TWI818026B

TWI818026B - Chemically amplified positive photosensitive resin composition, protective film and element

Info

Publication number: TWI818026B
Application number: TW108118289A
Authority: TW
Inventors: 劉騏銘; 施俊安
Original assignee: 奇美實業股份有限公司
Priority date: 2019-05-27
Filing date: 2019-05-27
Publication date: 2023-10-11
Also published as: TW202043308A; CN111999980A

Abstract

A chemically amplified positive photosensitive resin composition is provided, in which the composition includes resin (A), a photoacid generator (B), solvent (C) and an epoxy compound (D). A protective film formed by the chemically amplified positive photosensitive resin composition and an element including the protective film are also provided. The protective film has sufficient adhesiveness after a developing treatment and sufficient chemical resistance. The protective film may be applied to form a planarization film of a thin-film transistor, an interlayer insulating film, or a core material or a coating layer of an optical waveguide.

Description

化學增幅型正型感光性樹脂組成物、保護膜及元件 Chemically amplified positive photosensitive resin composition, protective Protective film and components

本發明係有關於一種化學增幅型正型感光性樹脂組成物，及由其形成之保護膜、及具有保護膜之元件。特別是，提供一種曝光、顯影後形成具有良好的顯影密著性佳、耐化性等特性之保護膜用正型感光性樹脂組成物。此保護膜適用於液晶顯示元件、有機EL顯示元件等之薄膜電晶體(Thin Film Transistor；TFT)基板用平坦化膜、層間絕緣膜或光波導路之芯材或包覆材。 The present invention relates to a chemically amplified positive photosensitive resin composition, a protective film formed therefrom, and an element with a protective film. In particular, the invention provides a positive photosensitive resin composition for forming a protective film with good development adhesion, chemical resistance and other characteristics after exposure and development. This protective film is suitable for flattening films, interlayer insulating films, or core materials or cladding materials for optical waveguides for thin film transistor (TFT) substrates such as liquid crystal display elements and organic EL display elements.

薄膜電晶體型液晶顯示元件或有機電致發光元件(organic electroluminescence device，有機EL元件)等顯示元件，通常包括層間絕緣膜或平坦化膜等絕緣膜。此種絕緣膜通常使用感放射線性組成物來形成。就圖案化性能的觀點而言，習知多使用利用萘醌二疊氮化物(naphthoquinone diazide)等酸產生劑的正型感放射線性樹脂組成物(參照日本專利特開2001-354822號公報)，做為此種感放射線性組成物，但近年來提出了多種感放射線性組成物。 Display elements such as thin film transistor liquid crystal display elements or organic electroluminescence devices (organic EL elements) generally include insulating films such as interlayer insulating films and planarizing films. Such an insulating film is usually formed using a radiation-sensitive composition. From the viewpoint of patterning performance, it is known that positive-type radiation-sensitive resin compositions using acid generators such as naphthoquinone diazide are often used (see Japanese Patent Laid-Open No. 2001-354822). for Such radiation-sensitive compositions are used, but in recent years, various radiation-sensitive compositions have been proposed.

舉例而言，提出了一種正型化學增幅材料，其目的在於：以較使用萘醌二疊氮化物等酸產生劑的前述正型感放射線性樹脂組成物具有更高的感度，來形成顯示元件用的硬化膜(參照日本專利特開2004-4669號公報)。所述正型化學增幅材料含有交聯劑、酸產生劑及酸解離性樹脂。酸解離性樹脂具有可利用酸的作用而解離的保護基，雖酸解離性樹脂本身不溶或者難溶於鹼性水溶液中，但通過利用酸的作用，使保護基解離而變得可溶於鹼性水溶液中。另外，也提出了含有具有縮醛結構及/或縮酮結構以及環氧基的樹脂及酸產生劑的正型感放射線性組成物(參照日本專利特開2004-264623號公報、日本專利特開2011-215596號公報以及日本專利特開2008-304902號公報)。 For example, a positive-type chemical amplification material is proposed, which aims to form a display element with a higher sensitivity than the aforementioned positive-type radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide. Cured film used (refer to Japanese Patent Application Laid-Open No. 2004-4669). The positive chemical amplification material contains a cross-linking agent, an acid generator and an acid-dissociating resin. Acid-dissociating resin has a protective group that can be dissociated by the action of an acid. Although the acid-dissociating resin itself is insoluble or poorly soluble in an alkaline aqueous solution, the protecting group is dissociated by the action of an acid and becomes soluble in alkali. in aqueous solution. In addition, a positive radiation-sensitive composition containing a resin having an acetal structure and/or a ketal structure and an epoxy group and an acid generator has also been proposed (see Japanese Patent Laid-Open No. 2004-264623, Japanese Patent Laid-Open No. Publication No. 2011-215596 and Japanese Patent Application Publication No. 2008-304902).

這些感放射線性樹脂組成物中，除了高放射線感度以外，還需要求即便長期保存，黏度也不會變化的保存穩定性，進而使這些感放射線性樹脂組成物形成的硬化膜，可達到不因顯影液等而膨潤的耐化性。進而，所述硬化膜形成的圖案也可達到：在顯影後，圖案與基板充分密合而難以剝離；硬化膜具有足夠的透明性；以及，即便在曝光後進行放置的情況下，圖案也與基板充分密合而難以剝離。 In addition to high radiation sensitivity, these radiation-sensitive resin compositions are required to have storage stability in which the viscosity does not change even if stored for a long period of time, so that the cured film formed by these radiation-sensitive resin compositions can achieve a level that is not affected by changes in the radiation sensitivity. Chemical resistance to swelling due to developer, etc. Furthermore, the pattern formed by the cured film can also achieve the following: after development, the pattern and the substrate are sufficiently adhered to each other to be difficult to peel off; the cured film has sufficient transparency; and even when placed after exposure, the pattern remains consistent with the substrate. The substrate is tightly adhered and difficult to peel off.

然而，目前的感光性樹脂組成物之所至得之膜的顯影密著性、耐化性仍無法令業界所接受。 However, the development adhesion and chemical resistance of the film obtained from the current photosensitive resin composition are still not acceptable to the industry.

本發明的一個態樣在於提出一種化學增幅型正型感光性樹脂組成物。在一些實施例中，此化學增幅型正型感光性樹脂組成物可包含樹脂(A)、光酸產生劑(B)、溶劑(C)及環氧化合物(D)，以下詳述之。 One aspect of the present invention provides a chemically amplified positive photosensitive resin composition. In some embodiments, the chemically amplified positive photosensitive resin composition may include resin (A), photoacid generator (B), solvent (C) and epoxy compound (D), as described in detail below.

樹脂(A)Resin(A)

樹脂(A)是由單體混合物所共聚合而得。在一些實施例中，此單體混合物至少包括不飽和羧酸單體(a-1)以及含酸解離性基之單體(a-2)。 Resin (A) is obtained by copolymerizing a monomer mixture. In some embodiments, the monomer mixture at least includes unsaturated carboxylic acid monomer (a-1) and acid-dissociable group-containing monomer (a-2).

不飽和羧酸單體(a-1)Unsaturated carboxylic acid monomer (a-1)

本發明之不飽和羧酸單體(a-1)係指包含羧酸基或羧酸酐結構及聚合結合用之不飽和鍵之化合物，其結構並無特別限制，可包括但不限於不飽和單羧酸化合物、不飽和二羧酸化合物、不飽和二羧酸酐化合物、多環型不飽和羧酸化合物、多環型不飽和二羧酸化合物、多環型不飽和二羧酸酐化合物。 The unsaturated carboxylic acid monomer (a-1) of the present invention refers to a compound containing a carboxylic acid group or a carboxylic acid anhydride structure and an unsaturated bond for polymerization. Its structure is not particularly limited and may include but is not limited to unsaturated monomers. Carboxylic acid compound, unsaturated dicarboxylic acid compound, unsaturated dicarboxylic acid anhydride compound, polycyclic unsaturated carboxylic acid compound, polycyclic unsaturated dicarboxylic acid compound, polycyclic unsaturated dicarboxylic acid anhydride compound.

前述不飽和單羧酸化合物之具體例如：(甲基)丙烯酸、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、2-(甲基)丙烯醯乙氧基丁二酸酯、2-(甲基)丙烯醯乙氧基六氫化苯二甲酸酯、2-(甲基)丙烯醯乙氧基苯二甲酸酯、omega-羧基聚己內酯多元醇單丙烯酸酯(商品名為ARONIX M-5300，東亞合成製)。 Specific examples of the aforementioned unsaturated monocarboxylic acid compounds include: (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-(meth)acrylethoxysuccinate, 2 -(Meth)acrylethoxyhexahydrophthalate, 2-(meth)acrylethoxyphthalate, omega-carboxypolycaprolactone polyol monoacrylate (trade name It is ARONIX M-5300, manufactured by Toa Gosei).

前述不飽和二羧酸化合物之具體例如：馬來酸、富馬酸、甲基富馬酸、衣康酸、檸康酸等。於本發明之具體例中，不飽和二羧酸酐化合物為前述不飽和二羧酸化合物之酸酐化合物。 Specific examples of the aforementioned unsaturated dicarboxylic acid compounds include maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid, etc. in the present invention In a specific example, the unsaturated dicarboxylic acid anhydride compound is an acid anhydride compound of the aforementioned unsaturated dicarboxylic acid compound.

前述多環型不飽和羧酸化合物之具體例如：5-羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯。 Specific examples of the aforementioned polycyclic unsaturated carboxylic acid compounds include: 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, Carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2. 1] Hept-2-ene.

前述多環型不飽和二羧酸化合物之具體例如：5,6-二羧酸二環[2.2.1]庚-2-烯。 Specific examples of the aforementioned polycyclic unsaturated dicarboxylic acid compounds include: 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

前述多環型不飽和二羧酸酐化合物為前述多環型不飽和二羧酸化合物之酸酐化合物。 The aforementioned polycyclic unsaturated dicarboxylic acid anhydride compound is an acid anhydride compound of the aforementioned polycyclic unsaturated dicarboxylic acid compound.

上述不飽和羧酸單體(a-1)之較佳具體例為丙烯酸、甲基丙烯酸、馬來酸酐、2-甲基丙烯醯乙氧基丁二酸酯、2-甲基丙烯醯基乙氧基六氫化苯二甲酸或其組合。 Preferable specific examples of the above-mentioned unsaturated carboxylic acid monomer (a-1) are acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloyl ethoxysuccinate, and 2-methacryloyl ethoxysuccinate. Oxyhexahydrophthalic acid or combinations thereof.

以單體混合物的使用量為100重量份，不飽和羧酸單體(a-1)的使用量為3重量份至50重量份，較佳為3重量份至45重量份，更佳為3重量份至40重量份。 Taking the usage amount of the monomer mixture as 100 parts by weight, the usage amount of the unsaturated carboxylic acid monomer (a-1) is 3 to 50 parts by weight, preferably 3 to 45 parts by weight, and more preferably 3 parts by weight to 40 parts by weight.

含酸解離性基之單體(a-2)Monomer (a-2) containing an acid-dissociable group

在一些實施例中，所述單體混合物的含酸解離性基之單體(a-2)具有如下式(1)所示之酸解離性基。含酸解離性基之單體(a-2)的酸解離性基，在曝光時藉由自後述之光酸產生劑(B)產生的酸的作用而解離，並產生極性基，因此原本不溶或難溶於鹼水溶液的樹脂(A)變成對鹼水溶液具可溶性。 In some embodiments, the acid-dissociating group-containing monomer (a-2) of the monomer mixture has an acid-dissociating group represented by the following formula (1). The acid-dissociable group of the acid-dissociable group-containing monomer (a-2) is dissociated by the action of the acid generated from the photoacid generator (B) described later during exposure, and a polar group is generated, so it is originally insoluble. Or the resin (A) that is poorly soluble in the alkali aqueous solution becomes soluble in the alkali aqueous solution.

所述含酸解離性基之單體(a-2)只要具有如式(1)的結構，則無特別限定。此式(1)之含酸解離性基之單體(a-2)可藉由酸而容易解離。於式(1)中，R¹和R²各自獨立為氫原子、烷基、脂環式烴基或芳基，其中所述烷基、脂環式烴基或芳基所具有的氫原子的一部分或全部可被取代；而且，R¹及R²不同時為氫原子；R³為烷基、脂環式烴基、芳烷基或者芳基，其中R³的所述烷基、脂環式烴基、芳烷基及芳基所具有的氫原子的一部分或全部可被取代；R¹與R³可相互鍵結而與R¹所鍵結的碳原子以及R³所鍵結的氧原子一起形成環狀醚結構；以及*¹代表鍵結處。 The acid-dissociable group-containing monomer (a-2) is not particularly limited as long as it has a structure such as formula (1). The acid-dissociable group-containing monomer (a-2) of the formula (1) can be easily dissociated by an acid. In formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein a part of the hydrogen atoms possessed by the alkyl group, an alicyclic hydrocarbon group or an aryl group or All can be substituted; moreover, ^R ¹ and R ² are not hydrogen atoms at the same time; R ³ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group, wherein the alkyl group, alicyclic hydrocarbon group, Part or all of the hydrogen atoms in the aralkyl group and the aryl group may be substituted; R ¹ and R ³ may be bonded to each other to form a ring together with the carbon atom to which R ¹ is bonded and the oxygen atom to which R ³ is bonded. ether structure; and * ¹ represents the bonding point.

上述R¹及R²所表示的脂環式烴基例如可列舉碳數為3至20的脂環式烴基等。另外，此碳數為3至20的脂環式烴基可以是多環。上述碳數為3至20的脂環式烴基例如可列舉：環丙基、環戊基、環己基、環庚基、環辛基、冰片基、降冰片基、金剛烷基等。 Examples of the alicyclic hydrocarbon group represented by R ¹ and R ² include an alicyclic hydrocarbon group having 3 to 20 carbon atoms. In addition, the alicyclic hydrocarbon group having 3 to 20 carbon atoms may be polycyclic. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bornyl, norbornyl, adamantyl, and the like.

上述R¹及R²所表示的芳基例如可列舉碳數為6至14的芳基等。上述碳數為6至14的芳基可以是單環，也可以是單環連結而成的結構，還可以是縮合環。上述碳數為6至14的芳基例如可列舉苯基、萘基等。 Examples of the aryl group represented by R ¹ and R ² include aryl groups having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be a single ring, a structure in which single rings are connected, or a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include phenyl group, naphthyl group, and the like.

上述R¹及R²所表示的可經取代的烷基、脂環式烴基以及芳基的取代基例如可列舉：鹵素原子、羥基、硝基、氰基、羧基、羰基、脂環式烴基(例如環丙基、環戊基、環己基、環庚基、環辛基、冰片基、降冰片基、金剛烷基等)、芳基(例如苯基、萘基等)、烷氧基(例如甲氧基、乙氧基、丙氧基、正丁氧基、戊氧基、己氧基、庚氧基、辛氧基等碳數為1至20的烷氧基等)、醯基(例如乙醯基、丙醯基、丁醯基、異丁醯基等碳數為2至20的醯基等)、醯氧基(例如乙醯氧基、丙醯氧基、丁醯氧基、第三丁醯氧基、第三戊醯氧基等碳數為2至10的醯氧基等)、烷氧基羰基(例如甲氧基羰基、乙氧基羰基、丙氧基羰基等碳數為2至20的烷氧基羰基)、鹵代烷基(例如甲基、乙基、正丙基、正丁基、正戊基、正己基、正辛基、正十二烷基、正十四烷基、正十八烷基等直鏈狀烷基，異丙基、異丁基、第三丁基、新戊基、2-己基、3-己基等分支狀烷基等烷基；環丙基、環丁基、環戊基、降冰片基、金剛烷基等脂環式烴基，將上述基團的一部分或者全部的氫原子經鹵素原子取代而得的基團)、羥基烷基(例如羥基甲基等)等。 Examples of the substituents of the optionally substituted alkyl group, alicyclic hydrocarbon group and aryl group represented by R ¹ and R ² above include: halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, carbonyl group, alicyclic hydrocarbon group ( For example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bornyl, norbornyl, adamantyl, etc.), aryl group (such as phenyl, naphthyl, etc.), alkoxy group (such as Methoxy, ethoxy, propoxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and other alkoxy groups with carbon numbers from 1 to 20, etc.), acyl group (such as Acetyl, propyl, butyl, isobutyl and other acyl groups with 2 to 20 carbon atoms, etc.), acyloxy (such as acetyloxy, propyloxy, butyloxy, tert-butyloxy) group, third pentyloxy group and other acyloxy groups with carbon numbers of 2 to 10, etc.), alkoxycarbonyl groups (such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and other carbon numbers of 2 to 20 Alkoxycarbonyl), haloalkyl (such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecyl Alkyl and other linear alkyl groups, isopropyl, isobutyl, tert-butyl, neopentyl, 2-hexyl, 3-hexyl and other branched alkyl groups; cyclopropyl, cyclobutyl, Alicyclic hydrocarbon groups such as cyclopentyl, norbornyl and adamantyl, groups obtained by replacing part or all of the hydrogen atoms of the above groups with halogen atoms), hydroxyalkyl groups (such as hydroxymethyl, etc.), etc. .

上述R³所表示的烷基、脂環式烴基、芳基可應用上述R¹及R²所表示的各基團的說明。此外，上述烷基較佳為碳數為1至6的烷基，更佳為甲基、乙基以及正丙基。上述R³所表示的芳烷基可列舉：苄基、苯乙基、萘基甲基、萘基乙基等。 For the alkyl group, alicyclic hydrocarbon group, and aryl group represented by the above-mentioned R ³ , the description of each group represented by the above-mentioned R ¹ and R ² can be applied. In addition, the above-mentioned alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group and an n-propyl group. Examples of the aralkyl group represented by R ³ include benzyl group, phenethyl group, naphthylmethyl group, naphthyl ethyl group, and the like.

上述R¹與R³可相互鍵結而形成的環狀醚結構，較佳為環員數3至20的環狀醚結構，更佳為環員數5至8的環狀醚結構，又更佳為四氫呋喃以及四氫吡喃。 The cyclic ether structure formed by the above-mentioned R ¹ and R ³ being bonded to each other is preferably a cyclic ether structure with 3 to 20 ring members, more preferably a cyclic ether structure with 5 to 8 ring members, and more preferably Tetrahydrofuran and tetrahydropyran are preferred.

上述式(1)所表示的基團例如可列舉下式所表示的基團等，其中，於此些具體例中，*¹代表與式(1)相同的定義。 Examples of the group represented by the above formula (1) include groups represented by the following formula, etc. In these specific examples, * ¹ represents the same definition as formula (1).

