TW201016799A

TW201016799A - Ink for inkjet and curing film formed form the ink

Info

Publication number: TW201016799A
Application number: TW98129444A
Authority: TW
Inventors: Shinta Morokoshi; Setsuo Itami; Katsuyuki Sugihara
Original assignee: Chisso Corp
Priority date: 2008-09-03
Filing date: 2009-09-01
Publication date: 2010-05-01
Also published as: JP2010059299A; KR20100027962A

Abstract

An ink for inkjet having resistance to a metallic etching liquid, peeling property in relation to a peeling liquid or resistance to a plating liquid is provided. The ink for inkjet includes a radical polymeric monomer (A) having a membered ring equal to or larger than 5 of cyclic ether, a radical polymeric monomer (B) having thermal reactivity functional group, a photopolymerization initiator (C) and a thermal reactive resin (D).

Description

201016799 六、發明說明：【發明所屬之技術領域】本發明是關於一種用於製造液晶顯示元件、el (Electro-Luminescence，電致發光）顯示元件、印刷配線基板（printed circuit board )等的噴墨（ink jet)用墨水。而且本發明是關於一種由該喷墨用墨水所得的硬化膜（包括經圖案化的硬化膜）、硬化膜形成方法、及形成有硬化膜的電子電路基板、電子零件、顯示元件。馨【先前技術】與光微影（photolithography)法相比，利用喷墨法的圖案形成不但步驟變得簡單，而且亦可期待減少材料的使用量，因此提出用於製造電子設備中所使用的印刷配線版等（例如參照日本專利特開2〇〇3_3〇2642號公報（專利文獻1 )、日本專利特開2005-68280號公報（專利文獻2))。近年來，往電子設備的小型化發展，使用輕量且可撓性（flexible)的印刷配線板的電子電路基板得到較多使 > 用。上述電子電路基板例如藉由抗_ (etching ， ❹ 形成具有特定電路圖案的金屬配線部，其後經過利用抗鍍敷劑的錄敷圖案製作、及對作為保護金屬層表面的保護膜的覆蓋層（c〇veriay)進行塗佈（c〇ating)的步驟而製作。 —藉由噴墨法實施這些步驟時，要求噴墨用墨水的保存穩定f·生’並要求穩定的墨水喷出性。而且，由喷墨用墨水所形成的硬化赚據各墨水㈣而要求各種性能。例如對於形成用於抗蝕用途的喷墨用墨水的硬化膜 4 201016799 •My43pll |要求對剝離液的剝離而吕’要求對金屬餘刻液的耐性，性。，對於形成用於抗鑛敷用途的嘴墨用墨水的硬化 = 鍍敷液的雜’且絲對_㈣剝離性。 =如對於形於覆蓋層用途㈣㈣墨水的硬化膜而5，要求雜敷㈣耐性，且要求焊錫耐轨性。201016799 6. Technical Field of the Invention The present invention relates to an inkjet for manufacturing a liquid crystal display element, an el (Electro-Luminescence) display element, a printed circuit board, or the like. (ink jet) with ink. Further, the present invention relates to a cured film (including a patterned cured film) obtained by the inkjet ink, a cured film forming method, and an electronic circuit board, an electronic component, and a display element on which a cured film is formed.馨 [Prior Art] Compared with the photolithography method, the pattern formation by the inkjet method is not only simple, but also expected to reduce the amount of material used, and thus it is proposed to be used for manufacturing electronic equipment. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2005-68280 (Patent Document 2). In recent years, the development of miniaturization of electronic devices has led to the use of electronic circuit boards using lightweight and flexible printed wiring boards. The electronic circuit board is formed by, for example, etching a metal wiring portion having a specific circuit pattern, and then forming a coating layer using a plating resist and a protective layer as a protective film on the surface of the protective metal layer. (c〇veriay) is produced by the step of coating. When these steps are carried out by the inkjet method, storage of the ink for inkjet is required to be stable and a stable ink discharge property is required. Further, the hardening by the inkjet ink yields various properties depending on the ink (4). For example, a cured film 4 for forming an inkjet ink for resist use 201016799 • My43pll | requires peeling of the peeling liquid 'Requires resistance to metal remnant, properties. For the formation of ink for nozzle ink for anti-mineral application, the hardness of the plating solution = the miscellaneous of the plating solution and the wire-to-four peelability. Use (4) (4) Hardened film of ink 5, requires hybrid (4) resistance, and requires solder resistance.

一上而接先=噴墨用墨水的硬化膜由於上述性能的任 :夕不充刀’因此僅為不適於實際應用的硬化膜。 [專利文獻1]日本專利特開2003_302642號公報 [專利文獻2]日本專利特開2〇〇5_6828〇號公報 [專利文獻3]曰本專利特開2〇〇8 5〇6〇1號公報 [專利文獻4]日本專利特開平9_183929號公【發明内容】 [發明所欲解決之問題] 於上述狀況下’例如要求墨水的保存穩定性優異的喷墨用墨水。而且，例如要求可實現穩定喷出的喷墨用墨水: 於是’於將噴墨用墨水製成硬化膜時，要求如下噴墨用墨水例如於抗蚀用途時，具有對金屬钱刻液的耐性及對剝離液的剝雜^且，例如於紐敷麟時，具有對鍍敷 ^的耐性及對___性；此外，例如於覆蓋層用途時’具有雜敷液的耐性及烊錫_性。另外，要求可靠性較高的可撓性配線板。 [解決問題之手段] 本發明者等人發現，若於喷墨用墨水中使用具有特定 5 201016799 ^Ι^Η^ριι 了構的自由基聚合性單體（A)，則可有效地處理上述問基於該見解而完成了本發明，即本發明是關於一種包二1由ΐ聚合性單體（A)、具有熱反應性官能基的自由基 =性單體（Β)、光聚合起始劑⑹、及熱反應性樹脂⑼ 墨用墨水。本發明提供如下的喷墨用墨水、由喷墨用墨水所得的硬化歧其形成方法等。環狀^噴㈣墨水，其包含：含有大於等於5員環的自由美平Ah ^聚合性單體（Α)、具有減應性官能基的樹脂3)°。·生單體（B)、光聚合起始劑（〇、及熱反應性 ]如上述[1]所述之喷墨用墨水苴員環的環狀_自由基聚合^3 於專於5 表示的化合物：叫體⑷是以通式⑷所 R1 H2C==C—C—〇__R2__r3The cured film of the inkjet ink is only a hardened film which is not suitable for practical use because of the above properties. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-302642 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] Under the above circumstances, for example, an inkjet ink excellent in storage stability of ink is required. Further, for example, an inkjet ink that can stably eject is required: Thus, when the inkjet ink is made into a cured film, the following inkjet ink is required to have resistance to metal money, for example, when used for resisting. And the stripping of the stripping liquid, and, for example, in the case of New Zealand Lin, has resistance to plating and ___ property; in addition, for example, in the case of a coating layer, 'having resistance to a mixed liquid and tin strontium _ Sex. In addition, a flexible wiring board with high reliability is required. [Means for Solving the Problem] The present inventors have found that the use of the radical polymerizable monomer (A) having a specific 5 201016799 ^Ι^Η^ριι structure in the ink for inkjet can effectively handle the above The present invention has been completed on the basis of this finding, that is, the present invention relates to a package of a polymerizable monomer (A), a radical having a thermally reactive functional group (a), a photopolymerization initiation. Agent (6), and heat-reactive resin (9) Ink ink. The present invention provides the following inkjet ink, a method of forming a hardened ink obtained by using the inkjet ink, and the like. The ring-shaped (four) ink comprises: a freemethine Ah ^ polymerizable monomer (Α) having a ring of 5 or more members, and a resin having an allergic functional group 3) °. - Raw monomer (B), photopolymerization initiator (〇, and thermal reactivity) The cyclic-radical polymerization of the inkjet ink employee ring of the above [1] is specified for 5 Compound: (4) is R1 H2C==C—C—〇__R2__r3 according to formula (4)

A (A)A (A)

(於通式（A)中，RU r為可具有分支結構的碳數為二的燒基，支結構的碳數為2〜5的 3的伸料或可具有分烧基取代的氧數為丨或2的大於為可被，數為1〜3的 [3]如上述[2]所述之噴墨用、里於5員環的環狀鰱）。 R1為氫、曱基或乙基，R2為其中於通式(A)中，可被魏為1〜3的燒基取代的^ 1〜3 _燒基，¥為員環的環狀醚。、氣數為1或2的5員環或6 201016799 [4]如上述[2]所述之噴墨用墨水，其，為氫或曱基，R2為亞曱基，R3為氧數為二；匕)1，狀驗。的5貝％的環 [5]如上述[2]所述之喷墨用墨水，其 W為氫或甲基，R、亞甲基，r3為被碳數為通;=)中其取代的氧數為2的ό員環的環狀醚。 ’、、、、、元基(In the general formula (A), RU r is a carbon group having a branched structure and having a carbon number of 2, and a branch having a carbon number of 2 to 5 in the branched structure or an oxygen having a divided alkyl group may be [3] [3] The inkjet for the inkjet according to the above [2], and the ring-shaped crucible of the 5-membered ring). R1 is hydrogen, a mercapto group or an ethyl group, and R2 is a cyclic ether in which a group of the formula (A) which can be substituted with a group of 1 to 3, and a ring of a ring of a ring. The ink for inkjet according to the above [2], which is hydrogen or a mercapto group, R2 is an anthracenylene group, and R3 is an oxygen number of two;匕) 1, test. The ink of the inkjet according to the above [2], wherein W is hydrogen or methyl, R, methylene, and r3 are carbon atoms; A cyclic ether of the oxime ring having an oxygen number of 2. ',,,,, yuan base

目^Λ6]如上述[1]至[5]中任—項所述之喷墨用墨水，其中 /、有，、，、反應性官能基的自由基聚合性單體（Β)具有選自由羥基、縣、環氧乙⑥（Gxi_ )及氧雜環丁烧（。諭狀) 所組成族群中的熱反應性官能基。 [7]如上述[1]至[5]中任一項所述之噴墨用墨水，其中具有熱反應性官能基的自由基聚合性單體（B)具有經基或羧基的熱交聯性官能基。 [8] 如上述[1]至[7]中任一項所述之噴墨用墨水，其中具有熱反應性官能基的自由基聚合性單體（B)具有1個熱反應性官能基。 [9] 如上述[1]至[8]中任一項所述之喷墨用墨水，其中具有熱反應性官能基的自由基聚合性單體（B)是以通式 (B-1)或（B-2)所表示的化合物： 201016799The inkjet ink according to any one of the above-mentioned [1], wherein the radically polymerizable monomer (/) having a reactive functional group is selected from the group consisting of A thermally reactive functional group in the group consisting of hydroxy, county, epoxy 6 (Gxi_), and oxetane (?). [7] The inkjet ink according to any one of [1] to [5] wherein the radically polymerizable monomer (B) having a thermally reactive functional group has a thermal crosslinking of a base group or a carboxyl group. Sex functional group. [8] The inkjet ink according to any one of [1] to [7] wherein the radically polymerizable monomer (B) having a thermally reactive functional group has one thermally reactive functional group. [9] The inkjet ink according to any one of [1] to [8] wherein the radically polymerizable monomer (B) having a thermally reactive functional group is a formula (B-1) Or the compound represented by (B-2): 201016799

r5-〇 (B-1) h2c=c—c—〇R5-〇 (B-1) h2c=c-c-〇

II oII o

H2C——c—H2C——c-

COOH (B-2) (於通式（B-1)及（B-2)巾，R4分別獨立地為氮或碳數為1〜3眺基，Μ分翻立地為可具有環狀結構的碳數為2〜12的伸烷基，n為丨〜3〇的整數）。 [10]如上述[1]至[5]中任一項所述之噴墨用墨水，其中具有熱反應性官能基的自由基聚合性單體（B)為選自由（甲基）丙烯酸-2-羥基乙酯、（曱基)丙烯酸_2_羥基丙酯、（曱基) 丙烯酸-2-羥基丁酯、（曱基）丙烯酸_4_羥基丁酯、14•環己烷二曱醇單（甲基）丙烯酸酯、鄰苯二甲酸單[(甲基）丙烯酸羥基乙酯]、及鄰苯二甲酸單-[2_(2·甲基丙烯醯氧基)_乙基] 醋所組成族群中的大於等於1種。 [11] 如上述[1]至[10]中任一項所述之噴墨用墨水，其中光聚合起始劑（C)為雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、或2,4,6-三甲基苯甲醯基二苯基氧化膦。 [12] 如上述[1]至pi]中任一項所述之喷墨用墨水，其中熱反應性樹脂（D)為三聚氰胺樹脂（melamine resin ) 0 [13] 如上述[1]至[u]中任一項所述之噴墨用墨水，其中熱反應性樹脂（D)為齡·樹脂。 [14] 如上述[1]至[12]中任一項所述之喷墨用墨水，其 201016799 中進一步含有阻燃劑（E)。 [15] 如上述[1]至[14]中任一項所述之喷墨用墨水，其中進一步含有多官能（甲基)丙烯酸酯（F)。、 [16] 種硬化膜形成方法，其是藉由喷墨法而塗佈如上述[1]至[15]十任一項所述之噴墨用墨水，並對所塗佈的墨水照射光’藉此形成硬化膜。 [17] —種硬化膜形成方法，其是藉由喷墨法而塗佈如〇上述[1]至[15]中任一項所述之喷墨用墨水，並對所塗佈的墨水同時進行光照射及加熱，或者依序進行〇光照射、2) 加熱’藉此形成硬化膜。 [18] —種硬化膜，其是利用如上述[16]或[17]所述之方法而獲得。 [19] 如上述[18]所述之硬化膜，其是以特定的圖案而形成。 [20] —種電子電路基板’其是於基板上形成有如上述 ' [18]或[19]所述之硬化膜。 ® [21]—種電子零件，其具有如上述[2〇]所述之電子電路基板。 [22]—種顯示元件，其具有如上述[2〇]所述之電子電路基板或如上述[21]所述之電子零件。另外’於本說明書中，為了表示丙烯酸酯與甲基丙烯酸酯兩者，有以「（曱基）丙稀酸酯」的方式進行標記的情形。 [發明之效果] 9 201016799 。1 ynopii 本發明的較好態樣的喷墨用墨水例如墨水的保存穩疋性優異，並可實現穩定地喷出。而且，由該喷墨用墨水所得的硬化膜例如具有對金屬蝕刻液的耐性及對剝離液的剝離性。例如由該喷墨用墨水所得的硬化膜具有對鍍敷液的耐性及對剝離液的剝離性。例如由喷墨用墨水所得的硬化膜具有對鍍敷液的耐性或焊錫耐熱性。而且，藉由使用本發明的較好態樣的喷墨用墨水，可縮短電子電路基板的製造中形成保護膜所花費的工夫及時間，亦可減少消耗品。為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。【實施方式】 1.本發明的喷墨用墨水本發明的喷墨用墨水包含：含有大於等於5員環的環狀_自由絲合性單體⑷、具有熱反應性官能基的自 t基聚合性單體⑻、絲合賴劑⑻、及熱反應性樹月曰⑻。另外’所謂「熱反應性」，例如是指藉由熱而產生交聯反應的性質，但並不限定於此。本發日㈣噴墨用墨水可為無色，亦可為有色。 φ另外，本發明的噴墨用墨水除了包含含有大於等於5 =的環_的自由基聚合性單體（Α)、具有熱反應性官此基的自由基聚合性單體（Β)、光聚合起始劑（c)、及熱 =性樹脂（D)以外’亦可任意地含有阻燃劑⑻、多基)丙稀酸醋（F)，。另外，可根據需要而進一步含有/谷劑、添加劑、聚合抑制劑、著色劑等。 201016799 體（A) 有大於等於5員環的環狀醚的自由基聚合性單含有大於等於5員戸认 ⑷若為自由絲纽狀醚的自由絲合性單體的環狀ϋ，則並無特觀=，且含有A於等於5員環藉由利用照射光所產生的自所11「自由絲合性」，是指合的性質。由基（free radical)而開始聚 ❹ 魯用以使自由基聚合性罩官能基可列舉··丙職（）具有自由基聚合性的丙烯酿胺等的官能基。白^丙婦基、丙婦酿腔、或甲基這些官能基的健可為多彳性單體（A) _所含的的是！個〜2個，進而好^是^。岐1㈣個，更好 <自由基聚合性單體> 含有大於等於5員環的& 如上所述，為自由基聚二^性單體以下物質。處自由基聚錢單_如可列舉性單=二基時聚合二單二如為異具，的多二（甲基)丙烯酸酯、季戊四醇二申f聚氰酸環氣乙烷改質二（甲基)丙稀酸醋單硬脂酸賴—1)丙烯酸略、季戊四醇酷、三經甲基丙烧二(曱基)兩烯_旨、甲基)丙稀酸丙埽酸醋、二季戊四醇三(甲基)丙歸^季戍四醇二(甲基） (曱基）丙烯酸酯、或二季戊四日一季戊四醇四 1甲基)内埽酸醋等。 201016799 3iy^pu 、自由基聚“生單體例合性單體的情形時，例如不基的早“匕聚醋、（曱基)丙稀酸-3,4-環氣产p砂（曱基)丙稀酸縮水甘油甘油酯、3-甲基-3-(甲曰、（甲基)丙烯酸甲基縮水乙基3 (甲幻而膝歸酿氧基曱基氧雜環丁烧、3_ 乙基-3·(曱基)丙稀醯氧基甲基氧雜環丁^ 丙烯酿氧基乙基氧雜環丁、ρ 土（土）乙基氧雜環丁烧、對乙；^^乙基a3-(甲基）丙稀酿氧基 A醚、2笑美席基基基虱雜環丁烷-3-基曱 ί甲其烯醢氧基曱基氧雜環丁烧、2-三氟曱基-3-(曱基)丙稀醯氧基甲基氧雜環丁院、*三氟曱基 =(甲基)丙婦酿氧基甲基氧雜環丁燒、（甲基)丙婦酸基)丙烯酸曱醋、（曱基)丙稀酸乙醋、（甲基)丙稀酸異丙醋、 (甲基)丙烯酸丁醋、（甲基)丙歸酸異丁醋、（甲基)丙稀酸第二丁醋、（曱基)丙烯酸環己酿、（甲基)丙蝉酸节醋、苯乙稀、 :基苯乙烯、氣甲基苯乙烯、（甲基)丙烯酸(3•乙基_3氧雜裱丁基）甲酯、N-環己基順丁烯二醯亞胺、N苯基順丁烯二醯亞胺、乙烯基甲苯、（甲基)丙烯酸三環[5 21 〇2,6]癸酯、 ❹ (曱基）丙烯酸二環戊烯氧基乙酯、（甲基)丙烯酸異冰片酯、 (甲基)丙烯酸苯酯、甘油單（甲基)丙烯酸酯、聚苯乙烯巨單體、聚甲基丙烯酸甲酯巨單體、（甲基）丙烯酸_5_四氫糠氧基羰基戊酯、月桂醇的環氧乙烷加成物的（曱基）丙烯酸酯、（甲基)丙烯酸、丁烯酸、氯丙烯酸、肉桂酸、順丁稀二酸、反丁烯二酸、衣康酸（itaconic acid)、檸康酸 (citraconicacid)、甲基反丁烯二酸（mesaconicacid)、ω -羧基聚己内酯單（甲基)丙烯酸酯、琥珀酸單[2-(甲基)丙烯 12 201016799 iiy45pil 醯氧基乙基]酯、順丁烯二酸單[2-(甲基）丙烯醯氧基乙基] 酯、環己烯-3,4-二甲酸單〇(甲基)丙烯醯氧基乙基;|酯、（甲基)丙烯醢胺、N，N-二甲基（曱基)丙烯醯胺、N，N_二乙基（甲基)丙烯醯胺、N，N-二甲基胺基丙基（甲基)丙烯醯胺、N—異丙基（曱基）丙稀醢胺、N-丙烯醯基嗎琳、N-苯基順丁烯二醯亞胺、或N-環己基順丁稀二醢亞胺等。於自由基聚合性單體例如為不具有羥基的多官能聚 ⑩ 合性單體的情形時，例如可列舉：雙酚F型環氧乙烷改質二丙烯酸酯、雙酚A型環氧乙烷改質二丙烯酸酯、聚乙二醇一丙烯酸g旨、聚丙一醇二丙烯酸醋、1，4_丁二醇二丙稀酸酯、1，6-己二醇二丙烯酸醋、a壬二醇二丙烯酸酯、M_ 環己烷二曱醇二丙烯酸酯、2-正丁基_2_乙基·L3-丙二醇^ 丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、環氧乙烷改質三羥曱基丙烷三（甲基）丙烯酸酯、環氧丙烷改質三羥曱基丙烧三（曱基)丙烯酸酯、表氯醇（epichl〇r〇hydrin) ^質二羥曱基丙烷三（甲基）丙烯酸酯、二(三羥甲基丙烷)四（甲 ® 基)丙烯酸酯、甘油三（甲基)丙烯酸酯、表氣醇改質甘油三 (甲基）丙烯酸酯、二甘油四（曱基)丙烯酸酯、季戊四醇四基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、己内酯 (capr〇iact〇ne)改質二季戊四醇六（甲基)丙烯酸酯、環乙燒改質鱗酸三（甲基)丙稀酸醋、三[(甲基)丙稀醜氧基乙基]異三聚氰酸醋、己内醋改質三[(甲基)丙_氧基乙異二聚氰酸酯、或（甲基)丙稀酸胺基甲酸酯等。 <大於等於5員環的環狀醚> 13 201016799COOH (B-2) (in the formulae (B-1) and (B-2), R4 is independently nitrogen or a carbon number of 1 to 3 fluorenyl groups, and the enthalpy is inverted to have a cyclic structure. The alkyl group having a carbon number of 2 to 12 and n is an integer of 丨~3〇). [10] The inkjet ink according to any one of [1] to [5] wherein the radically polymerizable monomer (B) having a thermally reactive functional group is selected from (meth)acrylic acid- 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylic acid ester, 2-hydroxybutyl (meth) acrylate, _4-hydroxybutyl (meth) acrylate, 14 • cyclohexane decyl alcohol Mono (meth) acrylate, phthalic acid mono [(meth) hydroxyethyl methacrylate], and phthalic acid mono-[2_(2·methacryloxy)-ethyl] vinegar One or more of the ethnic groups. [11] The ink for inkjet according to any one of [1] to [10] wherein the photopolymerization initiator (C) is bis(2,4,6-trimethylbenzylidene) Phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. [12] The ink for inkjet according to any one of the above [1] to [pi], wherein the thermally reactive resin (D) is a melamine resin 0 [13] as described above [1] to [u] The inkjet ink according to any one of the invention, wherein the thermally reactive resin (D) is an age resin. [14] The inkjet ink according to any one of [1] to [12] further comprising a flame retardant (E) in 201016799. [15] The inkjet ink according to any one of [1] to [14] further comprising a polyfunctional (meth) acrylate (F). [16] A method of forming a cured film by coating the ink according to any one of the above [1] to [15] by an inkjet method, and irradiating the applied ink with light. 'Thereby forming a cured film. [17] A method of forming a cured film, which is an inkjet ink according to any one of the above [1] to [15], which is simultaneously applied to the applied ink by an inkjet method. Light irradiation and heating are performed, or calendering is sequentially performed, and 2) heating is performed to form a cured film. [18] A cured film obtained by the method described in [16] or [17] above. [19] The cured film according to the above [18], which is formed in a specific pattern. [20] An electronic circuit board which is formed with a cured film as described in the above [18] or [19]. ® [21] An electronic component having the electronic circuit substrate as described in [2〇] above. [22] A display element comprising the electronic circuit substrate according to [2] above or the electronic component according to [21] above. Further, in the present specification, in order to indicate both the acrylate and the methacrylate, there is a case where "(mercapto) acrylate) is labeled. [Effects of the Invention] 9 201016799. 1 ynopii The inkjet ink of the preferred embodiment of the present invention, for example, ink, is excellent in storage stability and can be stably ejected. Further, the cured film obtained from the inkjet ink has, for example, resistance to a metal etching solution and peeling property to a peeling liquid. For example, the cured film obtained from the inkjet ink has resistance to a plating solution and peeling property to a peeling liquid. For example, a hardened film obtained from an inkjet ink has resistance to a plating solution or solder heat resistance. Further, by using the inkjet ink of the preferred embodiment of the present invention, the labor and time required to form the protective film in the production of the electronic circuit board can be shortened, and consumables can be reduced. The above described features and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] 1. Inkjet ink of the present invention The inkjet ink of the present invention comprises a cyclic-free-filable monomer (4) having a ring of 5 or more members and a self-t-group having a thermally reactive functional group. A polymerizable monomer (8), a silk compound (8), and a heat-reactive tree (8). Further, the term "thermal reactivity" means, for example, a property of causing a crosslinking reaction by heat, but is not limited thereto. This inkjet ink can be colorless or colored. In addition, the inkjet ink of the present invention contains a radical polymerizable monomer (Α) having a ring of 5 = 5 or more, a radically polymerizable monomer (Β) having a heat-reactive group, and light. The polymerization initiator (c) and the heat-reactive resin (D) may optionally contain a flame retardant (8) or a polybasic acrylic acid (F). Further, a granule, an additive, a polymerization inhibitor, a colorant or the like may be further contained as needed. 201016799 体 (A) The radically polymerizable monomer having a cyclic ether of 5 or more members has a ring-like enthalpy of 5 or more members, and (4) if it is a free-filament-forming monomer of free silk-like ether, There is no special =, and the inclusion of A is equal to the nature of the "free silk fission" produced by the irradiation of the light of the 5-member ring. Starting from the free radical, the functional group for the radical polymerizable capping functional group is exemplified by a radical polymerizable acrylamide. The white propylene base, the propylene brewing chamber, or the methyl group can be a multifunctional monomer (A) _ contained! ~ 2, and then ^ is ^.岐1 (four), more <radical polymerizable monomer>&> containing 5 or more members of the ring & as described above, it is a radical polydiphenyl monomer. Free radical money list _ such as enumeratable single = two-base polymerization, two single two, such as a heterogeneous, poly-di (meth) acrylate, pentaerythritol di-f-c-cyanate cyclohexane ethane modified two ( Methyl) acetoacetic acid monostearic acid lysine 1) acrylic acid slightly, pentaerythritol cool, trimethyl methacrylic acid bis(indenyl) alkene, methyl, acrylic acid propylene vinegar, dipentaerythritol Tris(methyl)propene quaternary tetraol di(methyl)(indenyl) acrylate, or diquaternary four-day pentaerythritol tetra-methyl phthalic acid vinegar. 201016799 3iy^pu, free radicals in the case of "monomeric monomer", such as non-based early "匕醋 vinegar, (mercapto) acrylic acid -3,4-ring gas production sand (曱Glycol glyceryl acrylate, 3-methyl-3-(methyl hydrazine, methyl methacrylate (ethyl methacrylate) 3 (methyl phantom and oxoloxy oxetane, 3_ Ethyl-3·(fluorenyl) propylene methoxymethyl oxetane propylene oxyethyl oxetane, ρ soil (earth) ethyl oxetane, bis; ^^ Ethyl a3-(methyl) propylene oxide oxy A ether, 2 sylmethicyl 虱 heterocyclobutane-3-yl 曱甲其醢醢醢氧氧、, 2- Trifluoromethyl-3-(indenyl) propylene sulfoxymethyl oxetane, *trifluoromethyl = (methyl) propyl methoxymethyl oxetane, (methyl ) acetophenate acrylate vinegar, (mercapto) acrylic acid vinegar, (meth) isopropyl isopropyl vinegar, (meth) butyl vinegar, (meth) acrylic acid isobutyl vinegar, (Methyl)acrylic acid second vinegar, (mercapto)acrylic acid ring, (meth)propionic acid vinegar, styrene, styrene, gas methyl benzene , (meth)acrylic acid (3•ethyl_3oxaindole butyl) methyl ester, N-cyclohexyl maleimide, N-phenyl maleimide, vinyl toluene, ( Trimethyl [5 21 〇 2,6] decyl methacrylate, dicyclopentenyloxyethyl decyl acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol Mono (meth) acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, (meth)acrylic acid _5_tetrahydrofurfuryloxycarbonyl pentyl ester, lauryl alcohol ethylene oxide plus Compound (mercapto) acrylate, (meth)acrylic acid, crotonic acid, chloroacrylic acid, cinnamic acid, cis-butane diacid, fumaric acid, itaconic acid, citraconic acid ( Citraconicacid), mesaconic acid, ω-carboxypolycaprolactone mono(meth)acrylate, succinic acid mono[2-(methyl)propene 12 201016799 iiy45pil oxiranylethyl ester , maleic acid mono [2-(methyl) propylene methoxyethyl] ester, cyclohexene-3,4-dicarboxylic acid mono-(methyl) propylene oxiranyl ethyl group; Methyl) acrylamide, N, N-dimethyl(fluorenyl) acrylamide, N,N-diethyl(meth) acrylamide, N,N-dimethylaminopropyl (meth) decylamine, N-iso Propyl (mercapto) acrylamide, N-propylene hydrazinyl, N-phenyl maleimide, or N-cyclohexyl cis-butane diimide, etc. When the monomer is, for example, a polyfunctional poly 10 monomer having no hydroxyl group, for example, bisphenol F type ethylene oxide modified diacrylate, bisphenol A type ethylene oxide modified diacrylic acid Ester, polyethylene glycol-acrylic acid, polypropanol diacrylate vinegar, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate vinegar, a decanediol diacrylate, M_cyclohexanediol diacrylate, 2-n-butyl-2- 2·ethyl·L3-propanediol acrylate, trimethylolpropane tri(meth) acrylate, ethylene oxide modified tris Mercaptopropane tri(meth)acrylate, propylene oxide modified trishydroxypropylpropane tris(decyl) acrylate, epichlorohydrin (epichl〇r〇hydrin) dihydroxy hydrazinopropane Acrylate, bis(trihydroxyl) Methylpropane) tetrakis(meth)acrylate, glycerol tri(meth)acrylate, surface alcohol modified glycerol tri(meth)acrylate, diglyceryl tetra(decyl)acrylate, pentaerythritol tetrayl) Acrylate, dipentaerythritol hexa(meth) acrylate, caprolactam (capr〇iact〇ne) modified dipentaerythritol hexa(meth) acrylate, cyclohexane sulphuric acid tris(methyl) acrylate Vinegar, tris[(methyl)propyl ugly oxyethyl]iso-cyanuric acid vinegar, caprolactone modified tris[(methyl)propenyloxyisocyanurate, or (methyl Acrylic acid urethane and the like. <cyclic ether of 5 or more members> 13 201016799

