TWI432531B - Inkjet ink - Google Patents
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- TWI432531B TWI432531B TW097110816A TW97110816A TWI432531B TW I432531 B TWI432531 B TW I432531B TW 097110816 A TW097110816 A TW 097110816A TW 97110816 A TW97110816 A TW 97110816A TW I432531 B TWI432531 B TW I432531B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Description
本發明是關於一種噴墨用墨水,是關於一種含有例如電子零件製作中用以形成絕緣膜層之矽化合物(A)以及/或者矽化合物(A')的噴墨用墨水、使用該噴墨用墨水而形成的聚醯亞胺膜、以及形成有該聚醯亞胺膜的薄膜基板、具有該薄膜基板的電子零件。The present invention relates to an ink for inkjet, relating to an inkjet ink containing, for example, a ruthenium compound (A) and/or a ruthenium compound (A') for forming an insulating film layer in the production of an electronic component, using the inkjet A polyimide film formed of ink, a film substrate on which the polyimide film is formed, and an electronic component having the film substrate.
聚醯亞胺之耐熱性、電絕緣性優異,因此是廣泛用於電子通訊領域的材料[例如,參照日本專利特開2000-039714號公報、日本專利特開2003-238683號公報、日本專利特開2004-094118號公報]。Polyimine is excellent in heat resistance and electrical insulation, and is therefore widely used in the field of electronic communication. For example, Japanese Patent Laid-Open No. 2000-039714, Japanese Patent Laid-Open No. 2003-238683, and Japanese Patent No. Japanese Patent Publication No. 2004-094118].
於將聚醯亞胺用作所需之圖案膜之情形時,先前通常是使用蝕刻(etching)或者感光性聚醯亞胺來形成圖案,而近年來正研究一種藉由噴墨來形成所需圖案膜的方法。In the case where polyimine is used as a desired pattern film, it is conventionally to use etching or photosensitive polyimide to form a pattern, and in recent years, a need for formation by inkjet is being studied. The method of patterning a film.
本領域技術人員提出有各種噴墨用墨水[例如,參照日本專利特開2003-213165號公報、日本專利特開2006-131730號公報],於製備聚醯亞胺系噴墨墨水時,因聚醯亞胺系墨水是較為高分子的墨水,故而為了製備最適合之黏度的墨水作為噴墨墨水,必須增加溶劑之比例且減少墨水中之聚醯胺酸含量。而如此一來,存在噴墨1次所得之膜的厚度變薄的問題。A person skilled in the art has proposed various types of inkjet inks. For example, refer to Japanese Laid-Open Patent Publication No. 2003-213165, and Japanese Patent Laid-Open No. Hei. No. 2006-131730. The quinone imine ink is a relatively high-molecular ink. Therefore, in order to prepare an ink of the most suitable viscosity as the inkjet ink, it is necessary to increase the ratio of the solvent and reduce the polyamine content in the ink. In this case, there is a problem that the thickness of the film obtained by one ink ejection becomes thin.
另一方面,已知若矽醯胺酸化合物(矽烷偶合劑)與環氧樹脂、酚樹脂併用,則由於與金屬發生反應或者形成 錯合物,故而膜的密著性提昇,耐焊裂性(solder crack resistance)提高[例如,參照日本專利特開2003-105059號公報]。On the other hand, it is known that if a proline acid compound (decane coupling agent) is used in combination with an epoxy resin or a phenol resin, it reacts with or forms a metal. In the case of the compound, the adhesion of the film is improved, and the solder crack resistance is improved [for example, refer to Japanese Laid-Open Patent Publication No. 2003-105059].
於上述狀況下,謀求一種噴射(噴出)1次即可形成較厚之聚醯亞胺膜(大於等於1 μm)的噴墨用墨水。Under the above circumstances, an inkjet ink having a thick polyimine film (1 μm or more) can be formed by spraying (discharging) once.
本發明者們鑒於上述狀況,發現一種含有至少一種矽化合物(A)以及/或者至少一種矽化合物(A')的噴墨用墨水、進而含有高分子化合物(B)的噴墨用墨水、進而含有烯基取代納迪克酸醯亞胺(alkenyl-substituted nadimide)(C)的噴墨用墨水、進而含有溶劑(D)的噴墨用墨水。In view of the above circumstances, the present inventors have found an inkjet ink containing at least one ruthenium compound (A) and/or at least one ruthenium compound (A'), and an inkjet ink containing the polymer compound (B), and further An inkjet ink containing an alkenyl group substituted with alkenyl-substituted nadimide (C) and an inkjet ink further containing a solvent (D).
本發明提供如下所述之噴墨用墨水等。The present invention provides an inkjet ink or the like as described below.
[1]一種噴墨用墨水,其含有:選自使用具有大於等於2個之酸酐基之化合物(a1)與單胺(a2)而獲得的矽化合物(A)、以及使用具有1個酸酐基之化合物(a1')與二胺(a2')而獲得的矽化合物(A')中的至少一種。[1] An ink for inkjet comprising: an anthracene compound (A) obtained by using a compound (a1) having an acid anhydride group of 2 or more and a monoamine (a2), and using an acid anhydride group At least one of the hydrazone compound (A') obtained by the compound (a1') and the diamine (a2').
[2]如上述第[1]項所述之噴墨用墨水,其中具有大於等於2個之酸酐基之化合物(a1)為下述通式(1)所表示之四羧酸二酐,單胺(a2)為下述通式(2)所表示之胺基矽化合物,
(通式(1)中,X為碳數2~100之四價有機基,通式(2)中,R1 、R2 以及R3 為氫、鹵素或者一價有機基,該些可相同或者不同,Y為碳數1~20之有機基)。(In the formula (1), X is a tetravalent organic group having 2 to 100 carbon atoms, and in the formula (2), R 1 , R 2 and R 3 are hydrogen, halogen or a monovalent organic group, and these may be the same Or different, Y is an organic group having 1 to 20 carbon atoms).
[3]如上述第[2]項所述之噴墨用墨水,其中上述四羧酸二酐為選自均苯四甲酸二酐、3,3',4,4'-二苯基酮四羧酸二酐、2,2',3,3'-二苯基酮四羧酸二酐、2,3,3',4'-二苯基酮四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、2,2',3,3'-二苯基碸四羧酸二酐、2,3,3',4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、2,2',3,3'-二苯基醚四羧酸二酐、2,3,3',4'-二苯基醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、乙二醇雙(偏苯三甲酸酐酯)、環丁烷四羧酸二酐、甲基環丁烷四羧酸二酐、環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、乙烷四羧酸二酐以及丁烷四羧酸二酐所組成之族群中的一種或一種以上,上述胺基矽化合物為選自對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、間胺基苯基三甲氧基矽烷、間胺基苯基三乙氧基矽烷、胺基丙基三甲氧基矽烷以及胺基丙基三乙氧基矽烷所組成之族群中的一種或一種以上。[3] The inkjet ink according to [2] above, wherein the tetracarboxylic dianhydride is selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-diphenyl ketone Carboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylfluorene Carboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(trimellitic anhydride), Cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethane tetracarboxylic acid One or more of the group consisting of acid dianhydride and butane tetracarboxylic dianhydride selected from the group consisting of p-aminophenyltrimethoxydecane and p-aminophenyltriethoxydecane , m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, aminopropyl trimethoxy One or more of the group consisting of decane and aminopropyltriethoxydecane.
[4]如上述第[1]項所述之噴墨用墨水,其中上述矽化合物(A)為下述通式(3)所表示之矽醯胺酸(A),
[化17]
(通式(3)中,X為碳數2~100之四價有機基,R1 、R2 以及R3 為氫、鹵素或者一價有機基,該些可相同或者不同,Y為碳數1~20之有機基)。(In the formula (3), X is a tetravalent organic group having 2 to 100 carbon atoms, and R 1 , R 2 and R 3 are hydrogen, halogen or a monovalent organic group, and these may be the same or different, and Y is a carbon number. 1 to 20 organic base).
[5]如上述第[4]項所述之噴墨用墨水,其中上述矽醯胺酸為下述通式(4-1)、(4-2)或者(4-3)所表示的矽醯胺酸,
(通式(4-1)、(4-2)或者(4-3)中,R1 、R2 以及R3 中的至少一個含有碳數1~20之烷氧基,a為1~20之整數)。(In the formula (4-1), (4-2) or (4-3), at least one of R 1 , R 2 and R 3 contains an alkoxy group having 1 to 20 carbon atoms, and a is 1 to 20 The integer).
[6]如上述第[1]項至第[5]項中任一項所述之噴墨用墨水,其中上述具有大於等於2個之酸酐基之化合物(a1)與上述單胺(a2)之比為1莫耳:0.5莫耳~8.0莫耳。[6] The inkjet ink according to any one of [1] to [5] wherein the compound (a1) having two or more acid anhydride groups and the above monoamine (a2) The ratio is 1 mole: 0.5 mole to 8.0 mole.