上述含酸解離性基之單體(a-2)例如可列舉：甲基丙烯酸1-乙氧基乙酯、甲基丙烯酸1-甲氧基乙酯、甲基丙烯酸1-正丁氧基乙酯、甲基丙烯酸1-異丁氧基乙酯、甲基丙烯酸1-第三丁氧基乙酯、甲基丙烯酸1-(2-氯乙氧基)乙酯、甲基丙烯酸1-(2-乙基己氧基)乙酯、甲基丙烯酸1-正丙氧基乙酯、甲基丙烯酸1-環己氧基乙酯、甲基丙烯酸1-(2-環己基乙氧基)乙酯、甲基丙烯酸1-苄氧基乙酯、甲基丙烯酸2-四氫吡喃基酯、甲基丙烯酸2-四氫呋喃基酯(2-Tetrahydrofuranyl methacrylate)、丙烯酸1-乙氧基乙酯、丙烯酸1-甲氧基乙酯、丙烯酸1-正丁氧基乙酯、丙烯酸1-異丁氧基乙酯、丙烯酸1-第三丁氧基乙酯、丙烯酸1-(2- 氯乙氧基)乙酯、丙烯酸1-(2-乙基己氧基)乙酯、丙烯酸1-正丙氧基乙酯、丙烯酸1-環己氧基乙酯、丙烯酸1-(2-環己基乙氧基)乙酯、丙烯酸1-苄氧基乙酯、丙烯酸2-四氫吡喃基酯、5,6-二(1-甲氧基乙氧基羰基)-2-降冰片烯、5,6-二(1-(環己氧基)乙氧基羰基)-2-降冰片烯、5,6-二(1-(苄氧基)乙氧基羰基)-2-降冰片烯、對-1-乙氧基乙氧基苯乙烯或間-1-乙氧基乙氧基苯乙烯、對-1-甲氧基乙氧基苯乙烯或間-1-甲氧基乙氧基苯乙烯、對-1-正丁氧基乙氧基苯乙烯或間-1-正丁氧基乙氧基苯乙烯、對-1-異丁氧基乙氧基苯乙烯或間-1-異丁氧基乙氧基苯乙烯、對-1-(1,1-二甲基乙氧基)乙氧基苯乙烯或間-1-(1,1-二甲基乙氧基)乙氧基苯乙烯、對-1-(2-氯乙氧基)乙氧基苯乙烯或間-1-(2-氯乙氧基)乙氧基苯乙烯、對-1-(2-乙基己氧基)乙氧基苯乙烯或間-1-(2-乙基己氧基)乙氧基苯乙烯、對-1-正丙氧基乙氧基苯乙烯或間-1-正丙氧基乙氧基苯乙烯、對-1-環己氧基乙氧基苯乙烯或間-1-環己氧基乙氧基苯乙烯、對-1-(2-環己基乙氧基)乙氧基苯乙烯或間-1-(2-環己基乙氧基)乙氧基苯乙烯、對-1-苄氧基乙氧基苯乙烯或間-1-苄氧基乙氧基苯乙烯等。 Examples of the acid-dissociable group-containing monomer (a-2) include 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, and 1-n-butoxyethyl methacrylate. Ester, 1-isobutoxyethyl methacrylate, 1-tert-butoxyethyl methacrylate, 1-(2-chloroethoxy)ethyl methacrylate, 1-(2 methacrylate) -Ethylhexyloxy)ethyl ester, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1-(2-cyclohexylethoxy)ethyl methacrylate , 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 2-Tetrahydrofuranyl methacrylate, 1-ethoxyethyl acrylate, 1 acrylic acid -Methoxyethyl ester, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-tert-butoxyethyl acrylate, 1-(2- Chloroethoxy)ethyl acrylate, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1-(2-cyclohexyl acrylate) Hexylethoxy)ethyl ester, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 5,6-bis(1-methoxyethoxycarbonyl)-2-norbornene, 5,6-bis(1-(cyclohexyloxy)ethoxycarbonyl)-2-norbornene, 5,6-bis(1-(benzyloxy)ethoxycarbonyl)-2-norbornene , p-1-ethoxyethoxystyrene or m-1-ethoxyethoxystyrene, p-1-methoxyethoxystyrene or m-1-methoxyethoxy Styrene, p-1-n-butoxyethoxystyrene or m-1-n-butoxyethoxystyrene, p-1-isobutoxyethoxystyrene or m-1-iso Butoxyethoxystyrene, p-1-(1,1-dimethylethoxy)ethoxystyrene or m-1-(1,1-dimethylethoxy)ethoxy Styrene, p-1-(2-chloroethoxy)ethoxystyrene or m-1-(2-chloroethoxy)ethoxystyrene, p-1-(2-ethylhexyloxy ethoxystyrene or m-1-(2-ethylhexyloxy)ethoxystyrene, p-1-n-propoxyethoxystyrene or m-1-n-propoxyethyl Oxystyrene, p-1-cyclohexyloxyethoxystyrene or m-1-cyclohexyloxyethoxystyrene, p-1-(2-cyclohexylethoxy)ethoxybenzene Ethylene or m-1-(2-cyclohexylethoxy)ethoxystyrene, p-1-benzyloxyethoxystyrene or m-1-benzyloxyethoxystyrene, etc.

含酸解離性基之單體(a-2)較佳為甲基丙烯酸1-乙氧基乙酯、甲基丙烯酸1-正丁氧基乙酯、甲基丙烯酸2-四氫吡喃基酯、甲基丙烯酸1-苄氧基乙酯、甲基丙烯酸1-環己氧基乙酯、甲基丙烯酸2-四氫呋喃基酯，更佳為甲基丙烯酸2-四氫吡喃基酯和甲基丙烯酸2-四氫呋喃基酯。 The acid-dissociable group-containing monomer (a-2) is preferably 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, or 2-tetrahydropyranyl methacrylate. , 1-benzyloxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 2-tetrahydrofuryl methacrylate, more preferably 2-tetrahydropyranyl methacrylate and methyl 2-Tetrahydrofuryl acrylate.

基於單體混合物的使用量為100重量份，含酸解離性保護基之單體(a-2)的使用量為10重量份至97重量份，較佳為15至80重量份，更佳為20至70重量份。倘若單體混合物未使用含酸解離性保護基之單體(a-2)，則由樹脂組成物所製得的保護膜之顯影密著性及耐化性不佳。 Usage amount based on 100 parts by weight of monomer mixture, containing acid The usage amount of the dissociable protective group monomer (a-2) is 10 to 97 parts by weight, preferably 15 to 80 parts by weight, and more preferably 20 to 70 parts by weight. If the monomer mixture does not use the monomer (a-2) containing an acid-dissociable protective group, the protective film produced from the resin composition will have poor development adhesion and chemical resistance.

含內酯結構之不飽和單體(a-3)Unsaturated monomer containing lactone structure (a-3)

在一些實施例中，所述單體混合物可進一步包括含內酯結構之不飽和單體(a-3)。做為本發明中所用的內酯結構，較佳為形成五員環至七員環的內酯結構，更佳為形成五員環或六員環的內酯結構。 In some embodiments, the monomer mixture may further include an unsaturated monomer (a-3) containing a lactone structure. As the lactone structure used in the present invention, a lactone structure forming a five- to seven-membered ring is preferred, and a lactone structure forming a five- or six-membered ring is more preferred.

另外，做為本發明所用之含內酯結構之不飽和單體(a-3)，於形成五員環至七員環的內酯結構中，其他環結構亦可縮環於內酯結構上而形成多環結構，但較佳為其他環結構不縮環於內酯結構上。較佳地，於其他環結構縮環於形成五員環至七員環的內酯結構上時，其他環結構以形成雙環結構或螺環結構的形式進行縮環。其他環結構可列舉碳數為3至20的環狀的烴基、碳數為3至20的雜環基等。所述雜環基並無特別限定，可列舉構成環的原子中的一個以上為雜原子者，或芳香族雜環基。另外，雜環基較佳為五員環或六員環，尤佳為五員環。具體而言，雜環基較佳為至少含有一個氧原子，例如可列舉：氧雜環戊烷環、噁烷環、二噁烷環等。 In addition, as the unsaturated monomer (a-3) containing a lactone structure used in the present invention, in the lactone structure forming a five- to seven-membered ring, other ring structures can also be condensed on the lactone structure. A polycyclic structure is formed, but it is preferred that other ring structures are not condensed on the lactone structure. Preferably, when other ring structures are ring-condensed on the lactone structure forming a five- to seven-membered ring, the other ring structures are ring-condensed to form a bicyclic structure or a spiro ring structure. Examples of other ring structures include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like. The heterocyclic group is not particularly limited, and examples thereof include those in which at least one of the atoms constituting the ring is a heteroatom, or an aromatic heterocyclic group. In addition, the heterocyclic group is preferably a five-membered ring or a six-membered ring, particularly preferably a five-membered ring. Specifically, the heterocyclic group preferably contains at least one oxygen atom, and examples thereof include: oxolane ring, oxane ring, dioxane ring, and the like.

含內酯結構之不飽和單體(a-3)中，於其他環結構縮環於內酯結構上而形成多環結構的情況下，縮環於內酯結構上的其他環結構的個數較佳為1至5，更佳為1至3。 In the unsaturated monomer (a-3) containing a lactone structure, when other ring structures condense on the lactone structure to form a polycyclic structure, the number of other ring structures that condense on the lactone structure Preferably it is 1 to 5, More preferably, it is 1 to 3.

另外，此內酯結構可具有取代基，亦可不具有取代基，較佳為不具有取代基。做為取代基並無特別限定，例如可列舉：碳數為1至8的烷基、碳數為3至7的環烷基、碳數為1至8的烷氧基、碳數為2至8的烷氧基羰基、羧基、鹵素原子、羥基、氰基、酸分解性基等。更佳為碳數為1至4的烷基、氰基。 In addition, the lactone structure may or may not have a substituent, and preferably has no substituent. The substituent is not particularly limited, and examples thereof include: alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and alkyl groups having 2 to 8 carbon atoms. 8’s alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group, etc. More preferred are alkyl groups and cyano groups having 1 to 4 carbon atoms.

做為烷基，較佳為直鏈狀的碳數為1至6的烷基、分支狀的碳數為3至6的烷基或環狀的碳數為3至6的烷基，更佳為直鏈狀的碳數為1至3的烷基。 The alkyl group is preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, more preferably It is a linear alkyl group having 1 to 3 carbon atoms.

於內酯結構具有取代基的情況下，取代基的個數並無特別限定，較佳為1至4，更佳為1或2。在所述內酯結構具有多個取代基的情況下，多個取代基彼此可相同亦可不同。另外，於其他環結構縮環於內酯結構上的情況下，所述其他環結構亦可具有取代基。 When the lactone structure has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2. When the lactone structure has multiple substituents, the multiple substituents may be the same or different from each other. In addition, when other ring structures are condensed on the lactone structure, the other ring structures may also have substituents.

在一些實施例中，較佳地，含內酯結構之不飽和單體(a-3)可包含如式(3)所示的部分結構：

In some embodiments, preferably, the unsaturated monomer (a-3) containing a lactone structure may include a partial structure as shown in formula (3):

於式(3)中，R⁸表示取代基，n7個的R⁸分別獨立，且為相同或不同；Z¹表示含有-O-C(=O)-的單環或多環結構；n7表示0以上的整數；以及，*³為鍵結處。 In formula (3), R ⁸ represents a substituent, and n7 R ^8s are independently independent and are the same or different; Z ¹ represents a monocyclic or polycyclic structure containing -OC(=O)-; n7 represents 0 or more an integer; and, * ³ is the bonding point.

於式(3)中，R⁸表示取代基，n7個的R⁸分別獨立，可相同亦可不同。R⁸與前述內酯結構可具有的取代基為相同含意，較佳範圍亦相同。 In formula (3), R ⁸ represents a substituent, and the n7 R ^8s are each independent and may be the same or different. R ⁸ has the same meaning as the substituent that the aforementioned lactone structure may have, and the preferred range is also the same.

於式(3)中，Z¹表示含有-O-C(=O)-的單環或多環結構，較佳為表示單環結構。於Z¹表示單環結構的情況下，做為單環結構，較佳為形成五員環至七員環的內酯結構，更佳為形成五員環或六員環的內酯結構。於Z¹表示多環結構的情況下，做為多環結構，較佳為其他環結構以形成雙環結構或螺環結構的形式縮環於內酯結構上。其他環結構與前述其他環結構為相同含意，較佳範圍亦相同。 In formula (3), Z ¹ represents a monocyclic or polycyclic structure containing -OC(=O)-, preferably a monocyclic structure. When Z ¹ represents a monocyclic structure, the monocyclic structure is preferably a lactone structure forming a five- to seven-membered ring, and more preferably a lactone structure forming a five- or six-membered ring. When Z ¹ represents a polycyclic structure, as the polycyclic structure, it is preferable that other ring structures condense on the lactone structure to form a bicyclic structure or a spirocyclic structure. Other ring structures have the same meaning as the other ring structures mentioned above, and the preferred ranges are also the same.

於式(3)中，n7表示0以上的整數，較佳為0至4的整數，較佳為0至2的整數，更佳為0。於n7表示2以上的整數時，多個取代基彼此可相同亦可不同。另外，多個取代基亦可相互鍵結而形成環，但較佳為不相互鍵結而形成環。 In formula (3), n7 represents an integer above 0, preferably an integer from 0 to 4, preferably an integer from 0 to 2, and more preferably 0. When n7 represents an integer of 2 or more, the plurality of substituents may be the same or different from each other. In addition, a plurality of substituents may be bonded to each other to form a ring, but it is preferred not to be bonded to each other to form a ring.

在一些實施例中，所述含有內酯結構的不飽和單體(a-3)較佳可為以下的式(3-1)表示的結構。 In some embodiments, the unsaturated monomer (a-3) containing a lactone structure may preferably have a structure represented by the following formula (3-1).

於式(3-1)中，R^8a表示氫原子或烷基。R^8b表示取代基，n8個的R^8b分別獨立，可相同亦可不同。A¹表示單鍵或二價的連結基。Z²表示含有-O-C(=O)-所表示的基的單環或多環結構。n8表示0以上的整數。 In formula (3-1), R ^8a represents a hydrogen atom or an alkyl group. R ^8b represents a substituent, and the n8 R ^8bs are each independent and may be the same or different. A ¹ represents a single bond or a bivalent linking group. Z ² represents a monocyclic or polycyclic structure containing the group represented by -OC(=O)-. n8 represents an integer above 0.

式(3-1)中，R^8a表示氫原子或烷基。烷基較佳為直鏈狀或分支狀的碳數為1至3的烷基，更佳為甲基。烷基可具有取代基。取代基較佳為羥基或鹵素原子(尤其是氟原子)。 In formula (3-1), R ^8a represents a hydrogen atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and is more preferably a methyl group. The alkyl group may have a substituent. The substituent is preferably a hydroxyl group or a halogen atom (especially a fluorine atom).

式(3-1)中，R^8b表示取代基，n8個的R^8b分別獨立，可相同亦可不同。R^8b與上述的內酯結構可具有的取代基為相同含意，較佳範圍亦相同。 In formula (3-1), R ^8b represents a substituent, and n8 R ^8b are each independent and may be the same or different. R ^8b has the same meaning as the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.

式(3-1)中，A¹表示單鍵或二價的連結基。做為二價的連結基，可列舉：直鏈狀、分支鏈狀或環狀的伸烷基、伸芳基，-O-、-COO-、-S-、-NR"-、-CO-、-NR"CO-、-SO₂-等二價基，或含有此些基的組合者。此處，R"表示氫原子或碳數為1至4的烷基，較佳為氫原子。做為二價的連結基，較佳為含有-O-、-COO-、-S-、-NH-及-CO-的至少一個、或此些基團與-(CH₂)_m-(m為1至10的整數，較佳為1至6的整數，更佳為1至4的整數)的組合的基團。 In formula (3-1), A ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include: linear, branched chain or cyclic alkylene groups, aryl groups, -O-, -COO-, -S-, -NR"-, -CO- , -NR"CO-, -SO ₂ - and other divalent groups, or a combination of these groups. Here, R" represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. As a divalent linking group, it is preferable to contain -O-, -COO-, -S-, - At least one of NH- and -CO-, or these groups and -(CH ₂ ) _m - (m is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4) combination of groups.

式(3-1)中，Z²表示含有-O-C(=O)-所表示的基團的單環或多環結構，且與式(3)中的Z¹為相同含意，較佳範圍亦相同。 In formula (3-1), Z ² represents a monocyclic or polycyclic structure containing a group represented by -OC(=O)-, and has the same meaning as Z ¹ in formula (3), and the preferred range is also same.

式(3-1)中，n8表示0以上的整數，且與通式(3)中的n1為相同含意，較佳範圍亦相同。 In the formula (3-1), n8 represents an integer above 0, and has the same meaning as n1 in the general formula (3), and the preferred range is also the same.

在一些其他的實施例中，所述含有內酯結構的不飽和單體(a-3)較佳可由以下的式(3-2)表示的結構。 In some other embodiments, the unsaturated monomer (a-3) containing a lactone structure can preferably have a structure represented by the following formula (3-2).

式(3-2)中，R^8c表示氫原子或烷基。R^8d表示取代基，n9個的R^8d分別獨立，可相同亦可不同。A²表示單鍵或二價的連結基。Z³表示含有-O-C(=O)-所表示的基的單環或多環結構。n9表示0以上的整數。X¹表示氧原子或-NR"-。R"表示氫原子或烷基。 In formula (3-2), R ^8c represents a hydrogen atom or an alkyl group. R ^8d represents a substituent, and the n9 R ^8ds are each independent and may be the same or different. A ² represents a single bond or a bivalent linking group. Z ³ represents a monocyclic or polycyclic structure containing the group represented by -OC(=O)-. n9 represents an integer above 0. X ¹ represents an oxygen atom or -NR"-. R" represents a hydrogen atom or an alkyl group.

式(3-2)中，R^8d表示取代基，n9個的R^8d分別獨立，可相同亦可不同。R^8d與上述的內酯結構可具有的取代基為相同含意，較佳範圍亦相同。 In formula (3-2), R ^8d represents a substituent, and n9 R ^8d are each independent and may be the same or different. R ^8d has the same meaning as the substituent that the above-mentioned lactone structure may have, and the preferred range is also the same.