Jiywpii 含有大於等於5員環的環狀驗的自由 „上所述，是自由基聚合性單體具有乂二口於“ 早二二處大於等於5員環的環狀，列如驗等，環中所含_鍵的個數例如可列舉丨個員【個=3 個等。另外，㈣環_可觀絲代，較被數為1〜3的絲，更好的是可被？基或代疋 =T:代基數可為多個，較好的是I個：，更好的疋1個。自由基聚合性單和士狀醚的個數可為多個，較好二：)中所含的這些環個。夕1固較好的疋1個〜2個，更好的是i 環狀^於等於5 S賴雜⑽频可轉具扣下結構的Jiywpii contains a ring test with a ring of 5 or more members. As described above, the radical polymerizable monomer has a ring-shaped ring at the early two or two points of 5 or more rings. The number of _ keys included in the middle can be exemplified by a single member [ etc.]. In addition, (4) ring _ observable silk generation, more than the number of 1 to 3 silk, better can be? Base or generation = T: The base number can be multiple, preferably one:, and the better one. The number of the radically polymerizable mono- and ether-like ethers may be plural, and it is preferred that these rings are contained in two:).夕1 solid is better 疋1~2, more preferably i ring^ is equal to 5 S 赖(10) frequency convertible buckle structure

Ό、 Ό、 ,〇、 Ό, 〇 \^° … v — (αΛ'ΑΓ等於5 M環的環狀_自由Q基聚合性單體 ^5疋_^^絲合性單财的任—種具有上述大於的所有财的任單體，其中包括可考慮自由基聚合性單體 =的疋以上速通式（A)所表示的化合物。可列裹、:(A) _，Rl為氫或碳數為1〜3 基，具體謂.&、甲基、乙基、正丙基、異丙基，較好的是氫〇、 .0 ❹ 14 201016799 3iy4^pit 或甲基。 _3iU)t，R2為可具有分支結構的碳數& 3 的伸烷基或可具有分支結構的碳數為2〜數為為1〜3的伸烷基具體為亞甲基、伸 ’ 一醇_。碳數些伸烧基上鍵結例如減取代基^可於f :形::=。另外，可具有分二:碳數為1二 ❹ 或新戊二_。㈣Hth ^通式⑷中，R3為可被碳數為Μ的烧基取代的二數為1或2的大於等於5員環的環_。該環狀_具體例例如可列舉上述環狀醚。以通式（A)所表示㈣合料體（A)的具體例可 =舉.（甲基)丙騎四氫糠醋、環狀三Μ基丙錢甲搭 (甲，)丙稀酸醋、烧氧基化（曱基)丙烯酸四氫糠醋、己内醋改質（甲基)丙烯酸四氫糠酯等。社這些聚合性單體中’較好的是丙烯酸四氮糠醋（下述、、’。構式（al-Ι))、甲基丙烯酸四氫糠酯（下述結構式 jal-2))、壤狀二經曱基丙烧縮曱㈣缚酸自旨（下述結構式U2-1))、或環狀三經曱基丙燒縮甲搭甲基丙稀酸醋（下述結構式（a2-2))。 15Ό, Ό, 〇, Ό, 〇\^° ... v — (αΛ'ΑΓ is equal to 5 M ring ring _ free Q-based polymerizable monomer ^5疋_^^ silky property Any of the above-mentioned monomers which are larger than the above, including a compound represented by the above formula (A) which can be considered as a radical polymerizable monomer = can be listed, : (A) _, Rl is hydrogen or The carbon number is 1 to 3 groups, specifically, &, methyl, ethyl, n-propyl, isopropyl, preferably hydroquinone, .0 ❹ 14 201016799 3iy4^pit or methyl. _3iU)t R2 is an alkylene group having a carbon number & 3 of a branched structure or a branched alkyl group having a carbon number of 2 to several 1 to 3, specifically a methylene group or a mercapto group. Carbon number Some extension groups, for example, a substituent group, can be used in f: shape::=. In addition, it may have a fraction of two: the carbon number is 1 ❹ or neopenta _. (4) Hth In the formula (4), R3 is a ring _ of 5 or more rings which may be substituted by a group having a carbon number of fluorene. Examples of the cyclic form include the above cyclic ether. The specific example of the (4) mixture (A) represented by the general formula (A) can be as follows: (meth) propyl riding tetrahydroanthraquinone vinegar, cyclic triterpene propyl ketone (a, acrylic acid vinegar) , alkoxylated (fluorenyl) methacrylate tetrahydroanthracene vinegar, caprolactone modified tetramethyl methacrylate (meth) acrylate, and the like. Among these polymerizable monomers, 'the preferred one is tetraammine vinegar acrylate (hereinafter, '.' (al-Ι)), tetrahydrofurfuryl methacrylate (the following structural formula jal-2)) , the second structural formula of the sulphuric acid, the sulphuric acid, the sulphuric acid, the sulphuric acid, the sulphuric acid, the sulphuric acid (the following structural formula U2-1) (a2-2)). 15

201016799 Jiy4DplI201016799 Jiy4DplI

丙烯酸四氫糠酯以Sartomer公司製造的SR285、共榮社化學股份有限公司製造的Ught Acrylate THF-A的形式市售，甲基丙烯酸四氫糠酯以Sartomer公司製造的 SR203、共榮社化學股份有限公司製造的Light Ester THF 的形式市售。另外，環狀三羥甲基丙烷縮甲醛丙烯酸酯以 Sartlmer:司製造的奶31的形式市售。喷墨用墨水中所含的聚合性單體（A)可為選自上述化合物的1種化舍物，另外，亦可為這些化合物的大於等於2種的混合物° 若於噴墨用墨水中含有1 Wt%〜7〇wt%(重量百分比）的自由基聚合性單體（A) ’則於噴墨時，自噴嘴的噴出穩定性變得良好，因此較好，若含有10 wt0/〇〜65 wt%的自由基聚合性單體（A) ’則更好，若含有20 wt%〜60 wt%的 201016799 D I yHDpil 自由基聚合性單體（a)，則進而更好。 1.2具有熱反應性官能基的自由基聚合性單體（b) 具有熱反應性宫能基的自由基聚合性單體（B)若為自由基聚合性化合物，且具有熱反應性官能基，則並無斗寺別限定。另外，所謂「熱反應性」，例如是指藉由產、交聯反應的性質，但並不限定於此。 ‘，、、產生熱反應性官能基若為藉由熱而產生反應（較好的是交 ❹聯反應）的官能基，則並無特別限定，例如可列舉：，基、環氧乙燒及氧雜環了烧等，這些官能基中尤其=的是羥基、羧基。另外，自由基聚合性單體（B)中所含的熱反應性官能基的個數可為多個，較好的是丨個〜3個，、更好的是1個〜2個，進而好的是丨個。 β，由基聚合性單體（B)中所含的熱反應性官能基具有提而與噴墨用墨水巾所含的其他成分的相容性的效果。尤其是於熱反應性官能基為羥基的情形時，提高與噴墨用義墨水巾所含的其他成分_容_效紐大。另外，於執 f應性官能基為竣基的情形時，具有提高由喷墨用墨水^ 得的硬化膜對鹼性水溶液的剝離性的效果。 <熱反應性官能基為羥基的自由基聚合性單體（Β) 主於自由基聚合性單體（Β)的熱反應性官能基為羥基 „時’較好例可列舉：具有羥基與1個自由基聚合：碳碳雙鍵的聚合性單體、具有經基與2個自由基聚合炭雙鍵的5^合性單體、或具有經基與大於等於3個自由基 17 201016799 ^ιν^ριι 聚合性碳碳雙鍵的聚合性單體。的且=祕Γ個自由絲合性碳碳韻㈣合性單體的具體例可列舉：（甲基)丙烯酸_2_祕乙自旨、（甲 ==:(甲基)峨，基丁醋、或W環己烧一曱醇早（曱基)丙烯酸酯等。〇具有減與2個自由基聚合性碳碳雙鍵的聚合性 =體=可列舉：異三聚氰酸環氧乙烧改質二（甲基)丙稀曰:甘油一丙烯酸酯、季戊四醇二（甲基）丙烯酸酯、戊四醇二(曱基)丙烯酸g旨單硬脂酸冑、三經甲基丙烧基)丙烯酸酯、或二季戊四醇二(甲基)丙烯酸酯等。一人降於等於3個自由基聚合性碳碳雙鍵的聚 1早體的具體例可列舉：季戊四醇三（甲基)丙稀酸醋、 :季戊畴五（甲基)丙_sl、絲改f二季戊四醇五（甲 f丙婦㈣、二季戊四醇四（甲基)丙稀酸醋、絲改質二 =戊四醇四（甲基旨、二季戊四醇三（甲基）丙稀酸 S曰、或絲改質二季戊四醇三（甲基)丙稀酸醋等。 ❹ 這些聚合性單體巾，於應麟光硬傾喷墨用墨水的月形時’就自喷嘴的噴出穩定性的觀點而言，具有經基作為熱反應性官能基的自由絲合性單體⑻，較好的是具有經基與1個自&絲纽碳碳雙賴聚合性單體，尤其好的是曱基丙烯酸·2·經基乙g旨、甲基丙烯酸_2_祕丙醋、丙婦酸·4·祕丁g旨、或1>4_環己烧二甲醇單丙烯酸醋。另外’具有熱反應性官能基的自由基聚合性單體（B) 較好的是以上述通式（^1；)所表示的化合物。於通式（B1) 18 201016799 ：>iy〇pii 中，R4分別獨立地為氫或碳數為舉：氫、甲基、乙基、正丙基、異丙武的^，具體可列基。於通式（B-1)中，R5分別獨立二^ ^疋氫或甲的碳數為2〜12的伸烧基，這此:可/、有環狀結構基、伸丙基、伸丁基或以如下結中^好的是伸乙於通式（Β-υ中，η為！〜30的整數°另外，更好的是1〜3，進而好的是i。較好的疋1〜10， -ch2- -ch2- 〉〈熱反應性官能基為縣的自由基聚合性單體⑻ 的：由較基能基繼 ❹ 碳碳雙鍵的聚合性單體、且有:、㈤自由基聚合性碳雙鍵的聚合性單體、或2古斑2個自由基聚合性碳聚合性碳碳雙鍵的聚^單體。、切等於3個自由基的具=^^\個甲^基^合性碳碳雙鍵的聚合性單體反丁歸二酸反严酸、順丁稀二酸、酸單[(甲基)丙烯酸^基乙= 酯早⑽_、或鄰苯二甲的具體:羧；基聚合性碳碳雙鍵的聚合性單體具有減_四醇二丙稀酸醋等。、；3個自由基聚合性碳碳雙鍵的聚 19 201016799 ^ly^Dpir 5性單體的具_，可尊伽酸改質季細醇三（甲基) 丙稀，編酸改質二季戊四醇五(甲基)丙烯酸醋等。攻些聚合性單體中，於應用於光硬化性喷墨用墨水的情形時，就自喷嘴时出穩定性、及㈣墨用墨水所得的硬化膜對m水溶液㈣^性峨點❿言具有缓基作為熱反應性官能基的自由基聚合性單體（B)，較好的是具有幾基與1個自由基聚合性碳碳雙鍵的聚合性單體，尤其好Tetrahydrofurfuryl acrylate is commercially available as SR285 manufactured by Sartomer Co., Ltd. and Ught Acrylate THF-A manufactured by Kyoeisha Chemical Co., Ltd., and tetrahydrofurfuryl methacrylate is manufactured by Sartomer Corporation as SR203 and Kyoritsu Chemical Co., Ltd. The company is manufactured in the form of Light Ester THF. Further, cyclic trimethylolpropane formal acrylate is commercially available as Milk 31 manufactured by Sartlmer: Division. The polymerizable monomer (A) contained in the inkjet ink may be one type of compound selected from the above compounds, or may be a mixture of two or more of these compounds. The radically polymerizable monomer (A) having 1 Wt% to 7 〇wt% (% by weight) is excellent in discharge stability from the nozzle when ink is ejected, and therefore it is preferably 10 wt0/〇. ～65 wt% of the radical polymerizable monomer (A)' is more preferable, and if it contains 20 wt% to 60 wt% of 201016799 DI yHDpil radical polymerizable monomer (a), it is further preferable. 1.2 Radical polymerizable monomer having a thermally reactive functional group (b) The radically polymerizable monomer (B) having a thermally reactive functional group (B) is a radically polymerizable compound and has a thermally reactive functional group, There is no limit to the temple. In addition, the term "thermal reactivity" means, for example, the nature of the reaction by the production and crosslinking, but is not limited thereto. The functional group which generates a heat-reactive functional group by heat (preferably, a cross-linking reaction) is not particularly limited, and examples thereof include a group, an epoxy group, and an epoxy group. The oxygen heterocyclic ring is burned or the like, and among these functional groups, in particular, a hydroxyl group or a carboxyl group is used. Further, the number of the thermally reactive functional groups contained in the radically polymerizable monomer (B) may be plural, preferably from 3,000 to 1, more preferably from one to two, and further Ok, it’s one. β has an effect of improving the compatibility with the other components contained in the ink jet ink towel by the heat-reactive functional group contained in the base polymerizable monomer (B). In particular, when the thermally reactive functional group is a hydroxyl group, the other components contained in the ink jet ink towel are improved. Further, when the functional group is a fluorenyl group, the effect of improving the peeling property of the cured film obtained from the inkjet ink to the alkaline aqueous solution is obtained. <Radically polymerizable monomer having a thermoreactive functional group as a hydroxyl group (Β) The thermoreactive functional group of the radically polymerizable monomer (Β) is a hydroxyl group, and a preferred example thereof is a hydroxyl group and a hydroxyl group. Radical polymerization: a polymerizable monomer having a carbon-carbon double bond, a 5^-bonding monomer having a double bond of a radical and 2 radically polymerized carbons, or having a radical and 3 radicals or more 17 201016799 ^ιν ^ριι A polymerizable monomer having a polymerizable carbon-carbon double bond. The specific example of the free-filamentous carbon-carbon rhyme (4)-complex monomer can be exemplified by (meth)acrylic acid _2 , (A ==: (methyl) hydrazine, butyl vinegar, or W ring hexanone sterol early (mercapto) acrylate, etc. 〇 has reduced polymerizability with two radical polymerizable carbon-carbon double bonds = body = can be exemplified: iso-cyanuric acid Ethylene-oxygen bromide modified di(methyl) acrylonitrile: glycerol monoacrylate, pentaerythritol di (meth) acrylate, pentaerythritol bis(indenyl) acrylate A single glyceryl stearate, a trimethyl methacrylate acrylate, or a dipentaerythritol di (meth) acrylate, etc. One person falls to equal three radicals Specific examples of the poly 1 precursor of the carbon-carbon double bond include pentaerythritol tris(meth)acrylic acid vinegar, pentavalent domain penta (methyl) propyl ssl, and silk modified f dipentaerythritol five (a f-propyl group) Women (4), dipentaerythritol tetrakis (meth) acrylate vinegar, silk modified bis = pentaerythritol tetra (methyl, dipentaerythritol tris(methyl) acrylate S 曰, or silk modified dipentaerythritol III ( Methyl) acrylic acid vinegar, etc. ❹ These polymerizable monomer sheets have a warp group as a thermal reaction from the viewpoint of the discharge stability of the nozzle when the film is formed in the shape of the ink of the ink film The free functional group-free free-synthesis monomer (8) preferably has a mercapto group and a self-fractional carbon-carbon double-polymerizable monomer, and particularly preferably a mercaptoacrylic acid·2· Or, methacrylic acid _2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The monomer (B) is preferably a compound represented by the above formula (^1;). In the formula (B1) 18 201016799 :>iy〇pii, R4 is independently hydrogen or The number is: hydrogen, methyl, ethyl, n-propyl, isopropanol ^, specifically can be listed. In the general formula (B-1), R5 is independent of two ^ ^ hydrogen or carbon number of A It is a stretching base of 2 to 12, which is: / can have a cyclic structural group, a propyl group, a butyl group or a condensed butyl group as follows: in the formula (Β-υ, η is In addition, it is more preferably 1 to 3, and further preferably i. Preferably, 疋1 to 10, -ch2- -ch2->Reactive reactive functional group is a free radical polymerizable property of the prefecture Monomer (8): a polymerizable monomer which is followed by a carbon-carbon double bond with a more basic group, and has: (5) a polymerizable monomer of a radical polymerizable carbon double bond, or 2 radical polymerization of 2 ancient spots A monomer of a carbon-polymerizable carbon-carbon double bond. , a polymerizable monomer with a chemo-carbon double bond, which is equivalent to 3 radicals, is a compound of the same carbon-carbon double bond, anti-succinic acid, cis-butane diacid, acid mono[(methyl Acrylate; ethyl acrylate = ester early (10) _, or phthalate specific: carboxy; polymerizable monomer having a base polymerizable carbon-carbon double bond having 1,4-tetraol diacrylic acid vinegar or the like. , 3 polyradical polymerizable carbon-carbon double bond poly 19 201016799 ^ ly ^ Dpir 5 monomer with _, can be changed to quaternary acid fine quaternary alcohol tris (methyl) propylene, acid-modified two Pentaerythritol penta (meth) acrylate vinegar and the like. Among the polymerizable monomers, when applied to a photocurable inkjet ink, the stability of the nozzle is obtained, and (4) the cured film obtained by the ink for ink has a m-solution (m) The radically polymerizable monomer (B) having a heat-reactive functional group as a heat-reactive functional group is preferably a polymerizable monomer having a radical of several radicals and one radical polymerizable carbon-carbon double bond, particularly preferably

的是鄰苯二曱酸單（丙烯酸羥基乙酯）、或鄰苯二曱酸單（曱基丙烯酸羥基乙酯）（新中村化學工業股份有限公司製造的 CB-1 (商品名））。It is phthalic acid mono(hydroxyethyl acrylate) or phthalic acid mono(hydroxyethyl methacrylate) (CB-1 (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd.).

而且，具有熱反應性官能基的自由基聚合性單體（B) 較好的是以上述通式（B_2)所表示的化合物。於通式（B_2) 中，R4分別獨立地為氫或碳數為1〜3的烧基，具體可列舉：氫、甲基、乙基、正丙基、異丙基，較好的是氮或甲基。於通式（B-2)中，R5分別獨立地為可具有環狀結構的碳數為2〜12的伸烧基（較好例與上述通式（B_〗）中的 R5的說明相同）’ η為1〜30的整數，較好的是1〜1〇，更好的是1〜3，進而好的是1。喷墨用墨水中所含的自由基聚合性單體（Β)可為選自上述化合物的1種化合物，另外，亦可為這些化合物的大於等於2種的混.合物。若於喷墨用墨水中含有1 wt%〜80 wt%的自由基聚合性單體（B)，則於製成光硬化性喷墨用墨水的情形時，自喷墨噴嘴的喷出穩定’因此較好，若含有3 wt〇/〇〜75 wt% 20 201016799 的自由基聚合性單體（B)，則更好，若含有5wt%〜70 wt% 的自由基聚合性單體（B)，則進而更好。 13光聚合起始劑（C) 光聚合起始劑（C)若為可藉由紫外線或可見光線的照射而產生自由基的化合物，則並無特別限定。光聚合起始齊丨（C )的具體例可列舉：二苯甲酮（benzophenone )、米其勒酮（Michler's ketone)、4,4i-雙(二乙基胺基)二苯曱 ^ 綱氣雜蒽酮（thioxanthone )、硫雜蒽酮（thioxanthone )、異丙基氧雜蒽酮、2,4-二乙基硫雜蒽酮、2-乙基蒽醌、苯乙嗣、2-經基-2-甲基苯丙酮、2-羥基-2-曱基-4，-異丙基苯丙酮、1-羥基環己基苯基酮、異丙基安息香醚、異丁基安息香謎、2,2-二乙氧基苯乙酮、2,2-二曱氧基-2-苯基苯乙酮、樟腦醌（camph〇r〇qUinone)、苯幷蒽酮（benzanthr〇ne)、 2-甲基_1-[4_(曱硫基)苯基]嗎琳基丙烧_1_酮、2_苄基_2_ 二甲基胺基-1-(4-嗎啉基苯基)_丁酮心、4_二甲基胺基苯甲酸乙酯、4-二甲基胺基苯曱酸異戊酯、4,4，_二(第三丁基過 ® 氧基羰基)二苯曱酮、3,4,4’-三（第三丁基過氧基羰基)二苯甲嗣、3,3，4,4 -四（第二丁基過氧基幾基)二苯甲酮、H4,4，_ 四（第三己基過氧基羰基）二苯曱酮、3,3，_二（曱氧基幾基M，4·-二(第三丁基過氧基幾基)二苯甲_、3,4'_二（曱氧基羰基)-4,3’-二(第二丁基過氧基幾基)二苯曱_、七心工(曱氧基羰基)-3,3’-二（第三丁基過氧基羰基)二苯曱酮、i，2-辛二酮，1-[4-(苯硫基)苯基]-，2·(鄰苯甲醯基將）、2_(4，_甲氧基笨乙婦基)-4,6-雙(二乳曱基)·均三β秦、2-(3’，4’-二甲氧基苯乙 21 201016799 ^iy4Dplt 雙(二氯曱基)-均三嗪、2-(2’，4，-二甲氧基苯乙烯二(三氣甲基)·均三嗪、2-(2，-曱氧基笨乙婦基)-4,6· )'均三°秦、2-(4’-戍氧基苯乙婦基)♦雙(三氯 =)句二嗪、4_[對N，N-二（乙氧基羰基甲基)]_2 6·二(三氯 ^^^^力令三氣曱基⑼广氣苯私均三嗅、1，3- 甲氧基苯基)-均三嗓、2-(對二甲基胺基焊基）本幷°惡哇、2-(對二甲基胺基苯乙烯基）苯幷噻嗤、2= 基笨幷嗔唾、3,3，幾基雙(7_二乙基胺基香豆素）、 2-(鄰氣笨基)'4,4,，5,5，-四苯基-1，2，·聯味唾、2,2，·雙(2-氣苯 ❹ 基)_4,4’，5,5’-四（4-乙氧基羰基苯基)-1，2，-聯咪唑、2,2，-雙 (2,4_二氣苯基)-4,4，，5,5，-四苯基-1,2，-聯咪唑、2,2，-雙(2,4-二溴苯基)-4,4’，5,5’-四苯基_1，2|_聯咪唑、2,2，-雙(2,4,6-三氣苯基)-4,4,5,5’_四苯基-1,2'-聯咪嗤、3-(2-甲基-2-二曱基胺基丙醯基)咔唑、3,6_雙(2-曱基-2-嗎啉基丙醯基)_9_正十二烷基十坐、1-經基環己基苯基酮、雙（7? 5-2,4_環戊二晞+基)· 雙(2,6-—氟-3-(1Η-η比洛-1-基)-苯基)鈦、雙(2,4,6-三甲基苯曱醯基)苯基氧化膦、或2,4,6-三曱基苯曱醯基二苯基氧化 ❹ 膦。其中，雙(2,4,6-三甲基苯甲醯基）苯基氧化膦（Ciba Japan股份有限公司製造的IRGACURE 819 (商品名））或 2,4,6-三甲基苯曱醯基二苯基氧化膦（Ciba Japan股份有限公司製造的DAR〇CURTPO (商品名））、及1-羥基環己基苯基鲷（Ciba Japan股份有限公司製造的IRGACURE I84 (商品名））等’與喷墨用墨水中所含的其他成分的相容性 22 201016799 :高因=噴墨用墨水能以較少的紫外線照射量進行硬光聚合起始劑⑹可為1#化於2種不同化合物的混合物。若於H為大於等 wt%〜2〇wt%的光聚合起㈣（c 製射7有0.2 =2為i Wt%〜2〇Wt% ’則更好4光聚合起“Further, the radically polymerizable monomer (B) having a thermally reactive functional group is preferably a compound represented by the above formula (B_2). In the formula (B_2), R4 is each independently hydrogen or a carbon group having 1 to 3 carbon atoms, and specific examples thereof include hydrogen, methyl, ethyl, n-propyl and isopropyl groups, preferably nitrogen. Or methyl. In the formula (B-2), R5 is each independently a stretching group having a cyclic structure and having a carbon number of 2 to 12 (a preferred example is the same as the description of R5 in the above formula (B_)) η is an integer of 1 to 30, preferably 1 to 1 Torr, more preferably 1 to 3, and further preferably 1. The radical polymerizable monomer (Β) contained in the inkjet ink may be one compound selected from the above compounds, or may be a mixture of two or more of these compounds. When the inkjet ink contains 1 wt% to 80 wt% of the radical polymerizable monomer (B), when the photocurable inkjet ink is used, the ejection from the inkjet nozzle is stable. Therefore, it is more preferable to contain a radical polymerizable monomer (B) of 3 wt%/〇 to 75 wt% 20 201016799, and if it contains 5 wt% to 70 wt% of a radical polymerizable monomer (B) , then better. (13) Photopolymerization initiator (C) The photopolymerization initiator (C) is not particularly limited as long as it is a compound capable of generating a radical by irradiation with ultraviolet rays or visible light. Specific examples of the photopolymerization initiation (C) include benzophenone, Michler's ketone, and 4,4i-bis(diethylamino)diphenyl hydrazine. Thioxanthone, thioxanthone, isopropyl oxazinone, 2,4-diethylthiazinone, 2-ethyl hydrazine, phenelzine, 2-perylene -2-methylpropiophenone, 2-hydroxy-2-mercapto-4,-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin, 2,2 -diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphor (camph〇r〇qUinone), benzophenone (benzanthr〇ne), 2-methyl _1-[4_(indolyl)phenyl]morphinylpropan-1-ol, 2-benzyl-2-1-dimethylamino-1-(4-morpholinylphenyl)-butanone , 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4,-di(t-butylperoxycarbonyl)benzophenone, 3 , 4,4'-tris(t-butylperoxycarbonyl)benzamide, 3,3,4,4-tetrakis(t-butylperoxymethyl)benzophenone, H4,4 , _ four (third hexylperoxy) Diphenyl fluorenone, 3,3,_di(decyloxy) M,4·-di(t-butylperoxymethyl)diphenyl-, 3,4'-di(oxyl) Benzyl)-4,3'-di(t-butylperoxy)diphenylhydrazine-, seven-ply (nonyloxycarbonyl)-3,3'-di(t-butylperoxy) Carbonyl)diphenyl fluorenone, i,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2·(o-benzylidene), 2_(4,_methoxy)乙妇基)-4,6-bis(di-mercapto-based)·s-tris-β, 2-(3',4'-dimethoxyphenylethyl 21 201016799 ^iy4Dplt bis(dichloroindenyl)-all Triazine, 2-(2',4,-dimethoxystyrene bis(trismethyl)·s-triazine, 2-(2,-decyloxyphenyl)-4,6· ) 'Equivalent three ° Qin, 2-(4'-decyloxyphenethyl) ♦ bis (trichloro =) sentence diazine, 4_[p-N,N-bis(ethoxycarbonylmethyl)]_2 6 ·Two (trichloro)^^^^ force three gas sulfhydryl groups (9) wide gas benzene private average tristimulus, 1,3-methoxyphenyl)-homo-trimium, 2-(p-dimethylamino base ) 幷幷恶、, 2- (p-dimethylaminostyryl) benzoquinone, 2 = alkaloid, 3,3, a few bis (7-diethylamine coumarin Prime), 2- (contiguous) Stupid base) '4,4,,5,5,-tetraphenyl-1,2,· 联唾, 2,2,· bis (2-p-benzophenyl)_4,4',5,5' -tetrakis(4-ethoxycarbonylphenyl)-1,2,-biimidazole, 2,2,-bis(2,4-diphenyl)-4,4,5,5,-tetraphenyl Base-1,2,-biimidazole, 2,2,-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2|-biimidazole, 2 ,2,-bis(2,4,6-trisylphenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidine, 3-(2-methyl-2- Dimethylaminopropionyl)carbazole, 3,6-bis(2-mercapto-2-morpholinylpropanyl)-9-n-dodecyldecane, 1-cyclohexylphenyl Ketone, bis(7? 5-2,4_cyclopentadienyl)-bis(2,6--fluoro-3-(1Η-η-pyr-1-yl)-phenyl)titanium, double 2,4,6-Trimethylphenylhydrazino)phenylphosphine oxide or 2,4,6-trimercaptophenylindenylphosphonium phosphine. Among them, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (IRGACURE 819 (trade name) manufactured by Ciba Japan Co., Ltd.) or 2,4,6-trimethylphenylhydrazine Diphenylphosphine oxide (DAR〇CURTPO (trade name) manufactured by Ciba Japan Co., Ltd.), and 1-hydroxycyclohexylphenyl hydrazine (IRGACURE I84 (trade name) manufactured by Ciba Japan Co., Ltd.), etc. Compatibility of other components contained in inkjet inks 22 201016799 : High cause = inkjet ink can be hard photopolymerization initiator with less ultraviolet radiation (6) can be 1# in 2 different compounds mixture. If H is greater than the equivalent wt%~2〇wt% of photopolymerization (4) (c is 7 and 0.2 = 2 is i Wt%~2〇Wt% ’, then better 4 photopolymerization”

