaka Gas Chemical Co., Ltd.) having an epoxy group equivalent of 257. The synthesis system was required to be 21 hours or more, and the productivity system was remarkably lowered as compared with Example 7 and Example 8 of the present invention.
除將實施例8之4-羥基丁基丙烯酸酯縮水甘油基醚80g變更成縮水甘油基甲基丙烯酸酯(三菱Rayon公司製品：GMA)60g以外，其餘係同樣地進行反應，得到感光性樹脂溶液(A8)。有關所得到之樹脂溶液，測定黏度、GPC之苯乙烯換算重量平均分子量及固形分酸價後，為黏度12400mPa．s/25℃、以GPC所得到之苯乙烯換算重量平均分子量16100，固形分酸價為74.2 mgKOH/g。In the same manner as in the case of changing 80 g of 4-hydroxybutyl acrylate glycidyl ether of Example 8 to 60 g of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.: GMA), the reaction was carried out in the same manner to obtain a photosensitive resin solution. (A8). The viscosity of the obtained resin solution, after measuring the viscosity, GPC styrene-converted weight average molecular weight and solid acid value, the viscosity is 12400 mPa. The weight average molecular weight of styrene in terms of styrene was 16100 at s/25 ° C, and the solid acid value was 74.2 mg KOH/g.
有關實施例7~8及比較例4~5之感光性樹脂，測定製造後與室溫保存1個月後的GPC所得到之聚苯乙烯換算重量平均分子量，研究其變化率。結果表示於表2中。The photosensitive resins of Examples 7 to 8 and Comparative Examples 4 to 5 were measured for the polystyrene-equivalent weight average molecular weight obtained by GPC after storage for one month after the production and at room temperature, and the rate of change was examined. The results are shown in Table 2.
實施例7~8之感光性樹脂係幾乎看不到變化，但，比較例2~3之感光性樹脂係可看到25%左右的分子量增加，為保存安定性差者。In the photosensitive resins of Examples 7 to 8, almost no change was observed. However, in the photosensitive resins of Comparative Examples 2 to 3, an increase in molecular weight of about 25% was observed, and the storage stability was poor.
使用實施例7~8及比較例4~6之感光性樹脂，以下述表3之調配製作感光性組成物。此感光性組成物於1.1mm厚之鈉玻璃基板以旋塗機塗佈成乾燥膜厚3μm，以100℃之加熱板乾燥90秒後，冷卻至室溫。繼而，以超高壓水銀燈曝光機，以紫外線照射15 mW/cm2 (365nm)、積算光量20mJ/cm2 ，以UGRA-OFFSET-TEST KAIL 1982作為掩罩之軟接觸曝光後，於25℃之1%碳酸鈉水浸漬顯像90秒，形成圖型，以殘留之步驟階數評估感度，以微細線評估解析度。結果一併表示於表3中。Using the photosensitive resins of Examples 7 to 8 and Comparative Examples 4 to 6, a photosensitive composition was prepared by the following Table 3. The photosensitive composition was applied to a dry glass film having a thickness of 3 μm on a 1.1 mm thick soda glass substrate, dried on a hot plate at 100 ° C for 90 seconds, and then cooled to room temperature. Then, with an ultra-high pressure mercury lamp exposure machine, ultraviolet light is irradiated at 15 mW/cm 2 (365 nm), the integrated light amount is 20 mJ/cm 2 , and UGRA-OFFSET-TEST KAIL 1982 is used as a mask for soft contact exposure, at 25 ° C. % sodium carbonate water was immersed for development for 90 seconds to form a pattern, and the sensitivity was evaluated by the order of the remaining steps, and the resolution was evaluated by a fine line. The results are shown together in Table 3.
相較於使用比較例4~6之感光性樹脂(A6~A8)的感光性組成物，使用實施例7~8(A4~A5)之感光性樹脂的感光性組成物係感度高，顯示良好的光阻特性。Compared with the photosensitive compositions using the photosensitive resins (A6 to A8) of Comparative Examples 4 to 6, the photosensitive compositions using the photosensitive resins of Examples 7 to 8 (A4 to A5) have high sensitivity and good display. Photoresist characteristics.
於具備攪拌機與冷卻管之1000 ml的燒瓶中，置入3,3’-4,4’-聯苯基四羧酸酐(宇部興產公司製：BPDA)71.8g、9,9-雙[4-(2-羥基乙氧基)3苯基苯基]芴(大阪瓦斯化學公司製：BOPPEF)109.7 g、丙二醇單甲基醚乙酸酯128g、4-二甲基胺基吡啶0.25g，一邊攪拌一邊以120℃之電熱包加熱4小時。繼而，加入對-甲氧基酚(東京化成製)0.1 g、羥基乙基丙烯酸酯(東京化成製)13.7g，以120℃加熱4小時。進一步，加入4-羥丁基丙烯酸酯縮水甘油基醚(日本化成公司製品：4HBAGE)34.68g，以120℃加熱攪拌4小時，得到淡黃色透明黏稠性之感光性樹脂(A9)溶液。In a 1000 ml flask equipped with a stirrer and a cooling tube, 3,3'-4,4'-biphenyltetracarboxylic anhydride (manufactured by Ube Industries, Ltd.: BPDA) was placed in a 71.8 g, 9,9-double [4] -(2-hydroxyethoxy)3phenylphenyl]indole (BOPPEF, manufactured by Osaka Gas Chemical Co., Ltd.) 109.7 g, propylene glycol monomethyl ether acetate 128 g, 4-dimethylaminopyridine 0.25 g, one side The mixture was heated while heating at 120 ° C for 4 hours while stirring. Then, 1 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 13.7 g of hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 120 ° C for 4 hours. Further, 34.68 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) was added, and the mixture was heated and stirred at 120 ° C for 4 hours to obtain a pale yellow transparent viscous photosensitive resin (A9) solution.