式(3-2)中，A²表示單鍵或二價的連結基。做為二價的連結基，與式(3-1)中的A¹表示二價的連結基時為相同含意。做為較佳的二價連結基，可為含有-COO-、-CO-的至少一個，或此些基團與-(CH₂)_m-(m為1至10的整數，較佳為1至6的整數，更佳為1至4的整數)的組合者。式(3-2)中的A²尤其較佳為單鍵。 In formula (3-2), A ² represents a single bond or a divalent linking group. As a bivalent connecting group, it has the same meaning as when A ¹ in the formula (3-1) represents a bivalent connecting group. As a preferred divalent linking group, it can be at least one containing -COO-, -CO-, or these groups and -(CH ₂ ) _m - (m is an integer from 1 to 10, preferably 1 an integer from 1 to 6, more preferably an integer from 1 to 4). A ² in formula (3-2) is particularly preferably a single bond.

式(3-2)中，Z³表示含有-O-C(=O)-所表示的基團的單環或多環結構，且與式(3-1)中的Z¹為相同含意，較佳範圍亦相同。 In formula (3-2), Z ³ represents a monocyclic or polycyclic structure containing a group represented by -OC(=O)-, and has the same meaning as Z ¹ in formula (3-1), which is preferred. The scope is also the same.

式(3-2)中，n9表示0以上的整數，且與式(3-1)中的n8為相同含意，較佳範圍亦相同。 In the formula (3-2), n9 represents an integer above 0, and has the same meaning as n8 in the formula (3-1), and the preferred range is also the same.

式(3-2)中，X¹表示氧原子或-NR"-，較佳為氧原子。R"表示氫原子或碳數為1至4的烷基，較佳為氫原子。 In formula (3-2), X ¹ represents an oxygen atom or -NR"-, preferably an oxygen atom. R" represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

本發明之含內酯結構之不飽和單體(a-3)的具體例可列舉如下式(3-3)至式(3-23)，但本發明並不限定於此些例子。此處所示的R^8e可代表式(3-1)的R^8a或式(3-2)的R^8c。 Specific examples of the unsaturated monomer (a-3) containing a lactone structure of the present invention include the following formulas (3-3) to formulas (3-23), but the present invention is not limited to these examples. R ^8e shown here may represent R ^8a of formula (3-1) or R ^8c of formula (3-2).

本發明的單體混合物中可包含兩種以上的含內酯結構之不飽和單體(a-3)。基於單體混合物的使用量為100重量份，含內酯結構之不飽和單體(a-3)的使用量為2重量份至20重量份，較佳為2至15重量份，更佳為2至10重量份。當單體混合物中包括含內酯結構之不飽和單體(a-3)時，可進一步改善由此組成物形成的保護膜之顯影密著性。 The monomer mixture of the present invention may contain two or more unsaturated monomers (a-3) containing a lactone structure. Based on 100 parts by weight of the monomer mixture, the usage amount of the unsaturated monomer (a-3) containing a lactone structure is 2 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 2 to 10 parts by weight. When the unsaturated monomer (a-3) containing a lactone structure is included in the monomer mixture, the development adhesion of the protective film formed from the composition can be further improved.

含環氧基之不飽和單體(a-4)Unsaturated monomer containing epoxy group (a-4)

在一些實施例中，合成本發明的化學增幅型正型感光性樹脂組成物的樹脂(A)所使用的單體混合物，可進一步包括含環氧基之不飽和單體(a-4)。 In some embodiments, the monomer mixture used to synthesize the resin (A) of the chemically amplified positive photosensitive resin composition of the present invention may further include an epoxy group-containing unsaturated monomer (a-4).

所述含環氧基之不飽和單體(a-4)可包括但不限於含環氧基之(甲基)丙烯酸酯化合物、含環氧基之α-烷基丙烯酸酯化合物、環氧丙醚化合物、如式(4)所示的具有氧雜環丁烷基之乙烯性不飽和單體，及上述之任意組合。 The epoxy group-containing unsaturated monomer (a-4) may include, but is not limited to, epoxy group-containing (meth)acrylate compounds, epoxy group-containing α-alkyl acrylate compounds, glycidyl propylene oxide Ether compounds, ethylenically unsaturated monomers having an oxetanyl group as represented by formula (4), and any combination of the above.

於式(4)中，R⁹代表氫原子或碳數為1至4之烷基；R¹⁰代表氫原子或碳數為1至4之烷基；R¹¹、R¹²、R¹³及R¹⁴分別獨立地代表氫原子、氟原子、苯基、碳數為1至4之烷基或碳數為1至4之全氟烷基；且a代表1至6之整數。 In formula (4), R ⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ¹¹ , R ¹² , R ¹³ and R ¹⁴ Each independently represents a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group with 1 to 4 carbon atoms, or a perfluoroalkyl group with 1 to 4 carbon atoms; and a represents an integer from 1 to 6.

前述含環氧基之(甲基)丙烯酸酯化合物之具體例如：(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸2-甲基環氧丙酯、(甲基)丙烯酸3,4-環氧丁酯、(甲基)丙烯酸6,7-環氧庚酯、(甲基)丙烯酸3,4-環氧環己酯、(甲基)丙烯酸3,4-環氧環己基甲酯。 Specific examples of the aforementioned epoxy group-containing (meth)acrylate compound are: (meth)glycidyl acrylate, (meth)acrylic acid 2-methylglycidyl Ester, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, (meth)acrylic acid 3,4-Epoxycyclohexylmethyl ester.

前述含環氧基之α-烷基丙烯酸酯化合物之具體例如：α-乙基丙烯酸環氧丙酯、α-正丙基丙烯酸環氧丙酯、α-正丁基丙烯酸環氧丙酯、α-乙基丙烯酸6,7-環氧庚酯。 Specific examples of the aforementioned α-alkyl acrylate compounds containing epoxy groups: α-glycidyl ethyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α -6,7-Epoxyheptyl ethylacrylate.

前述環氧丙醚化合物之具體例如：鄰-乙烯基苯甲基環氧丙醚(o-vinylbenzylglycidylether)、間-乙烯基苯甲基環氧丙醚(m-vinylbenzylglycidylether)、對-乙烯基苯甲基環氧丙醚(p-vinylbenzylglycidylether)。 Specific examples of the aforementioned glycidyl ether compounds include o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether. p-vinylbenzylglycidylether.

前述如式(4)所示的具有氧雜環丁烷基之乙烯性不飽和單體之具體例可包含但不限於甲基丙烯酸酯類化合物或丙烯酸酯類化合物。 Specific examples of the ethylenically unsaturated monomer having an oxetanyl group represented by formula (4) may include, but are not limited to, methacrylate compounds or acrylate compounds.

前述之甲基丙烯酸酯類化合物可包含但不限於3-(甲基丙烯醯甲氧基)氧雜環丁烷[3-(methacryloyloxy)oxetane；OXMA]、3-(甲基丙烯醯甲氧基)-3-乙基氧雜環丁烷[3-(methacryloyloxy)-3-ethyloxetane；EOXMA](如式(4-3)所示)、3-(甲基丙烯醯甲氧基)-3-甲基氧雜環丁烷[3-(methacryloyloxy)-3-methyloxetane；MOXMA](如式(4-1)所示)、3-(甲基丙烯醯甲氧基)-2-甲基氧雜環丁烷、3-(甲基丙烯醯甲氧基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯甲氧基)-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯甲氧基)-2-苯基氧雜環丁烷、3-(甲基丙烯醯甲氧基)-2,2-二氟氧雜環丁烷、3-(甲基丙烯醯甲氧基)-2,2,4-三氟氧雜環丁烷、3-(甲基丙烯醯甲氧基)-2,2,4,4-四氟氧雜環丁烷、3-(甲基丙烯醯乙氧基)氧雜環丁烷、3-(甲基丙烯醯乙氧基)-3-乙基氧雜環丁烷、2-乙基-3-(甲基丙烯醯乙氧基)氧雜環丁烷、3-(甲基丙烯醯乙氧基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯乙氧基)-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯乙氧基)-2-苯基氧雜環丁烷、2,2-二氟-3-(甲基丙烯醯乙氧基)氧雜環丁烷、3-(甲基丙烯醯乙氧基)-2,2,4-三氟氧雜環丁烷或3-(甲基丙烯醯乙氧基)-2,2,4,4-四氟氧雜環丁烷等之化合物。 The aforementioned methacrylate compounds may include, but are not limited to, 3-(methacryloyloxy)oxetane [3-(methacryloyloxy)oxetane; OXMA], 3-(methacryloyloxy)oxetane; )-3-ethyloxetane [3-(methacryloyloxy)-3-ethyloxetane; EOXMA] (shown in formula (4-3)), 3-(methacryloyloxy)-3- Methyloxetane [3-(methacryloyloxy)-3-methyloxetane; MOXMA] (shown in formula (4-1)), 3-(methacryloyloxy)-2-methyloxa Cyclobutane, 3-(methacrylmethoxy)-2-trifluoromethyloxetane, 3-(methacrylmethoxy)-2-pentafluoroethyloxetane alkane, 3-(methacrylmethoxy)-2-phenyloxetane, 3-(methacrylmethoxy)-2,2-difluoroxetane, 3- (methacrylamidemethoxy methyl)-2,2,4-trifluorooxetane, 3-(methacrylomethoxy)-2,2,4,4-tetrafluorooxetane, 3-(methyl Acrylyl ethoxy) oxetane, 3-(methacrylyl ethoxy)-3-ethyl oxetane, 2-ethyl-3-(methacrylyl ethoxy) Oxetane, 3-(methacrylethoxy)-2-trifluoromethyloxetane, 3-(methacrylethoxy)-2-pentafluoroethyloxa cyclobutane, 3-(methacrylethoxy)-2-phenyloxetane, 2,2-difluoro-3-(methacrylethoxy)oxetane, 3-(methacrylethoxy)-2,2,4-trifluorooxetane or 3-(methacrylethoxy)-2,2,4,4-tetrafluoroxa Compounds such as cyclobutane.

上述之丙烯酸酯類化合物可包含但不限於3-(丙烯醯甲氧基)氧雜環丁烷、3-(丙烯醯甲氧基)-3-乙基氧雜環丁烷(如式(4-4)所示)、3-(丙烯醯甲氧基)-3-甲基氧雜環丁烷(如式(4-2)所示)、3-(丙烯醯甲氧基)-2-甲基氧雜環丁烷、3-(丙烯醯甲氧基)-2-三氟甲基氧雜環丁烷、3-(丙烯醯甲氧基)-2-五氟乙基氧雜環丁烷、3-(丙烯醯甲氧基)-2-苯基氧雜環丁烷、3-(丙烯醯甲氧基)-2,2-二氟氧雜環丁烷、3-(丙烯醯甲氧基)-2,2,4-三氟氧雜環丁烷、3-(丙烯醯甲氧基)-2,2,4,4-四氟氧雜環丁烷、3-(丙烯醯乙氧基)氧雜環丁烷、3-(丙烯醯乙氧基)-3-乙基氧雜環丁烷、2-乙基-3-(丙烯醯乙氧基)氧雜環丁烷、3-(丙烯醯乙氧基)-2-三氟甲基氧雜環丁烷、3-(丙烯醯乙氧基)-2-五氟乙基氧雜環丁烷、3-(丙烯醯乙氧基)-2-苯基氧雜環丁烷、2,2-二氟-3-(丙烯醯乙氧基)氧雜環丁烷、3-(丙烯醯乙氧基)-2,2,4-三氟氧雜環丁烷或3-(丙烯醯乙氧基)-2,2,4,4-四氟氧雜環丁烷等之化合物。 The above-mentioned acrylate compounds may include but are not limited to 3-(acrylmethoxy)oxetane, 3-(acrylmethoxy)-3-ethyloxetane (such as formula (4 -4)), 3-(acrylmethoxy)-3-methyloxetane (shown in formula (4-2)), 3-(acrylmethoxy)-2- Methyl oxetane, 3-(acrylyl methoxy)-2-trifluoromethyl oxetane, 3-(acrylyl methoxy)-2-pentafluoroethyl oxetane Alkane, 3-(acrylmethoxy)-2-phenyloxetane, 3-(acrylmethoxy)-2,2-difluoroxetane, 3-(acrylmethoxy)-2-phenyloxetane Oxy)-2,2,4-trifluorooxetane, 3-(propenylmethoxy)-2,2,4,4-tetrafluorooxetane, 3-(propenylmethoxy)- oxy)oxetane, 3-(acrylylethoxy)-3-ethyloxetane, 2-ethyl-3-(acrylylethoxy)oxetane, 3 -(acrylyl ethoxy)-2-trifluoromethyloxetane, 3-(acrylyl ethoxy)-2-pentafluoroethyl oxetane, 3-(acrylyl ethoxy base)-2-phenyloxetane, 2,2-difluoro-3-(acrylylethoxy)oxetane, 3-(acrylylethoxy)-2,2,4 -Trifluorooxetane or 3-(acrylylethoxy)-2,2,4,4-tetrafluorooxetane Butane and other compounds.

在一些實施例中，所述含環氧基之不飽和單體(a-4)可更包含其他具有氧雜環丁烷基之乙烯性不飽和單體，如：3-甲基-3-(乙烯甲氧基)氧雜環丁烷[3-methyl-3-(vinyloxy)oxetane；MOXV]、3-乙基-3-(乙烯甲氧基)氧雜環丁烷[3-ethyl-3-(vinyloxy)oxetane；EOXV]、3-丙基-3-(乙烯甲氧基)氧雜環丁烷、3-甲基-3-(2-乙烯乙氧基)氧雜環丁烷、3-乙基-3-(2-乙烯乙氧基)氧雜環丁烷、3-丙基-3-(2-乙烯乙氧基)氧雜環丁烷、3-甲基-3-(3-乙烯丙氧基)氧雜環丁烷、3-乙基-3-(3-乙烯丙氧基)氧雜環丁烷、3-丙基-3-(3-乙烯丙氧基)氧雜環丁烷、3-甲基-3-(3-乙烯丁氧基)氧雜環丁烷、3-乙基-3-(3-乙烯丁氧基)氧雜環丁烷、3-丙基-3-(3-乙烯丁氧基)氧雜環丁烷、乙二醇[(3-乙基-3-氧雜環丁基)甲基]乙烯基醚、丙二醇[(3-乙基-3-氧雜環丁基)甲基]乙烯基醚或3,3-雙[(乙烯氧基)甲基]氧雜環丁烷等之具有氧雜環丁烷基的乙烯基醚化合物。 In some embodiments, the epoxy group-containing unsaturated monomer (a-4) may further include other ethylenically unsaturated monomers with oxetanyl groups, such as: 3-methyl-3- (Vinylmethoxy)oxetane [3-methyl-3-(vinyloxy)oxetane; MOXV], 3-ethyl-3-(vinylmethoxy)oxetane [3-ethyl-3 -(vinyloxy)oxetane; EOXV], 3-propyl-3-(vinylmethoxy)oxetane, 3-methyl-3-(2-vinylethoxy)oxetane, 3 -Ethyl-3-(2-ethyleneethoxy)oxetane, 3-propyl-3-(2-ethyleneethoxy)oxetane, 3-methyl-3-(3 -Ethylenepropoxy)oxetane, 3-ethyl-3-(3-ethylenepropoxy)oxetane, 3-propyl-3-(3-ethylenepropoxy)oxa cyclobutane, 3-methyl-3-(3-ethylenebutoxy)oxetane, 3-ethyl-3-(3-ethylenebutoxy)oxetane, 3-propyl -3-(3-Ethylenebutoxy)oxetane, ethylene glycol [(3-ethyl-3-oxetanyl)methyl]vinyl ether, propylene glycol [(3-ethyl- Vinyl ether compounds having an oxetanyl group such as 3-oxetanyl)methyl]vinyl ether or 3,3-bis[(vinyloxy)methyl]oxetane.

較佳地，3-(甲基丙烯醯甲氧基)氧雜環丁烷、3-(甲基丙烯醯甲氧基)-3-甲基氧雜環丁烷、3-(甲基丙烯醯甲氧基)-3-乙基氧雜環丁烷、3-(丙烯醯甲氧基)-3-甲基氧雜環丁烷或3-(丙烯醯甲氧基)-3-乙基氧雜環丁烷基於單體混合物的使用量為100重量份，含環氧基之不飽和單體(a-4)的使用量為10重量份至90重量份，較佳為15至80重量份，更佳為20至70重量份。當單體混合物中包括含環氧基之不飽和單體(a-4)時，可進一步改善樹脂組成物所製得的保護膜之耐化性。 Preferably, 3-(methacrylmethoxy)oxetane, 3-(methacrylmethoxy)-3-methyloxetane, 3-(methacrylmethoxy) Methoxy)-3-ethyloxetane, 3-(acrylylmethoxy)-3-methyloxetane or 3-(acrylylmethoxy)-3-ethyloxy The usage amount of heterocyclobutane is 100 parts by weight based on the monomer mixture, and the usage amount of the epoxy group-containing unsaturated monomer (a-4) is 10 to 90 parts by weight, preferably 15 to 80 parts by weight. , more preferably 20 to 70 parts by weight. When the monomer mixture includes the epoxy group-containing unsaturated monomer (a-4), the chemical resistance of the protective film produced from the resin composition can be further improved.

其他不飽和單體(a-5)Other unsaturated monomers (a-5)

所述用於形成樹脂(A)的單體混合物中，可更包含其他不飽和單體(a-5)。在一些實施例中，其他不飽和單體(a-5)可包括但不限於(甲基)丙烯酸烷基酯、(甲基)丙烯酸脂環族酯、(甲基)丙烯酸芳基酯、不飽和二羧酸二酯、(甲基)丙烯酸羥烷酯、(甲基)丙烯酸酯之聚醚、芳香乙烯化合物及前述以外之其他不飽和化合物。 The monomer mixture used to form resin (A) may further include other unsaturated monomers (a-5). In some embodiments, other unsaturated monomers (a-5) may include, but are not limited to, alkyl (meth)acrylate, cycloaliphatic (meth)acrylate, aryl (meth)acrylate, and other unsaturated monomers (a-5). Saturated dicarboxylic acid diesters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid ester polyethers, aromatic vinyl compounds and other unsaturated compounds other than the above.

前述(甲基)丙烯酸烷基酯之具體例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯。 Specific examples of the alkyl (meth)acrylate include: (methyl)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate ) n-butyl acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate.

前述(甲基)丙烯酸脂環族酯之具體例如：(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯、三環[5.2.1.0^2，6]癸-8-基(甲基)丙烯酸酯(或稱為(甲基)丙烯酸雙環戊酯)、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸四氫呋喃酯。 Specific examples of the aforementioned alicyclic (meth)acrylate are: (meth)acrylic acid cyclohexyl, (meth)acrylic acid-2-methylcyclohexyl, tricyclo[5.2.1.0 ^2,6 ]dec-8 -(meth)acrylate (or dicyclopentyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofuran (meth)acrylate ester.