的含篁為1 wt%〜15 wt%，則進而更好。（） 1.4熱反應性樹脂（D) 熱反應性樹脂（D)例如可列舉：環氧樹脂、三 =樹脂、「具有熱反應性官能基的自由絲合性單體;聚人物（例如_脂）」、或「具有熱反應性官能基的自由^ 合性單體與其他自由絲合性單_狀物」《。這脂就雜性、耐化學藥品㈣觀點而言，較好的是使用三聚氰胺賴’就硬化騎錄水溶液賴離性、耐酸性水溶液的觀誠言，較好的是使用「具有減應性官能基的自由基聚合性單體的聚合物（例如酴樹脂）」。三聚氰胺樹脂的具體例可列舉：三聚氰胺、羥曱基三聚氰胺、醚化經曱基三聚氰胺、苯幷胍胺 (benzoguanamine)、羥甲基笨幷胍胺、醚化羥曱基苯幷胍胺、及這些的縮合物。其中就耐化學藥品性良好的方面而言，較好的是醚化羥曱基三聚氰胺，而且下述化合物（dq) 及其縮合物的混合物以Sanwa Chemical股份有限公司製造的NikalacMW-30 (商品名）的形式市售。 23 201016799The yttrium content is from 1 wt% to 15 wt%, and thus further. () 1.4 Thermally Reactive Resin (D) Examples of the thermally reactive resin (D) include an epoxy resin, a tri-resin, a "free-filable monomer having a thermally reactive functional group, and a poly-human (for example, _lipid) "", or "free-reactive monomer having a thermally reactive functional group and other free-filament-single". In terms of impurities and chemical resistance (4), it is better to use melamine lysine to harden the aqueous solution of aqueous solution and acid-resistant aqueous solution. It is better to use "allergic functional". A polymer of a radical polymerizable monomer (for example, an anthracene resin). Specific examples of the melamine resin include melamine, hydroxydecyl melamine, etherified decyl melamine, benzoguanamine, hydroxymethyl cumylamine, etherified hydroxydecyl benzoguanamine, and the like. Condensate. Among them, in terms of good chemical resistance, etherified hydroxydecyl melamine is preferred, and a mixture of the following compound (dq) and its condensate is Nikalac MW-30 (trade name) manufactured by Sanwa Chemical Co., Ltd. The form is commercially available. 23 201016799

H3COH2Cn /N H3COH2C /CH2〇CH3J^ch2〇ch3 CH20CH3 'CH20CH3H3COH2Cn /N H3COH2C /CH2〇CH3J^ch2〇ch3 CH20CH3 'CH20CH3

(d-1) N N、「具有熱反應性官能基的自由基聚合性單體的聚合物」的具體例可列舉：聚乙烯醇、聚乙烯苯酚等酚樹脂、聚((曱基)丙烯酸縮水甘油酯）、聚((甲基)丙烯酸-3,4-環氧環己酯）、聚((甲基)丙稀酸甲基縮水甘油酯）、聚(3_曱基_3•(甲基）丙烯醯氧基甲基氧雜環丁烷）、聚(3_乙基_3_(甲基）丙稀 ® 酿氧基甲基氧雜ί衣丁炫>)、1(3-甲基-3-(甲基)丙稀酿氧基乙基氧雜環丁燒）、聚(3-乙基-3-(曱基)丙烯酿氧基乙基氧雜環丁烧）、聚(對乙烯基苯基-3-乙基氧雜環丁烧_3·基甲基驗）、聚(2_苯基-3·(甲基）丙烯醯氧基曱基氧雜環丁烷）、聚(2-三氟甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷）、聚(4_三氟甲基-2-(甲基)丙烯醯氧基曱基氧雜環丁烷）、聚（甲基)丙烯酸等。其中，就提高硬化膜對鹼性水溶液的剝離性而言，較 . 好的是聚乙烯苯酚等酚樹脂，其以丸善石油化學股份有限 ❹ 公司製造的MarukaLyncurMS-2P (商品名）的形式市售。匕若於噴墨用墨水中含有0.1 wt〇/〇〜30 wt0/〇的熱反應性樹月曰（D)，則所得的墨水的硬化膜的耐化學藥品性變高，故較好*含有〇 5 wt〇/❶〜25 的熱反應性樹脂（D)，則更好若含有1 wt%〜2〇 «的熱反應性樹脂（D)，則進而更好。 15阻燃劑（E) 24 201016799(d-1) Specific examples of the NN and the "polymer of a radically polymerizable monomer having a heat-reactive functional group" include a phenol resin such as polyvinyl alcohol or polyvinylphenol, and poly((mercapto)acrylic acid shrinkage. Glyceride), poly((meth)acrylic acid-3,4-epoxycyclohexyl ester), poly((methyl)acrylic acid methylglycidyl ester), poly(3_mercapto_3•(A) Base) propylene methoxymethyl oxetane), poly(3_ethyl_3_(methyl) propylene® ethoxymethyl oxalate & 炫 >), 1 (3- Benzyl-3-(methyl) propylene oxide ethoxyethyl oxetane), poly(3-ethyl-3-(indenyl) propylene ethoxyethyl oxetane), poly( P-vinylphenyl-3-ethyloxetane _3·methyl group), poly(2-phenyl-3·(meth) propylene fluorenyloxy oxetane), Poly(2-trifluoromethyl-3-(methyl)propenyloxymethyloxetane), poly(4-trifluoromethyl-2-(methyl)acryloxycarbonyloxyl Heterocyclic butane), poly(meth)acrylic acid, and the like. Among them, in order to improve the peeling property of the cured film to the alkaline aqueous solution, a phenol resin such as polyvinyl phenol is commercially available, and it is commercially available as MarukaLyncur MS-2P (trade name) manufactured by Maruzen Petrochemical Co., Ltd. . When the inkjet ink contains a thermal reactivity tree 曰 (D) of 0.1 wt% / 〇 30 30 Å / 〇, the chemical resistance of the cured film of the obtained ink becomes high, so it is preferable to contain Further, the thermally reactive resin (D) of 〇5 wt〇/❶~25 is more preferably further contained in the heat-reactive resin (D) of 1 wt% to 2 Å. 15 flame retardant (E) 24 201016799

^iy4^piT 為了對喷墨用墨水賦予阻燃性，而可含有阻燃劑 (E)。該阻燃劑（E)中磷系化合物對環境造成的影響較少，故較好。構系化合物的阻燃劑（E )的具體例可列舉：鱗酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、磷酸甲苯基苯酯、填酸2-乙基己基二苯酯、9，1〇_二氫_9_氛雜_1〇_磷雜菲 -10-氧化物、10-(2,5-二羥基苯基)_ι〇Η_9_氧雜·ι〇_磷雜菲 ❹ -10-氧化物、縮合9，10-二氫-9-氧雜_ι〇_磷雜菲_ι〇_氧化物等。這些阻燃劑中’若使用以下述式（e-Ι)所表示的化合物即縮合9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物（昭和高分子股份有限公司製造的HFA-3003(商品名）），則即便於將由喷墨用墨水所得的硬化膜曝露於高溫狀態下的情形下，亦不會有隊燃劑的滲出（bleed out) ’故較好。^iy4^piT A flame retardant (E) may be contained in order to impart flame retardancy to the ink for inkjet. The phosphorus-based compound in the flame retardant (E) has less influence on the environment, and is therefore preferred. Specific examples of the flame retardant (E) of the structural compound include triphenyl phthalate, tricresyl phosphate, tris(xylylene) phosphate, tolylphenyl phosphate, and 2-ethylhexyl diphenyl acid. Ester, 9,1〇_dihydro_9_azepine_1〇_phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)_ι〇Η_9_oxa·ι〇_phosphine Phenanthrenequinone -10-oxide, condensed 9,10-dihydro-9-oxa-am〇_phosphonium phenanthrene_oxide. Among these flame retardants, 'the compound represented by the following formula (e-Ι) is a condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Showa Polymer Co., Ltd. HFA-3003 (trade name) manufactured by the company, even if the cured film obtained from the inkjet ink is exposed to a high temperature state, there is no bleed out of the group fuel. .

25 20101679925 201016799

—u (e-1) (CH2)2—u (e-1) (CH2)2

阻燃劑（E)可為選自上述化合物的丨種化合物另外亦可為這些化合物的大於等於2種的混合物。若於噴墨用墨水中含l〇wt%〜50wt〇/〇的阻燃劑（E)，則由噴墨用墨水所得的硬化膜表現出較高的阻燃性（相當於ul (Underwriter Laboratories)燃燒試驗法 v_〇標準田），、因此較好。 1-6多官能（甲基)丙烯酸酯（f) 就提高光敏感度的觀點而言，可於喷墨用墨水能（曱基）丙烯酸酯（F)，尤其是若為不具有羥基二夕官能（甲基）丙烯酸酯則較好。此處，即便於不具^二多官能（甲基)丙烯酸g旨中含有製造時所混人的 :、的、或作為未反應物的具有羥基的多官能（曱美醋’上述情形下的含量亦極少，故仍可看作不^烯峻、,趣基的 26 201016799 J 1 jpil 多官能（曱基)丙烯酸酯（F)。多官能（甲基)丙烯酸酯（F) 可為選自以下所列舉的化合物的1種化合物，另外，亦可為這些化合物的大於等於2種的混合物。不具有經基的多官能（曱基)丙烯酸酯（F)的具體例可列舉：乙二醇二（甲基)丙烯酸酯、二乙二醇二（甲基)丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、丙二醇二（甲基）丙烯酸參酯、二丙二醇二（曱基）丙烯酸酯、三丙二醇二（甲基）丙烯酸酯、四丙二醇二（甲基)丙烯酸酯、聚丙二醇二（甲基)丙烯酸酯、雙酚A型環氧乙烷改質二（甲基）丙烯酸酯、雙酚F型環氧乙烷改質二（曱基）丙烯酸酯、三羥曱基丙烷三（曱基）丙烯酸酯、環氧乙烷改質三羥甲基丙烷三（曱基）丙烯酸酯、環氧丙烷改質三羥甲基丙烷三（甲基）丙烯酸酯、二(三羥甲基丙烷)四（甲基）丙烯酸酯、甘油三（曱基）丙烯酸酯、 1，6-己二醇二（曱基)丙烯酸酯、甲氧基化二（甲基)丙烯酸環 =酯、新戊二醇二（甲基)丙烯酸酯、二甘油四（曱基)丙烯酸酉曰、季戊四醇四（甲基）丙烯酸酯、二季戊四酵六（曱基)丙烯酸醋、己内S旨改質二季戊四醇六（甲基)丙稀酸醋、M_ 丁二醇二(曱基)丙烯酸醋、以丁二醇二(甲基)丙稀酸醋、二（甲基)丙烯酸二環戊醋、三[(曱基)丙稀酿氧基乙基]異三聚氮曰、及己内酯改質三曱基)丙烯醯氧基乙基]異三聚氰酸曰盼酸月漆型環氧丙烯酸S旨、雙紛a型環氧丙烯酸醋、雙紛I型環氧丙婦酸g旨、間苯二㈣環氧丙_酸醋等。這些多官能（甲基)丙稀酸酯中，若含有選自雙盼F型 27 201016799 3W：>pit 環氧乙院改質二（曱基）丙烯酸酯、季戊四醇四丙稀酸酯、一季戊四醇六丙烯酸酯、己内酯改質二季戊四醇六（曱基) 丙烯酸酯、三[(甲基)丙烯醯氧基乙基]異三聚氰酸酯、及己内酯改質三[(甲基)丙烯醯氧基乙基]異三聚氰酸酯、雙酚F 型環氧丙烯酸酯的大於等於1種，則硬化膜的耐化學藥品性變高，因此更好。於雙酚F型環氧丙烯酸酯中，市售有日本化藥股份有限公司製造的ZFR 1122、1401H、1491H(商品名），Japan U-pica股份有限公司製造的NE0P0L 8477 (商品名）等。若於喷墨用墨水中含有5 wt%〜80 wt%的多官能（甲基)丙烯酸酯（F)’則於製成喷墨用墨水的情形時，對光成尚感光度，另外，硬化膜的鑛敷液耐性變高，故較好，若多官能（曱基)丙烯酸酯（F)的含量為i〇wt〇/^〜7〇wt〇/。，則更好。 1.7其他成分為了提咼保存穩定性、或所形成的膜的耐久性、所形成的膜的膜面均勻性、所形成的膜的阻燃性、墨水的噴出特性、墨水的塗佈性等，噴墨用墨水可含有溶劑、反應性稀釋劑、聚合抑制劑、界面活性劑、著色劑、抗靜電劑等。這些成分可為1種化合物’亦可為大於等於2種化合物的混合物。另外，喷墨用墨水中的水分量並無特別限定，較好的是小於等於1_0 ppm ’更好的是小於等於5，_解。若為這些水分量，則喷墨用墨水_度變化較少，且保存 28 201016799The flame retardant (E) may be a ruthenium compound selected from the above compounds or a mixture of two or more of these compounds. If the inkjet ink contains 1% by weight to 50% by weight of the flame retardant (E), the cured film obtained from the inkjet ink exhibits high flame retardancy (equivalent to ul (Underwriter Laboratories) ) The combustion test method v_〇 standard field), so it is better. 1-6 polyfunctional (meth) acrylate (f) In terms of improving light sensitivity, it can be used in inkjet inks (fluorenyl) acrylate (F), especially if it has no hydroxy erbium function (Meth) acrylate is preferred. Here, even in the case where the non-difunctional (meth)acrylic acid g is contained, the polyfunctional (combined vinegar) having a hydroxyl group which is mixed at the time of production or as an unreacted product is contained in the above case. It is also rare, so it can still be regarded as a non-olefinic, funky 26 201016799 J 1 jpil polyfunctional (fluorenyl) acrylate (F). The polyfunctional (meth) acrylate (F) can be selected from the following The compound of the above-mentioned compound may be a mixture of two or more of these compounds. Specific examples of the polyfunctional (fluorenyl) acrylate (F) having no trans group may be exemplified by ethylene glycol. (Meth)acrylate, diethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(a) Acrylate, propylene glycol di(meth) acrylate, dipropylene glycol di(decyl) acrylate, tripropylene glycol di(meth) acrylate, tetrapropylene glycol di(meth) acrylate, polypropylene glycol di(a) Acrylate, bisphenol A type ethylene oxide modified II Acrylate, bisphenol F-type ethylene oxide modified bis(indenyl) acrylate, trishydroxypropyl propane tris(indenyl) acrylate, ethylene oxide modified trimethylolpropane tris(fluorenyl) Acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, glycerol tris(meth)acrylate, 1,6 - hexanediol di(decyl) acrylate, methoxylated di(meth)acrylic acid ring = ester, neopentyl glycol di(meth) acrylate, diglyceryl tetrakis(meth) ruthenium phthalate, pentaerythritol Tetrakis (meth) acrylate, dipentaerythra hexahydrate (mercapto) acryl vinegar, hexene succinate, dipentaerythritol hexa(methyl) acrylate vinegar, M-butanediol bis(indenyl) acrylate vinegar, Modified with butanediol di(meth)acrylic acid vinegar, di(pentameth)acrylic acid dicyclopentanacetic acid, tris[(indenyl)propyl oxyethyl]isotriazole, and caprolactone曱三曱) propylene methoxyethyl] isopropyl cyanuric acid lacquer type epoxy acrylate S, double a type epoxy acrylate vinegar, double sulphide type I epoxy glycerol , Isophthalic iv epoxypropyl _ vinegar and the like. Among these polyfunctional (meth) acrylates, if it contains a compound selected from the group consisting of double-prepared F type 27 201016799 3W: > pit epoxy epoxide modified bis(indenyl) acrylate, pentaerythritol tetrapropyl acrylate, Pentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexa(indenyl) acrylate, tris[(methyl)acryloxyethyl)isocyanate, and caprolactone modified three [(A) When one or more of the propylene oxyethylidene]isophthalocyanate and the bisphenol F-type epoxy acrylate are used, the chemical resistance of the cured film becomes high, which is preferable. Among the bisphenol F-type epoxy acrylates, ZFR 1122, 1401H, 1491H (trade name) manufactured by Nippon Chemical Co., Ltd., and NE0P0L 8477 (trade name) manufactured by Japan U-pica Co., Ltd., and the like are commercially available. When the inkjet ink contains 5 wt% to 80 wt% of a polyfunctional (meth)acrylate (F)', when it is used in an inkjet ink, sensitivity to light is formed, and hardening is performed. The mineralizing solution of the film becomes high in resistance, so it is preferred if the content of the polyfunctional (fluorenyl) acrylate (F) is i〇wt〇/^~7〇wt〇/. , it is better. 1.7 Other components In order to improve the storage stability, the durability of the formed film, the film surface uniformity of the formed film, the flame retardancy of the formed film, the discharge characteristics of the ink, and the coatability of the ink, etc., The ink for inkjet may contain a solvent, a reactive diluent, a polymerization inhibitor, a surfactant, a colorant, an antistatic agent, and the like. These components may be one compound' or a mixture of two or more compounds. Further, the amount of water in the ink for inkjet is not particularly limited, but is preferably 1_0 ppm or less, more preferably 5 or less. If it is these moisture content, the inkjet ink _ degree changes less, and saves 28 201016799

Jiy4^pit 穩定性優異，故較好。 1.7.1溶劑⑹ 為了提高墨水的喷出特性，喷墨用墨水可含有溶劑 (G)。該溶劑較好的是沸點大於等於100°C的溶劑。於室温下的喷墨用墨水的黏度大於等於50 mPa‘s的情形時，較好的是提高喷射溫度，於該情形下，所含的溶劑的沸點較好的是大於等於200°C。 ©沸點大於等於100°C的溶劑的具體例可列舉：乙酸丁酯、丙酸丁酯、乳酸乙酯、羥基乙酸曱酯、羥基乙酸乙酯、羥基乙酸丁酯、曱氧基乙酸曱酯、甲氧基乙酸乙酯、曱氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-羥基丙酸曱酯、3-羥基丙酸乙酯、3-甲氧基丙酸曱酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸曱酯、3-乙氧基丙酸乙酯、2-羥基丙酸曱酯、2-羥基丙酸乙酯、2-羥基丙酸丙酯、2-曱 • 氧基丙酸曱酯、2-曱氧基丙酸乙酯、2-甲氧基丙酸丙酯、 2-乙氧基丙酸曱酯、2-乙氧基丙酸乙酯、2-羥基-2-曱基丙 Ο 酸曱酯、2-羥基-2-甲基丙酸乙酯、2-曱氧基-2-曱基丙酸曱酯、2-乙氧基-2-曱基丙酸乙酯、丙酮酸曱酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸曱酯、乙醯乙酸乙酯、2-側氧丁酸曱酯、2-側氧丁酸乙酯、二氧陸圜（dioxane )、乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,4-丁二醇、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇單曱基醚、丙二醇單曱基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、二丙二醇單曱基醚乙酸酯、二丙 29 201016799 iiy4!)pit 二醇單乙基醚乙酸酯、二丙二醇單丁基醚乙酸酯、乙單丁基醚乙酸酯、環己酮、環戊酮、二乙二醇單甲基醚、二乙二醇單曱基醚乙酸酯、二乙二醇單乙基醚、二乙二醇單乙基謎乙酸醋、二乙二醇單丁基喊、二乙二醇單丁美醚乙酸酯、二乙二醇二曱基醚、二乙二醇二乙基醚、二^二醇曱基乙基醚、甲笨、二甲苯、苯㈣、r丁内醋、^_ 二曱基乙醯胺、Ν·甲基_2_料咬酮、二f基_嗤㈣ (dimethyl imidaZ〇lidinone)。這些溶劑中的水分量較理相的是以喷卵墨水中的水分量成為上述範圍的方式進行g ⑩ 整。 β 這些溶劑中’若使用二丙二醇單甲基謎乙酸醋、二醇單乙基醚乙酸醋、二丙二醇單丁基喊乙酸醋、丙二單曱細乙酸醋、丙二醇單乙細乙酸醋、3_甲氧基丙酸甲醋、3·乙氧基丙酸乙酯、二乙二醇單乙細乙酸醋、二乙二醇單丁基醚乙酸酯、二乙二醇二甲基醚、二乙 · 基乙基_等’則墨水的喷出穩定，故較好。若於喷墨用墨水中含有〇wt%〜5〇加％的溶劑，則製成光硬化性喷墨用墨水的情形時的噴出穩定，好，更好的是0 wt%〜20 wt%。而且’由於墨水的表面張力會對喷墨用墨水的塗佈性產生較大影響’因此較好的是將墨水的表面張力調整為2〇 mN/m〜45 mN/m，更好的是調整為”她〜仏_/m，進而好的是調整為30mN/m〜4〇mN/m。若表面張力為2〇 mN/m〜4 5 mN/m的範圍’則墨水噴出口的墨水彎液面（址 30 201016799 meniscus)變得穩定，並且墨水的噴出變得良好。為將表面張力調整為20mN/m〜45 mN/m的範圍，重要的是溶劑選擇。可使用表面張力處於2〇 mN/m〜45 mN/m的範圍的1種溶劑，若混合使用表面張力較大的溶劑（例如r -丁内酯：43 mN/m)及表面張力較小的溶劑（例如二乙二醇甲基乙基醚：24 mN/m、或乙二醇單丁基醚： 32 mN/m)，則能以溶劑組成對表面張力進行微調整，故較好。 ❹ 1.7.2反應性稀釋劑（H) 為了調整墨水的黏度或控制硬化膜的交聯度，嘴墨用墨水可含有反應性稀釋劑（H)。若使用反應性稀釋劑（η) 替代溶劑或置換溶劑的一部分，則墨水的固體成分濃度變同，故可形成厚膜。反應性稀釋劑（H)表示與含有大於等於5員環的環狀醚的自由基聚合性單體（a)、具有熱反應性官能基的自由基聚合性單體（B)、多官能（曱基)丙烯 " 酸醋（F)不同的化合物。 ® 反應性稀釋劑（H)的具體例可列舉：（甲基）丙稀酸正丁酯、（曱基）丙烯酸硬脂酯、（曱基)丙烯酸月桂酯、（甲基)丙烯酸異癸醋、（甲基）丙烯酸十三烧g旨、（曱基）丙稀酸 -2-(2-乙氧基乙氧基）乙醋、（甲基)丙烯酸環己g旨、（曱基)丙烯酸異冰片酯、丙烯酸-2-苯氧基乙酯等。這些反應性稀釋劑中’（曱基）丙烯酸正丁酯、（甲基) 丙烯酸環己酯藉由使用較少的量，便可較大地降低噴墨用墨水的黏度，故較好。 31 201016799 Jiy45pil 若於嗔墨用墨水中含有5 wt%〜⑹wt%的反應性稀釋劑H) ’則於製成光硬化性噴墨用墨水的情形時，利用E 型黏度計所败的坑下的黏度成為 2 mPa.s〜500 mPa. s的範圍，故較好，更好的是1〇wt%〜5〇wt%。 H3聚合抑制劑（I) 為了提高保存穩定性’喷墨用墨水可含有聚合抑制劑。聚合抑制劑的具體例可列舉4甲氧基苯酚、對苯二酚〇iydr0quinone)、紛噻嗪（phen〇thiazine)等這些聚合抑制劑中，就使喷射時加熱嘴墨喷頭的情形下的墨水轉 © 度變化為最小的觀點而言，較好的是使用盼嗟嗪作為聚合抑制劑。就使喷墨用墨水的保存穩定性與對光的高感光度性並存的觀點而言，較好的是於噴墨用墨水中含有⑶lwt% 〜1 wt%的聚合抑制劑。 1.7.4界面活性劑⑴ 為了提咼由喷墨用墨水所得的膜面的均勻性，噴墨用墨水可含有界面活性劑。界面活性劑可使用矽（siHc〇n) ❿ 系界面活性劑、丙烯酸系界面活性劑、及氟系界面活性劑等。具體可列舉：Byk-300、Byk-306、Byk-335、Byk-310、Jiy4^pit is excellent in stability, so it is better. 1.7.1 Solvent (6) In order to improve the discharge characteristics of the ink, the ink for inkjet may contain a solvent (G). The solvent is preferably a solvent having a boiling point of 100 ° C or higher. When the viscosity of the ink for ink jet at room temperature is 50 mPa or more, it is preferable to increase the ejection temperature. In this case, the boiling point of the solvent contained is preferably 200 ° C or more. Specific examples of the solvent having a boiling point of 100 ° C or more include butyl acetate, butyl propionate, ethyl lactate, decyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, decyl decyl acetate, Ethyl methoxyacetate, butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, decyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-methoxypropane Hydrate ester, ethyl 3-methoxypropionate, decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, Propyl 2-hydroxypropionate, decyl 2-oxoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, decyl 2-ethoxypropionate, 2 -ethyl ethoxypropionate, decyl 2-hydroxy-2-mercaptopropionate, ethyl 2-hydroxy-2-methylpropionate, decyl 2-methoxy-2-mercaptopropionate Ethyl 2-ethoxy-2-mercaptopropionate, decyl pyruvate, ethyl pyruvate, propyl pyruvate, decyl acetate, ethyl acetate, bismuth 2-oxobutanoate Ester, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monodecyl ether, propylene glycol monodecyl ether acetate, propylene glycol single Ethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monodecyl ether acetate, dipropylene 29 201016799 iiy4!) pit diol monoethyl ether acetate, dipropylene glycol monobutyl ether Acetate, ethylene monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monodecyl ether acetate, diethylene glycol monoethyl ether , diethylene glycol monoethyl acetal acetate, diethylene glycol monobutyl sulphate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , di-glycol decyl ethyl ether, methyl benzene, xylene, benzene (tetra), r butyl vinegar, ^ dimethyl acetamide, hydrazine methyl _2 ketone, bis ke ketone (iv) (dimethyl imidaZ〇lidinone). The amount of water in these solvents is relatively uniform in such a manner that the amount of water in the sprayed ink reaches the above range. β In these solvents, use dipropylene glycol monomethyl mycoacetic acid vinegar, diol monoethyl ether acetate vinegar, dipropylene glycol monobutyl ketone acetic acid vinegar, propylene dimethoate acetic acid vinegar, propylene glycol monoethyl acetate vinegar, 3 _Methoxypropionic acid methyl vinegar, 3 · ethoxy propionate ethyl ester, diethylene glycol monoethyl acetate vinegar, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, It is preferable that the ejection of the ink is stable, such as diethylidyl ethyl _ et al. When the ink for inkjet ink contains 5% by weight to 5% by weight of the solvent, the discharge is stable in the case of producing a photocurable inkjet ink, and more preferably 0 wt% to 20 wt%. Moreover, 'because the surface tension of the ink has a large influence on the coatability of the ink for inkjet ink', it is preferable to adjust the surface tension of the ink to 2 〇 mN/m to 45 mN/m, and more preferably to adjust It is "she ~ 仏 _ / m, and further preferably adjusted to 30 mN / m ~ 4 〇 mN / m. If the surface tension is in the range of 2 〇 mN / m ~ 4 5 mN / m ' then the ink jet of the ink jet The liquid level (address 30 201016799 meniscus) becomes stable and the ejection of the ink becomes good. To adjust the surface tension to the range of 20 mN/m to 45 mN/m, it is important to select the solvent. The surface tension can be used at 2〇. a solvent having a range of mN/m to 45 mN/m, if a solvent having a large surface tension (for example, r-butyrolactone: 43 mN/m) and a solvent having a small surface tension (for example, diethylene glycol) Methyl ethyl ether: 24 mN/m, or ethylene glycol monobutyl ether: 32 mN/m), it is better to finely adjust the surface tension with solvent composition. ❹ 1.7.2 Reactive diluent (H) In order to adjust the viscosity of the ink or to control the degree of crosslinking of the cured film, the ink for the nozzle ink may contain a reactive diluent (H). If reactive dilution is used. (η) In place of a part of the solvent or the replacement solvent, the solid content of the ink becomes the same, so that a thick film can be formed. The reactive diluent (H) represents a radical polymerizable property with a cyclic ether having a ring of 5 or more members. Monomer (a), a radically polymerizable monomer having a thermally reactive functional group (B), a polyfunctional (fluorenyl) propylene " vinegar (F) different compound. ® Reactive diluent (H) Specific examples thereof include (meth) n-butyl acrylate, stearyl (decyl) acrylate, lauryl (meth) acrylate, isophthalic acid (meth) acrylate, and tridecyl (meth) acrylate. g, (mercapto) acrylic acid-2-(2-ethoxyethoxy) ethyl acetonate, (meth)acrylic acid cyclohexyl, (fluorenyl) isobornyl acrylate, acrylic acid-2-benzene Ethyl ethoxide, etc. In these reactive diluents, n-butyl (meth) acrylate and cyclohexyl (meth) acrylate can greatly reduce the viscosity of the ink for inkjet by using a small amount. Therefore, it is better. 31 201016799 Jiy45pil If the ink used in the ink contains 5 wt% ~ (6) wt% of reactive diluent H) ' When the photocurable inkjet ink is used, the viscosity under the pit which is lost by the E-type viscometer is in the range of 2 mPa·s to 500 mPa·s, so it is better, and more preferably 1 〇wt. %〜5〇wt% H3 polymerization inhibitor (I) In order to improve storage stability, the inkjet ink may contain a polymerization inhibitor. Specific examples of the polymerization inhibitor include 4-methoxyphenol and hydroquinone 〇iydr0quinone. Among these polymerization inhibitors such as phenazine and phenazine thiazine, it is preferred to use the prostaglandin from the viewpoint of minimizing the change in the degree of change in the ink in the case of the nozzle nozzle during the ejection. As a polymerization inhibitor. From the viewpoint of coexisting the storage stability of the ink for inkjet and the high sensitivity to light, it is preferred that the inkjet ink contains (3) 1% by weight to 1% by weight of a polymerization inhibitor. 1.7.4 Surfactant (1) In order to improve the uniformity of the film surface obtained from the inkjet ink, the inkjet ink may contain a surfactant. As the surfactant, a cerium (siHc〇n) lanthanum surfactant, an acrylic surfactant, a fluorine-based surfactant, or the like can be used. Specific examples include: Byk-300, Byk-306, Byk-335, Byk-310,