[7]如上述第[1]項至第[6]項中任一項所述之噴墨用墨水,其中上述具有1個酸酐基之化合物(a1')為下述通式(1')所表示之羧酸酐,上述二胺(a2')為下述通式(2')所表示之二胺,
(通式(1')中,R1 、R2 以及R3 為氫、鹵素或者一價有機基,該些可相同或者不同,Y'為碳數1~20之有機基,通式(2')中,X'為碳數2~100之二價有機基)。(In the formula (1'), R 1 , R 2 and R 3 are hydrogen, halogen or a monovalent organic group, which may be the same or different, and Y' is an organic group having 1 to 20 carbon atoms, and the formula (2) In '), X' is a divalent organic group having a carbon number of 2 to 100).
[8]如上述第[7]項所述之噴墨用墨水,其中上述羧酸酐為選自對(三甲氧基矽烷基)苯基琥珀酸酐、對(三乙氧基矽烷基)苯基琥珀酸酐、間(三甲氧基矽烷基)苯基琥珀酸酐、間(三乙氧基矽烷基)苯基琥珀酸酐、三甲氧基矽烷基丙基琥珀酸酐以及三乙氧基矽烷基丙基琥珀酸酐所組成之族群中的一種或一種以上, 上述二胺為選自對苯二胺、間苯二胺、對二甲苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基-1,2-二苯基乙烷、4,4'-二胺基-1,3-二苯基丙烷、2,2-雙(4-胺基苯基)丙烷、雙(4-胺基-3-甲基苯基)甲烷、1,2-雙-(4-胺基-3-甲基苯基)乙烷、雙(4-胺基-2-甲基苯基)甲烷、1,2-雙-(4-胺基-2-甲基苯基)乙烷、4,4'-二胺基二苯基醚、3,3'-二胺基二苯基醚、4,4'-二胺基二苯基碸、4,4'-二胺基二苯硫醚、4,4'-二胺基二苯基酮、4,4'-二胺基二苯基-2,2'-丙烷、1,4-二胺基環己烷、4,4'-二胺基二環己基甲烷、1,4-雙[(4-胺基苯基)甲基]苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]氟丙烷、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]聯苯、1,3-雙[4-(4-胺基苄基)苯基]丙烷、1,6-雙[4-(4-胺基苄基)苯基]己烷、5-苯基甲基-1,3-二胺基苯、5-[4-(4-烷基環己基)苯基]甲基-1,3-二胺基苯、5-[4-(4-(4-烷基環己基)環己基)苯基]甲基-1,3-二胺基苯、5-[((烷基環己基)乙基環己基)苯基]甲基-1,3-二胺基苯、1,1-雙[4-(4-胺基苯氧基)苯基]環己烷、1,1-雙[4-(4-胺基苯氧基)苯基]-4-烷基環己烷、1,1-雙[4-(4-胺基苄基)苯基]環己烷、1,1-雙[4-(4-胺基苄基)苯基]-4-烷基環己烷、1,3-雙(3-胺基丙基)-四甲基二矽氧烷所組成之族群中的一種或一種以上。[8] The ink for inkjet according to [7] above, wherein the carboxylic acid anhydride is selected from the group consisting of p-(trimethoxydecyl)phenyl succinic anhydride and p-(triethoxydecyl)phenyl amber. Anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, trimethoxy decyl propyl succinic anhydride, and triethoxy decyl propyl succinic anhydride One or more of the constituent groups, The above diamine is selected from the group consisting of p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenyl Ethylethane, 4,4'-diamino-1,3-diphenylpropane, 2,2-bis(4-aminophenyl)propane, bis(4-amino-3-methylphenyl) Methane, 1,2-bis-(4-amino-3-methylphenyl)ethane, bis(4-amino-2-methylphenyl)methane, 1,2-bis-(4- Amino-2-methylphenyl)ethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl碸, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl-2,2'-propane, 1,4 -diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-bis[(4-aminophenyl)methyl]benzene, 1,4-bis(4-amino group) Phenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-double [ 4-(4-Aminophenoxy)phenyl]fluoropropane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl Biphenyl, 1,3-double [4- (4-Aminobenzyl)phenyl]propane, 1,6-bis[4-(4-aminobenzyl)phenyl]hexane, 5-phenylmethyl-1,3-diaminobenzene , 5-[4-(4-Alkylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 5-[4-(4-(4-alkylcyclohexyl)cyclohexyl)phenyl ]methyl-1,3-diaminobenzene, 5-[((alkylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 1,1-bis[4] -(4-Aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-alkylcyclohexane, 1,1- Bis[4-(4-aminobenzyl)phenyl]cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-alkylcyclohexane, 1,3 One or more of the group consisting of bis(3-aminopropyl)-tetramethyldioxane.
[9]如上述第[1]項至第[6]項中任一項所述之噴墨用墨水,其中上述矽化合物(A')為下述通式(3')所表示之矽醯胺酸(A'),
(通式(3')中,R1 、R2 以及R3 為氫、鹵素或者一價有機基,該些可相同或者不同,Y'為碳數1~20之有機基,X'為碳數2~100之有機基)。(In the formula (3'), R 1 , R 2 and R 3 are hydrogen, halogen or a monovalent organic group, which may be the same or different, Y' is an organic group having 1 to 20 carbon atoms, and X' is carbon Number 2~100 organic base).
[10]如上述第[9]項所述之噴墨用墨水,其中上述矽醯胺酸(A')為下述通式(4'-1)、(4'-2)、(4'-3)、(4'-4)或者(4'-5)所表示的矽醯胺酸(A'),
[化21]
(通式(4'-1)、(4'-2)、(4'-3)、(4'-4)或者(4'-5)中,R1 、R2 以及R3 中的至少一個含有碳數1~20之烷氧基,通式(4'-3)之R為碳數2~30之有機基,通式(4'-4)之R為氫或者碳數1~20之烷基,a為1~20之整數)。(in the general formula (4'-1), (4'-2), (4'-3), (4'-4) or (4'-5), at least one of R 1 , R 2 and R 3 An alkoxy group having 1 to 20 carbon atoms, R of the formula (4'-3) is an organic group having 2 to 30 carbon atoms, and R of the formula (4'-4) is hydrogen or a carbon number of 1 to 20 The alkyl group, a is an integer from 1 to 20).
[11]如上述第[1]項至第[10]項中任一項所述之噴墨用墨水,其中上述具有1個酸酐基之化合物(a1')與上述二 胺(a2')之比為0.5莫耳~8.0莫耳:1莫耳。[11] The inkjet ink according to any one of the above [1], wherein the compound (a1') having one acid anhydride group and the above two The ratio of amine (a2') is from 0.5 moles to 8.0 moles: 1 mole.
[12]如上述第[1]項至第[11]項中任一項所述之噴墨用墨水,其中此噴墨用墨水進而含有高分子化合物(B)。[12] The inkjet ink according to any one of [1], wherein the inkjet ink further contains a polymer compound (B).
[13]如上述第[12]項所述之噴墨用墨水,其中上述高分子化合物(B)為選自聚醯胺酸以及聚醯亞胺中的至少一種。[13] The inkjet ink according to [12], wherein the polymer compound (B) is at least one selected from the group consisting of polylysine and polyimine.
[14]如上述第[12]項或第[13]項所述之噴墨用墨水,其中上述高分子化合物(B)之重量平均分子量為1,000~5,000。[14] The inkjet ink according to [12], wherein the polymer compound (B) has a weight average molecular weight of 1,000 to 5,000.
[15]如上述第[1]項至第[14]項中任一項所述之噴墨用墨水,其中此噴墨用墨水進而含有烯基取代納迪克酸醯亞胺(C)。[15] The inkjet ink according to any one of [1] to [14] wherein the inkjet ink further contains an alkenyl group substituted with nadic acid yttrium imine (C).
[16]如上述第[15]項所述之噴墨用墨水,其中上述烯基取代納迪克酸醯亞胺(C)為使單胺、二胺、三胺或者四胺與下式(5')所表示之烯基取代納迪克酸酐進行反應而成的烯基取代納迪克酸醯亞胺,
式(5')中,R1 以及R2 分別獨立為氫、碳數1~12之烷基、碳數3~6之烯基、碳數5~8之環烷基、碳數6~12之芳基或者苄基中的任一種。In the formula (5'), R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12; Any of an aryl group or a benzyl group.