前述(甲基)丙烯酸芳基酯之具體例如：(甲基) 丙烯酸苯基酯、(甲基)丙烯酸苯甲酯。 Specific examples of the aforementioned aryl (meth)acrylate: (methyl) Phenyl acrylate, benzyl (meth)acrylate.

前述不飽和二羧酸二酯之具體例如馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯。 Specific examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate.

前述(甲基)丙烯酸羥烷酯之具體例如：(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯。 Specific examples of the aforementioned hydroxyalkyl (meth)acrylate include: (meth)acrylic acid-2-hydroxyethyl ester and (meth)acrylic acid-2-hydroxypropyl ester.

前述(甲基)丙烯酸酯之聚醚之具體例如：聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯。 Specific examples of the polyether of (meth)acrylate include polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate.

前述芳香乙烯化合物之具體例如：苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯，對-甲基苯乙烯、對-甲氧基苯乙烯。 Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

前述以外之其他不飽和化合物之具體例如：丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙烯乙酯、1,3-丁二烯、異戊二烯、2,3-二甲基1,3-丁二烯、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-芐基馬來醯亞胺，N-丁二醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-馬來醯亞胺丁酸酯、N-丁二醯亞胺基-6-馬來醯亞胺己酸酯、N-丁二醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺。 Specific examples of unsaturated compounds other than those mentioned above: acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, ethylene ethyl ester, 1,3-butadiene, isopropyl Pentadiene, 2,3-dimethyl1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N -Succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6 -Maleimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide.

基於單體混合物的使用量為100重量份，其他不飽和單體(a-5)的使用量為0至75重量份，較佳為0至65重量份，更佳為0至55重量份。 Based on the usage amount of the monomer mixture is 100 parts by weight, the usage amount of other unsaturated monomers (a-5) is 0 to 75 parts by weight, preferably 0 to 65 parts by weight, and more preferably 0 to 55 parts by weight.

製備樹脂(A)Preparation of resin (A)

本發明之樹脂(A)在製造時所使用溶劑可包括但不限於醇、醚、二醇醚、乙二醇烷基醚乙酸醋酸酯、二乙二醇、二丙二醇、丙二醇單烷基醚、丙二醇烷基醚乙酸醋酸酯、丙二醇烷基醚丙酸酯、芳香烴、酮、酯。 The solvent used in the production of the resin (A) of the present invention may include but is not limited to alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethyl acetate, etc. Diol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones, esters.

前述醇之具體例如：甲醇、乙醇、苯甲醇、2-苯乙醇、3-苯基-1-丙醇。前述醚之具體例如：四氫呋喃。前述二醇醚之具體例如：乙二醇單丙醚、乙二醇單甲醚、乙二醇單***。前述乙二醇烷基醚醋酸酯之具體例如：乙二醇丁醚醋酸酯、乙二醇***醋酸酯、乙二醇甲醚醋酸酯。前述二乙二醇之具體例如：二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲***。前述二丙二醇之具體例如：二丙二醇單甲醚、二丙二醇單***、二丙二醇二甲醚、二丙二醇二***、二丙二醇甲***。前述丙二醇單烷基醚之具體例如：丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚。前述丙二醇烷基醚醋酸酯之具體例如：丙二醇甲醚醋酸酯、丙二醇***醋酸酯、丙二醇丙醚醋酸酯、丙二醇丁醚醋酸酯。前述丙二醇烷基醚丙酸酯之具體例如：丙二醇甲醚丙酸酯、丙二醇***丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯。前述芳香烴之具體例如：甲苯、二甲苯。前述酮之具體例如：甲乙酮、環己酮、二丙酮醇。前述酯之具體例如：乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥乙酸甲酯、羥乙酸乙酯、羥乙酸丁酯、乳酸甲酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、3-甲氧基丁基乙酸酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯。 Specific examples of the aforementioned alcohol include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol. Specific examples of the aforementioned ether include tetrahydrofuran. Specific examples of the aforementioned glycol ethers include: ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Specific examples of the aforementioned ethylene glycol alkyl ether acetate include: ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, and ethylene glycol methyl ether acetate. Specific examples of the aforementioned diethylene glycol include: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol. Alcohol methyl ether. Specific examples of the aforementioned dipropylene glycol include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methylethyl ether. Specific examples of the aforementioned propylene glycol monoalkyl ether include: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. Specific examples of the aforementioned propylene glycol alkyl ether acetate include: propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate. Specific examples of the aforementioned propylene glycol alkyl ether propionate are: propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate. Specific examples of the aromatic hydrocarbons include toluene and xylene. Specific examples of the aforementioned ketone include methyl ethyl ketone, cyclohexanone, and diacetone alcohol. Specific examples of the aforementioned esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3 -Propyl hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, Methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, ethoxybutyl acetate, propoxymethyl acetate, propyl Ethyloxyacetate, propoxypropylacetate, butylpropoxyacetate, methylbutoxyacetate, ethylbutoxyacetate, propylbutoxyacetate, butylbutoxyacetate, 3- Methoxybutyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2 -Methyl butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, 3-methoxypropyl propionate, 3-butyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 -Propyl ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3 -Butyl propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate.

本發明之樹脂(A)在製造時所使用溶劑之較佳具體例為二乙二醇二甲醚、丙二醇甲醚醋酸酯。上述溶劑可單獨或混合複數種使用。 Preferred specific examples of the solvent used in the production of the resin (A) of the present invention are diethylene glycol dimethyl ether and propylene glycol methyl ether acetate. The above-mentioned solvents can be used individually or in mixture of multiple types.

本發明之樹脂(A)在製造時所使用之聚合起始劑，其具體例為偶氮化合物或過氧化物。前述偶氮化合物之具體例如：2,2'-偶氮二異丁腈、2,2'-偶氮二(2,4-二甲基戊腈)、2,2'-偶氮二(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮二(2-甲基丁腈)、4,4'-偶氮二(4-氰基戊酸)、2,2'-偶氮二(二甲基-2-甲基丙酸酯)。前述過氧化物之具體例如：過氧化二苯甲醯、過氧化二月桂醯(dilauroyl peroxide)、第三丁基過氧化新戊酸酯(tert-butyl peroxypivalate)、1,1-二(第三丁基過氧化)環己烷(1,1-di(tert-butylperoxy)cyclohexane)、過氧化氫。上述聚合起始劑可單獨或混合複數種使用。 Specific examples of the polymerization initiator used in the production of the resin (A) of the present invention are azo compounds or peroxides. Specific examples of the aforementioned azo compounds: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4 -Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-Azobis(dimethyl-2-methylpropionate). Specific examples of the aforementioned peroxide: peroxy Dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxypivalate, 1,1-di(tert-butylperoxy)cyclohexane ( 1,1-di(tert-butylperoxy)cyclohexane), hydrogen peroxide. The above-mentioned polymerization initiators can be used alone or in mixture of a plurality of types.

樹脂(A)的聚合反應中，為了調整分子量，可使用分子量調整劑，該分子量調整劑例如可列舉：氯仿、四溴化碳、正己基硫醇、正辛基硫醇、正十二烷基硫醇、異十二烷基硫醇(tert-dodecyl mercaptan)、巰基乙酸(thioglycolic acid)、3-巰基丙酸等。基於所述單體混合物的使用量為100重量份，此分子量調整劑的使用量可為1重量份至15重量份，較佳為1.5重量份至14重量份，更佳為2重量份至12重量份。 In the polymerization reaction of the resin (A), in order to adjust the molecular weight, a molecular weight regulator can be used. Examples of the molecular weight regulator include: chloroform, carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan. Thiol, isododecyl mercaptan (tert-dodecyl mercaptan), thioglycolic acid (thioglycolic acid), 3-mercaptopropionic acid, etc. Based on 100 parts by weight of the monomer mixture, the molecular weight adjuster can be used in an amount of 1 to 15 parts by weight, preferably 1.5 to 14 parts by weight, and more preferably 2 to 12 parts by weight. parts by weight.

本發明之樹脂(A)之藉由膠體滲透層析儀(Gel Permeation Chromatography,GPC)測定的聚苯乙烯換算的重量平均分子量一般為3000至100,000，較佳為4,000至80,000，更佳為5,000至60,000。本發明之樹脂(A)之分子量調整，可使用單一樹脂，亦可併用兩種或兩種以上不同分子量之樹脂來達成。 The polystyrene-converted weight average molecular weight of the resin (A) of the present invention measured by Gel Permeation Chromatography (GPC) is generally 3,000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 80,000. 60,000. The molecular weight adjustment of the resin (A) of the present invention can be achieved by using a single resin or by using two or more resins with different molecular weights in combination.

光酸產生劑(B)Photoacid generator (B)

光酸產生劑(B)是通過放射線的照射而產生酸的化合物，可使用選自下述式(5)所表示的肟磺酸酯化合物，以及N-磺醯氧基醯亞胺化合物中的至少一種。所述放射線可使用例如可見光線、紫外線、遠紫外線、電子束、X 射線等。由於本發明的化學增幅型正型感光性樹脂組成物含有光酸產生劑(B)，使得化學增幅型正型感光性樹脂組成物可發揮感放射線(或稱感光)的特性，且可具有良好的放射線感度。做為所述化學增幅型正型感光性樹脂組成物中的光酸產生劑(B)，如後所述可以是化合物的形態，也可以是做為構成樹脂(A)的聚合物的一部分而併入樹脂(A)的形態，也可以是此二種形態的結合。此些光酸產生劑(B)可單獨使用，也可以併用2種以上。 The photoacid generator (B) is a compound that generates acid upon irradiation with radiation, and one selected from the group consisting of an oxime sulfonate compound represented by the following formula (5) and an N-sulfonyloxyimide compound can be used. At least one. The radiation can use, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, Ray etc. Since the chemically amplified positive photosensitive resin composition of the present invention contains the photoacid generator (B), the chemically amplified positive photosensitive resin composition can exhibit radiation-sensitive (or photosensitive) properties and can have good radiation sensitivity. The photoacid generator (B) in the chemically amplified positive photosensitive resin composition may be in the form of a compound as described later, or may be a part of the polymer constituting the resin (A). The form of incorporating resin (A) may also be a combination of these two forms. These photoacid generators (B) may be used alone, or two or more types may be used in combination.

光酸產生劑(B)除了含有包含肟磺酸酯基的肟磺酸酯化合物、N-磺醯氧基醯亞胺化合物以外，還可以含有：鎓鹽、含鹵素的化合物、重氮甲烷化合物、碸化合物、磺酸酯化合物、羧酸酯化合物等。 The photoacid generator (B) may contain, in addition to an oxime sulfonate compound containing an oxime sulfonate group and an N-sulfonyloxyimide compound, an onium salt, a halogen-containing compound, and a diazomethane compound. , sulfonate compounds, sulfonate compounds, carboxylate compounds, etc.

在一些實施例中，所述肟磺酸酯化合物為包含如下式(5)的肟磺酸酯基的化合物。 In some embodiments, the oxime sulfonate compound is a compound comprising an oxime sulfonate group of formula (5) below.

於式(5)中，R¹⁵為碳數為1至20的烷基、脂環式烴基、芳基，或是上述基團所具有的氫原子被部分或全部取代之基團；以及，*⁴為鍵結處。 In formula (5), R ¹⁵ is an alkyl group, an alicyclic hydrocarbon group, an aryl group having 1 to 20 carbon atoms, or a group in which the hydrogen atoms of the above groups are partially or fully substituted; and, * ⁴ is the bonding point.

所述R¹⁵所表示的烷基較佳為碳數為1至12的直鏈狀或分支狀的烷基。 The alkyl group represented by R ¹⁵ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

所述R¹⁵所表示的一價脂環式烴基較佳為碳數為4至12的脂環式烴基。 The monovalent alicyclic hydrocarbon group represented by R ¹⁵ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

所述R¹⁵所表示的芳基較佳為碳數為6至20的芳基，更佳為苯基、萘基、甲苯基、二甲苯基。 The aryl group represented by R ¹⁵ is preferably an aryl group having 6 to 20 carbon atoms, more preferably phenyl, naphthyl, tolyl, or xylyl.

所述取代基例如可列舉：碳數為1至5的烷基、烷氧基、側氧基、鹵素原子等。 Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a side oxy group, a halogen atom, and the like.

含有式(5)所表示的肟磺酸酯基的化合物例如可列舉下述式(5-1)至式(5-3)所表示的肟磺酸酯化合物等。 Examples of the compound containing an oxime sulfonate group represented by formula (5) include oxime sulfonate compounds represented by the following formulas (5-1) to formula (5-3).

所述式(5-1)至式(5-3)中，R¹⁶與結構式(5)的R¹⁵為相同含義。所述式(5-1)及式(5-2)中，R¹⁷為碳數為1至12的烷基、碳數為1至12的氟烷基。式(5-3)中，X為烷基、烷氧基、或者鹵素原子。i為0至3的整數。其中，在i為2或3的情況下，多個X可相同，亦可不同。 In the formula (5-1) to formula (5-3), R ¹⁶ has the same meaning as R ¹⁵ of the structural formula (5). In the formula (5-1) and formula (5-2), R ¹⁷ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms. In formula (5-3), X is an alkyl group, an alkoxy group, or a halogen atom. i is an integer from 0 to 3. Among them, when i is 2 or 3, multiple Xs may be the same or different.

所述X所表示的烷基較佳為碳數為1至4的直鏈狀或分支狀的烷基。所述X所表示的烷氧基較佳為碳數為1至4的直鏈狀或分支狀的烷氧基。所述X所表示的鹵素原子較佳為氯原子、氟原子。 The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

所述式(5-3)所表示的肟磺酸酯化合物例如可列舉下述式(5-4)至式(5-8)所表示的化合物等。 The oxime sulfonate compound represented by the formula (5-3) can be, for example, Compounds represented by the following formula (5-4) to formula (5-8), etc. are listed.

所述式(5-4)至式(5-8)所表示的化合物分別為：(5-丙基磺醯氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、(5-辛基磺醯氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、(5-樟腦磺醯氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、(5-對甲苯磺醯氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈、2-(辛基磺醯氧基亞胺基)-2-(4-甲氧基苯基)乙腈、4-甲基苯基磺醯氧基亞胺基-α-(4-甲氧基苯基)乙腈，可使用市售的上述化合物。 The compounds represented by formula (5-4) to formula (5-8) are respectively: (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methyl Phenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-camphorsulfonyloxyimino- 5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) )acetonitrile, 2-(octylsulfonyloxyimine base)-2-(4-methoxyphenyl)acetonitrile, 4-methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile, the above-mentioned compounds that are commercially available can be used .

上述N-磺醯氧基醯亞胺化合物例如可列舉：N-(三氟甲基磺醯氧基)丁二醯亞胺、N-(樟腦磺醯氧基)丁二醯亞胺、N-(4-甲基苯基磺醯氧基)丁二醯亞胺、N-(2-三氟甲基苯基磺醯氧基)丁二醯亞胺、N-(4-氟苯基磺醯氧基)丁二醯亞胺、N-(三氟甲基磺醯氧基)鄰苯二甲醯亞胺、N-(樟腦磺醯氧基)鄰苯二甲醯亞胺、N-(2-三氟甲基苯基磺醯氧基)鄰苯二甲醯亞胺、N-(2-氟苯基磺醯氧基)鄰苯二甲醯亞胺、N-(三氟甲基磺醯氧基)二苯基順丁烯二醯亞胺、N-(樟腦磺醯氧基)二苯基順丁烯二醯亞胺、(4-甲基苯基磺醯氧基)二苯基順丁烯二醯亞胺、N-(2-三氟甲基苯基磺醯氧基)二苯基順丁烯二醯亞胺、N-(4-氟苯基磺醯氧基)二苯基順丁烯二醯亞胺、N-(苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-甲基苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(三氟甲磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(九氟丁磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(樟腦磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(樟腦磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(三氟甲基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-甲基苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-甲基苯基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-三氟甲基苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-三氟甲基苯基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-氟苯基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-氟苯基磺醯氧基)-7-氧雜雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(三氟甲基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(樟腦磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(4-甲基苯基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(2-三氟甲基苯基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(4-氟苯基磺醯氧基)雙環[2.2.1]庚烷-5,6-氧基-2,3-二羧基醯亞胺、N-(三氟甲基磺醯氧基)萘二甲醯亞胺(N-((trifluoromethylsulfonyl)oxy)naphthalene dicarboximide)、N-(樟腦磺醯氧基)萘二甲醯亞胺、N-(4-甲基苯基磺醯氧基)萘二甲醯亞胺、N-(苯基磺醯氧基)萘二甲醯亞胺、N-(2-三氟甲基苯基磺醯氧基)萘二甲醯亞胺、N-(4-氟苯基磺醯氧基)萘二甲醯亞胺、N-(五氟乙基磺醯氧基)萘二甲醯亞胺、N-(七氟丙基磺醯氧基)萘二甲醯亞胺、N-(九氟丁基磺醯氧基)萘二甲醯亞胺、N-(乙基磺醯氧基)萘二甲醯亞胺、N-(丙基磺醯氧基)萘二甲醯亞胺、N-(丁基磺醯氧基)萘二甲醯亞胺、N-(戊基磺醯氧基)萘二甲醯亞胺、N-(己基磺醯氧基)萘二甲醯亞胺、N-(庚基磺醯氧基)萘二甲醯亞胺、N-(辛基磺醯氧基)萘二甲醯亞胺、N-(壬基磺醯氧基)萘二甲醯亞胺等。 Examples of the above-mentioned N-sulfonyloxyimide compounds include: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N- (4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyl) Oxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2 -Trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyl) Oxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylcis Butenediimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenyl Maleic imide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(4-methylphenylsulfonate) Cyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxylimide, N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(camphorsulfonyloxy) )bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxylimide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboxylimide, N-(4-methylphenylsulfonyloxy)-7 -oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(2-trifluoromethylphenyl Sulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[ 2.2.1]Hept-5-ene-2,3-dicarboxylimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]Hept-5-ene-2,3-di Carboxylimide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-en-2,3-dicarboxylimide, N-(trifluoro Methylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane -5,6-oxy-2,3-dicarboxylimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2, 3-dicarboxylimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(trifluoromethylsulfonyloxy) )Naphthalene dicarboximide (N-((trifluoromethylsulfonyl)oxy)naphthalene dicarboximide), N-(camphorsulfonyloxy)naphthalene dicarboximide, N-(4-methylphenylsulfonyloxy) Naphthalenedimide, N-(phenylsulfonyloxy)naphthalenedimide, N-(2-trifluoromethylphenylsulfonyloxy)naphthalenedimine, N-( 4-Fluorophenylsulfonyloxy)naphthalenedimide, N-(pentafluoroethylsulfonyloxy)naphthalenedimide, N-(heptafluoropropylsulfonyloxy)naphthalenedimine Formimide, N-(nonafluorobutylsulfonyloxy)naphthalenedimide, N-(ethylsulfonyloxy)naphthalenedimide, N-(propylsulfonyloxy) )naphthalenedimide, N-(butylsulfonyloxy)naphthalenedimide, N-(pentylsulfonyloxy)naphthalenedimide, N-(hexylsulfonyloxy) )Naphthalenedimide, N-(heptylsulfonyloxy)naphthalenedimide, N-(octylsulfonyloxy)naphthalenedimide, N-(nonylsulfonyloxy) base) naphthalene dimethylimide, etc.