Byk-341、Byk-344、或 Byk-370(分別為商品名;Byk_chemie 股份有限公司製造）等矽系界面活性劑；Byk_354、Byk-341, Byk-344, or Byk-370 (commercial name; manufactured by Byk_chemie Co., Ltd.) and other lanthanide surfactants; Byk_354,

Byk-358、或Byk_361 (分別為商品名；Byk Chemie股份有限公司製造）4丙烯酸系界面活性劑；DFX_18、Ftergent 250、或Ftergent251 (分別為商品名；Ne〇s股份有限公司 32 201016799 31945pit 製造），Megafac F_410、Megafac F_443、他科趾 F 445、Byk-358, or Byk_361 (trade name; manufactured by Byk Chemie Co., Ltd.) 4 acrylic surfactant; DFX_18, Ftergent 250, or Ftergent 251 (trade name respectively; Ne〇s Co., Ltd. 32 201016799 31945pit) , Megafac F_410, Megafac F_443, and other toe F 445,

Megafac F-470、Megafac F-479、Megafac F-483、Megafac F-489 (为別為商品名；Dainipp〇n Ink股份有限公司製造）等氟系界面活性劑。A fluorine-based surfactant such as Megafac F-470, Megafac F-479, Megafac F-483, Megafac F-489 (trade name: manufactured by Dainipp〇n Ink Co., Ltd.).

若於熱硬化性組成物中含有大於等於〇〇1 wt%的界面活性劑，則硬化膜的膜面均勻性提高，故較好，若考慮到與其他特性的平衡，則較好的是〇〇1 wt%〜i wt%。 1.7.5著色劑（κ) 喷墨用墨水可含有著色劑，此時，例如於檢查所得的硬化膜的狀料可容易地與基板制。於嘴㈣墨水中可含有0.01 wt%〜1〇 wt%左右的著色劑，較好岐含有邊〜5感左右的著色劑。就墨水原料的相容性的觀點而言’著色劑較好的是染料。 1.7.6抗靜電劑（L) 抗靜電劑並無特別限定，可使用公知的抗靜體可列舉：氧化錫、氧化錫.氧化銻複合氧化物、錫氧化銦複合氧化物等金屬氧化物，或四級銨（amm〇nium; 鹽等。抗靜電劑是用以防止帶電的’較好岐相對）用墨水100重量份而添加使用〇.〇1重量份〜1重量份。 1.8喷墨用墨水的製備方法里刀。細墨水較好的是藉由對現合必需成膜液進行過_調整。於_、中’例如可使用氟樹脂製^ 過滤器（membrane filter)等。 1.9喷墨用墨水的黏度 33 201016799 3iy4^pit 若噴墨用墨水利用E型黏度計所測定的25。(：下的黏度為2mPa.s〜500mPa.s，則自喷墨喷頭的塗佈特性（喷射精度等）變得良好，因此較好。25。(：下的喷墨用墨水的黏度更好的是3 mPa.s〜300 mPa.s，進而好的是5 mPa.s 〜200 mPa· s 〇於25 C下的黏度超過3〇 mPa. s的情形時，若加熱喷墨喷頭而降低噴出時的黏度，則可實現更加穩定地喷出。於加熱噴墨嘴頭進行喷射的情形時，加熱溫度（較好的是 40C〜120°C )下的噴墨用墨水的黏度較好的是3 mPa.s 〜 30 mIVs ’若噴墨用墨水的黏度為5 mPa.s〜25 mPa.s，則更好’尤其好的是7 mPa.s〜2〇 mpa.s。喷墨用墨水的保存喷墨用墨水若於-2(TC〜2(TC下進行保存，則黏度變化較小，且保存穩定性良好。 2·藉由喷墨方法的喷墨用墨水的塗佈本發明的喷墨用墨水可使用公知的噴墨塗佈方法進 "Γ亍塗佈噴墨塗佈方法例如有：將機械能（mechanical energy)作用於墨水，而使墨水自喷頭喷出（塗佈）的方法（所明壓電方式（piez〇));以及將熱能作用於墨水而塗佈墨水的塗佈方法（所謂氣泡喷射（bubble-jet)(註冊商標）方式）等。 j v胃 # —藉由使用喷墨塗佈方法，可將喷墨用墨水塗佈成預先〇又疋的圖案狀。藉此，可僅於需要的部位塗佈墨水，與光微影法相比，可降低成本。 201016799 你^使用本發明的噴墨用墨水進行塗佈時較好的塗 ===?舉:包含，些墨水的墨水收、塗佈單元。塗佈單元例如可列舉：使與生對應的熱能作用於墨水，並藉由上述能量而產生墨水液滴的塗佈單元。 ❿ 熱部頭具或金屬氧化物的發具㈣i 赁述金屬及/或金屬氧化物的叙（AD等金HM(Ta)、錯㈤、钦（Ti)、錄（Ni)、〕等金屬、及這些金屬的氧化物等。置例明用墨水進行塗料較好的塗佈裝二裝置的固定部位，經由墨水供給構件例如管^ 而向塗钸喷頭供給墨水的形態。） 2外，喷墨时出（㈣）溫餘好的是阶〜 3〇时2溫度下时墨用墨柄減較好岐3时a.s〜 3.硬化膜的形成本發明的硬化膜可使用公知的喷墨塗佈方法，將上述 35 201016799When the thermosetting composition contains a surfactant of 大于1 wt% or more, the uniformity of the film surface of the cured film is improved, so that it is preferable to consider the balance with other characteristics. 〇1 wt%~i wt%. 1.7.5 Colorant (κ) The ink for inkjet may contain a coloring agent. In this case, for example, the material of the obtained cured film can be easily made into a substrate. The ink may be contained in the ink of the mouth (four) in an amount of about 0.01 wt% to about 1% by weight, and preferably contains a coloring agent of about 5% to about 5%. From the viewpoint of the compatibility of the ink raw material, the coloring agent is preferably a dye. 1.7.6 Antistatic agent (L) The antistatic agent is not particularly limited, and a known antistatic agent may be a metal oxide such as tin oxide, tin oxide, cerium oxide composite oxide or tin indium oxide composite oxide. Or a quaternary ammonium (amm〇nium; a salt, etc.. The antistatic agent is used to prevent charging.) It is used in an amount of 100 parts by weight of the ink, and 1 part by weight to 1 part by weight. 1.8 Preparation method of ink for inkjet. Fine ink is preferably adjusted by the necessary film forming solution. For example, a fluororesin filter or the like can be used. 1.9 Viscosity of ink for inkjet 33 201016799 3iy4^pit If the ink for inkjet is 25 measured by an E-type viscometer. (The viscosity of the lower ink is 2 mPa·s to 500 mPa·s, and the coating characteristics (ejection accuracy, etc.) from the ink jet head are good. Therefore, the viscosity of the inkjet ink is lower. Preferably, it is 3 mPa.s to 300 mPa.s, and further preferably 5 mPa.s to 200 mPa·s. When the viscosity at 25 C exceeds 3 〇 mPa·s, if the inkjet head is heated, When the viscosity at the time of ejection is lowered, a more stable discharge can be achieved. In the case of heating the ink jet head to eject, the ink of the ink jet at a heating temperature (preferably 40 C to 120 ° C) has a good viscosity. It is 3 mPa.s ~ 30 mIVs 'If the viscosity of inkjet ink is 5 mPa.s~25 mPa.s, then it is better', especially 7 mPa.s~2〇mpa.s. When the ink is stored at -2 (TC~2 (TC), the viscosity change is small and the storage stability is good. 2. The inkjet ink by the inkjet method is coated with the present invention. The inkjet ink can be sprayed by a known inkjet coating method. For example, the inkjet coating method is applied to: mechanical energy is applied to the ink, and the ink is self-sprayed. a method of ejecting (coating) a head (a piezoelectric method (piez)); and a coating method of applying ink by applying thermal energy to an ink (so-called bubble-jet (registered trademark) method) Jv stomach #— By using an inkjet coating method, the ink for inkjet can be applied in a pre-twisted pattern, whereby the ink can be applied only at a desired portion, and the photolithography method is used. In comparison, the cost can be reduced. 201016799 You can use the inkjet ink of the present invention to apply a better coating. ===: It includes an ink collecting and coating unit for some inks. A coating unit that generates thermal ink corresponding to the ink and generates ink droplets by the above energy. ❿ Hot head or metal oxide hair (4) i cites the metal and/or metal oxide Metals such as AD such as HM (Ta), er(5), chin (Ti), and (Ni), and oxides of these metals, etc. The use of inks for the coating of coatings is better. a portion that supplies ink to the coating nozzle via an ink supply member such as a tube State.) 2, when the ink is ejected ((4)) the temperature is good is the order ~ 3 〇 when the temperature is lower than 2 when the ink stalk is better 岐 3 as~ 3. The formation of the cured film The cured film of the present invention A well-known inkjet coating method can be used, which will be the above 35 201016799

Jiy4i5pit 喷墨用墨水噴出至基板表面後，對墨水照射紫外線或可見光線等光而獲得。經光照射的部分的墨水藉由自由基聚合性單體’例如（甲基）丙烯酸系單體的聚合而成為立體化交聯體而硬化’從而有效地抑制墨水的擴散。因此，若使用上述噴墨用墨水’則可實現高精細的圖案的描繪。所照射的光的量依存於喷墨用墨水的組成，於使用紫外線作為照射的光的情形時，辦照射的紫外線的量是利用Ushio Denki 股份有限公司製造的安裝有受光器UVD_405PD的累計光量計UIT-201進行測定，較好的是1〇 mj/cm2〜ι，〇〇〇 mJ/cm左右’更好的是10 mJ/em2〜800 mJ/cm2左右，進而好的是20 mJ/cm2〜500 mJ/cm2左右。另外，所照射的紫外線的波長較好的是200 nm〜450 nm，更好的是220 nm 〜430 nm ’進而好的是250 nm〜400nm。另外’視需要可進一步對藉由光的照射而硬化的上述硬化膜進行加熱、煅燒，尤其好的是於12(TC〜25CTC下加熱10分鐘〜60分鐘，更好的是於Mot〜24〇。(：下加熱1〇分鐘〜60分鐘’進而好的是於i8〇〇c〜23〇°c下加熱分鐘〜60分鐘。本發明中所使用的基板若為可成為塗佈上述喷墨用墨水的對象的基板，則並無特別限定，其形狀並不限於平板狀，亦可為曲面狀。另外，基板的材質並無特別限定，例如可列舉：聚對苯二甲酸乙二酯（PET，polyethylene terephthalate )、聚對苯二甲酸丁二酯（PBT，polybutylene terephthalate)等聚 201016799The Jiy4i5pit inkjet ink is ejected onto the surface of the substrate, and is then obtained by irradiating the ink with ultraviolet light or visible light. The ink of the portion irradiated with light is hardened by the polymerization of a radical polymerizable monomer, for example, a (meth)acrylic monomer, to form a three-dimensional crosslinked body, thereby effectively suppressing the diffusion of the ink. Therefore, the use of the inkjet ink described above enables the drawing of a high-definition pattern. The amount of light to be irradiated depends on the composition of the ink for inkjet. When ultraviolet light is used as the light to be irradiated, the amount of ultraviolet light to be irradiated is an integrated light meter equipped with a light receiver UVD_405PD manufactured by Ushio Denki Co., Ltd. UIT-201 is measured, preferably 1 〇 mj / cm 2 ~ i, 〇〇〇 mJ / cm or so 'better 10 mJ / em 2 ~ 800 mJ / cm 2 or so, and preferably 20 mJ / cm 2 ~ 500 mJ/cm2 or so. Further, the wavelength of the ultraviolet light to be irradiated is preferably from 200 nm to 450 nm, more preferably from 220 nm to 430 nm and further preferably from 250 nm to 400 nm. Further, the above-mentioned cured film which is hardened by irradiation with light may be further heated and calcined as needed, and it is particularly preferably heated at 12 (TC to 25 CTC for 10 minutes to 60 minutes, more preferably at Mot to 24 Torr). (: heating for 1 minute to 60 minutes), and further preferably heating at i8〇〇c~23〇°c for ~60 minutes. The substrate used in the present invention can be used for coating the above inkjet. The substrate of the ink is not particularly limited, and the shape thereof is not limited to a flat plate shape, and may be a curved shape. The material of the substrate is not particularly limited, and examples thereof include polyethylene terephthalate (PET). ,polyethylene terephthalate ), polybutylene terephthalate (PBT), etc. 201016799

Jiy43pit 酯系樹脂，聚乙烯、聚丙烯等聚烯烴樹脂，聚氯乙烯、氟樹脂、丙烯酸系樹脂、聚醯胺、聚碳酸酯、聚醯亞胺等塑膠膜，賽珞玢（cellophane)、乙酸酯、金屬箔、聚醯亞胺與金屬猪的積層膜、具有填充效果的玻璃紙（glassine paper)、羊皮紙（parchment paper)、或者利用聚乙烯、黏土黏合劑、聚乙烯醇、澱粉、羧基曱基纖維素（， carboxymethyl cellulose)等進行填充處理的紙，玻璃等。 ❹ 構成基板的物質中，於不對本發明的效果產生不良影響的範圍内，可進一步含有顏料、染料、抗氧化劑、抗劣化劑、填充劑、紫外線吸收劑、抗靜電劑及/或防電磁波劑等添加劑。另外，亦可於基板表面的_部分形成與基板不同的材質。基板的用途亦無特別限定，由本發明的噴墨用墨水所得的硬化膜由於耐蝕刻液性、鍍敷液耐性、對鹼性水溶液的剝離性、及耐熱性優異，因此較好的是用於美翁表面具有金屬製電路的電子電路基板等。形成電路的^屬 ® 並無特職定’較好的是金、銀、銅、銘或氧化銦錫（IT0, Indium Tin Oxide )。基板的厚度並無特別限定，通常為1〇左右，根據所使用的目的而進行適當調整，較好的是15以 m〜500 /zm，更好的是2〇 "m〜2〇〇 "瓜。亦可視需要於基板的軸硬化上實施斥水處理、電暈（corona)處理、電漿（plasma)處理、嘴擊（處理等易黏接處理，或者於表面設置易黏接層或彩色滤光 37 201016799 3194^pit 片（color filter)用保護膜。另外’將喷墨用墨水僅塗佈於特定的部位，藉此可形成特定圖案的硬化膜’並可謀求降低用於形成硬化膜的成本。尤其是於電子電路基板中，於金屬配線圖案形成或鍍敷圖案形成、金屬配線保護膜（覆蓋層）形成中，可將噴出性、保存穩定性優異的本發明的喷墨用墨水僅塗佈於特定的電路部分，因此可有效地形成符合各目的之硬化膜。 [實施例] ' 以下，藉由實施例進一步對本發明進行說明，但本發 _ 明並不受這些實施例限定。另外，以下只要無特別規定，則「份」是指重量份。實驗例及比較例中所使用的各成分如下所述。含有大於等於5員環的環狀醚的自由基聚合性單體 (A) A1 :甲基丙烯酸四氫糠酯 (商品名「SR203」、Sartomer公司製造；5員環化合物） A2 :環狀三羥甲基丙烷縮曱醛丙烯酸醋 % (商品名「SR531」、Sartomer公司製造；6員環化人物）〇具有熱反應性官能基的自由基聚合性單體（B) B1 :曱基丙烯酸-2-羥基乙酯 B2 :鄰苯二甲酸單（甲基丙烯酸羥基乙酯） (商品名「CB-1」、新中村化學工業股份有限公司製 38 201016799 3194^ρΐ1 造） Β3 :丙烯酸_4-羥基丁酯光聚合起始劑（C ) ci : 2,4,6-三曱基苯甲醯基二苯基氧化膦 (商品名「DAROCUR ΤΡΟ」、Ciba Japan股份有限公司製造）熱反應性樹脂（D) D1 ·聚乙稀苯盼 (商品名「Maruka Lyncur MS-2P」、丸善石油化學股份有限公司製造） D2 .以上述式（d-Ι)所表示的化合物及其縮合物的混合物 (商品名「Nikalac MW-30」、Sanwa Chemical 股份有限公司製造）阻燃劑（E) E1 :縮合9，10-二氫-9-氧雜-10-鱗雜菲_10_氧化物 (商品名「HFA-3003」、昭和高分子股份有限公司製造）多官能（甲基)丙烯酸酯（F) F1 :雙酚F型環氧丙烯酸酯 (商品名「NEOPOL 8477」、Japan U_pica股份有限公司製造） F2 :雙酚F型環氧乙烷改質二丙烯酸酯 (商品名「M-208」、東亞合成股份有限公司製造） 39 201016799 3iy45pltJiy43pit ester resin, polyolefin resin such as polyethylene, polypropylene, plastic film such as polyvinyl chloride, fluororesin, acrylic resin, polyamide, polycarbonate, polyimine, cellophane, B Acidic acid, metal foil, laminated film of polyimine and metal pig, glasse paper with filling effect, parchment paper, or polyethylene, clay adhesive, polyvinyl alcohol, starch, carboxyl group Paper, glass, etc., which are subjected to filling treatment, such as carboxymethyl cellulose.物质 A substance constituting the substrate may further contain a pigment, a dye, an antioxidant, an anti-deterioration agent, a filler, an ultraviolet absorber, an antistatic agent, and/or an anti-electromagnetic wave agent within a range that does not adversely affect the effects of the present invention. And other additives. Further, a material different from the substrate may be formed on the _ portion of the surface of the substrate. The use of the substrate is not particularly limited, and the cured film obtained by the inkjet ink of the present invention is preferably used for etching liquid resistance, plating solution resistance, peelability to an alkaline aqueous solution, and heat resistance. An electronic circuit board or the like having a metal circuit on the surface of the Meg. There is no special job to form a circuit. ‘Better is gold, silver, copper, indium or indium tin oxide (IT0, Indium Tin Oxide). The thickness of the substrate is not particularly limited, but is usually about 1 Torr, and is appropriately adjusted depending on the purpose of use. Preferably, it is 15 m to 500 /zm, more preferably 2 〇"m~2〇〇&quot ;melon. It is also possible to perform water repellent treatment, corona treatment, plasma treatment, mouth impact (treatment, etc.) on the shaft hardening of the substrate, or to provide an easy adhesion layer or color filter on the surface. 37 201016799 3194^Pit protective film for color filter. In addition, 'the inkjet ink is applied only to a specific part, whereby a cured film of a specific pattern can be formed' and the cost for forming a cured film can be reduced. In particular, in the electronic circuit board, in the formation of a metal wiring pattern, a plating pattern, and a metal wiring protective film (cover layer), the inkjet ink of the present invention excellent in discharge property and storage stability can be coated only. It is disposed on a specific circuit portion, so that a cured film suitable for each purpose can be effectively formed. [Embodiment] Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited by these examples. Unless otherwise specified, the "parts" means parts by weight. The components used in the experimental examples and the comparative examples are as follows. The cyclic ether having a ring of 5 or more members is contained. From the base polymerizable monomer (A) A1: tetrahydrofurfuryl methacrylate (trade name "SR203", manufactured by Sartomer Co., Ltd.; 5-membered ring compound) A2: cyclic trimethylolpropane acetal acrylate vinegar % ( Trade name "SR531", manufactured by Sartomer Co., Ltd.; 6-membered cyclized person) 自由基 Radical polymerizable monomer having a heat-reactive functional group (B) B1: 2-hydroxyethyl methacrylate B2: phthalic acid Mono (hydroxyethyl methacrylate) (trade name "CB-1", manufactured by Shin-Nakamura Chemical Co., Ltd. 38 201016799 3194^ρΐ1) Β3: Acrylic _4-hydroxybutyl ester photopolymerization initiator (C) Ci : 2,4,6-trimercaptobenzylidene diphenylphosphine oxide (trade name "DAROCUR ΤΡΟ", manufactured by Ciba Japan Co., Ltd.) Thermally reactive resin (D) D1 · Polyethylene benzene ( The product name "Maruka Lyncur MS-2P", manufactured by Maruzen Petrochemical Co., Ltd.) D2. A mixture of the compound represented by the above formula (d-Ι) and its condensate (trade name "Nikalac MW-30", Sanwa Chemical Manufacturing Co., Ltd.) Flame Retardant (E) E1 : Condensation 9,10-Dihydro-9- Miscellaneous 10-scale phenanthrene _10_oxide (trade name "HFA-3003", manufactured by Showa Polymer Co., Ltd.) Polyfunctional (meth) acrylate (F) F1: bisphenol F type epoxy acrylate (trade name "NEOPOL 8477", manufactured by Japan U_pica Co., Ltd.) F2: bisphenol F-type ethylene oxide modified diacrylate (trade name "M-208", manufactured by Toagosei Co., Ltd.) 39 201016799 3iy45plt

反應性稀釋劑（Η) HI :曱基丙烯酸環己酯 H2 :甲基丙烯酸丁酯 (實驗例1〜2、比較例1〜3)Reactive diluent (Η) HI : cyclohexyl methacrylate H2 : butyl methacrylate (Experimental Examples 1 to 2, Comparative Examples 1 to 3)

於本實驗例中，對形成含有5員環化合物作為含有大於等於5員環的環狀醚的自由基聚合性單體（a)的本發明的噴墨用墨水的硬化膜，來用於抗蝕用途或抗鍍敷用途的情形進行驗證。以表1中所記載的比例（重量份）進行調配，並混合、溶解，利用氟樹脂製薄膜過濾器（0.2以 m)進行過滤，而製備各喷墨用墨水。另外’比較例1及2是主要對不含具有大於等於5員環的環狀醚的自由基聚合性單體（A)成分的情形進行驗證的例子，比較例3是主要對雖含（A)成分但不含熱反應性樹脂（D)成分的情形進行驗證的例子。 40 3 201016799 ^ly^Dpu ❹ [表i] 成分實驗例比較例 1 2 1 2 A1 400 200 — — B1 50 50 50 50 B2 150 150 150 150 ---- C1 100 100 100 100 D1 30 30 30 30 F1 150 150 150 150 H1 — 200 400 H2 100 100 100 500 1 I〇o^In the present experimental example, a cured film of the inkjet ink of the present invention containing a 5-membered ring compound as a radically polymerizable monomer (a) having a cyclic ether of 5 or more members is used for the anti-corrosion film. Verification for etch or anti-plating applications. The ratio (parts by weight) described in Table 1 was adjusted, mixed, dissolved, and filtered through a fluororesin membrane filter (0.2 m) to prepare each inkjet ink. Further, 'Comparative Examples 1 and 2 are examples in which the radical polymerizable monomer (A) component having no cyclic ether of 5 or more members is contained, and Comparative Example 3 is mainly composed of (A). An example in which the component does not contain the component of the thermally reactive resin (D). 40 3 201016799 ^ly^Dpu ❹ [Table i] Ingredient Experimental Example Comparative Example 1 2 1 2 A1 400 200 — — B1 50 50 50 50 B2 150 150 150 150 ---- C1 100 100 100 100 D1 30 30 30 30 F1 150 150 150 150 H1 — 200 400 H2 100 100 100 500 1 I〇o^

〜3的噴墨用墨水份塞嗪r妝^ 另外，於實驗例1〜2及比較例1 中，聚合抑制劑（I)是添加0.05重量～3 inkjet inks ketazine r makeup^ In addition, in Experimental Examples 1 to 2 and Comparative Example 1, the polymerization inhibitor (I) was added with 0.05 weight.