[17]如上述第[15]項或第[16]項所述之噴墨用墨水,其
中上述烯基取代納迪克酸醯亞胺(C)為下述通式(5)所表示之化合物,
式(5)中,R1
以及R2
分別獨立為氫、碳數1~12之烷基、碳數3~6之烯基、碳數5~8之環烷基、碳數6~12之芳基或者苄基中的任一種,n為1~4之整數,n=1時,式(5)中之R3
為氫、碳數1~12之烷基、碳數1~12之羥烷基、碳數5~8之環烷基、碳數6~12之芳基、苄基、-{(Cq
H2q
)Ot
(Cr
H2r
O)u
Cs
H2s
X}(其中,q、r、s為分別獨立選擇之2~6之整數,t為0或者1之整數,u為1~30之整數,X為氫或者羥基)所表示聚氧亞烷基烷基、-(R)a
-C6
H4
-R4
(其中,a表示0或者1之整數,R表示碳數1~4之亞烷基,R4
表示氫或者碳數1~4之烷基)所表示之基團、-C6
H4
-T-C6
H5
{其中,T為-CH2
-、-C(CH3
)2
-、-CO-、-S-或者-SO2
-}所表示之基團、或者於該些基團之芳香環上直接鍵結的1個~3個氫經羥基取代的基團,n=2時,式(5)中之R3
為碳數2~20之亞烷基{亞烷基中之相互不鄰接的任意亞甲基可經-O-或者-CH=CH-取代,任意的氫可經氟取代}、碳數5~8之亞環烷基、-{(Cq
H2q
O)t
(Cr
H2r
O)u
Cs
H2s
}-(其中,q、r、s為分別獨立選擇之2~6之整數,t為0或者1之整數,u為1~30之整
數)所表示之聚氧亞烷基(polyoxyalkylene)、碳數6~12之亞芳基、-(R)a
-C6
H4
-R5
-(其中,a為0或者1之整數,R以及R5
分別獨立為碳數1~4之亞烷基)所表示之基團、由-C6
H4
-T-C6
H4
-、-C6
H4
-T-C6
H4
-T-C6
H4
-或者-C6
H4
-T'-C6
H4
-T-C6
H4
-T'-C6
H4
-{其中,T為單鍵、碳數1~6之亞烷基、-C(CH3
)2
-、-C(CF3
)2
-、-CO-、-O-、-OC6
H4
C(CH3
)2
C6
H4
O-、-S-或者-SO2
-,T'為-CH2
-或者-O-}所表示之基團、或者於該些基團之芳香環上直接鍵結的1個~3個氫經羥基取代的基團、下式(6-1)所表示之基團或者下式(6-2)所表示之基團,式(6-1)中,x獨立為1~6之整數,y為1~70之整數,
n=3時,式(5)中之R3
為下式(7-1)所表示之基團或者下式(7-2)所表示之基團,
[化25]
式(7-1)中,R為氫、氟、氯、-OH、-OCF3
、-OCF2
H、-CF3
、-CF2
H、-CFH2
、-OCF2
CF2
H、-OCF2
CFHCF3
、或者碳數1~10之烷基,式(7-1)以及式(7-2)中,R4
、R5
、R6
分別獨立為單鍵、反-1,4-亞環己基、1,3-二噁烷-2,5-二基、1,4-亞苯基、氫可經氟取代之1,4-亞苯基或者碳數1~10之亞烷基,亞烷基中之相互不鄰接的任意亞甲基可經-O-或者-CH=CH-取代,任意的氫可經氟取代,n=4時,式(5)中之R3
為下式(8)所表示之基團,
式(8)中,R4 、R5 、R6 、R7 分別獨立為單鍵、反-1,4-亞環己基、1,3-二噁烷-2,5-二基、1,4-亞苯基、氫可經氟取代之1,4-亞苯基或者碳數1~10之亞烷基,亞烷基中之相互不鄰接的任意亞甲基可經-O-或者-CH=CH-取代,任意的氫可經氟取代。In the formula (8), R 4 , R 5 , R 6 and R 7 are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1, 4-phenylene, hydrogen 1,4-phenylene substituted by fluorine or alkylene having 1 to 10 carbon atoms; any methylene group in the alkylene group which is not adjacent to each other may be -O- or - CH=CH-substituted, any hydrogen can be substituted by fluorine.
[18]如上述第[17]項所述之噴墨用墨水,其中n為2。[18] The ink for inkjet according to [17] above, wherein n is 2.
[19]如上述第[17]項所述之噴墨用墨水,其中n為2,式(5)中之R3 為碳數2~15之亞烷基{亞烷基中之相互 不鄰接的任意亞甲基可經-O-或者-CH=CH-取代,任意的氫可經氟取代}、-(R)a -C6 H4 -R5 -(其中,a為0或者1之整數,R以及R5 分別獨立為碳數1~4之亞烷基)所表示之基團、由-C6 H4 -T-C6 H4 -、-C6 H4 -T-C6 H4 -T-C6 H4 -或者-C6 H4 -T'-C6 H4 -T-C6 H4 -T'-C6 H4 -{其中,T為單鍵、-CH2 -、-C(CH3 )2 -、-C(CF3 )2 -、-CO-、-O-、-OC6 H4 C(CH3 )2 C6 H4 O-、-S-或者-SO2 -,T'為-CH2 -或者-O-}所表示之基團。[19] The ink for inkjet according to [17] above, wherein n is 2, and R 3 in the formula (5) is an alkylene group having 2 to 15 carbon atoms; the alkylene groups are not adjacent to each other. Any methylene group may be substituted by -O- or -CH=CH-, any hydrogen may be substituted by fluorine}, -(R) a -C 6 H 4 -R 5 - (where a is 0 or 1) a group represented by an integer, R and R 5 are each independently an alkylene group having 1 to 4 carbon atoms, and is represented by -C 6 H 4 -T-C 6 H 4 -, -C 6 H 4 -T-C 6 H 4 -T-C 6 H 4 - or -C 6 H 4 -T'-C 6 H 4 -T-C 6 H 4 -T'-C 6 H 4 -{ wherein T is a single bond, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -CO-, -O-, -OC 6 H 4 C(CH 3 ) 2 C 6 H 4 O-, -S- or -SO 2 -, T 'is -CH 2 - or -O-} group represented by the.
[20]如上述第[17]項所述之噴墨用墨水,其中式(5)中之R1
以及R2
分別獨立為氫或者碳數1~6之烷基,n為2,式(5)中之R3
為碳數2~15之亞烷基{亞烷基中之相互不鄰接的任意亞甲基可經-O-或者-CH=CH-取代,任意的氫可經氟取代}、式(6-1)所表示之基團、式(6-2)所表示之基團、式(6-3)所表示之基團、式(6-4)所表示之基團或者式(6-5)所表示之基團,
[化27]
式(6-1)中,x獨立為1~6之整數,y為1~70之整數,式(6-3)以及式(6-5)中,R為包含-CH2 -、-CH2 CH2 -、-O-、-C(CH3 )2 -、-C(CF3 )2 -、-SO2 -之有機基,式(6-5)中,X為包含-CH2 -、-O-之有機基。In the formula (6-1), x is independently an integer from 1 to 6, and y is an integer from 1 to 70. In the formula (6-3) and the formula (6-5), R is -CH 2 -, -CH An organic group of 2 CH 2 -, -O-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 -, and in the formula (6-5), X is -CH 2 - , -O-organic base.
[21]如上述第[17]項所述之噴墨用墨水,其中式(5)中之R1
以及R2
分別獨立為氫或者碳數1~6之烷基,n為3,式(5)中之R3
是以式(7-1-1)、式(7-2-1)或者式(7-2-2)表示,
式(7-1-1)中,R為碳數1~10之烷基或者-OH,式(7-2-2)中,R4 、R5 、R6 分別獨立為1,2-亞乙基、1,4-亞丁基。In the formula (7-1-1), R is an alkyl group having 1 to 10 carbon atoms or -OH, and in the formula (7-2-2), R 4 , R 5 and R 6 are each independently 1,2-Asia. Ethyl, 1,4-butylene.
[22]如上述第[17]項所述之噴墨用墨水,其中式(5)中之R1
以及R2
分別獨立為氫或者碳數1~6之烷基,n為4,式(5)中之R3
是以下式(8-1)表示,
[化29]
[23]如上述第[17]項所述之噴墨用墨水,其中此噴墨用墨水含有選自n為1之烯基取代納迪克酸醯亞胺(C)、n為2之烯基取代納迪克酸醯亞胺(C)、n為3之烯基取代納迪克酸醯亞胺(C)、以及n為4之烯基取代納迪克酸醯亞胺(C)中的至少兩種烯基取代納迪克酸醯亞胺(C)。[23] The ink for inkjet according to the above [17], wherein the ink for inkjet contains an alkenyl group selected from the group consisting of an alkenyl group having n of 1 and a naphthyl imine (C) having n of 2 Substituting at least two of Nadick's yttrium imine (C), n's alkenyl substituted nadic ylidene imine (C), and n's 4 alkenyl substituted nadic ylidene imide (C) Alkenyl substituted nadic acid ylide (C).