所述鎓鹽、含鹵素的化合物、重氮甲烷化合物、碸化合物、磺酸酯化合物、羧酸酯化合物等可使用日本專利特開2011-232632號公報中記載的化合物。例如：苄基(4-羥苯基)甲基硫鎓六氟銻酸鹽。 As the onium salt, halogen-containing compound, diazomethane compound, trine compound, sulfonate compound, carboxylate compound, etc., the compounds described in Japanese Patent Application Laid-Open No. 2011-232632 can be used. For example: benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate.

基於樹脂(A)的使用量為100重量份，光酸產生劑(B)的使用量為0.1重量份至10重量份，較佳為0.1至8重量份，更佳為0.1至5重量份。當樹脂組成物包含如式(5)所示結構的光酸產生劑(B)時，可進一步改善此樹脂組成物所製得之保護膜的耐化性。 Based on the usage amount of resin (A) being 100 parts by weight, the usage amount of photoacid generator (B) is 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, and more preferably 0.1 to 5 parts by weight. When the resin composition contains the photoacid generator (B) with the structure shown in formula (5), the chemical resistance of the protective film produced by the resin composition can be further improved.

溶劑(C)Solvent(C)

本發明之溶劑(C)的種類沒有特別的限制。溶劑(C)之具體例為含醇式羥基(alcoholic hydroxy)的化合物或含羰基(carbonyl group)的環狀化合物等。 The type of solvent (C) in the present invention is not particularly limited. Specific examples of the solvent (C) include alcoholic hydroxyl-containing compounds or carbonyl group-containing cyclic compounds.

含醇式羥基的化合物之具體例為丙酮醇(acetol)、3-羥基-3-甲基-2-丁酮(3-hydroxy-3-methyl-2-butanone)、4-羥基-3-甲基-2-丁酮(4-hydroxy-3-methyl-2-butanone)、5-羥基-2-戊酮(5-hydroxy-2-pentanone)、4-羥基-4-甲基-2-戊酮(4-hydroxy-4-methyl-2-pentanone)(亦稱為二丙酮醇(diacetone alcohol，簡稱DAA))、乳酸乙酯(ethyl lactate)、乳酸丁酯(butyl lactate)、丙二醇單甲醚propylene glycol monomethyl ether)、丙二醇單***(propylene glycol monoethyl ether，簡稱PGEE)、丙二醇甲醚醋酸酯(propylene glycol monomethyl ether acetate，簡稱PGMEA)、丙二醇單正丙醚(propylene glycol mono-n-propyl ether)、丙二醇單正丁醚(propylene glycol mono-n-butyl ether)、丙二醇單第三丁醚(propylene glycol mono-t-butyl ether)、3-甲氧基-1-丁醇(3-methoxy-1-butanol)、3-甲基-3-甲氧基-1-丁醇(3-methyl-3-methoxy-1-butanol)或其組合。值得注意的是，含醇式羥基的化合物較佳為二丙酮醇、乳酸乙酯、丙二醇單***、丙二醇甲醚醋酸酯或其組合。含醇式羥基的化合物可單獨使用或組合多種來使用。 Specific examples of compounds containing alcoholic hydroxyl groups are acetol, 3-hydroxy-3-methyl-2-butanone, and 4-hydroxy-3-methyl 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone Ketone (4-hydroxy-4-methyl-2-pentanone) (also known as diacetone alcohol (DAA)), ethyl lactate (ethyl lactate), butyl lactate (butyl lactate), propylene glycol monomethyl ether propylene glycol monomethyl ether), propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether) acetate (PGMEA for short), propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t -butyl ether), 3-methoxy-1-butanol (3-methoxy-1-butanol), 3-methyl-3-methoxy-1-butanol (3-methyl-3-methoxy-1 -butanol) or combinations thereof. It is worth noting that the compound containing alcoholic hydroxyl groups is preferably diacetone alcohol, ethyl lactate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate or a combination thereof. The alcoholic hydroxyl group-containing compound can be used alone or in combination of multiple types.

含羰基的環狀化合物之具體例為γ-丁內酯(γ-butyrolactone)、γ-戊內酯(γ-valerolactone)、δ-戊內酯(δ-valerolactone)、碳酸丙烯酯(propylene carbonate)、氮-甲基吡咯烷酮(N-methyl pyrrolidone)、環己酮(cyclohexanone)或環庚酮(cycloheptanone)等。值得注意的是，含羰基的環狀化合物較佳為γ-丁內酯、氮-甲基吡咯烷酮、環己酮或其組合。含羰基的環狀化合物可單獨使用或組合多種來使用。 Specific examples of the carbonyl group-containing cyclic compound are γ-butyrolactone, γ-valerolactone, δ-valerolactone, and propylene carbonate. , N-methyl pyrrolidone, cyclohexanone or cycloheptanone, etc. It is worth noting that the carbonyl-containing cyclic compound is preferably γ-butyrolactone, nitrogen-methylpyrrolidone, cyclohexanone or a combination thereof. The carbonyl group-containing cyclic compound can be used alone or in combination of multiple types.

含醇式羥基的化合物可與含羰基的環狀化合物組合使用，且其重量比率沒有特別限制。含醇式羥基的化合物與含羰基的環狀化合物的重量比值較佳為99/1至50/50；更佳為95/5至60/40。 The alcoholic hydroxyl group-containing compound can be used in combination with the carbonyl group-containing cyclic compound, and the weight ratio thereof is not particularly limited. The weight ratio of the alcoholic hydroxyl-containing compound to the carbonyl group-containing cyclic compound is preferably 99/1 to 50/50; more preferably, it is 95/5 to 60/40.

在不損及本發明的效果的範圍內，亦可以含有其他溶劑。其他溶劑之具體例為：(1)酯類：醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、丙二醇甲醚醋酸酯、3-甲氧基-1-醋酸丁酯或3-甲基-3-甲氧基-1-醋酸丁酯等；(2)酮類：甲基異丁酮、二異丙酮或二異丁酮等；或者(3)醚類：二***、二異丙醚、二正丁醚或二苯醚等。 Other solvents may also be contained within the scope that does not impair the effect of the present invention. Specific examples of other solvents are: (1) Esters: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol Methyl ether acetate, 3-methoxy-1-butyl acetate or 3-methyl-3-methoxy-1-butyl acetate, etc.; (2) Ketones: methyl isobutyl ketone, diisopropyl ketone Or diisobutyl ketone, etc.; or (3) Ethers: diethyl ether, diisopropyl ether, di-n-butyl ether or diphenyl ether, etc.

基於樹脂(A)的使用量為100重量份，溶劑(C)的使用量為200重量份至2000重量份，較佳為200至1500重量份，更佳為200至1000重量份。 Based on the usage amount of resin (A) being 100 parts by weight, the usage amount of solvent (C) is 200 to 2000 parts by weight, preferably 200 to 1500 parts by weight, and more preferably 200 to 1000 parts by weight.

環氧化合物(D)Epoxy compound (D)

本發明所使用的環氧化合物(D)具有如下式(2)所示的結構。 The epoxy compound (D) used in the present invention has a structure represented by the following formula (2).

A-(B)_n1 (2) A-(B) _n1 (2)

於式(2)中，A代表(n1)價的含氮環基，B代表式(2-1)所示的結構，以及n1表示2至8之整數。 In the formula (2), A represents a nitrogen-containing cyclic group with a valence of (n1), B represents the structure shown in the formula (2-1), and n1 represents an integer from 2 to 8.

於式(2-1)中，R⁴及R⁵分別獨立表示氫原子或碳數為1至10之烷基；R⁶表示(n4+1)價之烴基；n2表示1之整數；n3表示2之整數；n4表示2至5之整數；n5表示0或1之整數；n6表示0或1之整數；以及，*²為B與A的鍵結處。 In formula (2-1), R ⁴ and R ⁵ independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 10; R ⁶ represents a hydrocarbon group with a valence of (n4+1); n2 represents an integer of 1; n3 represents n4 represents an integer from 2 to 5; n5 represents an integer of 0 or 1; n6 represents an integer of 0 or 1; and, * ² is the bonding point between B and A.

上述式(2)所示的結構包含式(2-2)、式(2-3)或式(2-4)所示結構的環氧化合物。 The structure represented by the above formula (2) includes an epoxy compound having a structure represented by the formula (2-2), formula (2-3) or formula (2-4).

於式(2-2)、式(2-3)和式(2-4)中，A代表(n1)價的含氮環基；R⁴及R⁵分別獨立表示氫原子或碳數為1至10之烷基，R⁶表示(n4+1)價之烴基，n1表示2至8之整數；n2表示1之整數，n3表示2之整數；以及，n4表示2至5之整數。 In formula (2-2), formula (2-3) and formula (2-4), A represents a nitrogen-containing cyclic group with (n1) valence; R ⁴ and R ⁵ respectively independently represent a hydrogen atom or a carbon number of 1 to 10 alkyl groups, R ⁶ represents a (n4+1)-valent hydrocarbon group, n1 represents an integer from 2 to 8; n2 represents an integer of 1, n3 represents an integer of 2; and, n4 represents an integer from 2 to 5.

在式(2)、式(2-1)、式(2-2)、式(2-3)和式(2-4)中，A可以列舉出例如，從三烷基異氰脲酸酯去掉(n1)個氫原子後的(n1)價含氮環基，或從異氰脲酸、氰脲酸、乙內醯脲或巴比妥酸去掉(n1)個氫原子後的(n1)價含氮環基。 In formula (2), formula (2-1), formula (2-2), formula (2-3) and formula (2-4), A can include, for example, trialkyl isocyanurate (n1) valent nitrogen-containing ring group after removing (n1) hydrogen atoms, or (n1) after removing (n1) hydrogen atoms from isocyanuric acid, cyanuric acid, hydantoin or barbituric acid Nitrogen-containing ring group.

R⁴和R⁵分別獨立地表示氫原子或碳數為1至10的烷基，此碳數為1至10的烷基可列舉例如甲基、乙基、正丙基、異丙基、環丙基、正丁基、異丁基、第二丁基、第三丁基、環丁基、1-甲基-環丙基、2-甲基-環丙基、正戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2-甲基-2-乙基-正丙基、2-甲基-2-甲基-正丙基、2,2-二甲基-正丙基、1-乙基-正丙基、環戊基、1-甲基-環丁基、2-甲基-環丁基、3-甲基-環丁基、1,2-二甲基-環丙基、2,3-二甲基-環丙基、1-乙基-環丙基、2-乙基-環丙基、正己基、1-甲基-正戊基、2-甲基-正戊基、3-甲基-正戊基、4-甲基-正戊基、1,1-二甲基-正丁基、1,2-二甲基-正丁基、1,3-二甲基-正丁基、2,2-二甲基-正丁基、2,3-二甲基-正丁基、3,3-二甲基-正丁基、1-乙基-正丁基、2-乙基-正丁基、1,1,2-三甲基-正丙基、1,2,2-三甲基-正丙基、1-乙基-1-甲基-正丙基、1-乙基-2-甲基-正丙基、環己基、1-甲基-環戊基、2-甲基-環戊基、3-甲基-環戊基、1-乙基-環丁基、2-乙基-環丁基、3-乙基-環丁基、1,2-二甲基-環丁基、1,3-二甲基-環丁基、2,2-二甲基-環丁基、2,3-二甲基-環丁基、2,4-二甲基-環丁基、3,3-二甲基-環丁基、1-正丙基-環丙基、2-正丙基-環丙基、1-異丙基-環丙基、2-異丙基-環丙基、1,2,2-三甲基-環丙基、1,2,3-三甲基-環丙基、2,2,3-三甲基-環丙基、1-乙基-2-甲基-環丙基、2-乙基-1-甲基-環丙基、2-乙基-2-甲基-環丙基和2-乙基-3-甲基-環丙基等。 R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 10. Examples of the alkyl group with a carbon number of 1 to 10 include methyl, ethyl, n-propyl, isopropyl, cyclic Propyl, n-butyl, isobutyl, second butyl, third butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl -n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2- Methyl-2-ethyl-n-propyl, 2-methyl-2-methyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl , 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl base, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-Methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-di Methyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1 ,1,2-Trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl -n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclo Butyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl- Cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl base, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2 -Methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, etc.

R⁶表示(n4+1)價烴基，烴基可以列舉出例如從上述烷基去掉(n4+1)個氫原子後的(n4+1)價烴基。 R ⁶ represents a (n4+1)-valent hydrocarbon group. Examples of the hydrocarbon group include (n4+1)-valent hydrocarbon groups obtained by removing (n4+1) hydrogen atoms from the above-mentioned alkyl group.

在式(2)中，具有與A上取代的B相對應的結構可列舉如下所示之具有環氧基的烷基酯基、烷基和烷氧基。 In formula (2), it has a structure corresponding to B substituted on A Examples include alkyl ester groups, alkyl groups and alkoxy groups having an epoxy group as shown below.

於式(2-8)至式(2-11)中，n5表示0或1之整數；n6表示0或1之整數。 In formula (2-8) to formula (2-11), n5 represents an integer of 0 or 1; n6 represents an integer of 0 or 1.

此外，與式(2)中的A之含氮環基相對應的結構可列舉如下式(2-5)至式(2-7)所示，其中B可為上述式(2-8)至式(2-11)所示的多官能環氧基。 In addition, the structures corresponding to the nitrogen-containing ring group of A in formula (2) can be listed as shown in the following formulas (2-5) to formula (2-7), wherein B can be the above formulas (2-8) to Polyfunctional epoxy group represented by formula (2-11).

於式(2-5)中，R⁷表示氫原子或碳數為1至10的烷基。 In formula (2-5), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

在一些實施例中，上述式(2-2)所表示的環氧化合物，可以藉由使具有上述A的結構的羧酸或羧酸酐等的羧酸衍生物，與烯醇進行反應，以得到具有不飽和鍵的化合物(中間體)。接著，將此中間體和過氧化物反應而製造。此外，所述中間體可以用任意方法來製造，並不限於羧酸或羧酸酐與烯醇的反應。將此具有所述不飽和鍵的中間體和過氧化物進行反應，便能夠製得上述式(2-2)所表示的環氧化合物。 In some embodiments, the epoxy compound represented by the above formula (2-2) can be prepared by using a carboxylic acid or carboxylic acid anhydride having the structure of the above A. Acid derivatives react with enols to obtain compounds with unsaturated bonds (intermediates). Next, this intermediate is reacted with a peroxide to produce. In addition, the intermediate can be produced by any method and is not limited to the reaction of carboxylic acid or carboxylic anhydride and enol. The epoxy compound represented by the above formula (2-2) can be produced by reacting this intermediate having the unsaturated bond with a peroxide.

與上述A上取代的B(具有多官能環氧基的烷基酯基)對應的烯醇，可列舉如以下的烯醇。 Enols corresponding to B (alkyl ester group having a polyfunctional epoxy group) substituted on the above-mentioned A include the following enols.

做為A表示(n1)價含氮環基的羧酸，可以列舉出三羧烷基異氰脲酸酯(所述烷基可為碳數為1至5的烷基，較佳為碳數為1至3的烷基)，其具體例子可列示如下。 Examples of the carboxylic acid in which A represents a (n1)-valent nitrogen-containing ring group include tricarboxyalkyl isocyanurate (the alkyl group may be an alkyl group having a carbon number of 1 to 5, preferably an alkyl group having a carbon number of an alkyl group of 1 to 3), specific examples thereof are listed below.

式(2-13-1)中，R⁷表示氫原子或碳數為1至10的烷基。 In formula (2-13-1), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

做為具有上述A的結構的羧酸或羧酸酐與烯醇進行反應而得到的具有不飽和鍵的化合物(中間體)，可舉例如式(2-2-1)。 Examples of the compound (intermediate) having an unsaturated bond obtained by reacting a carboxylic acid or carboxylic acid anhydride having the structure of A above with an enol and having an unsaturated bond include formula (2-2-1).

式(2-2-1)中，A表示(n1)價含氮環基，R⁴和R⁵分別獨立地表示氫原子或碳數為1至10的烷基，R⁶表示(n4+1)價烴基，n1表示2至8的整數，n2表示1的整數，n3表示2的整數，以及n4表示2至5的整數。 In formula (2-2-1), A represents a (n1)-valent nitrogen-containing cyclic group, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 10, and R ⁶ represents (n4+1 )-valent hydrocarbon group, n1 represents an integer from 2 to 8, n2 represents an integer of 1, n3 represents an integer of 2, and n4 represents an integer from 2 to 5.

在一些實施例中，本發明所使用的式(2-2)所表示的環氧化合物(D)，可例如以式(2-12-1)和式(2-13-2)的化合物反應而得，其具體方法如下所示。 In some embodiments, the epoxy compound (D) represented by formula (2-2) used in the present invention can be reacted with compounds of formula (2-12-1) and formula (2-13-2), for example. The specific method is as follows.