聚合抑制劑（I)以外的噴墨用墨水的總量設為1()Q 份)。重量 (1 )墨水的黏度、由保管所引起的黏度的變化利用E型黏度計（東機產業股份有限公司製造 ❷ VISCOMETER TV-22) ’對各噴墨用墨水於25。(：下的=声進行測定。將結果示於表2中。 ^ 另外’將各喷墨用墨水的一部分（10 g)加入至3〇n^ 的樣品瓶中’並蓋緊，於100°C下保管5小時。並且，調查保管後的墨水的黏度相對於保管前的墨水的黏度的變化率。墨水的黏度均於保管後增加，將變化率小於1〇%的情形判為「〇」，將大於等於10%的情形判為「X」。將結果示於表2中。可知’實驗例1〜2的喷墨用墨水的保存穩定性優異。 41 201016799 3iy45pii (2)噴射特性的評價中，使用10pl用的嘴頭，於喷心電壓）為16 V、嘴頭溫声兔7Λ。件下，觀窣喰屮㈣又為驅動頻率為5kHz的僻The total amount of the inkjet ink other than the polymerization inhibitor (I) is 1 () Q parts). (1) The viscosity of the ink and the viscosity of the ink were changed by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd. ❷ VISCOMETER TV-22). (The following = sound was measured. The results are shown in Table 2. ^ In addition 'Part of each inkjet ink (10 g) was added to the vial of 3〇n^' and tightly closed at 100° The storage rate of the ink after storage was compared with the viscosity of the ink before storage. The viscosity of the ink was increased after storage, and the rate of change was less than 1%. The case where the ratio is 10% or more is judged as "X". The results are shown in Table 2. It is understood that the inkjet inks of Experimental Examples 1 to 2 are excellent in storage stability. 41 201016799 3iy45pii (2) Evaluation of ejection characteristics In the case of using 10 pl, the mouth voltage is 16 V, and the mouth is warm and the rabbit is 7 Λ. Under the condition, Guanlan (4) is also a secluded driving frequency of 5 kHz.

出，並:將噴射時的液柱沿著垂直方向，生衛星點Satdlite)的情形判為「〇」 =與相鄰的液柱接觸或產生衛星點的情形 < 結果示於表2中。 (3 )武驗基板的製作將各喷墨用墨水注入至嘴墨g中，並將其裝著於嘴墨褒置（FUJIFILMDimatix公司製造的DMp_28〇〇)中，於And: the case where the liquid column at the time of spraying is in the vertical direction, the position of the satellite point Satdlite) is judged as "〇" = the case of contact with an adjacent liquid column or the generation of a satellite point < The results are shown in Table 2. (3) Production of the test substrate The ink for each inkjet was injected into the nozzle ink g, and it was placed in the nozzle ink set (DMp_28〇〇 manufactured by FUJIFILM Dimatix Co., Ltd.).

以下的基板製作齡下，藉㈣墨印錢（说㈣扣嫩、) 將各喷墨用墨水塗佈（赠）於基板上，接著，進行紫外線（UV ’ ultraviolet)硬化，而製作形成有硬化膜的試驗基板。使用以上述方式製作的試驗基板，對以下（4)〜（6) 所示的硬化膜對蝕刻液的耐性、對鹼性水溶液（剝離液）的剝離性、對鍍敷液的耐性進行調查。基板製作條件基板：將銅箔積層於聚醯亞胺上而成的基板（厚度為 35 /i m) [(東洋紡績股份有限公司製造）Vyloflex (商品名）] 硬化膜的膜厚：30 //m 喷出條件：與上述（2)相同的喷出條件 42 201016799 3iy4^pit UV 曝光量：250mJ/cm2 (4)硬化膜對蚀刻液的耐性的評價為了評價硬化膜對蝕刻液的耐性，而將所製作的試驗基板於50°C的13%FeCl3水溶液中浸潰15分鐘，然後進行水洗，並目視判定硬化膜的表面狀態。將未產生剝離或變色的情形判為「〇」’將產生剝離或變色的情形判為「X」。將結果示於表2中。 ® (5)硬化膜對鹼性水溶液（剝離液）的剝離性的評價為了評價硬化膜對鹼性水溶液（剝離液）的剝離性，而將所製作的試驗基板於50°C的8%NaOH水溶液中浸潰1 分鐘，然後進行水洗，並目視判定硬化膜的剝離狀態。將完全溶解或剝離的情形判為「〇」，將未溶解或剝離的情形判為「X」。將結果不於表2中。 (6)硬化膜對鍍敷液的耐性的評價 • 為了評價硬化膜對鍍敷液的耐性，而將所製作的試驗〇基板於60°c的非電解鍍鎳液（商品名：Nimden NPR-4、 Ni濃度為4.5 g/L、上村工業股份有限公司製造）中浸潰 20分鐘，進行水洗，接著將其於60°C的金打底（Gold Strike ) 魏敷液（商品名：Acid Strike、日本高純度化學股份有限公司製造）中浸潰10分鐘，進行水洗，接著將其於100¾ 的非電解鍍金液（商品名：Goblite TAM-55、Au濃度為i g/L、上村工業股份有限公司製造）中浸潰30分鐘，進行水洗，藉此形成鍍敷皮膜。將該步驟中未產生鍍敷液滲入 43 201016799 3iy4i)pii =膜内部或剝離的情形判為「〇」，將產生鑛敷液渗入硬化膜内部或剝離的情形判為「X」。將結果示於表2中。硬化膜的特性實驗例比較例The following substrates are produced under the age of (4) ink-printed money (say (four) buckled,) each inkjet ink is coated (given) on a substrate, followed by ultraviolet (UV 'ultraviolet) hardening, and the resulting hardened Test substrate for the membrane. Using the test substrate prepared as described above, the resistance of the cured film shown in the following (4) to (6) to the etching solution, the peeling property to the alkaline aqueous solution (peeling liquid), and the resistance to the plating solution were examined. Substrate production condition substrate: a substrate obtained by laminating a copper foil on a polyimide (thickness: 35 / im) [(made by Toyobo Co., Ltd.) Vyloflex (trade name)] Thickness of cured film: 30 // m discharge condition: the same discharge condition as the above (2) 42 201016799 3iy4^pit UV exposure amount: 250 mJ/cm 2 (4) Evaluation of the resistance of the cured film to the etching liquid In order to evaluate the resistance of the cured film to the etching liquid, The prepared test substrate was immersed in a 13% FeCl3 aqueous solution at 50 ° C for 15 minutes, and then washed with water, and the surface state of the cured film was visually judged. The case where peeling or discoloration did not occur was judged as "〇", and the case where peeling or discoloration occurred was judged as "X". The results are shown in Table 2. ® (5) Evaluation of the peeling property of the cured film to the alkaline aqueous solution (release liquid) In order to evaluate the peelability of the cured film to the alkaline aqueous solution (release liquid), the prepared test substrate was 8% NaOH at 50 ° C. The solution was immersed in the aqueous solution for 1 minute, then washed with water, and the peeling state of the cured film was visually judged. The case of completely dissolving or peeling was judged as "〇", and the case of not being dissolved or peeled was judged as "X". The results are not in Table 2. (6) Evaluation of the resistance of the cured film to the plating solution • In order to evaluate the resistance of the cured film to the plating solution, the prepared test substrate was subjected to an electroless nickel plating solution at 60 ° C (trade name: Nimden NPR- 4, Ni concentration of 4.5 g / L, manufactured by Shangcun Industrial Co., Ltd.), soaked for 20 minutes, washed with water, and then placed at 60 ° C gold (Gold Strike) Wei dressing liquid (trade name: Acid Strike , manufactured by Japan High Purity Chemical Co., Ltd.), immersed for 10 minutes, washed with water, and then applied to 1003⁄4 of electroless gold plating solution (trade name: Goblite TAM-55, Au concentration ig/L, Shangcun Industrial Co., Ltd. The film was immersed for 30 minutes and washed with water to form a plating film. In the step, the plating solution was not infiltrated into the film, and the inside of the film or the peeling was judged as "〇", and the case where the ore solution was infiltrated into the hardened film or peeled off was judged as "X". The results are shown in Table 2. Characteristics of cured film Experimental example Comparative example

(實驗例3〜4、比較例4〜6) 於^驗射，對形成本發_喷㈣墨水的硬來用於覆蓋層用途的情形進行驗證。例（重詈份）糾偷Γ 所記載的比膜過遽器⑽w進行 1^，、=’利_脂製薄另外，比關4及5是主要料含H用等墨水^ 環的環狀醚的自由基聚合性單f「，大於專於5貝證的例子，比較例ό是主要對成分的情形進行驗應性樹脂⑼成分的情形進行碰=子成分但不含熱反 201016799 3iy4^plt [表3] 成为實辱会例比較例 3 4 4 5 1 6 A1 40 10 — _ 40 B3 15 15 15 15 15 C1 8 8 8 8 8 D2 10 10 10 10 E1 40 40 40 40 40 F2 70 70 70 70 70 H1 — 30 40 — 一 H2 — 一 — 40 — 另外，於實驗例3〜4及比較例4〜6的噴墨用墨水中，聚合抑制劑（I)是添加0.05重量份的盼η塞唤（將除聚合抑制劑（I)以外的噴墨用墨水的總量設為1〇〇重量份）。 (1) 墨水的黏度、由保管所引起的黏度的變化利用Ε型黏度計測定各噴墨用墨水於25。(：下的黏度。將結果示於表4中。(Experimental Examples 3 to 4 and Comparative Examples 4 to 6) The test was carried out to verify the case where the ink of the present invention was used for the use of the cover layer. For example, the 膜 Γ Γ Γ 比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比比The free-radical polymerization of ether is a single f", which is larger than the example of the 5-boiler. The comparative example is mainly for the case of the component. The component of the test resin (9) is subjected to the touch-subcomponent but does not contain heat. 201016799 3iy4^ Plt [Table 3] becomes a humiliation example Comparative Example 3 4 4 5 1 6 A1 40 10 — _ 40 B3 15 15 15 15 15 C1 8 8 8 8 8 D2 10 10 10 10 E1 40 40 40 40 40 F2 70 70 Further, in the inkjet inks of Experimental Examples 3 to 4 and Comparative Examples 4 to 6, the polymerization inhibitor (I) was added with 0.05 part by weight of η. The total amount of the ink for inkjet other than the polymerization inhibitor (I) is 1 part by weight. (1) The viscosity of the ink and the change in viscosity due to storage are measured by a Ε-type viscometer. Each of the inkjet inks had a viscosity of 25. (the lower viscosity). The results are shown in Table 4.

另外，將各喷墨用墨水的一部分（1〇g)加入至3〇mL 的樣品瓶中，並蓋緊’於100°C下保管5小時。並且，調查保管後的墨水的黏度相對於保管前的墨水的黏度的變化率。墨水的黏度均於保管後增加，將變化率小於1〇%的情形判為「〇」，將大於等於1〇%的情形判為Γχ」。將結果斧於表4中。 ° 可知’實驗例3〜4的喷墨用墨水的保存穩定性優異。 (2) 噴射特性的評價 45 201016799 31945pif 將各喷墨用墨水注入至噴墨匡中，並將其裝著於嘴墨裝置（FUJIFILM Dimatix公司製造的DMp_28〇〇)中，使用10 pl用的喷頭，於喷出電壓（壓電電壓）為16v、喷頭溫度為WC、驅動頻率為5 kHz的條件下，觀察喷出的情況。將噴射時的液柱沿著垂直方向喷出，並且未產生衛星點的情形判為「〇」’將液柱與相鄰的液柱接觸、或產生衛星點的情形判為「X」。將結果示於表4中。 (3) 試驗基板的製作將各噴墨用墨水注入至喷墨匣中，並將其裝著於喷墨 © 裝置（FUJIFILM Dimatix公司製造的DMP_28〇〇)中，於以下的基板製作條件下，藉由噴墨印表機將各噴墨用墨水塗佈（描緣）於基板上’接著進行uv硬化及熱硬化，而製作形成有硬化膜的試驗基板。使用以上述方式製作的試驗基板’對以下（4)及（5)所示的硬化膜對鍍敷液的对性及焊錫耐熱性進行調查。 · 基板製作條件基板：將銅箔積層於聚醯亞胺上而成的基板（厚度為 ❹ 35 β m) [(東洋纺績股份有限公司製造）Vyloflex (商品名）] 硬化膜的膜厚：30 /zm 喷出條件：與上述（2)相同的喷出條件 UV 曝光量：40 mJ/cm2 熱硬化條件：19(TCx30分鐘 (4) 硬化獏對鍍敷液的耐性的評價 46 201016799 3iy45plt 為了評價硬化膜對鍵敷液的耐性，而將所製作的試驗基板於30°c的鈀水溶液（商品名：KAT-450、Pd為濃度12 mg/L、上村工業股份有限公司製造）中浸潰1分鐘，進行水洗後’將其於8(TC的非電解鍍鎳液（商品名：Nimden NPR-4、Ni濃度為4.5 g/L、上村工業股份有限公司製造）中浸漬30分鐘’進行水洗’接著，將其於8〇它的非電解鍍金液（商品名：Goblite TAM-55、Au濃度為1 g/L、上 ❿ 村工業股份有限公司製造）中浸潰10分鐘，進行水洗，藉此形成鍍敷皮膜。將該步驟中未產生鍍敷液滲入硬化膜内部或硬化膜剝離的情形判為「〇」，將產生鍍敷液滲入硬化膜内部或硬化膜剝離的情形判為「X」。將結果示於表4中。 (5)硬化膜的焊錫财熱性的評價為了評價硬化膜的焊錫耐熱性’而於試驗基板的硬化膜表面塗佈松香（rosin)系助焊劑（flux)(商品名：Ns_829、 Nihon Superior股份有限公司製造），並將其k26〇〇c的焊錫浴中浸潰30秒’調查是否產生剝離或隆起。將完全未產 ® 生剝離與隆起的情形判為「〇」，將雖少但還是產生剝離或隆起的情形判為「X」。將結果示於表4中。 47 201016799 31945pifFurther, a part (1 μg) of each inkjet ink was placed in a 3 〇mL sample vial and capped and stored at 100 ° C for 5 hours. Further, the rate of change of the viscosity of the ink after storage with respect to the viscosity of the ink before storage was examined. The viscosity of the ink is increased after storage, and the case where the rate of change is less than 1% is judged as "〇", and the case where the rate is greater than or equal to 1% is judged as "Γχ". The result is shown in Table 4. ° It is understood that the inkjet inks of Experimental Examples 3 to 4 are excellent in storage stability. (2) Evaluation of ejection characteristics 45 201016799 31945pif Each inkjet ink was injected into an inkjet cartridge, and it was mounted in a nozzle ink device (DMp_28® manufactured by FUJIFILM Dimatix Co., Ltd.) using a spray of 10 pl. The head was observed under the conditions of a discharge voltage (piezoelectric voltage) of 16 v, a shower head temperature of WC, and a drive frequency of 5 kHz. The liquid column at the time of ejection was ejected in the vertical direction, and the case where no satellite point was generated was judged as "〇". The case where the liquid column was brought into contact with the adjacent liquid column or the satellite point was generated was judged as "X". The results are shown in Table 4. (3) Preparation of test substrate Each inkjet ink was injected into an inkjet cartridge, and was placed in an inkjet© device (DMP_28® manufactured by FUJIFILM Dimatix Co., Ltd.) under the following substrate production conditions. A test substrate on which a cured film was formed was produced by applying (painting) each inkjet ink onto a substrate by an inkjet printer followed by uv hardening and thermal curing. The test substrate prepared in the above manner was used to investigate the properties of the plating solution and the solder heat resistance of the cured films shown in the following (4) and (5). Substrate production condition substrate: a substrate obtained by laminating a copper foil on a polyimide (thickness: ❹ 35 β m) [(made by Toyobo Co., Ltd.) Vyloflex (trade name)] Thickness of cured film: 30 /zm Ejection conditions: The same ejection conditions as above (2) UV exposure: 40 mJ/cm2 Thermal curing conditions: 19 (TCx30 minutes (4) Evaluation of the resistance of the plating solution to the plating solution 46 201016799 3iy45plt Evaluation of the resistance of the cured film to the bonding liquid, and the prepared test substrate was immersed in a 30 ° C palladium aqueous solution (trade name: KAT-450, Pd concentration: 12 mg/L, manufactured by Uemura Industrial Co., Ltd.) After washing with water for 1 minute, it was immersed in 8 (TC non-electrolytic nickel plating solution (trade name: Nimden NPR-4, Ni concentration: 4.5 g/L, manufactured by Uemura Industrial Co., Ltd.) for 30 minutes. ' Next, it was immersed in an electroless gold plating solution (trade name: Goblite TAM-55, Au concentration of 1 g/L, manufactured by Shangyu Village Industrial Co., Ltd.) for 8 minutes, and washed with water. This forms a plating film. No plating solution is infiltrated in this step. In the case where the inside of the film or the cured film was peeled off, it was judged as "〇", and the case where the plating solution penetrated into the cured film or the cured film was peeled off was judged as "X". The results are shown in Table 4. (5) The cured film In order to evaluate the solder heat resistance of the cured film, a rosin-based flux (trade name: Ns_829, manufactured by Nihon Superior Co., Ltd.) was applied to the surface of the cured film of the test substrate, and In the solder bath of k26〇〇c, it was dipped for 30 seconds to investigate whether peeling or bulging occurred. The case of peeling and bulging of the completely unproductive product was judged as “〇”, and the case of peeling or bulging was small. It is "X". The results are shown in Table 4. 47 201016799 31945pif

[表4] 硬化膜的特性[Table 4] Characteristics of the cured film

(實驗例5〜6、比較例7〜9) 於本實驗彳料，對形成含有6貞環化合物作為含有大於等於5員環的環狀_的自由基聚合性單體（A)的本發明的噴墨用墨水的硬化膜，來用於抗蝕用途或抗鍍敷用途的障形進行驗證。以表5中所記載的比例（重量份）進行調配，並混合、溶解，利用氟樹脂製薄膜過濾器（〇2 # m)進行過濾，而製備各喷墨用墨水。 ❹ 另外，比較例7及8是主要對不含具有大於等於5員環的環狀醚的自由基聚合性單體（A)成分的情形進行驗證的例子，比較例9是主要對雖含（A)成分但不含熱反應性樹脂（D)成分的情形進行驗證的例子。 … 48 201016799(Experimental Examples 5 to 6 and Comparative Examples 7 to 9) In the present invention, the present invention for forming a cyclic polymerizable monomer (A) containing a 6-fluorene ring compound as a ring-shaped ring of 5 or more members was formed. The cured film of the inkjet ink is used for verification of a barrier for resisting or plating resistance. The ratio (parts by weight) described in Table 5 was adjusted, mixed, dissolved, and filtered using a fluororesin membrane filter (〇2 #m) to prepare each inkjet ink. Further, Comparative Examples 7 and 8 are examples in which the radical polymerizable monomer (A) component having no cyclic ether of 5 or more members is contained, and Comparative Example 9 is mainly An example in which the component A) does not contain the component of the thermally reactive resin (D). ... 48 201016799

Jiy4Dpit [表5] 成为實驗例比較例 5 6 7 8 9 A2 130 60 — — 130 B1 50 50 50 50 50 B2 — 一 — — — C1 60 60 60 60 60 D1 30 30 30 30 — F1 250 250 250 250 250 H1 — 70 130 — _ H2 50 50 50 180 50 另外，於實驗例5〜6及比較例7〜9的喷墨用墨水中，聚合抑制劑（I)是添加0.05重量份的酚噻嗪（將除聚合抑制劑（I)以外的喷墨用墨水的總量設為1〇〇重量份）。 ' (1)墨水的黏度、由保管所引起的黏度的變化 , 以與實驗例1相同的方法，測定各喷墨用墨水於25 φ °(：下的黏度。將結果示於表6中。另外，以與實驗例1相同的方法，調查墨水的黏度的變化率。將結果示於表6中。可知，實驗例5〜6的喷墨用墨水的保存穩定性優異。 (2) 喷射特性的評價以與實驗例1相同的方法，觀察各喷墨用墨水的喷出的情況。將結果示於表6中。 (3) 試驗基板的製作以與實驗例1相同的方法，製作形成有硬化膜的試驗 49 201016799 31945ριί 基板。使用以上述方式製作的試驗基板，對以下（4)〜（6) 所示的硬化膜對姓刻液的耐性、對鹼性水溶液（剝離液）的剝離性、對鍍敷液的耐性進行調查。 (4) 硬化膜對餘刻液的耐性的評價以與實驗例1相同的方法，評價硬化膜對蝕刻液的耐性。將結果示於表6中。 (5) 硬化膜對鹼性水溶液（剝離液）的剝離性的評價以與實驗例1相同的方法，評價硬化膜對鹼性水溶液 (剝離液）的剝離性。將結果示於表6中。 (6) 硬化膜對鍛敷液的耐性的評價以與實驗例1相同的方法，評價硬化膜對鍍敷液的耐性。將結果示於表6中。 [表6]Jiy4Dpit [Table 5] becomes an experimental example Comparative Example 5 6 7 8 9 A2 130 60 — — 130 B1 50 50 50 50 50 B2 — One — — — C1 60 60 60 60 60 D1 30 30 30 30 — F1 250 250 250 250 250 H1 — 70 130 — _ H2 50 50 50 180 50 Further, in the inkjet inks of Experimental Examples 5 to 6 and Comparative Examples 7 to 9, the polymerization inhibitor (I) was added with 0.05 part by weight of phenothiazine ( The total amount of the inkjet ink other than the polymerization inhibitor (I) was set to 1 part by weight. (1) Viscosity of ink and change in viscosity due to storage The viscosity of each inkjet ink at 25 φ ° (:) was measured in the same manner as in Experimental Example 1. The results are shown in Table 6. In addition, the change rate of the viscosity of the ink was examined in the same manner as in Experimental Example 1. The results are shown in Table 6. It is understood that the inkjet inks of Experimental Examples 5 to 6 are excellent in storage stability. (2) Spray characteristics Evaluation The ejection of each inkjet ink was observed in the same manner as in Experimental Example 1. The results are shown in Table 6. (3) Preparation of test substrate The same procedure as in Experimental Example 1 was carried out to prepare Test of cured film 49 201016799 31945ριί substrate. Using the test substrate prepared as described above, the resistance of the cured film shown in the following (4) to (6) to the surname and the peeling property to the alkaline aqueous solution (peeling solution) (4) Evaluation of the resistance of the cured film to the residual liquid The resistance of the cured film to the etching liquid was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 6. 5) The cured film is applied to an alkaline aqueous solution (peeling solution) Evaluation of Peelability The peeling property of the cured film to the alkaline aqueous solution (release liquid) was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 6. (6) Evaluation of the resistance of the cured film to the forging liquid was The resistance of the cured film to the plating solution was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 6. [Table 6]

(實驗例7〜8、比較例10〜12) 於本實驗例中’斜形成本發明的喷墨用墨水的硬化膜 50 201016799(Experimental Examples 7 to 8 and Comparative Examples 10 to 12) In the present experimental example, the cured film of the inkjet ink of the present invention was obliquely formed 50 201016799

Jiy4^pit 來用於覆蓋層用途的情形進行驗證。以表7中所記載的比例（重量份）進行調配’並混合、溶解，利用氟樹脂製薄膜過濾器（0.2 "m)進行過濾，而製備各噴墨用墨水。另外，比較例10及11是主要對不含具有大於等於5 貝環的環狀謎的自由基聚合性早體（A)成分的情形進行驗證的例子，比較例12是主要對雖含（A)成分但不含熱反應性樹脂（D)成分的情形進行驗證的例子。Jiy4^pit is used for verification of the use of the overlay. Each of the inkjet inks was prepared by mixing and dissolving in a ratio (parts by weight) described in Table 7, and mixing and dissolving them with a fluororesin membrane filter (0.2 "m). In addition, Comparative Examples 10 and 11 are examples in which the radically polymerizable early (A) component having no ring puzzle of 5 or more rings is mainly used, and Comparative Example 12 is mainly used for (A) An example in which the component does not contain the component of the thermally reactive resin (D).

[表7] 成分實驗例比較例 7 8 10 11 12 A2 90 45 — 一 90 B3 30 30 30 30 30 C1 8 8 8 8 8 D2 10 10 10 10 — E1 40 40 40 40 40 F2 60 60 60 60 60 H1 — 45 90 — — H2 — — — 90 一另外，於實驗例7〜8及比較例10〜12的噴墨用墨水中，聚合抑制劑（I)是添加0.05重量份的酚噻嗪（將除聚合抑制劑（I)以外的噴墨用墨水的總量設為1〇〇重量份）。 (1)墨水的黏度、由保管所引起的黏度的變化以與實驗例3相同的方法，測定各喷墨用墨水於25 °(：下的黏度。將結果示於表8中。另外，以與實驗例3相同的方法，調查墨水的黏度的 201016799 31945pif 變化率。將結果示於表8中。墨用墨水的保存穩定性優異。以與實驗例3相同的方法，觀察各的情況。將結果示於表8中。、墨水的喷出 (3) 試驗基板的製作〇以與實關3糊的方法，製作軸有硬化膜的試驗土板。使用以上述方式製作的試驗基板對以下⑷及所示的硬化膜對鍍敷液的耐性及焊錫耐熱性進行調查。 (4) 硬化膜對鑛敷液的耐性的評價以與實驗例3相同的方法’評價硬化膜對鍍敷液的财性。將結果示於表8中。 (5) 硬化膜的焊錫耐熱性的評價以與實驗例3相同的方法，評價硬化膜的焊錫耐熱性。將結果示於表8中。[Table 7] Ingredient Experimental Example Comparative Example 7 8 10 11 12 A2 90 45 - One 90 B3 30 30 30 30 30 C1 8 8 8 8 8 D2 10 10 10 10 - E1 40 40 40 40 40 F2 60 60 60 60 60 H1 — 45 90 — — H 2 — — — 90 In addition, in the inkjet inks of Experimental Examples 7 to 8 and Comparative Examples 10 to 12, the polymerization inhibitor (I) was added with 0.05 part by weight of phenothiazine (will The total amount of the inkjet ink other than the polymerization inhibitor (I) was set to 1 part by weight. (1) Viscosity of Ink and Change in Viscosity by Storage The viscosity of each inkjet ink was measured at 25 ° (in the same manner as in Experimental Example 3). The results are shown in Table 8. In the same manner as in Experimental Example 3, the change rate of the viscosity of the ink of 201016799 31945pif was examined. The results are shown in Table 8. The ink ink was excellent in storage stability. Each case was observed in the same manner as in Experimental Example 3. The results are shown in Table 8. Ejection of ink (3) Preparation of test substrate 试验 A test soil plate having a cured film was produced by a method of solid-state 3 paste. The test substrate prepared as described above was used (4). The cured film shown and the solder resist heat resistance were investigated. (4) Evaluation of the resistance of the cured film to the ore solution The same method as in Experimental Example 3 was used to evaluate the effect of the cured film on the plating solution. The results are shown in Table 8. (5) Evaluation of solder heat resistance of cured film The solder heat resistance of the cured film was evaluated in the same manner as in Experimental Example 3. The results are shown in Table 8.