[24]如上述第[17]項所述之噴墨用墨水,其中此噴墨用墨水含有至少兩種如下之烯基取代納迪克酸醯亞胺(C):式(5)中之R1
以及R2
分別獨立為氫或者碳數1~6之烷基,式(5)中之R3
為碳數1~12之烷基(n=1)、碳數6~12之芳基(n=1)、-(CH2
)對(
n=2,p為6~12之整數)、式(6-1-1)所表示之基團、式(6-2)所表示之基團、式(6-3-1)所表示之基團、式(6-4)所表示之基團、式(6-5-1)所表示之基團、式(7-1-2)所表示之基團、式(7-1-3)所表示之基團、式(7-2-1)所表示之基團、式(7-2-3)所表示之基團、式(8-1)所表示之基團,
另外,本發明之噴墨用墨水可為下述墨水。Further, the ink for inkjet of the present invention may be the following ink.
如上述第[17]項所述之噴墨用墨水,其中此噴墨用墨水含有至少一種如下之烯基取代納迪克酸醯亞胺(C):n為1,式(5)中之R3 為碳數1~12之烷基、碳數5~8之環烷基、碳數6~12之芳基、苄基、-{(Cq H2q )Ot (Cr H2r O)u Cs H2s+1 }(其中,q、r、s為分別獨立選擇之2~6之整數,t為0或者1之整數,u為1~30之整數)所表示聚氧亞烷基烷基、-(R)a -C6 H4 -R4 (其中,a表示0或者1之整數,R表示碳數1~4之亞烷基,R4 表示氫或者碳數1~4之烷基)所表示之基團、或者-C6 H4 -T-C6 H5 (其中,T為-CH2 -、-C(CH3 )3 -、-CO-、-S-或者SO2 -)所表示之基團;以及至少一種n為2之烯基取代納迪克酸醯亞胺(C)。The inkjet ink according to the above [17], wherein the inkjet ink contains at least one alkenyl-substituted nadic acid ylide (C): n is 1, R in the formula (5) 3 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, -{(C q H 2q )O t (C r H 2r O) u C s H 2s+1 } (wherein q, r, s are independently selected integers of 2-6, t is an integer of 0 or 1, u is an integer from 1 to 30), and the polyoxyalkylene alkyl group is represented by , -(R) a -C 6 H 4 -R 4 (wherein a represents an integer of 0 or 1, R represents an alkylene group having 1 to 4 carbon atoms, and R 4 represents hydrogen or an alkyl group having 1 to 4 carbon atoms; a group represented by, or -C 6 H 4 -T-C 6 H 5 (wherein T is -CH 2 -, -C(CH 3 ) 3 -, -CO-, -S- or SO 2 - a group represented by the group; and at least one alkenyl group having n of 2 in place of the nadic acid ylide (C).
又,本發明之噴墨用墨水可為下述墨水。Further, the ink for inkjet of the present invention may be the following ink.
如上述第[171項所述之噴墨用墨水,其中此噴墨用墨水含有至少一種如下之烯基取代納迪克酸醯亞胺(C):式(5)中之R1 以及R2 分別獨立為氫或者碳數1~6之烷基,n為1,式(5)中之R3 為碳數1~12之烷基、碳數5~8之環烷基、碳數6~12之芳基、或者苄基;以及至少一種n為2之烯基取代納迪克酸醯亞胺(C)。The inkjet ink according to the above item [171], wherein the inkjet ink contains at least one of the following alkenyl-substituted nadic acid ylides (C): R 1 and R 2 in the formula (5), respectively Independently hydrogen or an alkyl group having 1 to 6 carbon atoms, n is 1, and R 3 in the formula (5) is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12 An aryl group, or a benzyl group; and at least one alkenyl group having n is 2 substituted with nadic acid ylide (C).
進而,本發明之噴墨用墨水為下述墨水。Further, the ink for inkjet of the present invention is the following ink.
如上述第[17]項所述之噴墨用墨水,其中此噴墨用墨水含有至少一種如下之烯基取代納迪克酸醯亞胺(C):式 (5)中之R1 以及R2 分別獨立為氫或者碳數1~6之烷基,n為1,式(5)中之R3 為碳數1~12之烷基或者碳數6~12之芳基;以及至少一種如下之烯基取代納迪克酸醯亞胺(C):式(5)中之R1 以及R2 分別獨立為氫或者碳數1~6之烷基,n為2,式(5)中之R3 為-(CH2 )6 -、上式(6-3-1)所表示之基團或者上式(6-4)所表示之基團。The inkjet ink according to the above [17], wherein the inkjet ink contains at least one of the following alkenyl-substituted nadic acid ruthenium imides (C): R 1 and R 2 in the formula (5) Each of them is independently hydrogen or an alkyl group having 1 to 6 carbon atoms, n is 1, and R 3 in the formula (5) is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms; and at least one of the following Alkenyl substituted nadic acid ylide (C): R 1 and R 2 in the formula (5) are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, n is 2, and R 3 in the formula (5) It is a group represented by -(CH 2 ) 6 -, the above formula (6-3-1) or a group represented by the above formula (6-4).
[25]如上述第[1]項至第[24]項中任一項所述之噴墨用墨水,其中此噴墨用墨水進而含有溶劑(D)。[25] The inkjet ink according to any one of [1], wherein the inkjet ink further contains a solvent (D).
[26]如上述第[25]項所述之噴墨用墨水,其中溶劑(D)為選自乳酸乙酯、乙醇、乙二醇、丙二醇、甘油、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基乙基醚、二乙二醇單***乙酸酯、乙二醇單丁醚、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、環己酮以及γ-丁內酯所組成之族群中的一種或一種以上。[26] The inkjet ink according to [25] above, wherein the solvent (D) is selected from the group consisting of ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, and diethyl ether. Glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3 One or more of the group consisting of methyl methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, and γ-butyrolactone.
[27]如上述第[1]項至第[26]項中任一項所述之噴墨用墨水,其中相對於100重量份之噴墨用墨水,上述矽化合物(A)以及上述矽化合物(A')之總含量為1重量份~99重量份。The inkjet ink according to any one of the above [1], wherein the ruthenium compound (A) and the ruthenium compound are the same as the ink for inkjet of 100 parts by weight. The total content of (A') is from 1 part by weight to 99 parts by weight.
[28]如上述第[1]項至第[26]項中任一項所述之噴墨用墨水,其中相對於100重量份之噴墨用墨水,上述矽化合物(A)以及上述矽化合物(A')之總含量為10重量份~80重量份。The inkjet ink according to any one of the above [1], wherein the ruthenium compound (A) and the ruthenium compound are the same as the ink for inkjet of 100 parts by weight. The total content of (A') is from 10 parts by weight to 80 parts by weight.
[29]如上述第[11項至第[26]項中任一項所述之噴墨用墨水,其中相對於100重量份之噴墨用墨水,上述矽化合物(A)以及上述矽化合物(A')之總含量為22重量份~70重量份。The inkjet ink according to any one of the above-mentioned [11], wherein the ruthenium compound (A) and the ruthenium compound (the above-mentioned ruthenium compound) are used with respect to 100 parts by weight of the ink for inkjet. The total content of A') is from 22 parts by weight to 70 parts by weight.
[30]一種聚醯亞胺膜或者圖案狀聚醯亞胺膜,此聚醯亞胺膜或者圖案狀聚醯亞胺膜是以如下方法獲得:藉由噴墨塗佈方法,塗佈如上述第[1]項至第[29]項中任一項所述之噴墨用墨水而形成塗膜後,對該塗膜進行固化處理而形成聚醯亞胺膜。[30] A polyimine film or a patterned polyimide film, the polyimide film or the patterned polyimide film is obtained by the following method: by the inkjet coating method, coating as described above After the coating film is formed by the inkjet ink according to any one of the items [1] to [29], the coating film is cured to form a polyimide film.
[31]一種聚醯亞胺膜或者圖案狀聚醯亞胺膜之形成方法,此方法包含如下製程:藉由噴墨塗佈方法,塗佈如上述第[1]項至第[29]項中任一項所述之噴墨用墨水而形成塗膜的製程;以及對該塗膜進行固化處理而形成聚醯亞胺膜的製程。[31] A method for forming a polyimide film or a patterned polyimide film, the method comprising the following steps: coating by the inkjet coating method as in the above items [1] to [29] A process for forming a coating film by using the inkjet ink according to any one of the preceding claims; and a process of curing the coating film to form a polyimide film.
[32]一種薄膜基板,其具有聚醯亞胺膜或者圖案狀聚醯亞胺膜,此聚醯亞胺膜或者圖案狀聚醯亞胺膜是藉由如上述第[31]項所述之方法而形成於基板上。[32] A film substrate having a polyimide film or a patterned polyimide film, wherein the polyimide film or the patterned polyimide film is as described in the above [31] The method is formed on a substrate.
[33]一種電子零件,其具有如上述第[32]項所述之薄膜基板。[33] An electronic component comprising the film substrate according to the above [32].