首先，使羧酸和烯醇進行反應，合成中間體(烯烴)。此反應是在甲苯等溶劑中，使用對甲苯磺酸、硫酸等催化劑，在室溫(例如20℃)至110℃的溫度下進行大於0小時至小於或等於100小時。然後，藉由過氧化物氧化不飽和化合物(中間體)，以獲得環氧化合物。所述過氧化物可以使用例如：間氯過苯甲酸、過乙酸、過氧化氫-鎢酸等。此過氧化的反應，是在氯仿等溶劑中，於0℃至60℃下進行1小時至200小時。上述反應，可以使用酸酐代替三羧酸化合物做為原料來進行。此外，當使用的羧酸為難溶於甲苯等溶劑時，可藉由使用甲醇等醇類將羧酸酯化，接著與烯醇進行酯交換反應的方法；或者，可利用碳二亞胺等縮合劑使羧酸和烯醇進行反應的方法；或者，可利用氯化亞碸等使羧酸變為醯氯化物，然後與烯醇反應的方法，也可以合成上述中間體(烯烴)。 First, carboxylic acid and enol are reacted to synthesize an intermediate (olefin). This reaction is carried out in a solvent such as toluene, using a catalyst such as p-toluenesulfonic acid, sulfuric acid, etc., at a temperature from room temperature (for example, 20°C) to 110°C for more than 0 hours to less than or equal to 100 hours. Then, the unsaturated compound (intermediate) is oxidized by peroxide to obtain an epoxy compound. As the peroxide, for example, m-chloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid, etc. can be used. This peroxidation reaction is carried out in a solvent such as chloroform at 0°C to 60°C for 1 hour to 200 hours. In the above reaction, acid anhydrides can be used instead of tricarboxylic acid compounds. Used as raw materials. In addition, when the carboxylic acid used is poorly soluble in solvents such as toluene, the carboxylic acid can be esterified with an alcohol such as methanol, and then transesterified with enol; or condensation with carbodiimide can be used The above-mentioned intermediate (olefin) can also be synthesized by reacting a carboxylic acid and an enol with a reagent; alternatively, the carboxylic acid can be converted into a chloride chloride using tyrene chloride, etc., and then reacted with the enol.

上述式(2-3)所表示的環氧化合物，可以藉由使具有A的結構的含氮環化合物(此化合物具有NH基)與具有可脫去基的烯醇或烯丙基鹵化物進行反應，然後使得到的具有不飽和鍵的化合物(中間體)和過氧化物進行反應而製造。 The epoxy compound represented by the above formula (2-3) can be prepared by combining a nitrogen-containing cyclic compound having a structure of A (this compound has an NH group) and an enol or allyl halide having a removable group. reaction, and then the obtained compound (intermediate) having an unsaturated bond is reacted with a peroxide to produce it.

此外，上述式(2-3)所表示的環氧化合物，可以通過使具有A的結構的含氮化合物(此化合物具有NH基)和具有不飽和鍵的環氧化合物進行反應，然後將得到的醇化合物與具有可脫去基的烯醇或烯丙基鹵化物進行反應，再使得到的具有不飽和鍵的化合物(中間體)和過氧化物進行反應而製造。 In addition, the epoxy compound represented by the above formula (2-3) can be obtained by reacting a nitrogen-containing compound having a structure of A (this compound has an NH group) and an epoxy compound having an unsaturated bond. It is produced by reacting an alcohol compound with an enol or allyl halide having a removable group, and then reacting the obtained compound (intermediate) having an unsaturated bond with a peroxide.

具有與A上取代的B相對應的可脫去基的烯醇、烯丙基鹵化物，可以使用例如，通過使上述式(2-12-1)、式(2-12-2)、式(2-12-3)和(2-12-4)所表示的化合物與甲磺醯鹵、三氟甲磺酸酐、甲苯磺醯鹵、硝基苯磺醯鹵、乙醯鹵、乙酸酐、三氟乙酸酐、三氯氧磷、三溴氧磷、鹵化亞碸、鹵化硫醯、氯化氫、溴化氫、碘化氫等進行反應而所得到的下述式(2-12-5)、式(2-12-6)、式(2-12-7)和式(2-12-8)所表示的化合物。 Enols and allyl halides having a removable group corresponding to B substituted on A can be used, for example, by using the above formula (2-12-1), formula (2-12-2), formula The compounds represented by (2-12-3) and (2-12-4) are similar to methanesulfonyl halide, trifluoromethanesulfonic acid anhydride, toluenesulfonyl halide, nitrobenzene sulfonyl halide, acetyl halide, acetic anhydride, The following formula (2-12-5) obtained by reacting trifluoroacetic anhydride, phosphorus oxychloride, phosphorus oxybromide, tyrene halide, sulfonyl halide, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc., Compounds represented by formula (2-12-6), formula (2-12-7) and formula (2-12-8).

於式(2-12-5)、式(2-12-6)、式(2-12-7)和式(2-12-8)中，Y表示甲磺醯氧基、三氟甲磺醯氧基、甲苯磺醯氧基、硝基苯磺醯氧基、乙醯氧基、三氟乙醯氧基、氯原子、溴原子或碘原子。 In formula (2-12-5), formula (2-12-6), formula (2-12-7) and formula (2-12-8), Y represents methanesulfonyloxy group, trifluoromethanesulfonate Cyloxy group, toluenesulfonyloxy group, nitrobenzenesulfonyloxy group, acetyloxy group, trifluoroacetyloxy group, chlorine atom, bromine atom or iodine atom.

所述具有A的結構的含氮化合物(此化合物具有NH基)，可列舉如下。 The nitrogen-containing compound having a structure of A (this compound has an NH group) can be listed as follows.

具有A的結構的含氮環化合物(此化合物具有NH基)與具有可脫去基的烯醇或烯丙基鹵化物進行反應而得到的具有不飽和鍵的化合物(中間體)，可以例示出式(2-3-1)。 Examples of compounds (intermediate) having an unsaturated bond obtained by reacting a nitrogen-containing ring compound having the structure A (this compound has an NH group) and an enol or allyl halide having a removable group are Formula (2-3-1).

於式(2-3-1)中，A表示(n1)價含氮環基，R⁴和R⁵分別獨立地表示氫原子或碳數為1至10的烷基，R⁶表示(n4+1)價烴基，n1表示2至8的整數，n2表示1的整數，n3表示2的整數，以及n4表示2至5的整數。 In formula (2-3-1), A represents a (n1)-valent nitrogen-containing cyclic group, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 10, and R ⁶ represents (n4+ 1) A valent hydrocarbon group, n1 represents an integer from 2 to 8, n2 represents an integer of 1, n3 represents an integer of 2, and n4 represents an integer from 2 to 5.

在一些實施例中，本發明中使用的式(2-3)所表示的環氧化合物，可例如以式(2-12-5)和式(2-13-3)的化合物反應而得，其具體方法如下所示。 In some embodiments, the epoxy compound represented by formula (2-3) used in the present invention can be obtained by reacting the compounds of formula (2-12-5) and formula (2-13-3), for example, The specific method is as follows.

首先，使含氮環化合物(此化合物具有NH基)和具有可脫去基的烯醇進行反應來合成中間體(烯烴)。此反應是在二甲基甲醯胺(DMF)等溶劑中使用氫化鈉、碳酸鉀、第三丁醇鉀、三乙胺等鹼，在室溫(例如20℃)以上至溶劑的沸點溫度以下之溫度下，進行反應達大於0小時至等於或小於100小時。然後，用過氧化物使此不飽和化合物氧化而得到環氧化合物。所述過氧化物，可以使用例如：間氯過苯甲酸、過乙酸、過氧化氫-鎢酸等。此反應是在氯仿等溶劑中，於0℃至60℃下進行10小時至200小時。 First, a nitrogen-containing cyclic compound (this compound has an NH group) and an enol having a removable group are reacted to synthesize an intermediate (olefin). This reaction uses bases such as sodium hydride, potassium carbonate, potassium tert-butoxide, and triethylamine in a solvent such as dimethylformamide (DMF) at a temperature above room temperature (for example, 20°C) and below the boiling point of the solvent. At the temperature, the reaction is carried out for greater than 0 hours to equal to or less than 100 hours. Then, this unsaturated compound is oxidized with peroxide to obtain an epoxy compound. As the peroxide, for example, m-chloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid, etc. can be used. This reaction is carried out in a solvent such as chloroform at 0°C to 60°C for 10 hours to 200 hours.

再者，上述式(2-4)所表示的環氧化合物，可例如藉由使具有上述A的結構的醇，與具有可脫去基的烯醇或烯丙基鹵化物進行反應，並使得到的具有不飽和鍵的化合物 (中間體)和過氧化物進行反應而製造。 Furthermore, the epoxy compound represented by the above formula (2-4) can be obtained by reacting an alcohol having the structure of the above A with an enol or allyl halide having a removable group, for example. Compounds with unsaturated bonds (intermediate) and peroxide are reacted to produce it.

做為具有與A上取代的B相對應的可脫去基的烯醇或烯丙基鹵化物，可以例如藉由使上述式(2-12-1)、式(2-12-2)、式(2-12-3)、和(2-12-4)所表示的化合物與甲磺醯鹵、三氟甲磺酸酐、甲苯磺醯鹵、硝基苯磺醯鹵、乙醯鹵、乙酸酐、三氟乙酸酐、三氯氧磷、三溴氧磷、鹵化亞碸、鹵化硫醯、氯化氫、溴化氫或碘化氫等進行反應，以得到的上述式(2-12-5)、式(2-12-6)、式(2-12-7)和式(2-12-8)所表示的化合物。 As the enol or allyl halide having a removable group corresponding to B substituted on A, for example, the above formula (2-12-1), formula (2-12-2), Compounds represented by formulas (2-12-3) and (2-12-4) and methanesulfonyl halide, trifluoromethanesulfonic anhydride, toluenesulfonyl halide, nitrobenzene sulfonyl halide, acetyl halide, ethanol halide Acid anhydride, trifluoroacetic anhydride, phosphorus oxychloride, phosphorus oxybromide, terine halide, thiol halide, hydrogen chloride, hydrogen bromide or hydrogen iodide, etc. are reacted to obtain the above formula (2-12-5) , compounds represented by formula (2-12-6), formula (2-12-7) and formula (2-12-8).

做為A表示(n1)價含氮環基時的醇，可以例示以下的醇。 Examples of the alcohol when A represents a (n1)-valent nitrogen-containing cyclic group include the following alcohols.

式(2-13-4)中，R⁷表示氫原子或碳數為1至10的烷基。 In formula (2-13-4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

具有上述A的結構的醇與具有可脫去基的烯醇或烯丙基鹵化物進行反應而得到的具有不飽和鍵的化合物(中間體)，可以例示出式(2-4-1)。 An example of a compound (intermediate) having an unsaturated bond obtained by reacting an alcohol having the structure of A above with an enol or allyl halide having a removable group is formula (2-4-1).

於式(2-4-1)中，A表示(n1)價含氮環基，R⁴和R⁵分別獨立地表示氫原子或碳數為1至10的烷基，R⁶表示(n4+1) 價烴基，n1表示2至8的整數，n2表示1的整數，n3表示2的整數，以及n4表示2至5的整數。 In formula (2-4-1), A represents a (n1)-valent nitrogen-containing cyclic group, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 10, and R ⁶ represents (n4+ 1) For a valent hydrocarbon group, n1 represents an integer from 2 to 8, n2 represents an integer of 1, n3 represents an integer of 2, and n4 represents an integer from 2 to 5.

在一些實施例中，本發明中使用的式(2-4)所表示的環氧化合物，可例如以式(2-12-5)和式(2-13-5)的化合物反應而得，其具體方法如下所示。 In some embodiments, the epoxy compound represented by formula (2-4) used in the present invention can be obtained by reacting the compounds of formula (2-12-5) and formula (2-13-5), for example, The specific method is as follows.

首先，使醇和具有可脫去基的烯醇進行反應來合成中間體(烯烴)。此反應是在醚、醯胺等溶劑中，使用氫氧化鈉、碳酸鉀、第三丁醇鉀、三乙胺等鹼，在室溫(例如20℃)以上和溶劑的沸點溫度以下，進行大於0小時至小於或等於100小時。然後，用過氧化物將此不飽和化合物氧化而得到環氧化合物。所述過氧化物可以使用例如：間氯過苯甲酸、過乙酸、過氧化氫-鎢酸等。此反應是在氯仿等溶劑中，於0℃至60℃下進行1小時至200小時。 First, an alcohol and an enol having a removable group are reacted to synthesize an intermediate (olefin). This reaction is carried out in solvents such as ether and amide, using bases such as sodium hydroxide, potassium carbonate, potassium tert-butoxide, and triethylamine, at a temperature above room temperature (for example, 20°C) and below the boiling point of the solvent. 0 hours to less than or equal to 100 hours. Then, this unsaturated compound is oxidized with peroxide to obtain an epoxy compound. As the peroxide, for example, m-chloroperbenzoic acid, peracetic acid, hydrogen peroxide-tungstic acid, etc. can be used. This reaction is carried out in a solvent such as chloroform at 0°C to 60°C for 1 hour to 200 hours.

上述式(2-4)所表示的環氧化合物，可例如藉由使三聚氯化氰與式(2-12-1)、式(2-12-2)、式(2-12-3)、和式(2-12-4)等所表示的烯丙基醇進行反應，再如前所述，使得到的具有不飽和鍵的化合物(中間體)和過氧化物進行反應而製造。 The epoxy compound represented by the above formula (2-4) can be obtained, for example, by cyanogen chloride and allyl groups represented by formula (2-12-1), formula (2-12-2), formula (2-12-3), and formula (2-12-4), etc. The alcohol is reacted, and the obtained compound (intermediate) having an unsaturated bond is reacted with the peroxide as described above to produce the compound.

在一些實施例中，如式(2-2)所示的環氧化合物可列舉如下式(2-2-2)至式(2-2-9)。 In some embodiments, the epoxy compound represented by formula (2-2) can be listed as the following formulas (2-2-2) to formula (2-2-9).

在一些實施例中，如式(2-3)所示的環氧化合物可列舉如下式(2-3-2)至式(2-3-5)。 In some embodiments, the epoxy compound represented by formula (2-3) can be listed as the following formulas (2-3-2) to formula (2-3-5).

在一些實施例中，如式(2-4)所示的環氧化合物可列舉如下式(2-4-2)至式(2-4-10)。 In some embodiments, the epoxy compound represented by formula (2-4) can be listed as the following formulas (2-4-2) to formula (2-4-10).

在一些較佳的實施例中，本發明的環氧化合物(D)較佳為具有式(2-2)所示的結構。 In some preferred embodiments, the epoxy compound (D) of the present invention preferably has a structure represented by formula (2-2).

基於樹脂(A)的使用量為100重量份，環氧化合物(D)的使用量為1重量份至20重量份，較佳為1至15重量份，更佳為1至10重量份。倘若未使用環氧化合物(D)，則由樹脂組成物所製得的保護膜之顯影密著性及耐化性不佳。 Based on the usage amount of resin (A) being 100 parts by weight, the usage amount of epoxy compound (D) is 1 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight. If the epoxy compound (D) is not used, the protective film produced from the resin composition will have poor development adhesion and chemical resistance.

其他添加劑(E)Other additives(E)

選擇性地，本發明的化學增幅型正型感光性樹脂組成物可包含其他添加劑(E)。具體而言，其他添加劑(E)之具體例為增感劑(sensitizer)、密著助劑(adhesion auxiliary agent)、界面活性劑(surfactant)、溶解促進劑(solubility promoter)、消泡劑(defoamer)或其組合。 Optionally, the chemically amplified positive photosensitive resin composition of the present invention may contain other additives (E). Specifically, specific examples of other additives (E) are sensitizer, adhesion auxiliary agent, surfactant, solubility promoter, and defoamer. ) or a combination thereof.

增感劑的種類並無特別的限制。增感劑較佳為使用含有酚式羥基(phenolic hydroxy)的化合物，之具體例為：(1)三苯酚型化合物(trisphenol type compound)：如三(4-羥基苯基)甲烷、雙(4-羥基-3-甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-2,3,5-三甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3-羥基苯基甲烷、雙(4-羥基-3,5-甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-4-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3-羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2-羥基苯基甲烷、雙(4-羥基-3,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-3,4-二羥基苯基甲烷、雙(4-羥基-2,5-二甲基苯基)-2,4-二羥基苯基甲烷、雙(4-羥基苯基)-3-甲氧基-4-羥基苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-4-羥基苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-3-羥基苯基甲烷、雙(5-環己基-4-羥基-2-甲基苯基)-2-羥基苯基甲烷或雙(5-環己基-4-羥基-2-甲基苯基)-3,4-二羥基苯基甲烷等；(2)雙苯酚型化合物(bisphenol type compound)：如雙(2,3,4-三羥基苯基)甲烷、雙(2,4-二羥基苯基)甲烷、2,3,4-三羥基苯基-4'-羥基苯基甲烷、2-(2,3,4-三羥基苯基)-2-(2',3',4'-三羥基苯基)丙烷、2-(2,4-二羥基苯基)-2-(2',4'-二羥基苯基)丙烷、2-(4-羥基苯基)-2-(4'-羥基苯基)丙烷、2-(3-氟基-4-羥基苯基)-2-(3'-氟基-4'-羥基苯基)丙烷、2-(2,4-二羥基苯基)-2-(4'-羥基苯基)丙烷、2-(2,3,4-三羥基苯基)-2-(4'-羥基苯基)丙烷或2-(2,3,4-三羥基苯基)-2-(4'-羥基-3',5'-二甲基苯基)丙烷等； (3)多核分枝型化合物(polynuclear branched compound)：如1-[1-(4-羥基苯基)異丙基]-4-[1,1-雙(4-羥基苯基)乙基]苯或1-[1-(3-甲基-4-羥基苯基)異丙基]-4-[1,1-雙(3-甲基-4-羥基苯基)乙基]苯等；(4)縮合型苯酚化合物(condensation type phenol compound)：如1,1-雙(4-羥基苯基)環己烷等；(5)多羥基二苯甲酮類(polyhydroxy benzophenone)：如2,3,4-三羥基二苯甲酮、2,4,4'-三羥基二苯甲酮、2,4,6-三羥基二苯甲酮、2,3,4-三羥基-2'-甲基二苯甲酮、2,3,4,4'-四羥基二苯甲酮、2,4,2',4'-四羥基二苯甲酮、2,4,6,3',4'-五羥基二苯甲酮、2,3,4,2',4'-五羥基二苯甲酮、2,3,4,2',5'-五羥基二苯甲酮、2,4,6,3',4',5'-六羥基二苯甲酮或2,3,4,3',4',5'-六羥基二苯甲酮等；或(6)上述各種類含有酚式羥基的化合物的組合。 The type of sensitizer is not particularly limited. The sensitizer is preferably a compound containing a phenolic hydroxyl group. Specific examples are: (1) trisphenol type compound: Such as tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl) -2-Hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3 -Hydroxyphenylmethane, bis(4-hydroxy-3,5-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxybenzene methylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane , bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-di Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxy Phenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3 -Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, etc.; (2) bisphenol type compound: such as bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl) methyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'- Trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4 '-Hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxy Phenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane or 2-(2,3, 4-Trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane, etc.; (3) Polynuclear branched compound: such as 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl] Benzene or 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, etc.; (4) Condensation type phenol compound: such as 1,1-bis(4-hydroxyphenyl)cyclohexane, etc.; (5) Polyhydroxy benzophenone: such as 2, 3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'- Methyl benzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,4,2',4'-tetrahydroxybenzophenone, 2,4,6,3',4 '-Pentahydroxybenzophenone, 2,3,4,2',4'-Pentahydroxybenzophenone, 2,3,4,2',5'-Pentahydroxybenzophenone, 2,4 ,6,3',4',5'-hexahydroxybenzophenone or 2,3,4,3',4',5'-hexahydroxybenzophenone, etc.; or (6) the above types contain A combination of compounds with phenolic hydroxyl groups.