52 201016799 3iy45plt [表8]52 201016799 3iy45plt [Table 8]

❹ ❹ [產業上之可利用性] 本發明例如可用於電子電路基板中所使用的保護膜或絕緣膜、或者金屬圖案配線形成用阻劑、或者鑛敷圖宏形成用阻劑。瑕驭圚累雖然本發明已以實施例揭露如上，然其本發明，任何所屬技術領域中具有通常 '^疋本發明之精神和範圍内，當可作些許之^ ’不脫離 ,明之保護範圍當視後附之申請專利範圍㈡【圖式簡單說明】 I疋者為準。益【主要元件符號說明】 53产业 ❹ [Industrial Applicability] The present invention can be applied, for example, to a protective film or an insulating film used in an electronic circuit board, or a resist for forming a metal pattern wiring, or a resist for forming a mineral pattern. Although the present invention has been disclosed in the above embodiments, the present invention is intended to be within the spirit and scope of the present invention. The scope of the patent application attached to it (2) [Simple description of the drawing] I shall prevail. Benefit [Main component symbol description] 53

Claims

201016799 3iy4!) plt 7. Patent application scope: 1. An inkjet ink comprising: a cyclic polymerizable monomer IA having a ring of 5 M or more, a radical having a heat-reactive functional group Polymerizable monomer (B); photopolymerization initiator (C); and thermally reactive resin (D). The ink for inkjet according to the first aspect of the invention, wherein the free-filable monomer (a) having the general formula (Γϋ(四)环(四) is a compound represented by i): R1 一〇 R2—R3 0 (8) H2C=:c- VJ ❹ R2 is a ^^A) towel R R is hydrogen or a carbon number of 1 to 3, and the carbon structure of the branched structure has a carbon number of 1 to 3 Or the glycol ether 'R3 which may have a partial-substituted oxygen is a ring having a carbon number of 1 to 3, such as a ring of 1 or 2, which is greater than or equal to a 5-membered ring. The ink for inkjet according to the above formula (4), wherein the V is B; the carbon number is 1 to 3 or 2, such as a member ring (4), and the number of turns is 1 (.= In the inkjet S water of the second item of the range 3^, Α + R is hydrogen or methyl, R2 is an anthracene group, and R3 is a soil test of a 5-member ring having a gas number of 54 201016799 1. 5. In the patent application formula (A), R1 is a hydrogen or inkjet ink, wherein the oxy gold substituted in the alkyl group of 1 to 3 is a methylene group, and R3 is a carbon number 6 For example, the cyclic ether of the 6-membered ring of the patent application Fan Park 笫f 2 . Ink ink, which has a heat-reactive 庳^ (B) i ^ A ''~g radically polymerizable monomer group The heat-reactive functional group in the ink-jet ink of the ink-filled ink of any one of the above-mentioned items of the first to fifth aspects of the patent application. (8) Id Μ Γ 的 Free silky monomer) A heat-crosslinkable functional group having a base or a thiol group. Ink L is a freely reactive (Β) having a thermal reactivity function as described in any of items 1 to 7 of the scope of the application. base. ❹ 9. The ink-jet water of the ink-jet water according to any one of the above-mentioned claims, wherein the free-filing monomer of the surface of the towel has a general formula (g·1) or (Β-2) Compounds indicated: H2〇==C, Γ〇 and 士 η ο (Β-1)

(Β-2) (in the formula (Β-1) and (β_2) towel, r4 is independently chlorine or 55 201016799 31945pif, the carbon number is 1~3, R5 is from a... 〇1〇刀Independently, it is an extensor having an inverse number of 2 to 12, and n is an integer of mo). The inkjet ink according to any one of the above-mentioned items, wherein the radically polymerizable single having a heat-reactive 4-g-energy group is selected from the group consisting of (fluorenyl)-propyl Dilute H-based butyl vinegar, 1 4 · Λ Λ & & ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° , , , , , , , , , , , ,

η) Propyl B, and phthalic acid monoethylidene I propyl)-ethyl]S are intended to be greater than or equal to the species. The inkjet ink according to any one of the items 1 to 1 wherein the photopolymerization initiator (c) is bis(2,4,6-trimethylphenylhydrazine). Phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. The inkjet ink according to any one of the preceding claims, wherein the thermally reactive resin (D) is a melamine resin.

The ink for inkjet according to any one of the items 1 to 5, wherein the thermally reactive resin (D) is a phenol resin. The ink for inkjet according to any one of claims 12 to 12, further comprising a flame retardant (E). The inkjet ink according to any one of claims 1 to 14, which further contains a polyfunctional (meth) acrylate (F). A method of forming a cured film by applying an inkjet ink according to any one of items 1 to 15 of the invention, and coating the ink by the inkjet method. Light is irradiated, thereby forming a cured film. 56 201016799 31945pif Patent application scope! The item is opened to the first side = it is inked by inkjet ~^ coated at the same time =: 3⁄4 with ink into the 仃), 2) heating, by the blue into the Wei film: cut the hardened film of the museum, It is obtained by the method as described in claim 17 of the patent application. 16 items or

The sclerosing film according to Item 18 of the patent scope is characterized in that it is an electro-electronic plate which is formed on the substrate to form a cured film according to Item 18 or Item 19. An electronic component having an electronic circuit substrate as described in the scope of the patent application. And a display element of the electronic circuit substrate as described in claim 2 or the electronic component according to claim 21 of the patent application.

57 201016799 IV. Designated representative map: (1) Designated representative figure of the case: None (2) Simple description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ❿ No 201016799 ^ ly^DpiIi is the Chinese manual of No. 98129444 without a slash correction. The patent specification of the present invention is amended: secluded /> month

(The format and order of this manual are not changed. Please do not fill in the ※ part of the mark.) ※Application number: ^ I iz〇〇6.〇n ※Application date: Sword PC classification: ^. 6. (10) I. Name of the invention :(Chinese / English) Qing (2006.0« inkjet ink and cured film obtained from the ink

INK FOR INKJET AND CURING FILM FORMED FORM THE INK % (2〇〇6M^i II. Abstract of Chinese invention: % <2006.011 (2006.011 requires a metal etchant resistance, peelability to the stripping solution, or ore fluid tolerance) The inkjet ink of the present invention comprises: a radical polymerizable monomer (?) containing a cyclic ether of 5 or more members, and a radically polymerizable monomer having a thermally reactive functional group ( Ink), photopolymerization initiator (C), and heat-reactive resin (D). An ink for inkjet having resistance to a metallic etching liquid, peeling property in relation to a peeling liquid or resistance To a plating liquid is provided. The ink for inkjet includes a radical polymerization monomer (A) having a membered ring equal to or larger than 5 of cyclic ether, a radical transparent monomer (B) having thermal reactivity 201016799 ^ly^Dpui [Technical Field] The present invention relates to a method for manufacturing a liquid crystal display element, EL (Electro-Luminesc) An ink for inkjet (inkjet) such as a display element or a printed circuit board. The present invention relates to a cured film obtained by the ink for inkjet (including patterned hardening) Film), method of forming a cured film, and electronic circuit board, electronic component, and display element on which a cured film is formed. [Prior Art] The pattern formation by the inkjet method is not only simpler than the photolithography method. In addition, it is also expected to reduce the amount of material used, and it is proposed to use a printed wiring board or the like for use in the manufacture of an electronic device (for example, Japanese Patent Laid-Open Publication No. 2003-302642 (Patent Document 1), Japanese Patent Laid-Open Japanese Patent Publication No. 2005-68280 (Patent Document 2)) In recent years, electronic circuit boards using a lightweight and flexible printed wiring board have been widely used for miniaturization of electronic equipment. The electronic circuit board is formed of a metal wiring portion having a specific circuit pattern by, for example, an etching resist, and then is formed by using a plating resist, a mineral coating, and a protective film on the surface of the metal layer. The coverlay is made by the step of coating (c〇adng). When these steps are carried out by the ink jet method, the ink for inkjet ink is required to be stored stably, and stable ink ejection properties are required. Further, the cured film formed by the inkjet ink requires various properties in accordance with the use of each ink. For example, for the cured film 201016799 31945plil for forming an inkjet ink for resist use, resistance to a metal rice squirt is required, and the property to the peeling liquid is required. For example, for inkjet for anti-recording use. In the case of a cured film of ink, it is required to be resistant to a liquid dressing liquid, and it is required to be stripped of the peeling liquid. = For the hardened film of the ink when the cover layer is formed, the resistance to the plating solution is required, and the solder heat resistance is required. However, the "cured film of the inkjet ink of the prior art is not sufficient due to any of the above properties", and thus is only a cured film which is not suitable for practical use. [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-302642 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 5-6 828 No. [Patent Document 3] Japanese Patent Laid-Open Publication No. 2〇〇8_5〇6〇ι [Problem to be Solved by the Invention] In the above-described circumstances, for example, an ink for jetting S which is excellent in storage stability of ink is required. Further, for example, an ink for inkjet which can stably eject is required. Therefore, when the ink for inkjet is used as a cured film, the following ink for inkjet is required: for example, when used for resisting, it has resistance to a metal etching solution and peeling property to a peeling liquid; and, for example, plating resisting When it is used for application, it has resistance to a plating liquid and peeling property to a peeling liquid. Moreover, when it is used for a coating layer, it has resistance with a plating liquid, and solder heat resistance. In addition, a flexible wiring board with high reliability is required. [Means for Solving the Problem] The present inventors have found that the use of the radical polymerizable monomer (A) having a specific 5 201016799 il 945 pitl structure in the ink for inkjet can effectively handle the above problem 'based on the knowledge The present invention has been completed, that is, the present invention relates to a radical polymerizable monomer (A), a radically polymerizable monomer (B) having a thermally reactive functional group, a photopolymerization initiator (C), and heat. Inkjet ink of reactive resin (D). The present invention provides the following ink for inkjet, a cured film obtained from ink for inkjet, a method for forming the same, and the like.喷墨] an inkjet ink comprising: a free-filable monomer (A) having a ring of 5 or more members, a merging monomer (B) having a thermally reactive functional group, and a photopolymerization initiator (2) The ink for inkjet according to the above [1], which contains a radical polyisomer I of a cyclic ether equal to or greater than the s-membered ring, and the like; The precursor (4) is (4) R1 H2C of the formula (4): C—〇—R2_r3 (A) (in the formula (A), the RU R is a carbon number of the (6) branch structure having a branched structure and having a carbon number of 1 to 3 It is a 2~:3 extended alkyl group or an oxygen group which may be substituted with a g alkyl group, a hydrazine, R is a carbon number of 丨~, and R1 is hydrogen, a methyl group or an ethyl group, wherein the formula (4) The burnt number of the carbon number of i~3 is the extension base of the 3, and the ring of the R member ring is replaced by the 5 member ring of the 1 or 2" 201016799 [4] as described in the above [2] Inkjet ink, wherein R1 is hydrogen or methyl, R2 is methylene, r3 is oxygen, and (A) is an ether. The ring of the 5-membered ring [5] is sprayed as described in [2] above. Ink ink, R1 is hydrogen or methyl, R2 is methylene, and carbon number = formula (A) makes ' The ink for inkjet according to any one of the above [1] to [5], wherein the ink has a thermal reaction The radically polymerizable monomer (B) having a functional group has a thermally reactive functional group selected from the group consisting of a hydroxyl group, a mercapto group, an ethylene oxide group, and an oxetane group. [7] The inkjet ink according to any one of [1] to [5] wherein the radically polymerizable monomer (B) having a thermally reactive functional group has a thermal crosslinkability of a hydroxyl group or a carboxyl group. The inkjet ink according to any one of the above [1] to [7] wherein the radically polymerizable monomer (B) having a thermally reactive functional group has one thermal reactivity. [9] The inkjet ink according to any one of [1] to [8] wherein the radically polymerizable monomer (B) having a thermally reactive functional group is a formula ( Compound represented by B-1) or (B-2): 201016799 Jiy4) pin R4 H2〇=C-C--0 Ten R5 _〇tH (BD h』t+-¥KToh (4) o N-f * (in In the general formulae (Bl) and (B-2), R4 is independently Hydrogen or an alkyl group having a number of 1 to 3, and R5 is independently an alkylene group having a cyclic structure of 2 to 12 carbon atoms, and n is an integer of 丨~3〇). The inkjet ink according to any one of [1], wherein the radically polymerizable monomer (B) having a thermally reactive functional group is selected from the group consisting of hydroxyethyl (meth)acrylate, ) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, _4-hydroxybutyl (meth) acrylate, • cyclohexane decyl mono(decyl) acrylate, adjacent One or more of the group consisting of phthalic acid mono [(hydroxy)ethyl methacrylate] and phthalic acid mono-[2_(2-methylpropenyloxy)ethyl] vinegar. [11] The ink for inkjet according to any one of [1] to [1], wherein the photopolymerization initiator (C) is bis(2,4,6-trimercaptobenzoquinone) Phenylphosphine oxide or 2,4,6-tridecyl adenyl diphenylphosphine oxide. [12] The inkjet ink according to any one of the above [1] to [A], wherein the thermal reaction is carried out by a melamine resin. [13] The ink for inkjet according to any one of [1] to [u], wherein the thermally reactive resin (D) is a resin. [14] The inkjet ink according to any one of [1] to [12] further comprising a flame retardant (E) in 201016799 JiyHjpui. [15] The inkjet ink according to any one of [1] to [14] further comprising a polyfunctional (fluorenyl) acrylate (F). [16] A method of forming a cured film by applying the ink for inkjet according to any one of the above [1] to [15] by an inkjet method, and irradiating the applied ink with light. 'Thereby forming a cured film. [17] A method for forming a cured film, which is characterized by the inkjet method, wherein the ink for inkjet according to any one of [Fourth] to [15] is coated by the inkjet method, and the applied ink is simultaneously Light irradiation and heating are performed 'or sequentially 1 light irradiation and 2) heating to form a cured film. [18] A cured film obtained by the method described in [16] or [17] above. [19] The cured film as described in [18] above, which is formed in a specific pattern. [20] An electronic circuit substrate, wherein the cured film according to the above [18] or [19] is formed on the substrate. [21] An electronic component comprising the electronic circuit substrate as described in [2] above. [22] A display element having the electronic circuit substrate according to [20] or the electronic component according to [21] above. In addition, in the present specification, in order to indicate both acryl vinegar and methacrylic acid ester, there is a case where "(meth) acrylate" is used for labeling. [Effect of the Invention] 201016799 3iy43pltl ιΐΓ月: Compared with the ink of the nozzle, the ink is excellent in storage stability, and can be stably ejected. Further, it has resistance to the metal retentive liquid and peeling resistance = for example, the hard (10) obtained from the inkjet ink has releasability for forging liquefaction. For example, the hard ink obtained from the ink for the nozzle ink: Ming ===: heat resistance. Further, an embodiment is used by using ◎ to manufacture a film, and the following is attached:: ^^^ [Embodiment] 1. The ink-jet ink of the present invention contains an ink containing: greater than or equal to Ring of 5-membered ring ====== Self-lipid with thermally reactive functional group (9). In addition, the "=;=) is that the water may be colorless or may be used in the inkjet ink of the present invention. In addition, the ink for ink according to the present invention contains, in addition to the polymerizable monomer having 5 or more groups (4). , with a heat-reactive reactive resin;;:: body 2 of the 3 start agent (8), and thermal officer _ propylene axis two S = = _ (8), multi-person ancient 1 (), etc., another 'can be made according to needs - step 3 There are a mixture, an additive, a polymerization inhibitor, a coloring agent, etc. 10 201016799 体含含 5 5 5 5 自自自自自自自自自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基自由基A) The radically polymerizable compound is not particularly limited as long as it contains greater than or equal to $=ring scale. The so-called "free silkyness", the Hi-ray light generated by the Hi-light, starts to polymerize. 妒 The base-polymerizable monomer (A) has a radical polymerizable property: a propylene group, a methyl group. The acryl group, the acrylamide, or the methyl group ==^ from the base polymerizable monomer (A) = : = the base may be a plurality of, preferably η 个 1 ~ 2, and further Ok is i. More preferably <radical polymerizable monomer> (4) A cyclic monomer having a ring derived from a cyclic-radical polymerizable monomer, and containing not more than 5 members. Examples of the poly-based monomer include, for example, di(methyl) propylene vinegar, pentaerythritol, polycyanic acid, ethylene bromide, and di(methyl) acrylate succinic acid succinic acid vinegar. , pentaerythritol ester, trimethyl ketone bromide (曱9, pentaerythritol tris(methyl) acrylate acid §, quaternary fine alcohol =, deliberate, diquaternary fine alcohol di(indenyl) (methyl)丙轮的,或二四醇四201016799 31945ρίΠ ^ 〇〇基聚〇^ Early body, for example, in the case of a monofunctional polymeric early body having no hydroxyl group, for example, can be listed | 鬈S 3曰上=) Oxyloxymethyloxeane, 3-methyl)-oxymethyloxetane == oxetane, 3, methyl) propylene = ίί ethyl phenyl _ 3_Ethyloxetane _3_ylmethyzine j 2,benyl-3·(methyl)propoxy-oxo-oxetane, 2•trimethylmethyl (methyl ) propylene methoxymethyl oxetane, 4 _ trigas 甲 = (methyl) propenyloxy oxetane, (meth) propylene ketone vinegar, (曱Acetate, acetoacetate, isopropyl methacrylate, (butyl) butyl acrylate, (mercapto) propyl acid Butai vinegar, (meth)acrylic acid third butyl vinegar, (mercapto) acrylic acid cyclohexan vinegar, (meth) acrylic acid vinegar, phenylethyl benzene, ▼ phenyl ethene, gas methyl benzene Ethylene, (meth)acrylic acid (3 ethyl_3_oxetanyl) methyl vinegar, N-cyclohexyl cis-butyl diimide, N-phenyl cis-butyl diimide, vinyl toluene , (5,5,6,5-yl) methacrylate, (meth) propyl St-cyclopentenyloxyethylene, (fluorenyl) isopropyl ketone, (meth) acrylate Ester, glycerol mono(indenyl) acrylate, polystyrene macromonomer, polymethyl methacrylate M S macromonomer, (meth)acrylic acid _5_tetrahydrosaccharoxycarbonylpentyl ester, lauryl alcohol Ethylene oxide adducts of (meth) acrylate, (meth) acrylate, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, trans-butyric acid, itaconic acid ( Itac〇nic acid ), citmconic acid, mesac〇nicadd, 〇-carboxypolycaprolactone mono(meth)acrylate, succinic acid mono[2_(fluorenyl) Propylene 12 201016799 3iy43pm oxiranyl ethyl ester Maleic acid mono [2-(indenyl) propylene oxiranyl ethyl] oxime, cycloheximide-3,4-methylidene [2-(indolyl) propylene oxiranyloxy] Vinegar, (mercapto) acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(methyl)propene amine, N,N-methylamino Propyl (mercapto) acrylamide, N-isopropyl (meth) acrylamide, N-propenyl morpholine, n-phenyl maleimide, or N-cyclohexyl cis Ene diimine and the like. When the radical polymerizable monomer is, for example, a polyfunctional polymerizable monomer having no radical, for example, bisphenol F-type ethylene oxide modified diacrylate or bisphenol A epoxy Ethyl modified diacrylate, polyethylene glycol monopropionate, polypropylene glycol diacrylate, butanediol diacrylate, 1,6-hexanediol diacrylate, decanediol II Acrylate, 1>4_cyclohexanedimethanol diacrylate, 2_n-butyl-2-ethyl-1,3-propylene glycol diacrylate, trimethylolpropane tri(meth)acrylate, epoxy Ethyl modification: dimethyl propyl acetonate (methyl) acrylate vinegar, propylene propylene modified ternary methyl, propyl propyl di(methyl) acrylate, epichlorohydrin (epichlorohydrin) Dihydroxymercaptopropane tris(methyl)propionate, bis(trihydroxydecylpropan)tetrakis(meth)acrylate, glycerol tri(meth)acrylate, epichlorohydrin modified glycerol Tris(meth)acrylate, diglycerin tetra(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, dipentaerythritol hexa(meth)acrylate Caprolactone (capr〇lactone) modified dipentaerythritol hexa(meth) acrylate, ethylene oxide modified tris(meth) acrylate, tris[(indenyl) propylene oxyethyl] _ The cyanurate or caprolactone is modified with tris((meth)acryloxyethyl)isocyanate or (mercapto)acrylic acid urethane. <A cyclic ether having a ring of 5 or more members> 13 201016799 31945ρίΠ A ring-shaped self-synthesis monomer (Α) having a ring of 5 or more and more is a radical polymerizable monomer having a larger than ί For the cyclic ether having a value of 5 or more members, the number of the _ bond contained in the ring, for example, may be exemplified by a ring of a ring of 5 rings or a ring of a ring of 6 members. Listed by a pure fine Wei group, it is (4) a wire with a number of 1 to 3, and more preferably a methyl group or an ethyl group. Further, the number of the substituents of the substituted leukoyl group may be plural, and preferably 1 to 2, and these rings are contained in the base polymerizable monomer (4). The number can be multiple 'better! ~ 2, better! Ring i is equal to 5 贞 ring _ concrete can _ with the town structure

Ό, Ό, Ό, .0 〇, Ο Included, greater than or equal to 5 S_cyclic _ free silky mersible monomer is equal to the singularity of the singularity of the genus The body, which includes a compound represented by the above formula (A), which is a radical polymerizable monomer having a cyclic ether having a ruthenium of 5 or more members, is exemplified by: (A) ^, Rl is hydrogen or a carbon number of 1 to 3, specifically • lin, methyl, ethyl, n-propyl, isopropyl, preferably hydrogen 201016799 iiy45piti or methyl.

In the formula (A), R is a stretching group having a branched structure and having a carbon number of 1 to 3 or a diol having a branched structure and having a carbon number of 2 to 5. The alkylene group having a carbon number of 1 to 3 is specifically a methylene group, an ethyl group or a propyl group, and may be bonded to the alkyl group such as an alkyl group (preferably, the carbon number is 丨~'3). ) and form a branch structure. Further, the monool ether having a branched structure and having a carbon number of 2 to 5 is specifically ethylene glycol_, 1,2-propylene glycol ether, hydrazine, 3-butanediol_, or neopentyl glycol ether. In the formula (A), R3 is a cyclic ether having a ring number of 5 or more and having an oxygen number of 1 or 2 which may be substituted with an alkyl group having a carbon number of i3. Specific examples of the cyclic ether include the above-mentioned cyclic ring. Specific examples of the polymerizable monomer (a) represented by the formula (A) include tetrahydrofurfuryl (meth)acrylate and cyclic tris-propyl thioglycolate (methyl)acrylic acid. Vinegar, alkoxylated (methyl)propionic acid tetrahydroanthracene vinegar, caprolactone modified (meth)acrylic acid tetrahydrofurfuryl ester, and the like. Among the polymerized early bodies, (10) acid tetrahydroanthracene vinegar (the following formula (al-Ι)), methyl propyl_tetrahydroanthracene vinegar (the following structural formula Ui-2), Cyclic tris(tetra)ylpropenyl acetal (4) thin _ (the following structural formula (a2-l)), or cyclic dipyridyl propyl sulphuric acid vinegar (the following structural formula U2-2)). τ τι π 201016799 31945pifl η

(a1-2) h2c

(32-2)