若使用本發明之較佳形態之噴墨用墨水,則噴射1次即可形成具有較厚之膜厚的聚醯亞胺膜。又,由本發明之較佳形態之噴墨用墨水形成的聚醯亞胺膜,例如耐熱性、電絕緣性高,從而提高電子零件之可靠性、良率。When the ink for inkjet according to the preferred embodiment of the present invention is used, a polyimide film having a relatively thick film thickness can be formed by spraying once. Moreover, the polyimide film formed by the inkjet ink of the preferred embodiment of the present invention has high heat resistance and electrical insulating properties, for example, and improves the reliability and yield of the electronic component.
為讓本發明之上述和其他目的、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。The above and other objects, features and advantages of the present invention will become more <RTIgt;
本發明提供一種含有矽化合物(A)以及/或者矽化合物(A')的噴墨用墨水、使用該墨水之聚醯亞胺膜形成方法等。另外,本發明之噴墨用墨水可為無色,亦可為有色。The present invention provides an inkjet ink containing a ruthenium compound (A) and/or a ruthenium compound (A'), a method for forming a polyimide film using the ink, and the like. Further, the ink for inkjet of the present invention may be colorless or colored.
該噴墨用墨水是含有至少一種矽化合物(A)以及/或者至少一種矽化合物(A')的噴墨用墨水、進而含有高分子化合物(B)的噴墨用墨水、進而含有烯基取代納迪克酸醯亞胺(nadicimide)(C)的噴墨用墨水、進而含有溶劑(D)的噴墨用墨水。The inkjet ink is an inkjet ink containing at least one ruthenium compound (A) and/or at least one ruthenium compound (A'), and further contains an inkjet ink containing a polymer compound (B), and further contains an alkenyl group. An inkjet ink of nadicimide (C) and an inkjet ink further containing a solvent (D).
矽化合物(A)可藉由至少使用具有大於等於2個之酸酐基之化合物(a1)與單胺(a2)而獲得,例如,可為使(a1)與(a2)反應而獲得的生成物(矽醯胺酸(A)),例如,可為(a1)與(a2)形成鹽的化合物,只要為使用具有大於等於2個之酸酐基之化合物(a1)與單胺(a2)可獲得的矽化合物,則並不限定於上述例子。The hydrazine compound (A) can be obtained by using at least a compound (a1) having two or more acid anhydride groups and a monoamine (a2), for example, a product obtained by reacting (a1) with (a2). (Proline (A)), for example, a compound which can form a salt of (a1) and (a2), as long as it is a compound (a1) and a monoamine (a2) which have an acid anhydride group of 2 or more The ruthenium compound is not limited to the above examples.
又,矽化合物(A)中之矽,可來源於具有大於等於2個之酸酐基之化合物(a1),可來源於單胺(a2),亦可來源於(a1)與(a2)兩者。於以下之詳細說明中,是使用來源於單胺(a2)之矽而獲得矽化合物(A),至於具有大於等於2個之酸酐基之化合物(a1)具有矽之例,例如,可列舉日本專利特開昭61-205285號公報、日本專利特開 平5-271245號公報或者日本專利特開平5-320172號公報等中揭示的化合物。Further, the oxime in the ruthenium compound (A) may be derived from the compound (a1) having two or more acid anhydride groups, may be derived from the monoamine (a2), or may be derived from both (a1) and (a2). . In the following detailed description, the ruthenium compound (A) is obtained by using a ruthenium derived from a monoamine (a2), and the compound (a1) having an acid anhydride group of 2 or more has an anthracene. For example, Japan is exemplified. Japanese Patent Laid-Open No. 61-205285, Japanese Patent Laid-Open The compound disclosed in Japanese Laid-Open Patent Publication No. Hei 5-- No. Hei.
又,矽化合物(A')可藉由至少使用具有1個酸酐基之化合物(a1')與二胺(a2')而獲得,例如,可為使(a1')與(a2')反應而獲得的生成物(矽醯胺酸(A')),例如,可為(a1')與(a2')形成鹽的化合物,只要為使用具有1個酸酐基之化合物(a1')與二胺(a2')可獲得的矽化合物,則並不限定於上述例子。Further, the hydrazine compound (A') can be obtained by using at least a compound (a1') having one acid anhydride group and a diamine (a2'), for example, by reacting (a1') with (a2'). The obtained product (proline (A')), for example, may be a compound in which (a1') forms a salt with (a2') as long as a compound (a1') having one anhydride group and a diamine are used. The ruthenium compound obtainable by (a2') is not limited to the above examples.
又,矽化合物(A')中之矽,可來源於具有1個酸酐基之化合物(a1'),可來源於二胺(a2'),亦可來源於(a1')與(a2')兩者。於以下之詳細說明中,是使用來源於具有1個酸酐基之化合物(a1')之矽而獲得矽化合物(A'),至於二胺(a2')具有矽之例,例如,可列舉下述通式(XV)所表示之矽氧烷系二胺等。Further, the ruthenium compound (A') may be derived from a compound (a1') having one acid anhydride group, may be derived from a diamine (a2'), or may be derived from (a1') and (a2'). Both. In the following detailed description, the ruthenium compound (A') is obtained by using a ruthenium derived from the compound (a1') having one acid anhydride group, and the ruthenium (a2') has an oxime. For example, The azepine-based diamine represented by the formula (XV).
1矽醯胺酸(A)以及矽醯胺酸(A')1 proline (A) and proline (A')
本發明之噴墨用墨水中所含的矽醯胺酸(A)可藉由至少使用具有大於等於2個之酸酐基之化合物(a1)與單胺(a2),利用以下說明之製法而獲得,但並不限定於利用該製法獲得的矽醯胺酸。矽醯胺酸(A)可列舉上述通式(3)所表示之化合物,較好的是上述通式(4-1)、(4-2)或者(4-3)所表示之化合物。The lysine (A) contained in the inkjet ink of the present invention can be obtained by the following method using at least a compound (a1) and a monoamine (a2) having an acid anhydride group of 2 or more. However, it is not limited to the proline acid obtained by the production method. The guanamine (A) is a compound represented by the above formula (3), and preferably a compound represented by the above formula (4-1), (4-2) or (4-3).
又,本發明之噴墨用墨水中所含的矽醯胺酸(A')可藉由至少使用具有1個酸酐基之化合物(a1')與二胺(a2'),利用以下說明之製法而獲得,但並不限定於利用 該製法獲得的矽醯胺酸。矽醯胺酸(A')可列舉上述通式(3')所表示之化合物,較好的是上述通式(4'-1)、(4'-2)、(4'-3)或者(4'-4)所表示之化合物。Further, the lysine (A') contained in the inkjet ink of the present invention can be produced by using at least the compound (a1') having one anhydride group and the diamine (a2'). Obtained, but not limited to use The proline obtained by the process. The proline acid (A') may, for example, be a compound represented by the above formula (3'), preferably the above formula (4'-1), (4'-2), (4'-3) or (4'-4) the compound represented.
1.1用以獲得矽醯胺酸(A)以及矽醯胺酸(A')的反應條件1.1 Reaction conditions for obtaining valine (A) and valine (A')
本發明中可使用的矽醯胺酸(A)較好的是相對於1莫耳之具有大於等於2個之酸酐基之化合物(a1),與0.5莫耳~8.0莫耳之單胺(a2)反應而獲得。又,進而好的是相對於1莫耳之具有大於等於2個之酸酐基之化合物(a1),與1.0莫耳~4.0莫耳之單胺(a2)反應而獲得。更好的是相對於1莫耳之具有大於等於2個之酸酐基之化合物(a1),與1.5莫耳~2.5莫耳之單胺(a2)反應而獲得。The valine acid (A) which can be used in the present invention is preferably a compound (a1) having an acid anhydride group of 2 or more with respect to 1 mol, and a monoamine of 0.5 mol to 8.0 mol (a2) ) obtained by reaction. Further, it is further preferably obtained by reacting a compound (a1) having 1 or more acid anhydride groups of 1 mol with 1.0 mol to 4.0 mol of the monoamine (a2). More preferably, it is obtained by reacting a compound (a1) having 1 or more acid anhydride groups of 1 mol with 1.5 mol to 2.5 mol of the monoamine (a2).
又,本發明中可使用之矽醯胺酸(A')較好的是相對於1莫耳之二胺(a2'),與0.5莫耳~8.0莫耳之具有1個酸酐基之化合物(a1')反應而獲得。又,進而好的是相對於1莫耳之二胺(a2'),與1.0莫耳~4.0莫耳之具有1個酸酐基之化合物(a1')反應而獲得。更好的是,相對於1莫耳之二胺(a2'),與1.5莫耳~2.5莫耳之具有1個酸酐基之化合物(a1')反應而獲得。Further, the proline (A') which can be used in the present invention is preferably a compound having one acid anhydride group with respect to 1 mol of the diamine (a2') and 0.5 mol to 8.0 mol. A1') obtained by reaction. Further, it is preferably obtained by reacting with 1.0 mol% to 4.0 mol of the compound (a1') having one acid anhydride group per 1 mol of the diamine (a2'). More preferably, it is obtained by reacting with 1.5 mol to 2.5 mol of the compound (a1') having one acid anhydride group with respect to 1 mol of the diamine (a2').