基於樹脂(A)之使用量為100重量份，增感劑之使用量為5重量份至50重量份；較佳為8重量份至40重量份；且更佳為10重量份至35重量份。 Based on the usage amount of resin (A) being 100 parts by weight, the usage amount of sensitizer is 5 to 50 parts by weight; preferably, it is 8 to 40 parts by weight; and more preferably, it is 10 to 35 parts by weight. .

密著助劑之具體例為三聚氰胺(melamine)化合物及矽烷系化合物等。密著助劑的作用在於增加由光硬化性聚矽氧烷組成物所形成的薄膜與元件或基板之間的密著性。 Specific examples of adhesion aids include melamine compounds, silane compounds, and the like. The function of the adhesion additive is to increase the adhesion between the film formed of the photocurable polysiloxane composition and the component or substrate.

三聚氰胺的市售品之具體例為由三井化學製造的商品名為Cymel-300或Cymel-303等；或者由三和化學製造的商品名為MW-30MH、MW-30、MS-11、MS-001、 MX-750或MX-706等。 Specific examples of commercially available melamine products are Cymel-300, Cymel-303, etc. manufactured by Mitsui Chemicals; or MW-30MH, MW-30, MS-11, MS-, manufactured by Sanwa Chemicals. 001. MX-750 or MX-706 etc.

當使用三聚氰胺化合物做為密著助劑時，基於樹脂(A)之使用量為100重量份，三聚氰胺化合物之使用量為0重量份至20重量份；較佳為0.5重量份至18重量份；且更佳為1.0重量份至15重量份。 When using a melamine compound as an adhesion aid, the usage amount of the melamine compound is 0 to 20 parts by weight based on 100 parts by weight of resin (A); preferably, it is 0.5 to 18 parts by weight; And more preferably, it is 1.0 parts by weight to 15 parts by weight.

矽烷系化合物之具體例為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、氮-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、氮-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基二甲基甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰丙基三甲氧基矽烷或由信越化學公司製造的市售品(商品名如KBM403)等。 Specific examples of the silane-based compound are vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, Nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-amine Propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl )Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane or commercially available products manufactured by Shin-Etsu Chemical Co., Ltd. (trade name such as KBM403), etc.

當使用矽烷系化合物作為密著助劑時，基於樹脂(A)之使用量為100重量份，矽烷系化合物之使用量為0重量份至2重量份；較佳為0.05重量份至1重量份；且更佳為0.1重量份至0.8重量份。 When a silane compound is used as an adhesion aid, the usage amount of the silane compound is 0 to 2 parts by weight based on 100 parts by weight of the resin (A); preferably, it is 0.05 to 1 part by weight. ; And more preferably, it is 0.1 to 0.8 parts by weight.

界面活性劑之具體例為陰離子系界面活性劑、陽離子系界面活性劑、非離子系界面活性劑、兩性界面活性劑、聚矽氧烷系界面活性劑、氟系界面活性劑或其組合。 Specific examples of surfactants are anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants, or combinations thereof.

界面活性劑的實例包括(1)聚乙二醇烷基醚類(polyoxyethylene alkyl ethers)：聚乙二醇十二烷基醚等；(2)聚乙二醇烷基苯基醚類(polyoxyethylene alkyl phenyl ethers)：聚乙二醇辛基苯基醚、聚乙二醇壬基苯基醚等；(3)聚乙二醇二酯類(polyethylene glycol diesters)：聚乙二醇二月桂酸酯、聚乙二醇二硬酸酯等；(4)山梨糖醇酐脂肪酸酯類(sorbitan fatty acid esters)；以及(5)經脂肪酸改質的聚酯類(fatty acid modified poly esters)；及(6)經三級胺改質的聚胺基甲酸酯類(tertiary amine modified polyurethanes)等。界面活性劑的市售商品之具體例為KP(由信越化學工業製造)、SF-8427(由道康寧東麗聚矽氧股份有限公司(Dow Corning Toray Silicone Co.,Ltd.)製造)、Polyflow(由共榮社油脂化學工業製造)、F-Top(由得克姆股份有限公司製造(Tochem Products Co.,Ltd.)製造)、Megaface(由大日本印墨化學工業(DIC)製造)、Fluorade(由住友3M股份有限公司(Sumitomo 3M Ltd.)製造)、Surflon(由旭硝子製造)、SINOPOL E8008(由中日合成化學製造)、F-475(由大日本印墨化學工業製造)或其組合。 Examples of surfactants include (1) polyoxyethylene alkyl ethers: polyethylene glycol lauryl ether etc.; (2) Polyoxyethylene alkyl phenyl ethers: polyethylene glycol octyl phenyl ether, polyethylene glycol nonyl phenyl ether, etc.; (3) Polyethylene glycol Diesters (polyethylene glycol diesters): polyethylene glycol dilaurate, polyethylene glycol distearate, etc.; (4) sorbitan fatty acid esters (sorbitan fatty acid esters); and (5) via Fatty acid modified polyesters; and (6) tertiary amine modified polyurethanes, etc. Specific examples of commercially available surfactants are KP (manufactured by Shin-Etsu Chemical Industry), SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), Polyflow ( Manufactured by Kyeisha Oleochemical Industry), F-Top (manufactured by Tochem Products Co., Ltd.), Megaface (manufactured by Dainippon Ink Chemical Industry (DIC)), Fluorade (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Asahi Glass), SINOPOL E8008 (manufactured by Chunippon Chemical Industry), F-475 (manufactured by Dainippon Ink Chemical Industries), or combinations thereof .

基於樹脂(A)之使用量為100重量份，界面活性劑之使用量為0.5重量份至50重量份；較佳為1重量份至40重量份；且更佳為3至30重量份。 Based on 100 parts by weight of the resin (A), the surfactant is used in an amount of 0.5 to 50 parts by weight; preferably 1 to 40 parts by weight; and more preferably 3 to 30 parts by weight.

消泡劑的實例包括Surfynol MD-20、Surfynol MD-30、EnviroGem AD01、EnviroGem AE01、EnviroGem AE02、Surfynol DF110D、Surfynol 104E、Surfynol 420、Surfynol DF37、Surfynol DF58、 Surfynol DF66、Surfynol DF70以及Surfynol DF210(由氣體產品(Air products)製造)等。 Examples of defoaming agents include Surfynol MD-20, Surfynol MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58, Surfynol DF66, Surfynol DF70 and Surfynol DF210 (manufactured by Air products), etc.

基於樹脂(A)之使用量為100重量份，消泡劑之使用量為1重量份至10重量份；較佳為2重量份至9重量份；且更佳為3重量份至8重量份。 Based on the usage amount of resin (A) being 100 parts by weight, the usage amount of defoaming agent is 1 to 10 parts by weight; preferably, it is 2 to 9 parts by weight; and more preferably, it is 3 to 8 parts by weight. .

溶解促進劑的實例包括氮-羥基二羧基醯亞胺化合物(N-hydroxydicarboxylic imide)以及含酚式羥基的化合物。溶解促進劑之具體例為鄰萘醌二疊氮磺酸酯(B)中所使用的含酚式羥基的化合物。 Examples of dissolution promoters include N-hydroxydicarboxylic imide compounds and phenolic hydroxyl-containing compounds. A specific example of the dissolution accelerator is a phenolic hydroxyl group-containing compound used for o-naphthoquinonediazide sulfonate (B).

基於樹脂(A)之使用量為100重量份，溶解促進劑之使用量為1重量份至20重量份；較佳為2重量份至15重量份；且更佳為3重量份至10重量份。 Based on the usage amount of resin (A) being 100 parts by weight, the usage amount of the dissolution accelerator is 1 to 20 parts by weight; preferably, it is 2 to 15 parts by weight; and more preferably, it is 3 to 10 parts by weight. .

化學增幅型正型感光性樹脂組成物之具體例為以下列方式來製備：將樹脂(A)、光酸產生劑(B)、溶劑(C)以及環氧化合物(D)放置於攪拌器中攪拌，使其均勻混合成溶液狀態，必要時，可添加其他添加劑(E)。 A specific example of the chemically amplified positive photosensitive resin composition is prepared in the following manner: resin (A), photoacid generator (B), solvent (C) and epoxy compound (D) are placed in a stirrer Stir until it is evenly mixed into a solution. If necessary, add other additives (E).

本發明亦提供一種保護膜，其包含將上述化學增幅型正型感光性樹脂組成物塗佈於基材上，再經預烤、曝光、顯影及後烤處理後所形成。 The present invention also provides a protective film, which is formed by coating the above-mentioned chemically amplified positive photosensitive resin composition on a substrate, and then undergoing pre-baking, exposure, development and post-baking.

本發明更提供一種具有保護膜的元件，其包含基材以及所述保護膜。 The present invention further provides an element with a protective film, which includes a base material and the protective film.

保護膜的形成方法How to form protective film

在一些實施例中，本發明的化學增幅型正型感光性樹脂組成物可用於顯示元件的保護膜之形成材料。另外，本發明也包含適用於由化學增幅型正型感光性樹脂組成物形成的顯示元件用保護膜。 In some embodiments, the chemically amplified positive photosensitive resin composition of the present invention can be used as a material for forming a protective film of a display element. Other In addition, the present invention also includes application to a protective film for a display element formed of a chemically amplified positive photosensitive resin composition.

所述保護膜的形成方法包括下述步驟：(1)使用化學增幅型正型感光性樹脂組成物，在基板上形成塗膜的步驟(以下也稱為“步驟(1)”)；(2)對上述塗膜的至少一部分照射放射線的步驟(以下也稱為“步驟(2)”)；(3)對照射放射線後的上述塗膜進行顯影的步驟(以下也稱為“步驟(3)”)；以及(4)對顯影後的上述塗膜進行加熱的步驟(以下也稱為“步驟(4)”)。 The method for forming a protective film includes the following steps: (1) using a chemically amplified positive photosensitive resin composition to form a coating film on a substrate (hereinafter also referred to as "step (1)"); (2) ) a step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as "step (2)"); (3) a step of developing the above-mentioned coating film after irradiation with radiation (hereinafter also referred to as "step (3)" "); and (4) a step of heating the developed coating film (hereinafter also referred to as "step (4)").

依據此形成方法，能夠形成表面硬度、耐溶劑性、耐熱性以及電壓保持率優異的顯示元件用保護膜。另外，藉由使用具有良好感度的化學增幅型正型感光性樹脂組成物，能夠容易地形成具有微細且精巧的圖案的顯示元件用保護膜。因此，所形成的顯示元件用保護膜適用於液晶顯示元件、有機EL顯示元件等顯示元件。 According to this formation method, a protective film for display elements that is excellent in surface hardness, solvent resistance, heat resistance, and voltage retention can be formed. In addition, by using a chemically amplified positive photosensitive resin composition having good sensitivity, a protective film for a display element having a fine and delicate pattern can be easily formed. Therefore, the formed protective film for display elements is suitable for display elements such as liquid crystal display elements and organic EL display elements.

[步驟(1)] [Step (1)]

本步驟中，將化學增幅型正型感光性樹脂組成物塗布於基板上而形成塗膜。較佳地，藉由預烘烤塗布去除溶劑。 In this step, the chemically amplified positive photosensitive resin composition is coated on the substrate to form a coating film. Preferably, the solvent is removed by pre-bake coating.

基板例如可列舉：玻璃、石英、矽基材、樹脂等。樹脂例如可列舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚酮碸、聚碳酸酯、聚醯亞胺、環狀烯烴的開環聚合物以及其氫化物等。預烘烤的條件也根據各成分的種類、調配比例等而有所不同，可設為70℃至120℃、1分鐘至10分鐘左右。 Examples of the substrate include glass, quartz, silicon substrate, resin, and the like. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyketone, polycarbonate, polyimide, ring-opened polymers of cyclic olefins, and hydrogenated products thereof. Pre-baking conditions also depend on the types of ingredients, It varies depending on the mixing ratio, etc., but can be set to about 70°C to 120°C, 1 minute to 10 minutes.

[步驟(2)] [Step (2)]

本步驟中，對所形成的上述塗膜的至少一部分照射放射線來進行曝光。曝光時，通常隔著具有預定圖案的光罩進行曝光。用於曝光的放射線較佳為波長於190nm至450nm的範圍內的放射線，更佳為包含365nm的紫外線的放射線。曝光量是利用照度計(OAI model 356，OAI光學協會(OAI Optical Associates)製造)來測定放射線的波長365nm下的強度而得的值，較佳為500J/m²至6,000J/m²，更佳為1,500J/m²至1,800J/m²。 In this step, at least a part of the formed coating film is irradiated with radiation and exposed. During exposure, exposure is usually performed through a photomask having a predetermined pattern. The radiation used for exposure is preferably radiation with a wavelength in the range of 190 nm to 450 nm, and more preferably radiation including ultraviolet rays of 365 nm. The exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm using an illuminance meter (OAI model 356, manufactured by OAI Optical Associates), and is preferably 500 J/m ² to 6,000 J/m ² , more preferably The optimal range is 1,500J/m ² to 1,800J/m ² .

[步驟(3)] [Step (3)]

本步驟中，對照射放射線後的上述塗膜進行顯影。藉由將曝光後的塗膜進行顯影，去除不需要的部分(放射線的照射部分)，以形成預定的圖案。顯影步驟中使用的顯影液較佳為鹼性的水溶液。鹼例如可列舉：氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、胺等無機鹼；四甲基氫氧化銨、四乙基氫氧化銨等四級銨鹽等。 In this step, the coating film irradiated with radiation is developed. By developing the exposed coating film, unnecessary parts (radiation-irradiated parts) are removed to form a predetermined pattern. The developer used in the development step is preferably an alkaline aqueous solution. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and amines; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

鹼水溶液中，也可以適量添加甲醇、乙醇等水溶性有機溶劑或界面活性劑來使用。就獲得適當顯影性的觀點而言，鹼水溶液中的鹼的濃度較佳為0.1質量%以上、5質量%以下。顯影方法例如可列舉：覆液法(puddle method)、浸漬法、搖動浸漬法、噴淋法等。顯影時間根據化學增幅型正型感光性樹脂組成物的組成而有所不同，為 10秒至180秒左右。在顯影處理之後，藉由進行例如流水清洗30秒至90秒，然後利用例如壓縮空氣或壓縮氮，風乾塗膜，以形成所需圖案。 The alkali aqueous solution may also be used by adding an appropriate amount of water-soluble organic solvents such as methanol and ethanol or a surfactant. From the viewpoint of obtaining appropriate developability, the concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less. Examples of the development method include puddle method, dipping method, shaking dipping method, and spray method. The development time varies depending on the composition of the chemically amplified positive photosensitive resin composition, and is About 10 seconds to 180 seconds. After the development process, for example, running water cleaning is performed for 30 seconds to 90 seconds, and then the coating film is air-dried using, for example, compressed air or compressed nitrogen to form the desired pattern.

[步驟(4)] [Step (4)]

本步驟中，將上述經顯影的塗膜進行加熱。加熱時，藉由使用加熱板、烘箱等加熱裝置，加熱圖案化的薄膜，以促進樹脂(A)的硬化反應，並獲得硬化物。加熱溫度例如為120℃至250℃左右。加熱時間根據加熱機器的種類而有所不同，例如在加熱板上為5分鐘至30分鐘左右，在烘箱中為30分鐘至90分鐘左右。另外，也可以使用進行2次以上加熱步驟的階段式烘烤法等。如此一來，可將與做為目標的顯示元件用保護膜對應的圖案狀薄膜形成於基板的表面上。此外，上述硬化膜的用途並不限定於顯示元件用保護膜，也可以作為間隔件或層間絕緣膜來利用。 In this step, the developed coating film is heated. During heating, the patterned film is heated by using heating devices such as a hot plate and an oven to promote the curing reaction of the resin (A) and obtain a cured product. The heating temperature is, for example, about 120°C to 250°C. The heating time varies depending on the type of heating machine, for example, it is about 5 minutes to 30 minutes on a hot plate, and about 30 minutes to 90 minutes in an oven. In addition, a staged baking method in which heating steps are performed two or more times may also be used. In this way, a patterned thin film corresponding to the target protective film for display elements can be formed on the surface of the substrate. In addition, the use of the said cured film is not limited to the protective film for a display element, It can also be utilized as a spacer or an interlayer insulating film.

所形成的顯示元件用保護膜的膜厚較佳為0.1μm至8μm，更佳為0.1μm至6μm，又更佳為0.1μm至4μm。 The film thickness of the formed protective film for display elements is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and still more preferably 0.1 μm to 4 μm.

以下藉由數個製備例、實施例和比較例說明本發明的化學增幅型正型感光性樹脂組成物的製造方法及其應用。 The manufacturing method and application of the chemically amplified positive photosensitive resin composition of the present invention will be described below through several preparation examples, examples and comparative examples.

製備樹脂(A)Preparation of resin (A)

製備例A-1Preparation Example A-1

在一容積1000毫升之四頸錐瓶上設置氮氣入口、攪拌器、加熱器、冷凝管及溫度計，導入氮氣後，添加3重量份之甲基丙烯酸(以下簡稱MAA)、97重量份的甲基丙烯酸1-乙氧基乙酯(a-2-1)、10重量份的2,2’-偶氮雙(2,4-二甲基戊腈)(以下簡稱ADVN)以及240重量份的二乙二醇二甲酮(以下簡稱Diglyme)溶劑。接著，緩慢攪拌上述成份使溶液昇溫至70℃，並於此溫度下聚縮合6小時。然後，將溶劑脫揮後，可得樹脂(A-1)。 Set up a nitrogen inlet, stirrer, heater, condenser tube and thermometer on a four-necked conical flask with a volume of 1000 ml. After introducing nitrogen, add 3 parts by weight of methacrylic acid (hereinafter referred to as MAA) and 97 parts by weight of methyl. 1-ethoxyethyl acrylate (a-2-1), 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as ADVN) and 240 parts by weight of dimethyl Ethylene glycol dimethyl ketone (hereinafter referred to as Diglyme) solvent. Then, the above ingredients were slowly stirred to raise the temperature of the solution to 70°C, and polycondensation was carried out at this temperature for 6 hours. Then, the solvent is devolatilized to obtain resin (A-1).