Tetrahydrofurfuryl acrylate is commercially available as SR 285 manufactured by Sartomer Co., Ltd., and Light Acrylate THF-A manufactured by Kyoritsu Chemical Co., Ltd., as a product of S-Mercapone, SR203, Co., Ltd. The form of Light Ester THF manufactured by Chemical Co., Ltd. is commercially available. Further, cyclic trihydroxydecylpropane acetal acrylate is commercially available in the form of SR531 manufactured by -Sartomer Co., Ltd. The polymerizable monomer (A) contained in the inkjet ink may be one compound selected from the above compounds, or a mixture of more than two of these compounds. If the inkjet ink contains 1% by weight to 70% by weight of the radically polymerized fluorene monomer (A)', the discharge stability from the nozzle becomes good when the ink is inked, which is preferable. If it contains 10 wt% to 65 wt% of the radical polymerizable monomer (A), it is more preferable if it contains 20 wt% to 60 wt%/〇16 201016799 ^iy^opui radical polymerizable monomer (A) ), then better. 1.2 Radical polymerizable monomer having a thermally reactive functional group (b) Radical polymerizable monomer having a thermally reactive functional group Free radically polymerizable compound and having a heat anti-ship functional group: Du = determinate. In addition, the term "thermal reactivity" means, for example, the nature of the parent-linked reaction by heat, but is not limited thereto. The functional group of the Φ _ ί 反反若若产生产生产生产生产生产生产生产生产生细并无并无并无并无 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' He said that the base and the county. Further, the number of the thermally reactive functional groups in the radical polymerizable monomer (8) may be plural, more preferably 3, more preferably 1 to 2, and still more preferably i. The heat-reactive functional group contained in the solid right polymerizable monomer (8) is compatible with other components contained in the ink for inkjet ink, and is contained in (iv) The compatibility of the other components of the silk-cured hardened film of the aqueous solution:: disproportion = by the ink for the nozzle ink ><The thermal reactive functional group is the combination of the free radical polymerizable monomer (8) The monomer (b) is a polymerizable monomer having a hydroxyl group and a carbon double bond, a polymerizable single bond having a hetero and a carbon double bond, or having a filament and a greater than or equal to 17 201016799 31945ptfl polymerizable carbon A double bond polymerizable monomer. Specific examples of the polymerizable monomer having a hydroxyl group and one radical polymerizable carbon-carbon double bond include (meth)acrylic acid 2 -hydroxyethyl vinegar, (methyl) diacid acid-2-pyridyl vinegar , (曱基) propyl benzoic acid by butyl vinegar, or 14 • ring corpse steroid mono (indenyl) propyl vinegar and so on. Specific examples of the polymerizable sheet having a hydroxyl group and two radical polymerizable carbon-carbon double bonds include isomeric cyanuric acid epoxide modified di(methyl) adienoate: glycerin diacrylate, Pentaerythritol bis(indenyl) acrylate, pentaerythritol bis(indenyl) acrylate monostearate, trishydroxypropyl propane di(meth) acrylate, or dipentaerythritol di(meth) acrylate, and the like. Specific examples of the radical having 3 or more radically polymerizable carbon-carbon double-bonding monomers include quaternary alcohol tris(mercapto)acrylic acid vinegar, dipentaerythritol penta (meth) acrylate, and alkane. Base modified dipentaerythritol pentayl acrylate, dipentaerythritol tetra(meth) acrylate, alkyl modified di vinegar, dipentaerythritol tris(methyl) propyl s hydrazine or alkyl modified pentaerythritol tris (A) Base) acrylate and the like. Among these polymerizable monomers, in the case of application to photocurable inkjet, a radically polymerizable monomer (Β) having a thermally reactive functional group is used from the viewpoint of qualitative (4) of the nozzle. Good: There are a ketone group and a free silky carbon-carbon double-polymerizable monomer, = good is methacrylic acid · 2 · hetero-ethyl s, f-based acrylic acid /, acrylic · 4 · butyl Vinegar, or cyclohexane dimethanol monoacetic acid vinegar. Further, the radically polymerizable monomer having a thermal reactivity is preferably a compound represented by the above formula (B-1). In the general formula (4)) 18 201016799 Jiy^pin lift gas · ', the site is hydrogen or a carbon number of 1 ~ 3, specifically can be ί ί, s I ethyl, n-propyl, isopropyl ' Preferably, hydrogen or ▼: 浐 = (5)) _ 'R5 are independently a stretching base having an annulus number of 2 to 12 which may have a cyclic structure, and among these stretching bases, a preferred group, a propyl group, A butyl group or a group represented by the following structure. Further, =yr)/, n is 1 to (four) integer ', preferably =' is more preferably 疋1 to 3' and further preferably 1. -CH: 〉 <The radically polymerizable monomer (B) having a thermoreactive functional group is a carboxyl group, and the carbon-based double bond monomer is bonded to a self-sulfhydryl polymerizable ❹ carbon double bond monomer. a polymerizable monomer having a neokyl group and two self-polymerizable carbon=bonds, or a polymerizable monomer having a slit group and three or more radical poly-B carbon-carbon double bonds. Oral acid monopropyl _, or o- dimethyl benzoic acid and two free silky carbon-carbon double bonds (four) comonomers, /, more J, can be cited fatty acid modified pentaerythritol dipropylene vinegar, etc. . Poly 19 201016799 3I945pifl conjugated monomer having a fluorenyl group and three or more radically polymerizable carbon-carbon double bonds, exemplified by a succinyl (10) modified (tetra)pentaerythritol tris (acrylate or succinic acid modified dipentaerythritol) Penta(meth)acrylic acid. These polymerizable properties are used in the t-shaped shape of the photocurable inkjet ink, and the stability from the nozzle and the film to the alkali cured by the inkjet ink From the viewpoint of the releasability of the aqueous solution, the free-filable monomer (8) having a carboxyl group as a thermally reactive functional group is preferably a polymerizable single having a divalent group and a radically polymerizable carbon-carbon double bond. Body, especially for phthalic acid mono (acrylic acid woven or phthalic acid monomethyl acrylate hydroxyethyl vinegar) (CB-1 (trade name) made by Shin-Nakamura 4 Industrial Co., Ltd.) Further, the radically polymerizable monomer having a thermally reactive functional group is preferably a compound represented by the above formula (Β·2). In the formula (wherein R 4 is independently hydrogen or carbon number) For the silk of 丨~3, it can be listed as nitrogen, methyl, ethyl, positive, basic, The propyl group is preferably a nitrogen or a methyl group. In the formula (Β·2), R 5 is independently a decene alkyl group having a carbon number of 2 to 12 (better case and the above formula (ID) The description of R5 is the same), and η is an integer of 1 to 30, preferably 丨~(1), more preferably 1 to 3, and still more preferably 1. Free radical polymerizable monomer contained in the ink for inkjet. (Β) may be one compound selected from the above compounds, or a mixture of two or more of these compounds. If the inkjet ink contains i wt% to 8 〇wt% of a radical polymerizable material In the case of the ink for ink, it is preferable to eject the crucible from the nozzle of the nozzle, and it is more preferable to contain the radical polymerizable monomer (B) of 3 wt% to 75 (10) 20 201016799 3 iy 4 pm. The radical polymerizable monomer (B) of wt% to 7〇wt% is further preferably. 13 Photopolymerization initiator (C) The photopolymerization initiator (C) is ultraviolet or visible light. The compound which generates a radical by irradiation is not particularly limited. Specific examples of the agent (C) by photopolymerization include diphenyl hydrazine ( benzophenon). e), Michelin, 蜩 (Michler, s ^^咖卜七心双^ethylamine benzoquinone thioxanthone, thioxanthone, isopropyl oxazepine , 2,4-Diethylthioxanthone, 2-ethyl hydrazine, acetophenone, 2-hydroxy-2-mercaptopropiophenone, 2-hydroxy-2-methyl-2-yl, 4-isopropyl Propiophenone 1-cyclohexyl phenyl ketone, isopropyl benzoin test, isobutyl benzoin, 2,2-diethoxyphenethyl, 2,2-dimethoxy-2-phenylbenzene Class B, camphoroquinone, benzocanthone (benzanthr〇ne), 2 methyl-ΐ·[4-(decylthio)phenyl]_2-morphinylpropanoid _, 2_benzyl 2·Dimethylamino-1-(4-morpholinylphenyl)-butanone 4,4-dimethylaminobenzoquinone acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl Ester, 4,4,-di(t-butylperoxyloxy)benzophenone, 3,4,4'-tris(t-butylperoxyoxy)diphenylhydrazine 3,3,4,4-tetra(t-butylperoxymethyl)dimercaptoketone, 3,3,,4,4匕tetrakis (second hexylperoxymethyl)benzyl-, 3,3'_di(methoxyl group)_4,4'-one (second butyl peroxyl) Alkyl)diphenylhydrazine-, 3,4,-di(decyloxylk)-4,3-((t-butylperoxy)diphenyl-, 4,4,-di ( Methoxycarbonyl: ^ volunteer (9) tributylperoxycarbonyl benzophenone ~ octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzylidene fluorenyl) , 2_(4,_曱oxystyryl)_4,6_bis(dimethylmethyl)·s-triazine, 2—(3′,4,-dioxaphenylbenzene 21 201016799 31945pifl alkenyl)- 4,6-bis(trimethyl)-s-triazine, 2-(2',4,-dimethoxystyrene)-4,6-bis(trichloromethyl)-s-triazine , 2_(2,_曱oxy stupid vinyl)_4,6_ bis(dimethylmethyl)-all three 11 Qin, 2-(4'-pentyloxystyryl)_4,6_double (three gases Mercapto)-s-triazine, 4_[p-quinone, hydrazine-(ethoxycarbonyl fluorenyl);]_2,6-bis(trichloromethyl)-s-triazine, I,3·bis (trichloro) Sulfhydryl)_5-(2,_gasphenyl)_s-triazine, 13_bis(di-p-mentyl)-5-(4'-methoxyphenyl)--trimethylene, 2-(p-dimethyl Aminobutyryl)benzoxazole, 2-(p-didecylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3,-carbonylbis(7-diethylamine Ketomarin), 2- (o-chlorophenyl)_4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2,-bis(2-p-phenylphenyl)·4,4',5, 5'-tetrakis(4-ethoxycarbonylphenyl)-1,2,-biimidazole, 2,2,-bis(2,4-one gas-based)-4,4',5,5'-four Ben-1,2,-linked β sitting, 2,2'-bis(2,4-di> stinyl)-4,4',5,5|-tetraphenyl-1,2| - 〇米〇, 2,2'-bis(2,4,6-triphenyl)-4,4',5,5'-tetraphenyl-1,2·-biimidazole, 3·( 2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinylpropanyl)_9_正十二院基咔, 1-cyclohexyl phenyl ketone, bis(7? 5-2,4-cyclopentadienyl i)-bis(2,6-difluoro-3-(1Η-«比咯-1- Base)-phenyl)titanium, bis(2,4,6-trimethylphenylhydrazino)phenylphosphine oxide, or 2,4,6-trimercaptobenzylidenediphenylphosphonium phosphine. Among them, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide (IRGACURE 819 (trade name) manufactured by Ciba Japan Co., Ltd.) or 2,4,6-trimethylphenylhydrazine Diphenylphosphine oxide (DAROCURTPO (trade name) manufactured by Ciba Japan Co., Ltd.), and 1-hydroxycyclohexylphenyl hydrazine (IRGACURE 184 (trade name) manufactured by Ciba Japan Co., Ltd.), etc., and ink for inkjet Compatibility of other components contained in the film 22 201016799 Jiy45pm It is preferable that the obtained inkjet ink can be hardened with less ultraviolet irradiation amount. The photoinitiator (C) may be one compound or a mixture of more than two different compounds. When the inkjet ink contains wt% to 2 Gwt% of the photopolymerization initiator (c), when the ink for inkjet is used, the sensitivity to ultraviolet rays is south, so it is preferable if the photopolymerization initiator is used. It is more preferable that the content of (c) is from 1 wt% to 20 wt%, and further preferably if the content of the photopolymerization initiator (6) is from 1 wt% to 15 wt%. 1.4 Thermally Reactive Resin (D) Examples of the thermally reactive resin (D) include an epoxy resin, a melamine resin, and a "polymer of a radically polymerizable monomer having a thermally reactive functional group (for example, a phenol resin)", Or a "copolymer of a radically polymerizable monomer having a heat-reactive functional group and another radical polymerizable monomer". From the viewpoint of heat resistance and chemical resistance, it is preferred to use a melamine resin, and it is preferable from the viewpoint of the peeling property of the cured film to the alkaline aqueous solution and the acid-resistant aqueous solution. It is a polymer (for example, a phenol resin) which uses a radically polymerizable monomer having a thermally reactive functional group. Specific examples of the melamine resin include melamine, mercaptotriamine, etherified mercapto melamine, benzoguanamine, hydroxymethyl benzoguanamine, etherified hydroxydecyl benzoguanamine. And the condensates of these. Among them, in terms of good chemical resistance, it is preferred to etherify hydroxydecyl melamine, and a mixture of the following compound (dd) and its condensate is Nikalac MW-30 manufactured by Sanwa Chemical Co., Ltd. The name is commercially available. 23 201016799 H3COH2C H3COH2C.

Specific examples of the polymerization of the NNN /CH2OCH3, the ch2och3 /CH2OCH3 (d'1) I, and the CH20CH3 monomer "a radically polymerizable substance having a thermally reactive functional group" include a phenol resin such as polyvinyl alcohol or polyvinylphenol. Poly((fluorenyl)glycidyl acrylate), poly((indenyl)acrylic acid_3 4_cyclo[cyclohexanyl]S), K(methyl)acrylic acid decyl glycidol g), polymethylamine 3 (methyl) propylene oxime oxetane oxetane), poly(3-ethyl (methacryl oxime oxetyl oxetane), poly (3-methyl | (methyl) ) propylene oxyethyl oxaxanthene), poly(3-ethyl-3-(methyl) propylene oxiranoxy oxetane), poly(p-vinylphenyl _3) _Ethyloxetane_3_ylmethylether), poly(2-phenyl-3-(methyl)propenyloxymethyloxetane), poly(2-trifluoromethyl) 3-(methyl)propenyloxymethyloxetane), poly(4trifluoromethyl)propenyloxymethyloxetane), poly(meth)acrylic acid Among them, in terms of the peelability of the Titanic hardening film to the aqueous test solution, a phenol resin such as polyvinylphenol is preferred. MarukaLyncurMS-2P it to Maruzen Petrochemical Co., ⑩ manufactured (trade name) commercially available form. When the inkjet ink contains a thermal reactive resin (D) of 0.1 wt%/o to 30 wt〇/0, the chemical resistance of the cured film of the obtained ink becomes high, so it is preferable to contain 0.5. It is more preferable that the heat-reactive resin (D) is wt% to 25 wt%, and it is more preferable to contain 1 wt% to 20 wt% of the heat-reactive resin (D). 1.5 Flame Retardant 24 201016799 •3 iS^tJpLU In order to impart flame retardancy to inkjet ink, it may contain flame retardant (E). The phosphorus-based compound in the flame retardant (E) has less influence on the environment, and is therefore preferred. Specific examples of the flame retardant (E) of the phosphorus-based compound include triphenyl phthalate, tricresyl phosphate, tris(xylylene) phosphate, tolylphenyl phosphate, and 2-ethylhexyl diphenyl phosphate. , 9,10_Dihydrooxa-11〇_phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-1〇-conformation phenanthrene-10 - Oxide, condensed 9,10-diin-9-oxa-1〇_璘phenanthrene-1-oxide-etc. Among these flame retardants, a compound represented by the following formula (e-i) is used, that is, a condensed 9,1 〇dihydro-9-oxaxanium phosphaphenanthene oxime oxide (Showa Takahashi) HFA-3003 (trade name) manufactured by Molecular Co., Ltd., even if the cured film obtained from the inkjet ink is exposed to a high temperature state, there is no bleed out of the flame retardant. Therefore, it is better. 10 25 201016799 31945pifl

Ch2-o

The flame retardant (E) may be one compound selected from the above compounds, or a mixture of two or more of these compounds. If the ink for ink in the mouth contains 10% by weight to 50% by weight of the flame retardant (E), the cured film obtained from the black water for inkjet exhibits high flame retardancy (equivalent to (Underwriter Laboratories) combustion test) Method ν·〇 standard), so it is better. (1) more than 1 g. (meth) acrylate (F) can be contained in the ink for inkjet, especially if it is light sensitivity. It is preferred to have no hydroxyl group = polyfunctional (meth) acrylate. Here, even if the hydroxy difunctional (meth) acrylate does not contain a polyfunctional group having a hydroxyl group which is mixed in at the time of production or is an unreacted product, the content in the above case is extremely small. Therefore, you can still see the 'base' acrylic arm as a non-hydroxyl 26 201016799 Jiy^pm polyfunctional (fluorenyl) propyl vinegar (F). The cyclamate (methyl) acrylate (7) may be a quinone compound selected from the compounds listed below, or a mixture of two or more of these compounds.具体 Specific examples of the polyfunctional (meth)acrylic acid (F) having no trans group may be ethylene glycol di(meth)acrylic acid vinegar, diethylene glycol di(methyl)acrylic acid=ethylene glycol Di(meth)acrylic acid vinegar, tetraethylene glycol di(meth)acrylic acid di, t ethyl: alcohol di(meth)acrylic acid vinegar, propylene glycol di(methyl)acrylic acid: one propane: alcohol one ( Methyl) propyl acetoacetate, tripropylene glycol di(methyl) acrylate acid r曰:: 1 acrylic acid vinegar, polypropylene glycol di(meth)acrylic acid dioxin ^' Wei Yiyuan modified di(meth)acrylic acid Vinegar, double-aged clothing _ 'meta-modified one (meth) acrylate, trimethylol propyl three (methanoate, ethylene oxide modified trimethylolpropane: Methyl propyl tris(methyl) acrylate vinegar) propylene di succinyl propyl acetonate tetrakis (meth) acrylate vinegar, glycerol tris(methyl) acrylate vinegar: , hexanol di ketone Acetate vinegar, methoxylated di(methyl)-propyl succinyl vinegar, neopentyl glycol di(meth)acrylic acid vinegar, diglyceryl tetra(methyl)propane diester, pentaerythritol tetra ( Methyl acrylate vinegar, two seasons $ knee two = dipentaerythritol six ( Trisyl propyl acetoacetate, tris[(methyl)propoxy-oxyethyl]trimer I, and caprolactone modified tris[(methyl)acryloxyethyl) heterotrimerization Cyanate bisphenol? Milk = bismuth, bisphenol A type epoxy propylene acrylate, double oxy-acrylic vinegar, isophthalic acid acrylate vinegar, etc. 'If it contains a selected from F-type 27 201016799 31945pifl Ethylene-epoxy modified dimethyl (meth) acrylate acid, pentaerythritol tetraacrylic acid g, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol six ( Methyl) acrylate, tris[(indenyl)propenyloxyethyl]isocyanate, and caprolactone modified tris[(methyl)acryloxyethyl]isocyanuric acid When the ester or bisphenol p-type epoxy acrylate is one or more, the chemical resistance of the cured film becomes higher, and therefore it is better. Among the bisphenol F-type epoxy acrylates, there are limited shares of Nippon Chemical Co., Ltd. ZFR 1122, 1401H, 1491H (trade name) manufactured by the company, NEOPOL 8477 (trade name) manufactured by japan ϋ-pica Co., Ltd., etc. © Right to inkjet ink Containing 5 wt% to 80 wt% of a polyfunctional (meth) acrylate (F), when used in the case of an inkjet ink, it has a high sensitivity to light and, in addition, a hardening film mineralization resistance. It is preferable to increase the content of the polyfunctional (fluorenyl) acrylate (F) by 10 wt% to 7 〇 wt%. 1.7 Other components for the purpose of improving storage stability or the formed film The durability of the film, the uniformity of the film surface of the formed film, the flame retardancy of the formed film, the discharge characteristics of the ink, the coatability of the ink, and the like, and the ink for inkjet may contain a solvent, a reactivity, and a release agent. , polymerization inhibitors, surfactants, colorants, antistatic agents, and the like. These components may be one compound or a mixture of two or more compounds. Further, the amount of water in the ink for inkjet is not particularly limited, and it is preferably that the smaller is equal to 1 G, and the GGG ppm is more preferably 5 or less. Less change, and preservation 28 201016799 Excellent stability, so it is better. 1_7.1 Solvent (6) In order to improve the discharge characteristics of the ink, the ink for inkjet may contain a solvent (G). The solvent is preferably a solvent having a boiling point of 100 ° C or higher. When the viscosity of the ink for ink jet at room temperature is 50 mPa or more, it is preferable to increase the ejection temperature. In this case, the boiling point of the solvent contained is preferably 200 ° C or more. Specific examples of the solvent having a boiling point of 100 ° C or more include butyl acetate, butyl propionate, ethyl lactate, hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, decyl decyl acetate, Ethyl methoxyacetate, butyl oxyacetate, decyl ethoxyacetate, ethyl ethoxyacetate, decyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-methoxypropane Hydrate ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, Propyl 2-hydroxypropionate, decyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-decoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, decyl pyruvate, ethyl pyruvate, propyl pyruvate, decyl acetate, ethyl acetate, ethyl 2-oxobutanoate , 2-oxo-oxybutyrate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, Glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monodecyl ether, propylene glycol monodecyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monodecyl ether acetate, dipropylene 29 201016799 31945pitl diol monoethyl _ _, dipropylene glycol single ethyl butyl bromide Ether acetate, cyclohexanone, cyclopentyl _, _ ethylene-diethylene glycol monodecyl ether acetate, diethylene glycol monoether early: f ether alcohol monoethyl ether acetate, diethylene Alcohol monobutyl hydrazine, _ B = alcohol acetate vinegar, diethylene glycol dimercapto riddle, diethylene bis- early butyl ether alcohol decyl ethyl ether, toluene, diterpene benzene, stupid Ether, diethylenedimethyl b-, N_methyl_2_ bite ^ TT ' N'N_

(dimethyl imidazolidinone ). This solvent: methyl t sputum _ f uses the amount of water in the ink to become upper ==: - bismuth ethoxide using dipropylene glycol monodecyl ether acetic acid, dipropanol oxime ethyl ketone acetate, one propylene Acid monodecyl ether acetate, propylene glycol monoethyl acetonitrile = ether acetate 酉曰 propylene glycol methyl vinegar, 3-ethoxy propionate ethoxy methoxy propionate ethylene glycol monobutyl _ _ _, 2: alcohol% Ethyl ether acetate, diethyl ethyl ether, etc., the ink is ejected stably, so Ethyl alcohol A contains ruthenium in inkjet ink.

Then, the solvent (G) of the photocurable inkjet ink is made at a temperature of 5% to 50% by weight. Preferably, the sputum is stable when 〇Wt%~, and therefore, the surface of the ink is more Great influence, so better /t coating performance for inkjet ink mN / m ~ 45_ / m, better = adjust the surface tension of the ink to 20 and then adjust to 30 mN / ^ (four) 27 Seoul 111 ~42 mN/m, mN/m~45 mN/m range, then ~4〇mN/m. If the surface tension is 20 J, the ink meniscus of the ink ejection port (ink 3〇 201016799 Jiy^pux meniscus) becomes stable, and the ejection of the ink becomes good. In order to adjust the surface tension to a range of 20 mN/m to 45 mN/m, it is important to select a solvent. A solvent having a surface tension in the range of 2 〇 mN/m to 45 mN/m can be used. If a solvent having a large surface tension (for example, r · butyrolactone: 43 mN/m) is used, and a surface tension is small, Solvent (for example, diethylene glycol decyl ethyl ether: 24 mN/m, or ethylene glycol monobutyl ether: 32 mN/m), the surface tension can be finely adjusted with solvent composition, so

1.7.2 Reactive diluent (H) In order to adjust the viscosity of the ink or to control the degree of crosslinking of the cured film, the inkjet ink may contain a reactive diluent (H). When a reactive diluent (?) is used instead of a solvent or a part of the solvent, the solid content of the ink becomes high, so that a thick film can be formed. The reactive diluent (H) represents a radically polymerizable monomer (A) having a cyclic ether of 5 or more members, a radically polymerizable monomer (B) having a thermally reactive functional group, and a polyfunctional ( Methyl) acrylate (F) different compounds. Specific examples of the reactive diluent (H) include n-butyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isodecyl acrylate (decyl), (曱) Tridecyl acrylate, 2-(2-ethoxyethoxy)ethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylic acid-2 -Phenoxyethyl ester and the like. Among these reactive diluents, n-butyl (meth)acrylate and cyclohexyl (meth)acrylate can greatly reduce the viscosity of the inkjet ink by using a small amount, which is awkward. 31 201016799 31945pifl In the case of a two-ink ink measured by a reactive dilution type viscometer of a human agent to 6 Gwt% in inkjet ink, the viscosity is 2 mPa using E 2 , *^τε\. s~500 mPa. s minus ' is better, better _%~ 1.7.3 polymerization inhibitor (1)

The stability of the high-definition, the inkjet ink may contain a polymerization inhibitor. The specific examples of the inhibitor include 4-methoxybenzene, hydroqmnone, and phenazine. From the viewpoint of minimizing the change in viscosity of the ink in the case where the ink jet is heated during the injection of the above-mentioned polymerization inhibitor, it is preferred to use the chalcedony as a polymerization inhibitor. From the viewpoint of coexisting the storage stability of the ink for inkjet and the high sensitivity to light, it is preferred that the inkjet foam contains a polymerization inhibitor of G.Olwt% to 1% by weight. 1_7.4 surfactant (j)

In order to improve the uniformity of the film surface obtained from the ink for inkjet, the ink for inkjet may contain a surfactant. As the surfactant, a cerium (siUc〇n)-based surfactant, an acrylic surfactant, a fluorine-based surfactant, or the like can be used. Specific examples thereof include a quinone-based surfactant such as Byk-300, Byk-306, Byk-335, Byk-310, Byk-34, Byk-344, or Byk-370 (trade name; manufactured by Byk_chemie Co., Ltd., respectively). ; a fine acid surfactant such as Byk_354, Byk-358, or Byk-361 (trade name; manufactured by Byk_chemie Co., Ltd.); DFX-18, Ftergent 250, or Ftergent 251 (trade name; Ne〇s, respectively) Co., Ltd. 32 201016799 ^ly^pui manufacture), Megafac F-410, Megafac F-443, Megafac F-445, Megafac F-470, Megafac F-479 ' Megafac F-483, Megafac F-489 (products respectively Name; manufactured by Dainippon Ink Co., Ltd.) Fluorine-based surfactant. When the thermosetting composition contains a surfactant of 大于1 wt% or more, the uniformity of the film surface of the cured film is improved, so that it is preferable to consider the balance with other characteristics. .〇1 wt%~1 wt%. ❹ 1.7.5 Colorant (K) The ink for inkjet may contain a coloring agent, and in this case, for example, when the state of the obtained cured film is inspected, it can be easily recognized with the substrate. The inkjet ink may contain a coloring agent of about 0.01 wt% to about 1% by weight, preferably containing Q1 wt0/. ~5 wt% or so of coloring agent. From the viewpoint of the compatibility of the ink raw material, the coloring agent is preferably a dye. 1.7.6 Antistatic Agent (L) The antistatic agent is not particularly limited, and a known antistatic agent can be used. Specific examples thereof include metal oxides such as oxidative kicking, tin oxide-oxidation recording composite oxide, and tin oxide _ ❿ indium oxide composite oxide, or aquarium ammonium salts. The antistatic agent is for preventing electrification, and it is preferably added in an amount of from 1 part by weight to 1 part by weight based on 1 part by weight of the ink for inkjet. 1.8 Method for Producing Inkjet Ink The inkjet ink is preferably prepared by filtering a solution obtained by mixing necessary components. For the filtration, for example, a membrane filter made of a fluororesin or the like can be used. Viscosity of ink for inkjet ink of 1·9 33 201016799 31945pifl The ink for inkjet is 25 measured by an E-type viscometer. When the viscosity of the underarm is 2 mPa·s to 500 mPa·s, the coating characteristics (ejection accuracy, etc.) from the ink jet head become good, which is preferable. The inkjet ink at 25t has a viscosity of 3 mPa.s to mPa.s, and is preferably 5 mpa s to 200 mPa·s. When the viscosity at 25 C exceeds 30 mpa.s, if the ink jet nozzle is added to reduce the viscosity at the time of mouth discharge, a more stable (four) discharge can be achieved. In the case of heating the ink jet head to eject, the heating temperature (preferably 40 ° C ~ 12 〇. The viscosity of the inkjet ink under the arm is preferably 3 rit. 8 ~ 〇 30 mPa s ' if sprayed The ink ink viscosity is 5 mpa s~mpa.s, which is better, especially 7 mPa.s~20 mPa.s. 1·1〇 inkjet ink storage inkjet ink if-thief The old viscosity change is small and the storage stability is good. 2. The inkjet ink by the inkjet method/the inkjet ink of the present invention can be formed by using a known inkjet coating method. _ a coating inkjet coating method, for example, a mechanical energy (mechanicai 〇energy) is applied to the ink, and the ink is ejected (coated) from the nozzle = (so-called piezoelectric method); And a coating method (so-called bubble-jet (registered trademark) method) in which thermal energy is applied to the ink to apply the ink. The inkjet ink can be applied by using an inkjet coating method. The shape of the sigh is preliminarily smudged, whereby the ink can be applied only to the desired portion, and can be reduced in comparison with the photolithography method. ... 34 m ❹ 201016799 Cloth book:: OK = Lifting of the applicator and the applicator head: The ink containing the ink is coated and coated with a sweet spot. The coating unit is exemplified. : acting with ink; droplets; cloth f acts on the ink, and by the above energy, the heat generating head or the metal oxide is similar, >&1, the member of the above metal and/or Metal oxides (such as AU and other gold 1 listed as twisted metal (5), wrong (Zr), chin (Τ〇, Ni (Ni), (5)) and other metals, and oxides of these metals. The coating material which is preferably applied at the time of coating is not separable from the energy of the coating head having the ink accommodating portion for accommodating the ink, and is not limited to the coating money and is different from the sinus portion. In addition, the ink accommodating portion may be a form-to-coating water supply member such as a tube (-) in addition to a form in which the coating head can be separated or not provided. The inkjet ejection (coating) temperature is better than the viscosity of the mouth ink used to listen to the temperature of ~3〇^= Preferably, the formation of the cured film is 31111^~ 3. The cured film of the present invention can be irradiated with ultraviolet rays or visible rays by ejecting the above-mentioned 35 201016799 31945pitl inkjet ink onto the surface of the substrate by a known inkjet coating method. The ink obtained by the light irradiation is cured by a polymerization of a radical polymerizable monomer such as a (meth)acrylic monomer to form a three-dimensional crosslinked body, thereby effectively suppressing the diffusion of the ink. Therefore, when the ink for inkjet described above is used, the drawing of a high-definition pattern can be realized. The amount of light to be irradiated depends on the composition of the ink for inkjet. When ultraviolet light is used as the light to be irradiated, the amount of ultraviolet light to be irradiated is the cumulative amount of the light-receiver UVD-405PD manufactured by Ushio Denki Co., Ltd. The light amount e 10 ^ JIT-201 is measured, preferably 1 〇 mj / cm 2 ~ © mJ / cm 2 or so 'better 10 mJ / cm 2 ~ 800 mJ / cm 2 or so, and better 疋 20 mJ / cm 2 ~ 500 mJ/cm2 or so. Further, the wavelength of the ultraviolet light to be irradiated is preferably from 2 〇〇 nm to 45 〇 nm, more preferably from 220 nm to 430 nm, and further preferably from 250 nm to 400 rnn. Further, the above-mentioned cured film which is hardened by irradiation with light may be further heated and calcined as needed, and is particularly preferably at 120. (: ~250. (: heating under 10 minutes ~ 60 minutes, better at 150. (: ~240 ° C heating for 10 minutes ~ 60 minutes, and then good is at 180 ° C ~ 230. (: under The substrate to be used in the present invention is not particularly limited as long as it can be a substrate to which the inkjet ink is applied, and the shape is not limited to a flat shape. Further, the material of the substrate is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like. 3iy4^pitX s is intended to be a resin such as polythene resin such as polyethylene or polypropylene, or a plastic film such as polyvinyl chloride, gas resin, acrylic resin, polyamide, polycarbonate or polyimine. Cellophane, acetic acid vinegar, metal foil, laminated film of polyimine and metal foil, glasse paper with filling effect, parchment paper, or polyethylene, clay adhesive, polyvinyl alcohol Starch, carboxy Paper, glass, etc. which are filled with CMc (carboxymethyl cellulose), etc. φ Among these materials which constitute a substrate, pigments, dyes, and antioxidants may be further contained in a range that does not adversely affect the effects of the present invention. An additive such as an anti-deterioration agent, a filler, an ultraviolet absorber, an antistatic agent, and/or an electromagnetic wave preventer. Further, a material different from the substrate may be formed on a part of the surface of the substrate. The use of the substrate is not particularly limited, and the present invention is not limited thereto. Since the cured film obtained by the inkjet ink is excellent in etching liquid resistance, plating solution resistance, repellent property to the aqueous solution, and heat resistance, it is preferably used for manufacturing an electron having a metal circuit on the surface of the substrate. The circuit board or the like. The metal forming the circuit _ is not particularly limited. It is preferably gold, silver, copper, or indium tin oxide (Indium Tin Oxide). The thickness of the substrate is not particularly limited, and is usually about 10, According to the purpose of use, the appropriate adjustment is preferably 15 #m~500 //m' is better 20 "m~200 #m. It is necessary to perform an easy adhesion treatment such as a water repellent treatment, a corona treatment, a piasma treatment, a biast treatment, or the like on the surface on which the cured film is formed on the substrate, or an easy adhesion layer is provided on the surface. Or color filter 37 201016799 31945ρΐΠ Protective film for color filter. In addition, 'the inkjet angle ink is applied only to a specific portion, whereby a cured film of a specific pattern can be formed, and the cured film can be reduced. the cost of. In particular, in the electronic circuit board, in the formation of a metal wiring pattern, a plating pattern, and a metal wiring protective film (cover layer), the inkjet ink of the present invention excellent in discharge property and storage stability can be coated only. In the circuit portion of the special, it is possible to effectively form a cured film suitable for each purpose. [Examples] Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by these examples. In addition, unless otherwise specified, the following is a part by weight. The components used in the experimental examples and the comparative examples are as follows. A radical polymerizable monomer (A) containing a cyclic ether of 5 or more members A1 · Tetrahydrofurfuryl methacrylate (trade name "SR203", manufactured by Sartomer Co., Ltd.; 5-member ring compound) A2 · Ring three Hydroxymercaptopropane acetal acrylate (trade name "SR531", manufactured by Sartomer Co., Ltd.; 6-membered ring compound) Radical polymerizable monomer having a thermally reactive functional group (B) B1 · 2-hydroxy methacrylate Ethyl ester B2: o-p-dicarboxylic acid mono(hydroxyethyl methacrylate) (trade name "CB-1", manufactured by Shin-Nakamura Chemical Co., Ltd. 201016799 Jiy^piu) B3: Acrylic _4_hydroxybutyl ester light Polymerization initiator (C) Cl : 2,4,6-trimethylbenzimidyl diphenylphosphine oxide (trade name "DAROCUR TPO", manufactured by Ciba Japan Co., Ltd.) Thermally reactive resin (D) D1 : Polyvinylphenol (trade name "Maruka Lyncur MS-2P", manufactured by Maruzen Petrochemical Co., Ltd.) D2: a mixture of a compound represented by the above formula (d-Ι) and a condensate thereof (trade name "Nikalac MW-" 30", manufactured by Sanwa Chemical Co., Ltd. ) Flame Retardant (E) · E1. Condensation 9,10-Dihydro-9-oxa-10-linanphenanthrene-10-oxide (trade name "HFA-3003", manufactured by Showa Polymer Co., Ltd.) Polyfunctional (fluorenyl) acrylate (F) F1: bisphenol F type epoxy acrylate (trade name "NEOPOL 8477", manufactured by Japan U-pica Co., Ltd.) A F2 : bisphenol F type ethylene oxide modification Diisopropyl acrylate (trade name "M-208", manufactured by Toagosei Co., Ltd.) 39 201016799 31945pifl