1.1(1)反應溶劑1.1 (1) reaction solvent
用於獲得本發明之矽醯胺酸(A)以及矽醯胺酸(A')的溶劑,若可合成該化合物則並無特別限定,例如可列舉:二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基乙基醚、 二乙二醇單***乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、環己酮、γ-丁內酯、N-甲基-2-吡咯烷酮以及N,N-二甲基乙醯胺等。The solvent for obtaining the proline (A) and the valine (A') of the present invention is not particularly limited as long as it can be synthesized, and examples thereof include diethylene glycol dimethyl ether and diethyl ether. Glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone , γ-butyrolactone, N-methyl-2-pyrrolidone, and N,N-dimethylacetamide.
於上述溶劑中,若使用丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、環己酮、二乙二醇甲基乙基醚、二乙二醇二甲醚以及γ-丁內酯,則可製備為對噴墨頭之損傷較少的墨水,故而較好。In the above solvent, if propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyl are used. The lactone is preferably prepared as an ink which is less damaged to the ink jet head.
該些反應溶劑可單獨使用,亦可用作兩種或兩種以上之混合溶劑。又,除上述反應溶劑以外,亦可混合使用其他溶劑。These reaction solvents may be used singly or as a mixed solvent of two or more kinds. Further, in addition to the above reaction solvent, other solvents may be used in combination.
反應溶劑若相對於具有大於等於2個之酸酐基之化合物(a1)與單胺(a2)之總計100重量份,使用大於等於100重量份,或者相對於具有1個酸酐基之化合物(a1')與二胺(a2')之總計100重量份,使用大於等於100重量份,則反應順利進行,故而較好。較好的是反應於0℃~100℃(較好的是8℃~70℃)下進行0.2小時~20小時(較好的是2小時~10小時)。When the reaction solvent is 100 parts by weight or more with respect to 100 parts by weight of the total of the compound (a1) and the monoamine (a2) having an acid anhydride group of 2 or more, or a compound having 1 anhydride group (a1') When 100 parts by weight or more of the total amount of the diamine (a2') is used, the reaction proceeds smoothly, which is preferable. Preferably, the reaction is carried out at from 0 ° C to 100 ° C (preferably from 8 ° C to 70 ° C) for from 0.2 hours to 20 hours (preferably from 2 hours to 10 hours).
1.1(2)添加至反應系中的順序1.1 (2) order added to the reaction system
另外,反應原料添加至反應系中的順序並無特別限定。即,對於矽醯胺酸(A)而言,可使用如下方法中的任一種方法:將具有大於等於2個之酸酐基之化合物(a1)與單胺(a2)同時添加至反應溶劑中的方法;將單胺(a2)溶解於反應溶劑中後添加具有大於等於2個之酸酐基之化 合物(a1)的方法;於具有大於等於2個之酸酐基之化合物(a1)中添加單胺(a2)的方法等。Further, the order in which the reaction raw material is added to the reaction system is not particularly limited. That is, for the valine acid (A), any one of the following methods may be used: a compound (a1) having two or more acid anhydride groups and a monoamine (a2) are simultaneously added to the reaction solvent. Method; adding a monoamine (a2) to a reaction solvent and adding an acid anhydride group having two or more The method of the compound (a1); the method of adding a monoamine (a2) to the compound (a1) having an acid anhydride group of 2 or more.
又,對於矽醯胺酸(A')而言,可使用如下方法中的任一種方法:將具有1個酸酐基之化合物(a1')與二胺(a2')同時添加至反應溶劑中的方法;將二胺(a2')溶解於反應溶劑中後添加具有1個酸酐基之化合物(a1')的方法;於具有1個酸酐基之化合物(a1')中添加二胺(a2')的方法等。Further, as the valine acid (A'), any one of the following methods may be used: a compound (a1') having one acid anhydride group and a diamine (a2') are simultaneously added to a reaction solvent. Method; a method of adding a compound (a1') having one acid anhydride group after dissolving a diamine (a2') in a reaction solvent; adding a diamine (a2') to a compound (a1') having one acid anhydride group Method etc.
1.2矽醯胺酸(A)以及矽醯胺酸(A')之優越性1.2 Advantages of proline (A) and proline (A')
已知若矽醯胺酸(A)與環氧樹脂、酚樹脂併用,則作為矽烷偶合劑而起作用,與金屬發生反應或者形成錯合物,從而使膜之密著性提昇,耐焊裂性提高。又,對於矽醯胺酸(A')而言,可預測若與環氧樹脂、酚樹脂併用,則作為矽烷偶合劑而起作用,與金屬發生反應或者形成錯合物,從而使膜之密著性提昇,耐焊裂性提高。When phthalic acid (A) is used in combination with an epoxy resin or a phenol resin, it is known to act as a decane coupling agent, react with a metal or form a complex compound, thereby improving the adhesion of the film and preventing cracking. Sexual improvement. Further, the proline (A') is predictively used as a decane coupling agent when used in combination with an epoxy resin or a phenol resin, and reacts with a metal or forms a complex compound to form a dense film. Improved performance and improved weld resistance.
進而,本發明者們經努力研究之結果發現,矽醯胺酸(A)是可藉由加熱而水解、脫水縮合,從而成為具有醯亞胺鍵之固體生成物(聚醯亞胺)的熱固性化合物。又發現,矽醯胺酸(A')也是可藉由加熱而水解、脫水縮合,從而成為具有醯亞胺鍵之固體生成物(聚醯亞胺)的熱固性化合物。Further, as a result of intensive studies, the present inventors have found that proline (A) is a thermosetting property which can be hydrolyzed by heating, dehydrated and condensed, and becomes a solid product (polyimine) having a quinone bond. Compound. Further, it has been found that proline (A') is a thermosetting compound which can be hydrolyzed by heating, dehydrated and condensed to form a solid product (polyimine) having a quinone bond.
矽化合物可藉由立體交聯而獲得膜,相比先前之線狀之聚醯亞胺,加工更加容易。又,矽化合物顯示良好之耐熱性,於固化時孔隙或裂縫之發生少,因此作為成形材料 或者積層材料之基質樹脂(matrix resin)而具有優異之特性。The ruthenium compound can be obtained by stereocrosslinking, which is easier to process than the prior linear polyimine. Further, the ruthenium compound exhibits good heat resistance and has little occurrence of voids or cracks during curing, and thus is used as a molding material. Or a matrix resin of a build-up material has excellent properties.
1.3用以獲得矽醯胺酸(A)以及矽醯胺酸(A')之各成分的說明1.3 Instructions for obtaining the components of proline (A) and proline (A')
以下,對可用以獲得矽醯胺酸(A)的具有大於等於2個之酸酐基之化合物(a1)與單胺(a2)加以說明。進而,對可用以獲得矽醯胺酸(A')的具有1個酸酐基之化合物(a1')與二胺(a2')加以說明。Hereinafter, the compound (a1) and the monoamine (a2) having two or more acid anhydride groups which can be used to obtain the valine acid (A) will be described. Further, a compound (a1') having one acid anhydride group and a diamine (a2') which can be used to obtain valeric acid (A') will be described.
1.3(1)具有大於等於2個之酸酐基之化合物(a1)1.3(1) Compound having two or more acid anhydride groups (a1)
本發明中所使用的具有大於等於2個之酸酐基之化合物(a1),可列舉上述通式(1)所表示之四羧酸二酐。The compound (a1) having two or more acid anhydride groups used in the present invention may, for example, be a tetracarboxylic dianhydride represented by the above formula (1).
本發明中所使用的具有大於等於2個之酸酐基之化合物(a1)之具體例,可列舉:苯乙烯-順丁烯二酸酐共聚物、甲基丙烯酸甲酯-順丁烯二酸酐共聚物等具有酸酐基的自由基聚合性單體與其他自由基聚合性單體的共聚物,或者四羧酸二酐等。四羧酸二酐例如可列舉:2,2',3,3'-二苯基酮四羧酸二酐、2,3,3',4'-二苯基酮四羧酸二酐、2,2',3,3'-二苯基碸四羧酸二酐、2,3,3',4'-二苯基碸四羧酸二酐、2,2',3,3'-二苯基醚四羧酸二酐、2,3,3',4'-二苯基醚四羧酸二酐、乙二醇雙(偏苯三甲酸酐酯)、乙烷四羧酸二酐、4-(2,5-二氧四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸酐、5-(2,5-二氧四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐,具體而言,可列舉下式(b1-1)~(b1-73)所表示之化合物等四羧酸二酐。Specific examples of the compound (a1) having two or more acid anhydride groups used in the present invention include styrene-maleic anhydride copolymer and methyl methacrylate-maleic anhydride copolymer. A copolymer of a radical polymerizable monomer having an acid anhydride group and another radical polymerizable monomer, or a tetracarboxylic dianhydride or the like. Examples of the tetracarboxylic dianhydride include 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic dianhydride, and 2 , 2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3,3'-di Phenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis(trimellitic anhydride), ethane tetracarboxylic dianhydride, 4 -(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3- Specific examples of the methyl-3-cyclohexene-1,2-dicarboxylic anhydride include tetracarboxylic dianhydrides such as compounds represented by the following formulas (b1-1) to (b1-73).