製備例A-2至A-12以及製備比較例A’-1至A’-2Preparation Examples A-2 to A-12 and Preparation Comparative Examples A’-1 to A’-2

樹脂(A-2)至(A-12)以及製備比較例A’-1至A’-2之製備與前述樹脂(A-1)之製備例類似，其中，單體之種類及使用量如表1所示。惟其中溶劑、觸媒、分子量調整劑之使用量、反應溫度及聚縮合之反應時間與前述樹脂(A-1)不同，亦示於表1。 The preparation of resins (A-2) to (A-12) and the preparation comparative examples A'-1 to A'-2 is similar to the preparation example of the aforementioned resin (A-1), in which the types and amounts of monomers are as follows As shown in Table 1. However, the usage amounts of solvents, catalysts, and molecular weight regulators, reaction temperatures, and reaction times of polycondensation are different from those of the aforementioned resin (A-1), which are also shown in Table 1.

實施例1Example 1

製備化學增幅型正型感光性樹脂組成物Preparation of chemically amplified positive photosensitive resin composition

將100重量份的樹脂(A-1)、0.1重量份的(5-對甲苯磺醯氧基亞胺基-5H-噻吩-2-亞基)-(2-甲基苯基)乙腈(B-3)和1重量份的由式(2-2-2)所示之環氧化合物(D-1)，加入200重量份的丙二醇甲醚醋酸酯(C-1)中，並以搖動式攪拌器(shaking type stirrer)攪拌均勻後，即可製得實施例1的化學增幅型正型感光性樹脂組成物。 100 parts by weight of resin (A-1), 0.1 part by weight of (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile (B -3) and 1 part by weight of the epoxy compound (D-1) represented by formula (2-2-2), are added to 200 parts by weight of propylene glycol methyl ether acetate (C-1), and shaken After stirring evenly with a shaking type stirrer, the chemically amplified positive photosensitive resin composition of Example 1 can be prepared.

形成保護膜form protective film

於素玻璃基板(100×100×0.7mm)上，以旋轉塗佈方式得到約3μm之塗膜，接續以110℃預烤2分鐘後，在曝光機與塗膜間置入正光阻用光罩，並以曝光機之紫外光照射塗膜，其能量為800J/m²。將曝光後的塗膜浸漬於23℃之2.38%之TMAH水溶液70秒，除去曝光之部分後，以清水清洗。最後以220℃後烤45分鐘，可獲得實施例1的素玻璃基板上之保護膜。關於實施例1的具體條件以及評價結果，悉如表2所示。 On the plain glass substrate (100×100×0.7mm), obtain a coating film of about 3 μm by spin coating, then pre-bake at 110°C for 2 minutes, and place a positive photoresist mask between the exposure machine and the coating film. , and irradiate the coating film with ultraviolet light from the exposure machine, whose energy is 800J/m ² . Immerse the exposed coating film in 2.38% TMAH aqueous solution at 23°C for 70 seconds, remove the exposed part, and then rinse with clean water. Finally, post-bake at 220°C for 45 minutes to obtain the protective film on the plain glass substrate of Example 1. The specific conditions and evaluation results of Example 1 are shown in Table 2.

實施例2至16及比較例1至7Examples 2 to 16 and Comparative Examples 1 to 7

實施例2至16及比較例1至7的化學增幅型正型感光性樹脂組成物及保護膜是使用與實施例1相同的方式進行而得。不同的是，實施例2至16及比較例1至7改變組成或使用量等條件。關於實施例2至16及比較例1至7的具體條件及評價結果如表2和表3所示。 The chemically amplified positive photosensitive resin compositions and protective films of Examples 2 to 16 and Comparative Examples 1 to 7 were obtained in the same manner as Example 1. The difference is that conditions such as composition or usage amount were changed in Examples 2 to 16 and Comparative Examples 1 to 7. Specific conditions and evaluation results of Examples 2 to 16 and Comparative Examples 1 to 7 are shown in Tables 2 and 3.

評價方式Evaluation method

(1)顯影密著性：以上述保護膜的形成方法，形成化學增幅型正型感光性樹脂組成物的塗膜後，隔著具有寬1μm至10μm的線與空間圖案的圖案光阻，利用水銀燈對所述塗膜照射80mJ/cm²的紫外線。接著，使用四甲基氫氧化銨2.38質量%水溶液，在25℃下進行70秒顯影處理後，以超純水進行1分鐘流水清洗。利用顯微鏡來觀察清洗後的寬1μm至10μm的線與空間圖案的剝離情況，作為顯影密著性的評價。 (1) Development adhesion: After forming a coating film of a chemically amplified positive photosensitive resin composition using the above protective film formation method, use The mercury lamp irradiates the coating film with ultraviolet light of 80mJ/ ^cm2 . Next, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used to perform development processing at 25° C. for 70 seconds, and then washed with running water for 1 minute with ultrapure water. The peeling of the line and space pattern with a width of 1 μm to 10 μm after cleaning was observed using a microscope as an evaluation of the development adhesion.

◎：無圖案剝離。 ◎: No pattern peeling off.

○：圖案少量剝離。 ○: The pattern is peeled off slightly.

△：圖案的一部分剝離。 △: Part of the pattern is peeled off.

×：圖案的整個面剝離。 ×: The entire surface of the pattern is peeled off.

(2)耐化性：以上述保護膜的形成方法，形成化學增幅型正型感光性樹脂組成物的塗膜後，使用加溫至230℃的烘箱，煅燒所述塗膜30分鐘，形成硬化膜。使所述硬化膜在加溫至40℃的N-甲基吡咯烷酮溶劑中浸漬6分鐘，求出浸漬前後的膜厚變化率(%)，作為耐化學品性的指標。 (2) Chemical resistance: After forming a coating film of a chemically amplified positive photosensitive resin composition using the above protective film formation method, use an oven heated to 230°C to calcine the coating film for 30 minutes to form a hardened film. membrane. The cured film was immersed in an N-methylpyrrolidone solvent heated to 40° C. for 6 minutes, and the film thickness change rate (%) before and after immersion was determined as an index of chemical resistance.

◎：膜厚變化率<5%。 ◎: Film thickness change rate <5%.

○：5%≦膜厚變化率<10%。 ○: 5%≦Film thickness change rate<10%.

△：10%≦膜厚變化率<15%。 △: 10%≦ film thickness change rate <15%.

△：15%≦膜厚變化率。 △: 15%≦Film thickness change rate.

如表2的結果所示，當化學增幅型正型感光性樹脂組成物中包含環氧化合物(D)，以及形成樹脂(A)的單體混合物使用含酸解離性基之單體(a-2)時，由此樹脂組成物所形成的保護膜可具有良好的顯影密著性以及耐化性。在一些實施例中，當形成樹脂組成物的樹脂(A)之單體混合物包括含內酯結構之不飽和單體(a-3)時，可進一步改善保護膜的顯影密著性。在另一些實施例中，當形成樹脂組成物的樹脂(A)之單體混合物包括特定結構之含環氧基之不飽和單體(a-4)，或樹脂組成物使用特定的光酸產生劑(B)時，可進一步改善保護膜的耐化性。另一方面，如表3所示，倘若化學增幅型正型感光性樹脂組成物中未使用環氧化合物(D)時，由此樹脂組成物所形成的保護膜的顯影密著性以及耐化性不佳。 As shown in the results in Table 2, when the chemically amplified positive photosensitive resin composition contains the epoxy compound (D), and the monomer mixture forming the resin (A) uses the acid-dissociable group-containing monomer (a- 2), the protective film formed from the resin composition can have good development adhesion and chemical resistance. In some embodiments, when the monomer mixture of the resin (A) forming the resin composition includes the unsaturated monomer (a-3) containing a lactone structure, the development adhesion of the protective film can be further improved. In other embodiments, when the monomer mixture of the resin (A) forming the resin composition includes an epoxy group-containing unsaturated monomer (a-4) of a specific structure, or the resin composition uses a specific photoacid to generate When using agent (B), the chemical resistance of the protective film can be further improved. On the other hand, as shown in Table 3, if When the epoxy compound (D) is not used in the chemically amplified positive photosensitive resin composition, the development adhesion and chemical resistance of the protective film formed from the resin composition are poor.

雖然本發明已以數個實施例揭露如上，然其並非用以限定本發明，在本發明所屬技術領域中任何具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in several embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention belongs can make various modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended patent application scope.

Claims

一種化學增幅型正型感光性樹脂組成物，包括：樹脂(A)，由單體混合物共聚合而得，該單體混合物包括不飽和羧酸單體(a-1)以及含式(1)所示之含酸解離性基之單體(a-2)；

於該式(1)中，該R¹和該R²各自獨立為氫原子、烷基、脂環式烴基或芳基，其中該烷基、該脂環式烴基或該芳基所具有的氫原子的一部分或全部可被取代；而且，該R¹及該R²不同時為氫原子；該R³為烷基、脂環式烴基、芳烷基或者芳基；其中該R³的該烷基、該脂環式烴基、該芳烷基及該芳基所具有的氫原子的一部分或全部可被取代；該R¹與該R³可相互鍵結而與該R¹所鍵結的碳原子以及該R³所鍵結的氧原子一起形成環狀醚結構；以及，該*¹代表鍵結處；一光酸產生劑(B)；一溶劑(C)；以及一環氧化合物(D)，具有如式(2)所示的結構：A-(B)_n1 (2)於該式(2)中，該A代表(n1)價的含氮環基，該B代表式(2-1)所示的結構，以及該n1表示2至8之整數；

於該式(2-1)中，該R⁴及該R⁵分別獨立表示氫原子或碳數為1至10之烷基；該R⁶表示(n4+1)價之烴基；該n2表示1之整數；該n3表示2之整數；該n4表示2至5之整數；該n5表示0或1之整數；該n6表示0或1之整數；以及，該*²為該B與該A的鍵結處；其中基於該樹脂(A)的使用量為100重量份，該光酸產生劑(B)的使用量為0.1重量份至10重量份，該溶劑(C)的使用量為200重量份至2000重量份，以及該環氧化合物(D)的使用量為1重量份至20重量份。 A chemically amplified positive photosensitive resin composition, including: resin (A), obtained by copolymerization of a monomer mixture, the monomer mixture including unsaturated carboxylic acid monomer (a-1) and formula (1) The monomer (a-2) containing an acid-dissociable group is shown;

In the formula (1), the R ¹ and the R ² are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, wherein the hydrogen possessed by the alkyl group, the alicyclic hydrocarbon group or the aryl group is Part or all of the atoms may be substituted; moreover, the R ¹ and the R ² are not hydrogen atoms at the same time; the R ³ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group or an aryl group; wherein the alkyl group of the R ³ A part or all of the hydrogen atoms of the alicyclic hydrocarbon group, the aralkyl group and the aryl group may be substituted; the R ¹ and the R ³ may be bonded to each other and to the carbon to which the R ¹ is bonded The atoms and the oxygen atom to which R ³ is bonded together form a cyclic ether structure; and, the * ¹ represents the bonding point; a photoacid generator (B); a solvent (C); and an epoxy compound (D ), has a structure as shown in formula (2): A-(B) _n1 (2) In the formula (2), the A represents a nitrogen-containing cyclic group with a valence of (n1), and the B represents the formula (2- 1) The structure shown, and n1 represents an integer from 2 to 8;

In the formula (2-1), the R ⁴ and the R ⁵ each independently represent a hydrogen atom or an alkyl group with a carbon number of 1 to 10; the R ⁶ represents a hydrocarbon group with a (n4+1) valence; the n2 represents 1 n3 represents an integer of 2; n4 represents an integer of 2 to 5; n5 represents an integer of 0 or 1; n6 represents an integer of 0 or 1; and, * ² is the key of B and A. The junction; wherein the usage amount of the resin (A) is 100 parts by weight, the usage amount of the photoacid generator (B) is 0.1 to 10 parts by weight, and the usage amount of the solvent (C) is 200 parts by weight to 2000 parts by weight, and the usage amount of the epoxy compound (D) is 1 to 20 parts by weight.

如申請專利範圍第1項所述之化學增幅型正型感光性樹脂組成物，其中該式(2)所示的結構包含式(2-2)、式(2-3)或式(2-4)所示的結構：

於該式(2-2)、該式(2-3)和該式(2-4)中，該A代表(n1)價的含氮環基；該R⁴及該R⁵分別獨立表示氫原子或碳數為1至10之烷基，該R⁶表示(n4+1)價之烴基，該n1表示2至8之整數；該n2表示1之整數，該n3表示2之整數；以及，該n4表示2至5之整數。 The chemically amplified positive photosensitive resin composition described in item 1 of the patent application, wherein the structure represented by formula (2) includes formula (2-2), formula (2-3) or formula (2- 4) Structure shown:

In the formula (2-2), the formula (2-3) and the formula (2-4), the A represents a nitrogen-containing cyclic group with a valence of (n1); the R ⁴ and the R ⁵ each independently represent hydrogen An atom or an alkyl group with a carbon number of 1 to 10, the R ⁶ represents a hydrocarbon group with a (n4+1) valence, the n1 represents an integer from 2 to 8; the n2 represents an integer of 1, and the n3 represents an integer of 2; and, This n4 represents an integer from 2 to 5.

如申請專利範圍第1項所述之化學增幅型正型感光性樹脂組成物，其中該式(2)包含如式(2-5)至式(2-7)的結構：

於該式(2-5)中，該R⁷表示氫原子或碳數為1至10 的烷基，B代表上述式(2-1)所示的結構。 The chemically amplified positive photosensitive resin composition described in item 1 of the patent application, wherein the formula (2) includes structures such as formula (2-5) to formula (2-7):

In the formula (2-5), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and B represents the structure represented by the above formula (2-1).

如申請專利範圍第1項所述之化學增幅型正型感光性樹脂組成物，其中該單體混合物包括含內酯結構之不飽和單體(a-3)。 The chemically amplified positive photosensitive resin composition described in item 1 of the patent application, wherein the monomer mixture includes an unsaturated monomer (a-3) containing a lactone structure.

如申請專利範圍第4項所述之化學增幅型正型感光性樹脂組成物，其中該含內酯結構之不飽和單體(a-3)包含如式(3)所示的部分結構：

於該式(3)中，該R⁸表示取代基，n7個的該R⁸分別獨立，且為相同或不同；該Z¹表示含有-O-C(=O)-的單環或多環結構；該n7表示0以上的整數；以及，該*³為鍵結處。 The chemically amplified positive photosensitive resin composition described in item 4 of the patent application, wherein the unsaturated monomer (a-3) containing a lactone structure includes a partial structure shown in formula (3):

In the formula (3), the R ⁸ represents a substituent, and the n7 R ⁸ are independently independent and the same or different; the Z ¹ represents a monocyclic or polycyclic structure containing -OC(=O)-; The n7 represents an integer above 0; and the * ³ is the bonding point.

如申請專利範圍第1項所述之化學增幅型正型感光性樹脂組成物，其中該單體混合物包括一含環氧基之不飽和單體(a-4)。 The chemically amplified positive-type photosensitive resin composition described in item 1 of the patent application, wherein the monomer mixture includes an epoxy group-containing unsaturated monomer (a-4).

如申請專利範圍第6項所述之化學增幅型正型感光性樹脂組成物，其中該含環氧基之不飽和單體(a-4)具有如下式(4)所示之結構的不飽和單體：

於該式(4)中，該R⁹代表氫原子或碳數為1至4之烷基；該R¹⁰代表氫原子或碳數為1至4之烷基；該R¹¹、該R¹²、該R¹³及該R¹⁴分別獨立地代表氫原子、氟原子、苯基、碳數為1至4之烷基或碳數為1至4之全氟烷基；且該a代表1至6之整數。 The chemically amplified positive photosensitive resin composition described in item 6 of the patent application, wherein the epoxy group-containing unsaturated monomer (a-4) has an unsaturated structure represented by the following formula (4) Single unit:

In the formula (4), the R ⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the R ¹⁰ represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4; the R ¹¹ , the R ¹² , The R ¹³ and the R ¹⁴ each independently represent a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group having a carbon number of 1 to 4; and the a represents a group of 1 to 6 carbon atoms. integer.

如申請專利範圍第1項所述之化學增幅型正型感光性樹脂組成物，其中該光酸產生劑(B)為含下式(5)之肟磺酸酯基的化合物：

於該式(5)中，該R¹⁵為碳數為1至20的烷基、脂環式烴基、芳基，或是上述基團所具有的氫原子被部分或全部取代之基團；以及，該*⁴為鍵結處。 The chemically amplified positive photosensitive resin composition described in item 1 of the patent application, wherein the photoacid generator (B) is a compound containing an oxime sulfonate group of the following formula (5):

In the formula (5), the R ¹⁵ is an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a group in which the hydrogen atoms of the above groups are partially or fully substituted; and , the * ⁴ is the bonding point.

如申請專利範圍第1項所述之化學增幅型正型感光性樹脂組成物，其中基於該單體混合物的使用量為100重量份，該含酸解離性保護基之該單體(a-2)的使用量為10重量份至97重量份。 The chemically amplified positive photosensitive resin composition described in item 1 of the patent application, wherein based on the usage amount of the monomer mixture is 100 parts by weight, the monomer (a-2) containing an acid-dissociable protecting group ) is used in an amount of 10 parts by weight to 97 parts by weight.

如申請專利範圍第4項所述之化學增幅型正型感光性樹脂組成物，其中基於該單體混合物的使用量為100重量份，該含內酯結構之不飽和單體(a-3)的使用量為2重量份至20重量份。 The chemically amplified positive photosensitive resin composition described in item 4 of the patent application, wherein the unsaturated monomer (a-3) containing a lactone structure is used in an amount of 100 parts by weight based on the monomer mixture. The usage amount is 2 to 20 parts by weight.

如申請專利範圍第6項所述之化學增幅型正型感光性樹脂組成物，其中基於該單體混合物的使用量為100重量份，該含環氧基之不飽和單體(a-4)的使用量為10重量份至90重量份。 The chemically amplified positive photosensitive resin composition described in item 6 of the patent application, wherein the epoxy group-containing unsaturated monomer (a-4) is used in an amount of 100 parts by weight based on the monomer mixture. The usage amount is 10 parts by weight to 90 parts by weight.

一種保護膜，係將一如申請專利範圍第1至11項之任一項所述之化學增幅型正型感光性樹脂組成物塗佈於一基材上，再經預烤、曝光、顯影及後烤處理後所形成。 A protective film is made by coating a chemically amplified positive photosensitive resin composition as described in any one of items 1 to 11 of the patent application on a substrate, and then prebaking, exposing, developing and Formed after post-baking treatment.

一種具有保護膜的元件，包含一基材以及如申請專利範圍第12項所述之一保護膜。 An element with a protective film includes a base material and a protective film as described in Item 12 of the patent application.