有關所得到之樹脂溶液，測定黏度、GPC之苯乙烯換算重量平均分子量、固形分及固形分酸價後，為黏度187100mPa．s/25℃、以GPC所得到之苯乙烯換算重量平均分子量4170、固形分66.8%、固形分酸價為85.4mgKOH/g。For the obtained resin solution, the viscosity, the styrene-converted weight average molecular weight of GPC, the solid content and the solid acid value were measured, and the viscosity was 187100 mPa. The weight average molecular weight of 4170, the solid content of 66.8%, and the solid content acid value of 85.4 mgKOH/g in terms of styrene in terms of GPC obtained at s/25 °C.
於具備攪拌機與冷卻管之1000 ml的燒瓶中，置入3,3’-4,4’-聯苯基四羧酸酐(宇部興產公司製：BPDA)61.22g、9,9-雙[6-(2-羥基乙氧基)萘基]芴(大阪瓦斯化學公司製：BNFEO)95.89 g、丙二醇單甲基醚乙酸酯125g、4-二甲基胺基吡啶0.25g，一邊攪拌一邊以120℃之電熱包加熱4小時。繼而，加入對-甲氧基酚(東京化成製)0.1 g、羥基乙基丙烯酸酯(東京化成製)13.3g，以120℃加熱4小時。進一步，加入4-羥丁基丙烯酸酯縮水甘油基醚(日本化成公司製品：4HBAGE)56g，以120℃加熱攪拌4小時，得到淡黃色透明黏稠性之感光性樹脂(A10)溶液。3,3'-4,4'-biphenyltetracarboxylic anhydride (manufactured by Ube Industries, Ltd.: BPDA) was placed in a 1000 ml flask equipped with a stirrer and a cooling tube. 61.22 g, 9,9-double [6] -(2-hydroxyethoxy)naphthyl]anthracene (BNFEO, Osaka Gas Chemical Co., Ltd.) 95.89 g, propylene glycol monomethyl ether acetate 125 g, and 4-dimethylaminopyridine 0.25 g, while stirring The electric heating pack at 120 ° C was heated for 4 hours. Then, 0.1 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 13.3 g of hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 120 ° C for 4 hours. Further, 56 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) was added, and the mixture was heated and stirred at 120 ° C for 4 hours to obtain a pale yellow transparent viscous photosensitive resin (A10) solution.
有關所得到之樹脂溶液，測定黏度、GPC之苯乙烯換算重量平均分子量、固形分及固形分酸價後，為黏度586700mPa．s/25℃、以GPC所得到之苯乙烯換算重量平均分子量9250、固形分59.0%、固形分酸價為60.4mgKOH/g。For the obtained resin solution, the viscosity, the weight average molecular weight of GPC, the solid content and the solid acid value were measured, and the viscosity was 586700 mPa. The weight average molecular weight of styrene was 9250 at s/25 ° C, the solid content was 59.0%, and the solid acid value was 60.4 mg KOH/g.
使用實施例13之感光性樹脂，以表4之調配製作成感光性組成物。使此感光性組成物進行與實施例9~12同樣之評估。Using the photosensitive resin of Example 13, the photosensitive composition was prepared by the preparation of Table 4. This photosensitive composition was evaluated in the same manner as in Examples 9 to 12.
任一者之感光性組成物係感度亦高，顯示良好的光阻特性。The photosensitive composition of either of them has high sensitivity and exhibits good photoresist characteristics.
本發明之感光性樹脂係可以低成本容易地製造，容易調整交聯密度或酸價，具備高耐熱性、高透明性、高折射率及低線膨脹率等優異之特性者。因此，使用此感光性樹脂之樹脂組成物係可用於調製在液晶顯示器或電子零件等的層間絕緣膜或保護膜(例如彩色濾光片、液晶顯示元件、積體電路元件、固體攝影元件等所使用之層間絕緣膜或保護膜)等。The photosensitive resin of the present invention can be easily produced at low cost, and it is easy to adjust the crosslinking density or the acid value, and has excellent properties such as high heat resistance, high transparency, high refractive index, and low linear expansion ratio. Therefore, the resin composition using the photosensitive resin can be used for preparing an interlayer insulating film or a protective film (for example, a color filter, a liquid crystal display element, an integrated circuit element, a solid-state imaging device, etc.) such as a liquid crystal display or an electronic component. An interlayer insulating film or a protective film to be used, and the like.
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| JP6123620B2 (en) * | 2013-09-30 | 2017-05-10 | Jsr株式会社 | Radiation-sensitive resin composition, display element insulating film, method for forming the same, and display element |
| JP2015069181A (en) * | 2013-09-30 | 2015-04-13 | Jsr株式会社 | Radiation-sensitive resin composition, cured film, method for forming the same and display element |
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| JP6487308B2 (en) * | 2014-10-20 | 2019-03-20 | 大阪ガスケミカル株式会社 | Polyester poly (meth) acrylate having fluorene skeleton, curable composition and cured product thereof, and production method thereof |
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| JP6588719B2 (en) * | 2015-03-30 | 2019-10-09 | 日鉄ケミカル＆マテリアル株式会社 | Photosensitive material, holographic recording medium, and holographic recording method |
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| JP6875929B2 (en) * | 2016-06-02 | 2021-05-26 | 大阪ガスケミカル株式会社 | Photosensitive resin composition |
| CN106397752B (en) * | 2016-10-14 | 2019-03-29 | 常州强力电子新材料股份有限公司 | Photoresist, preparation method containing fluorenes and the Photocurable composition and photoresist with it |
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