於具有大於等於2個之酸酐之化合物之上述具體例中,因苯乙烯-順丁烯二酸酐共聚物、由式(b1-1)、(b1-5)、(b1-6)、(b1-7)、(b1-8)、(b1-9)、(b1-14)、(b1-18)、(b1-20)所表示之化合物於溶劑中的溶解性高,可製備高濃度之墨水,故而較好。又,根據噴墨用墨水之用途,有時要求高透明性,於此情形時,尤其好的是使用苯乙烯-順丁烯二酸 酐共聚物、由式(b1-6)、(b1-7)、(b1-8)、(b1-9)、(b1-14)、(b1-18)等所表示之化合物。In the above specific examples of the compound having two or more acid anhydrides, the styrene-maleic anhydride copolymer, from the formula (b1-1), (b1-5), (b1-6), (b1) The compounds represented by -7), (b1-8), (b1-9), (b1-14), (b1-18), and (b1-20) have high solubility in a solvent, and can be prepared at a high concentration. Ink is therefore better. Further, depending on the use of the ink for inkjet, high transparency is sometimes required, and in this case, it is particularly preferable to use styrene-maleic acid. An anhydride copolymer, a compound represented by the formula (b1-6), (b1-7), (b1-8), (b1-9), (b1-14), (b1-18) or the like.
又,上述揭示之具有大於等於2個之酸酐基之化合物可單獨使用一種,或者組合兩種或兩種以上使用。Further, the above-described compounds having two or more acid anhydride groups may be used singly or in combination of two or more kinds.
1.3(2)單胺(a2)1.3(2) monoamine (a2)
本發明中所使用的單胺(a2),可列舉上述通式(2)所表示之胺基矽化合物。The monoamine (a2) used in the present invention may, for example, be an aminoguanidine compound represented by the above formula (2).
本發明中所使用的單胺(a2)並無特別限定,具體例可列舉:3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、4-胺基丁基三甲氧基矽烷、4-胺基丁基三乙氧基矽烷、4-胺基丁基甲基二乙氧基矽烷、對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、對胺基苯基甲基二甲氧基矽烷、對胺基苯基甲基二乙氧基矽烷、間胺基苯基三甲氧基矽烷、間胺基苯基三乙氧基矽烷以及間胺基苯基甲基二乙氧基矽烷等。The monoamine (a2) used in the present invention is not particularly limited, and specific examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropyl group. Methyl dimethoxy decane, 3-aminopropyl methyl diethoxy decane, 4-aminobutyl trimethoxy decane, 4-aminobutyl triethoxy decane, 4-aminobutyl group Diethoxy decane, p-aminophenyl trimethoxy decane, p-aminophenyl triethoxy decane, p-aminophenyl methyl dimethoxy decane, p-aminophenyl methyl di Oxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, m-aminophenyl dimethyl diethoxy decane, and the like.
上述單胺之中,就所得膜之耐久性優異之方面而言,較好的是對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、間胺基苯基三甲氧基矽烷、間胺基苯基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷以及3-胺基丙基三乙氧基矽烷,尤其好的是3-胺基丙基三乙氧基矽烷。Among the above monoamines, in terms of excellent durability of the obtained film, preferred are p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyltrimethoxy. Particularly preferred are 3-aminopropyltriethoxylates, decanones, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, and 3-aminopropyltriethoxydecane. Base decane.
該些單胺可單獨使用一種或者組合兩種或兩種以上使用。These monoamines may be used alone or in combination of two or more.
1.3(3)具有1個酸酐基之化合物(a1')1.3(3) Compound having one anhydride group (a1')
本發明中所使用的具有1個酸酐基之化合物(a1'),可列舉上述通式(1')所表示之羧酸酐。The compound (a1') having one acid anhydride group used in the present invention may, for example, be a carboxylic acid anhydride represented by the above formula (1').
本發明中所使用的具有1個酸酐基之化合物(a1')並無特別限定,具體例可列舉:三甲氧基矽烷基丙基琥珀酸酐、三乙氧基矽烷基丙基琥珀酸酐、甲基二甲氧基矽烷基丙基琥珀酸酐、甲基二乙氧基矽烷基丙基琥珀酸酐、三甲氧基矽烷基丁基琥珀酸酐、三乙氧基矽烷基丁基琥珀酸酐、甲基二乙氧基矽烷基丁基琥珀酸酐、對(三甲氧基矽烷基)苯基琥珀酸酐、對(三乙氧基矽烷基)苯基琥珀酸酐、對(甲基二甲氧基矽烷基)苯基琥珀酸酐、對(甲基二乙氧基矽烷基)苯基琥珀酸酐、間(三甲氧基矽烷基)苯基琥珀酸酐、間(三乙氧基矽烷基)苯基琥珀酸酐、間(甲基二乙氧基矽烷基)苯基琥珀酸酐等。The compound (a1') having one acid anhydride group used in the present invention is not particularly limited, and specific examples thereof include trimethoxydecylpropyl succinic anhydride, triethoxydecylpropyl succinic anhydride, and methyl group. Dimethoxydecyl propyl succinic anhydride, methyl diethoxy decyl propyl succinic anhydride, trimethoxy decyl butyl succinic anhydride, triethoxy decyl butyl succinic anhydride, methyl diethoxy Base alkyl butyl succinic anhydride, p-(trimethoxydecyl) phenyl succinic anhydride, p-(triethoxydecyl) phenyl succinic anhydride, p-(methyl dimethoxy decyl) phenyl succinic anhydride , p-(methyldiethoxydecyl)phenyl succinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, m (methyldiethyl) Oxonium alkyl) phenyl succinic anhydride or the like.
於上述化合物中,就所得膜之耐久性優異之方面而言,較好的是對(三甲氧基矽烷基)苯基琥珀酸酐、對(三乙氧基矽烷基)苯基琥珀酸酐、間(三甲氧基矽烷基)苯基琥珀酸酐、間(三乙氧基矽烷基)苯基琥珀酸酐、三甲氧基矽烷基丙基琥珀酸酐以及三乙氧基矽烷基丙基琥珀酸酐,尤其好的是三乙氧基矽烷基丙基琥珀酸酐。Among the above compounds, p-(trimethoxydecyl)phenylsuccinic anhydride, p-(triethoxydecyl)phenylsuccinic anhydride, and (preferably) are excellent in terms of durability of the obtained film. Particularly preferred is trimethoxydecyl)phenylsuccinic anhydride, m-(triethoxydecyl)phenylsuccinic anhydride, trimethoxydecylpropyl succinic anhydride, and triethoxydecylpropyl succinic anhydride. Triethoxydecyl propyl succinic anhydride.
該些具有1個酸酐基之化合物可單獨使用一種或者組合兩種或兩種以上使用。These compounds having one acid anhydride group may be used alone or in combination of two or more.
1.3(4)二胺(a2')1.3(4) diamine (a2')
本發明中所使用的二胺(a2'),可列舉上述通式(2')所表示之二胺。The diamine (a2') used in the present invention may, for example, be a diamine represented by the above formula (2').