HI: cyclohexyl acrylate H2: butyl methacrylate (Experimental Examples 1 to 2, Comparative Examples 1 to 3) In the present experimental example, 'the formation of a 5-membered ring compound as a ring containing 5 or more members of the ring The case where the cured film of the inkjet ink of the present invention of the radical polymerizable monomer (a) is used for resisting or anti-mineral use is verified. Each of the inkjet inks was prepared by blending, dissolving, and dissolving in a ratio (parts by weight) as shown in Table 1 by filtration using a fluororesin membrane filter (m. 2). In addition, Comparative Examples 1 and 2 are examples in which the radical polymerizable monomer (A) component having no cyclic ether of 5 or more members is contained, and Comparative Example 3 is mainly used for (A) An example in which the component does not contain the component of the thermal anti-resin (D) component. ❹ 40 201016799 3iy4^pm [Table i] Ingredient Experimental Example Comparative Example 1 2 1 2 3 A1 400 200 — One 400 B1 50 50 50 50Π 50 B2 150 150 150 150 150 C1 100 100 100 100 100 D1 30 30 30 30 — Further, in the inkjet inks of Experimental Examples 1 to 2 and Comparative Examples 1 to 3, the polymerization inhibitor (I) was added in an amount of 0.05 part by weight in terms of F1 150 150 150 150 150 H1 - 200 400 The phenothiazine (the total amount of the ink for inkjet other than the polymerization inhibitor (I) is 1 part by weight). (1) Viscosity of ink and viscosity change by storage The viscosity of each inkjet ink at 25 ° C was measured by an E-type viscometer (VISCOMETER TV-22 manufactured by Toki Sangyo Co., Ltd.). . The results are shown in Table 2. Separately, a part (10 g) of each inkjet ink was placed in a 30 mL sample vial, capped, and stored at 100 ° C for 5 hours. Further, the rate of change of the viscosity of the ink after storage with respect to the viscosity of the ink before storage was examined. The viscosity of the ink was increased after storage, and the case where the rate of change was less than 10% was judged as "〇", and the case where the rate of change was 10% or more was judged as "X". The results are shown in Table 2. It is understood that the inkjet inks of Experimental Examples 1 to 2 are excellent in storage stability. 201016799 31945ρΐΠ (2) Evaluation of ejection characteristics Each inkjet ink was injected into an ink jet cartridge and mounted in an inkjet device (DMP-2800 manufactured by FUJIFILM Dimatix Co., Ltd.). The nozzle for use of the crucible was used to observe the discharge when the discharge voltage (piezoelectric voltage) was 16 V, the nozzle temperature was 7 ° C, and the drive frequency was 5 kHz. The liquid column at the time of ejection was ejected in the vertical direction, and the case where no satellite was generated was judged as "〇", and the case where the liquid column was in contact with the adjacent liquid column or the satellite point was generated was judged as "X". The results are shown in Table 2. 3 (3) Preparation of the test substrate The inkjet ink was injected into the ink in the nozzle, and it was placed in an inkjet apparatus (〇 ^ ^ FU FU FU FU FU FU FU FU , , , , , , , , , , , , , , , , , , , , , The next 'inkjet printer' (inkjet printer) applied (painted) each inkjet ink onto a substrate, followed by ultraviolet (UV, aviolet) hardening, to produce a test with a cured film. Using the test substrate prepared as described above, the peeling property of the hardened side __, the female water miscellaneous (_liquid) 所示 shown in the following (4) to (4), and the resistance to the plating liquid were examined. Substrate preparation conditions _ base f - a substrate obtained by reading copper on a polyimine (thickness: 35 /zm) [(made by Toyobo Co., Ltd.) VylGflex (trade name)] Thickness of cured film: 30 Edge discharge conditions: the same discharge conditions as above 1 + & [2) 42 201016799 jiyopin UV exposure: 250 mJ/cm 2 (4) Evaluation of the resistance of the cured film to the etching solution In order to evaluate the resistance of the cured film to the surname The prepared test substrate was immersed in a 13% FeCl3 aqueous solution at 50 ° C for 15 minutes, and then washed with water, and the surface state of the cured film was visually judged. The case where no peeling or discoloration occurred was judged as "〇", and the case where peeling or discoloration occurred was judged as "x". The results are shown in Table 2. _ (5) Evaluation of the peeling property of the cured film to the alkaline aqueous solution (release liquid) In order to evaluate the peelability of the cured film to the aqueous solution (peeling solution), the prepared test substrate was set at 50 ° C. The solution was immersed in an aqueous solution of NaOH for 1 minute, then washed with water, and the peeling state of the cured film was visually judged. The case of completely dissolving or peeling was judged as "〇", and the case of not being dissolved or peeled was judged as "X". The results are shown in Table 2. (6) Evaluation of the resistance of the cured film to the ore solution In order to evaluate the resistance of the cured film to the ore dressing liquid, the test ruthenium substrate produced was applied to a 60 c non-electrolytic ore liquid (trade name: Nimden NPR-4, Νι concentration is 4.5 g/L, manufactured by Uemura Industrial Co., Ltd.), immersed for 20 minutes, washed with water, and then applied to a 6 〇t: gold (w strike plating solution (trade name: Acid) Strike, manufactured by Japan High Purity Chemical Co., Ltd., was immersed for 1 minute, washed with water, and then washed at 1 Torr. A non-electrolytic gold liquid (trade name: Goblite TAM-55, Au concentration: 1 g/L, manufactured by Uemura Industrial Co., Ltd.) was dipped for 3 minutes to be washed with water to form a plating film. In the step, the plating solution was not infiltrated into the interior of the cured film or the peeling of the film was judged as "〇", and the plating solution was allowed to penetrate into the cured film or peeled off, and the result was judged as "Χ". 2 in. [Table 2] Characteristics of the cured film Comparative Example 1 2 1 ?, 3 Viscosity (25C) (mPa.s) 78 76 77 65 32 Change rate of viscosity 〇〇 XX 〇 Spray characteristics 〇〇 XX 〇 For residual liquid Resistance 〇〇〇 XX peeling property to alkaline aqueous solution 〇〇 X 〇〇 resistance to ore solution () () 〇 XX (Experimental Examples 3 to 4, Comparative Examples 4 to 6) In this experimental example, The case where the cured film of the ink for nozzle ink of the present invention is used for the use of the cover layer is verified. In the proportions (parts by weight) described in Table 3, they were mixed, dissolved, and filtered through a fluororesin membrane filter (0.2 /zm) to prepare inks for inkjet. Further, Comparative Examples 4 and 5 are examples in which the case of the ring-free free-synthesis monomer (4) having no or more than 5 membered rings is mainly verified, and Comparative Example 6 is mainly composed of (4) but not containing heat. An example of verification of the case of the reactive resin (D) component. 201016799 Jiy45piti [Table 3] becomes an experimental example ----------- Comparative Example 3 4 4 5 A 6 ----- A1 40 10 — A 40 B3 15 15 15 15 15 C1 8 8 8 8 8 D2 10 10 10 10 One E1 40 40 40 40 40 ----- F2 70 70 70 70 70 H1 — 30 40 — _ —- H2 — — 40 _ » -----1 In addition, in Experimental Example 3 In the inkjet ink of ～4 and Comparative Examples 4 to 6, the polymerization inhibitor (I) is added with 0.05 parts by weight of phenolphthalein (the total amount of ink for inkjet other than the polymerization inhibitor (I) is set to 100 parts by weight). (1) Viscosity of ink and change in viscosity due to storage The viscosity of each inkjet ink at 25 ° C was measured by an E-type viscometer. The results are shown in Table 4. Further, a part (10 g) of each inkjet ink was placed in a 30 mL sample vial and capped at 1 Torr. (3 hours of storage. The rate of change of the viscosity of the ink after storage is compared with the viscosity of the ink before storage. The viscosity of the ink is increased after storage, and the rate of change is less than 10%. In the case of the above, the result is shown as "X". The results are shown in Table 4. It is understood that the inkjet inks of Experimental Examples 3 to 4 are excellent in storage stability. (2) Evaluation of ejection characteristics 45 201016799 31945pifi Each inkjet ink is injected into the crucible device (10) JIFILM Dimatlx: = it is mounted on the nozzle for inkjet (4), and the discharge temperature is 7 (TC, the drive frequency is the core voltage) ) is 16V, spray condition. The liquid column at the time of injection is along the vertical direction: the spray: down and = ί == 〇 "", the liquid column is in contact with the adjacent liquid column, or the production: It is X". The results are shown in Table 4. (3) Production of test substrate

The device inkjet ink is mounted on a substrate under the conditions of substrate fabrication in an inkjet device (DMp_28® manufactured by FUJIFILM Dunatix Co., Ltd.), and the silk plate is drawn by the inkjet ink_inkjet ink. The upper layer is then subjected to W hardening and thermal hardening, and the test substrate having a cured film is formed. Using the test prepared in the above manner, the substrate 's investigation of the properties of the hardened platoon plating liquid shown in the following (4) * (1) and the solder heat resistance were examined. Substrate fabrication conditions

Substrate: A substrate (thickness of 35 /zm) in which copper is laminated on polyimide. [(Toyo Spinning Co., Ltd.) Vyl〇flex (trade name)] Thickness of cured film: 30 Ejection conditions : The same ejection conditions as in the above (2) UV exposure amount: 40 mJ/em2 Thermal curing condition: 190 ° C x 30 minutes (4) Evaluation of the resistance of the cured film to the plating solution 46 201016799 jiy^piii In order to evaluate the cured film pair The prepared test substrate was immersed in a 30 C palladium aqueous solution (trade name: KAT-eo'pd, concentration: 12 mg/L, manufactured by Uemura Industrial Co., Ltd.) for a minute, and washed with water. 'Put it at 80. (: The electroless nickel plating solution (trade name: Nimden NPR-4, Νι concentration: 4.5 g/L, manufactured by Uemura Industrial Co., Ltd.) was immersed for 30 minutes, washed with water, and then, it was subjected to 8 (rc An electroless gold plating solution (trade name: Goblite TAM-55, Au concentration of 1 g/L, manufactured by Sigma Electronics Co., Ltd.) was immersed for 10 minutes, and washed with water to form a mineral coating film. The case where the ore-forming liquid did not penetrate into the inside of the cured film or the cured film was peeled off was judged as "〇", and the case where the plating solution penetrated into the cured film or the cured film was peeled off was judged as "X". The results are shown in Table 4. (5) Evaluation of solder heat resistance of the cured film In order to evaluate the heat resistance of the cured film, a rosin-based flux was applied to the surface of the cured film of the test substrate (trade name: NS-829, Nihon Superior Co., Ltd.), and it was immersed in a solder bath at 260 ° C for 30 seconds to investigate whether peeling or bulging occurred. The case of peeling and bulging of completely unproductive sputum was judged as "〇", although Less but still caused by peeling or bulging X. The results are shown in Table 4. 47 201016799 31945pifl [Table 4] Intrinsic viscosity of cured film (2) Experimental example Comparative Example 132 146 4 131 125 6 121 Change rate of viscosity ^ 〇〇 XX Ο Jet characteristics - 々 Red T/__, two ''''-_ 〇〇 XX 耐 resistance to forging liquid 〇〇〇 XX solder heat resistance: ϋ ~ one _ -~---^JL^J 〇X Ljl_ (Experimental Example 5 ～6, tb, and the examples 7 to 9) In the present experimental example, the inkjet ink of the present invention is formed by forming a cyclic polymerizable monomer (4) containing a 6-membered ring compound as a ring-shaped ring of 5 or more members. The cured film is used for resisting or anti-plating applications. It is formulated in the proportions (parts by weight) shown in Table 5, mixed and dissolved, and a membrane filter made of fluororesin (〇2) Each of the inkjet inks was prepared by filtration. Further, Comparative Examples 7 and 8 are mainly for the verification of the radical polymerizable monomer (Α) component containing no cyclic ether having 5 or more members. For example, Comparative Example 9 is mainly for the component containing the (Α) component but not containing the heat-reactive resin (D). Example of verification of situation. 201016799 31945ρΐί1 [Table 5] Becoming an experimental example Comparative example 5 6 7 8 9 Α 2 130 60 — — 130 Β 1 50 50 50 50 50 Β 2 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 30 — F1 250 250 250 250 250 Η1 — 70 130 — _ Η 2 50 50 50 180 50 Further, in the inkjet inks of Experimental Examples 5 to 6 and Comparative Examples 7 to 9, the polymerization inhibitor (I) was added 0.05. The phenol thiazine (the total amount of the inkjet ink other than the polymerization inhibitor (I) is 100 parts by weight). (1) Viscosity of Ink and Change in Viscosity Caused by Storage • The viscosity of each inkjet ink at 25 φ ° (:) was measured in the same manner as in Experimental Example 1. The results are shown in Table 6. In addition, the change rate of the viscosity of the ink was examined in the same manner as in Experimental Example 1. The results are shown in Table 6. It is understood that the inkjet inks of Experimental Examples 5 to 6 are excellent in storage stability. (2) Spray characteristics Evaluation The discharge of each inkjet ink was observed in the same manner as in Experimental Example 1. The results are shown in Table 6. (3) Preparation of Test Substrate The same procedure as in Experimental Example 1 was carried out to produce hardening. Film test 49 201016799 31945pifl Substrate. Using the test substrate prepared as described above, the peelability of the hard-drawn female ship (the peeling liquid) and the resistance to the plating solution of the hard-dipping female ship shown in the following (4) to (4) (4) Evaluation of the resistance of the cured film to the money engraving solution The resistance of the cured film to the surname was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 6. (5) Cured film pair Peeling of an aqueous solution (peeling solution) Evaluation of the properties The peeling property of the cured film against the aqueous solution 剥离 (peeling solution) was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 6. (6) Evaluation of the resistance of the cured film to the ore solution was The resistance of the cured film to the ore solution was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 6. [Table 6] Characteristics of the cured film Experimental Example Comparative Example 5 6 7 8 9 Viscosity (25 C ) ( mPa s ) 150 102 70 62 80 Viscosity change rate 〇〇 XX 〇 Ejection characteristics 〇〇 XXX resistance to etching solution ~ ΤΓΙ XX Stripping of an aqueous solution if1 〇〇X 〇〇 resistance to plating solution〇〇〇 XX (Experimental Examples 7 to 8 and Comparative Examples 1 to 12) In the present experimental example, the case where the cured film 50 201016799 ^iy45piu which forms the inkjet ink of the present invention was used for the use of the cover layer was verified. Each of the inkjet inks was prepared by mixing in a ratio (parts by weight) shown in Table 7 and mixing and dissolving, and filtering using a fluororesin membrane filter (0.2 /zm). Further, Comparative Examples 10 and 11 were prepared. Is mainly for the absence of having a large Example of verifying the case of the radically polymerizable monomer (A) component of the cyclic ether of the 5-membered ring. Comparative Example 12 is mainly for the component containing the component (a) but not containing the thermally reactive resin (D). An example of verification of the situation.

[Table 7] Component Real Example Comparative Example 7 8 10 11 12 A2 90 45 One - 90 B3 30 30 30 30 30 C1 8 8 8 8 8 D2 10 10 10 10 - E1 40 40 40 40 40 F2 60 60 60 60 60 H1 ——' 45 90 — H2 _ _ 90 — Further, in the inkjet inks of Experimental Examples 7 to 8 and Comparative Examples 10 to 12, the polymerization inhibitor (I) was added with 0.05 part by weight of phenolthiophene. The total amount of the inkjet ink other than the polymerization inhibitor (I) is 100 parts by weight. (1) Viscosity of ink and change in viscosity due to storage In the same manner as in Experimental Example 3, the viscosity of each inkjet ink was measured at 25 degrees. The results are shown in Table 8. Further, in the same manner as in Experimental Example 3, the change rate of the viscosity of the ink of 51 201016799 31945pifl was investigated. The results are shown in Table 8. ^知'^ Inkjet 〇 of the example 7 to 8 (2) Evaluation of the mouth escaping 疋疋呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉呉The results are shown in Table 8. Lease of ink (3) Production of test substrate

α A test substrate on which a cured film was formed was produced in the same manner as in Test 3. Using the test substrate prepared as described above, the resistance of the hardened lining liquid shown in the following (4) and (5) and the solder resistance were investigated. (4) Evaluation of the resistance of the cured film to the ore solution In the same manner as in Experimental Example 3, the compatibility of the cured film with the money dressing liquid was evaluated. The results are shown in Table 8. (5) Evaluation of heat of solder of cured film The soldering property of the cured film was evaluated in the same manner as in Experimental Example 3. The results are shown in Table 8. ”

52 201016799 [Table 8] Characteristics of cured film Comparative example 7 8 10 11 12 Viscosity (25 ° C ) (mPa-s) 123 73 42 37 89 Change rate of viscosity 〇〇 XX 〇 Spray characteristics 〇〇 XX 〇 Resistance of plating solution 〇〇〇 XX Solder heat resistance 〇〇〇 XX ® [Industrial Applicability] The present invention can be used, for example, as a protective film or an insulating film used in an electronic circuit board, or as a resistance for forming a metal pattern wiring. A resist or a plating pattern forming resist. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of protection of the invention is defined by the scope of the appended patent application. • [Simple diagram description] None [Main component symbol description] None 53 201016799 ^ ly^DpiIi is the 98129444 Chinese manual without a slash correction. Patent description

INK FOR INKJET AND CURING FILM FORMED FORM THE INK % (2〇〇6M^i II. Abstract of Chinese invention: % <2006.011 (2006.011 requires a metal etchant resistance, peelability to the stripping solution, or ore fluid tolerance) The inkjet ink of the present invention comprises: a radical polymerizable monomer (?) containing a cyclic ether of 5 or more members, and a radically polymerizable monomer having a thermally reactive functional group ( Ink), photopolymerization initiator (C), and heat-reactive resin (D). An ink for inkjet having resistance to a metallic etching liquid, peeling property in relation to a peeling liquid or resistance The ink for inkjet includes a radical polymerization monomer (A) having a membered ring equal to or larger than 5 of cyclic ether, a radical diffusion monomer (B) to thermal reactivity 201016799 functional group, a photopolymerization initiator (C) and a thermal reactive resin (D). 201016799 31945pifl VII. Patent application scope: 1· An inkjet ink comprising: a radical polymerizable monomer (A) having a cyclic ether of 5 or more members; a radically polymerizable monomer (B) having a thermally reactive functional group; The inkjet ink according to the first aspect of the invention, which is a radically polymerizable monomer containing a cyclic ether having a ring of 5 or more members, and a heat-reactive resin (D). A compound represented by the formula (A): R1 H2C: I (VIII) 〇=c-R2—r3 ο 2. (In the formula (4), R1 is hydrogen or a carbon number of 1 to 3, R is acceptable The carbon number having a branched structure is 丨ς d branched structure having a carbon number of 2 to 5, and r3 is = or may have a calcined hydrazine or a fluorenyl group of the formula (4) = B = Take the ring of 5 or 6 members of the ring with a number of 1 to 3 or 2. "The number of gas is j 4 · As in the inkjet formula (A) described in the second paragraph of the patent application, 'R is hydrogen or methyl, and the ruler 2 is an anthracene group: the helmet is in the number of oxygen is 54 201016799 The 5-membered ring of the i-ring is 5. The patent application formula (A) tj is hydrogen or ink ink 'where the oxygen substituted in the alkyl group of 1 to 3:, *,, ' Methyl, R3 is a cyclic ether of a 6-membered ring of carbon number 6.螓m = r has a free radical of its trir functional group == Ink used in the 7th black m patent range No. 1 to 5 of the spray-ink's free filaments having an allergic functional group A compatible monomer) has a thermally or crosslinkable functional group via a thiol group. 8. The two-in-one ink according to any one of claims 1 to 5, wherein the radically polymerizable monomer CB) having a thermally reactive functional group has one thermally reactive functional group. 9. The ink for inkjet according to any one of claims 1 to 5, wherein the radically polymerizable monomer (B) having a thermally reactive functional group is a formula (B-1) Or the compound represented by (B_2): R4 H2C=C—C〇〇"T-R5—〇-4—h S Π (B-1)

=yC00H (Β-2) Τ Ο h2c=c——c One. Ο η (in the formulae (Β-1) and (Β-2), r4 is independently hydrogen or 55 201016799 31945pifl a carbon number of 1 to 3, and R5 is independently a ring structure. The number of breaks is 2 to 12, and η is an integer from 1 to 30). 10. The inkjet ink according to any one of claims 1 to 5, wherein the radically polymerizable monomer (Β) having a thermally reactive functional group is selected from (meth)acrylic acid. -2-hydroxyethyl ester, (mercapto)acrylic acid _2 _ propyl propyl vinegar, (methyl) acrylic acid-2-butyl butyl acrylate, (methyl) acrylic acid _ 4 _ butyl vinegar , 1,4-cyclohexanol dioctanol mono(indenyl) acrylate, phthalic acid mono [(meth)acrylic acid hydroxyethyl ester], and phthalic acid mono-[2_(2_mercaptopropene) One or more of the group consisting of the dilute oxy)-ethyl] ester. The ink for inkjet according to any one of the items 1 to 5, wherein the photopolymerization initiator (c) is bis(2,4,6•trimercaptobenzamide) Phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. The ink for inkjet according to any one of claims 1 to 5, wherein the thermally reactive resin (D) is a melamine resin. The ink for inkjet according to any one of the preceding claims, wherein the thermally reactive resin (D) is a phenol resin. 14. The ink for ink jets according to any one of claims 1 to 5, further comprising a flame retardant (E). The ink for inkjet according to any one of claims 1 to 5, further comprising a polyfunctional (meth)acrylic acid vinegar (7). 16. A method of forming a cured film by coating an inkjet ink according to any one of claims 1 to 15 by an inkjet method, and irradiating the applied ink Light, thereby forming a cured film. 201016799 17. A method for forming a cured film by applying an inkjet ink according to the first to the fifteenth item of the patent scope of the invention by inkjet method and ink of (4) At the same time, light riding and heating are performed, or 1) light irradiation and 2) heating are sequentially performed, thereby forming a cured film. 18. A hardened film' obtained by the method of claim 16 or item 17 of the patent application. Iy. For example, please apply the hardened film of the patent scope, which is

Formed by a predetermined pattern. 20. An electronic circuit substrate which is a cured film as described in the 18th or 19th item of the substrate. _ As stated in the specification. 21. An electronic material having an electronic circuit substrate as described in the specification. Item 20. 22. The surface of the electronic circuit board as described in the patent application or the part of the 21st item of the patent application. 9Electronics 57 201016799 ly^JUlLL IV. Designated representative map: (1) The designated representative figure of the case: None (2) The symbolic symbol of the representative figure is simple: No. If there is a chemical formula in this case, please reveal the most Chemical formula showing the characteristics of the invention: β