本發明中所使用的二胺(a2')只要具有2個胺基,則並無特別限定,例如可列舉:對苯二胺、間苯二胺、對二甲苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基-1,2-二苯基乙烷、4,4'-二胺基-1,3-二苯基丙烷、2,2-雙(4-胺基苯基)丙烷、雙(4-胺基-3-甲基苯基)甲烷、1,2-雙-(4-胺基-3-甲基苯基)乙烷、雙(4-胺基-2-甲基苯基)甲烷、1,2-雙-(4-胺基-2-甲基苯基)乙烷、4,4'-二胺基二苯基醚、3,3'-二胺基二苯基醚、4,4'-二胺基二苯基碸、4,4'-二胺基二苯硫醚、4,4'-二胺基二苯基酮、4,4'-二胺基二苯基-2,2'-丙烷、1,4-二胺基環己烷、4,4'-二胺基二環己基甲烷、1,4-雙[(4-胺基苯基)甲基]苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]氟丙烷、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]聯苯、1,3-雙[4-(4-胺基苄基)苯基]丙烷、1,6-雙[4-(4-胺基苄基)苯基]己烷、5-苯基甲基-1,3-二胺基苯、5-[4-(4-烷基環己基)苯基]甲基-1,3-二胺基苯、5-[4-(4-(4-烷基環己基)環己基)苯基]甲基-1,3-二胺基苯、5-[((烷基環己基)乙基環己基)苯基]甲基-1,3-二胺基苯、1,1-雙[4-(4-胺基苯氧基)苯基]環己烷、1,1-雙[4-(4-胺基苯氧基)苯基]-4-烷基環己烷、1,1-雙[4-(4-胺基苄基)苯基]環己烷、1,1-雙[4-(4-胺基苄基)苯基]-4-烷基環己烷、1,3-雙(3-胺基丙基)-四甲基二矽氧烷,且可列舉下述通式(Ⅱ)~(Ⅷ)所表示之化合物。The diamine (a2') used in the present invention is not particularly limited as long as it has two amine groups, and examples thereof include p-phenylenediamine, m-phenylenediamine, p-xylenediamine, and 4,4'-. Diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-1,3-diphenylpropane, 2,2-double (4-Aminophenyl)propane, bis(4-amino-3-methylphenyl)methane, 1,2-bis-(4-amino-3-methylphenyl)ethane, bis ( 4-amino-2-methylphenyl)methane, 1,2-bis-(4-amino-2-methylphenyl)ethane, 4,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone , 4,4'-diaminodiphenyl-2,2'-propane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-double [ (4-Aminophenyl)methyl]benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-double [4-(4-Aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]fluoropropane, bis[4-(4-amino) Oxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]biphenyl, 1,3-bis[4-(4-aminobenzyl)phenyl]propane, 1, 6-bis[4-(4-aminobenzyl)phenyl]hexane, 5-phenylmethyl-1,3-diaminobenzene, 5-[4-(4-alkylcyclohexyl)benzene Methyl-1,3-diaminobenzene, 5-[4-(4-(4-alkylcyclohexyl)cyclohexyl)phenyl]methyl-1,3-diaminobenzene, 5- [((Alkylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane Alkane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-alkylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl] Cyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]-4-alkylcyclohexane, 1,3-bis(3-aminopropyl)-tetramethyl The oxime may be a compound represented by the following general formulae (II) to (VIII).
[化37]
(通式(Ⅱ)中,A1 為-(CH2 )m -,其中m為1~6之整數,通式(Ⅳ)以及(Ⅵ)~(Ⅷ)中,A1 為單鍵、-O-、-S-、-S-S-、-SO2 -、-CO-、-CONH-、-NHCO-、-C(CH3 )2 -、-C(CF3 )2 -、-(CH2 )m -、-O-(CH2 )m -O-、-S-(CH2 )m -S-,其中m為1~6之整數,A2 為單鍵、-O-、-S-、-CO-、-C(CH3 )2 -、-C(CF3 )2 -或者碳數1~3之亞烷基,於環己烷環或者苯環上鍵結之氫可經-F、-CH3 取代。)(In the formula (II), A 1 is -(CH 2 ) m -, wherein m is an integer of 1 to 6, and in the formula (IV) and (VI) to (VIII), A 1 is a single bond, - O-, -S-, -S-S-, -SO 2 -, -CO-, -CONH-, -NHCO-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -( CH 2 ) m -, -O-(CH 2 ) m -O-, -S-(CH 2 ) m -S-, wherein m is an integer from 1 to 6, and A 2 is a single bond, -O-, - S-, -CO-, -C(CH 3 ) 2 -, -C(CF 3 ) 2 - or an alkylene group having 1 to 3 carbon atoms, which may be bonded to a cyclohexane ring or a benzene ring. -F, -CH 3 replaced.)
通式(Ⅱ)所表示之二胺,例如可列舉下式(Ⅱ-1)~(Ⅱ-3)所表示之二胺。The diamine represented by the formula (II) is, for example, a diamine represented by the following formulas (II-1) to (II-3).
通式(Ⅲ)所表示之二胺,例如可列舉下式(Ⅲ-1)以及(Ⅲ-2)所表示之二胺。The diamine represented by the formula (III) is, for example, a diamine represented by the following formulas (III-1) and (III-2).
通式(Ⅳ)所表示之二胺,例如可列舉下式(Ⅳ-1)~(Ⅳ-3)所表示之二胺。The diamine represented by the formula (IV) is, for example, a diamine represented by the following formulas (IV-1) to (IV-3).
通式(V)所表示之二胺,例如可列舉下式(V-1)~(V-5)所表示之二胺。The diamine represented by the formula (V) is, for example, a diamine represented by the following formulas (V-1) to (V-5).
[化41]
通式(Ⅵ)所表示之二胺,例如可列舉下式(Ⅵ-1)~(Ⅵ-30)所表示之二胺。The diamine represented by the formula (VI) is, for example, a diamine represented by the following formulas (VI-1) to (VI-30).
通式(Ⅶ)所表示之二胺,例如可列舉下式(Ⅶ-1)~(Ⅶ-6)所表示之二胺。The diamine represented by the formula (VII) is, for example, a diamine represented by the following formulas (VII-1) to (VII-6).
[化46]
通式(Ⅷ)所表示之二胺,例如可列舉下式(Ⅷ-1)~(Ⅷ-11)所表示之二胺。The diamine represented by the formula (VIII) is, for example, a diamine represented by the following formulas (VIII-1) to (VIII-11).
[化47]
通式(Ⅱ)~(Ⅷ)所表示之二胺(a2')之上述具體例中,更好的可列舉由式(V-1)~(V-5)、式(Ⅵ-1)~(Ⅵ-12)、式(Ⅵ-26)、式(Ⅵ-27)、式(Ⅶ-1)、式(Ⅶ -2)、式(Ⅶ-6)、式(Ⅷ-1)~(Ⅷ-5)所表示之二胺,進而好的可列舉由式(V-6)、式(V-7)、式(Ⅵ-1)~(Ⅵ-12)所表示之二胺。In the above specific examples of the diamine (a2') represented by the general formulae (II) to (VIII), the formula (V-1) to (V-5) and the formula (VI-1) are more preferable. (VI-12), formula (VI-26), formula (VI-27), formula (VII-1), formula (VII) -2), the diamine represented by the formula (VII-6) and the formula (VIII-1) to (VIII-5), and further preferably, the formula (V-6), the formula (V-7), and the formula The diamine represented by (VI-1) to (VI-12).
本發明中所使用的二胺(a2'),進而可列舉下述通式(Ⅸ)所表示之二胺。The diamine (a2') used in the present invention may, for example, be a diamine represented by the following formula (IX).
(通式(Ⅸ)中,A3 為單鍵、-O-、-COO-、-OCO-、-CO-、-CONH-或者-(CH2 )m -(式中,m為1~6之整數),R6 為具有類固醇骨架之基團、下述通式(X)所表示之基團或者於苯環上鍵結之2個胺基之位置關係為對位時為碳數1~30的烷基、或該位置關係為間位時為碳數1~30之烷基或者苯基,該烷基中,任意的-CH2 -可經-CF2 -、-CHF-、-O-、-CH=CH-或者-C≡C-取代,-CH3 可經-CH2 F、-CHF2 或者-CF3 取代’於該苯基之成環碳上鍵結的氫可經-F、-CH3 、-OCH3 、-OCH2 F、-OCHF2 或者-OCF3 取代。)(General formula (IX) in, A 3 is a single bond, -O -, - COO -, - OCO -, - CO -, - CONH- , or - (CH 2) m - (wherein, m is 1 to 6 In the integer), R 6 is a group having a steroid skeleton, a group represented by the following formula (X) or a positional relationship of two amine groups bonded to a benzene ring is a carbon number of 1 to a para position. An alkyl group of 30, or an alkyl group having a carbon number of 1 to 30 or a phenyl group in the positional relationship, wherein any -CH 2 - may be via -CF 2 -, -CHF-, -O -, -CH=CH- or -C≡C-substitution, -CH 3 may be substituted by -CH 2 F, -CHF 2 or -CF 3 'hydrogen bonded to the ring carbon of the phenyl group may be - F, -CH 3 , -OCH 3 , -OCH 2 F, -OCHF 2 or -OCF 3 substitution.)
[化49]
(通式(X)中,A4 以及A5 分別獨立為單鍵、-O-、-COO-、-OCO-、-CONH-、-CH=CH-或者碳數1~12之亞烷基,R7 以及R8 分別獨立為-F或者-CH3 ,環S為1,4-亞苯基、1,4-亞環己基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、萘-1,5-二基、萘-2,7-二基或者蒽-9,10-二基,R9 為-H、-F、碳數1~30之烷基、碳數1~30之氟取代烷基、碳數1~30之烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 ,a以及b分別獨立表示0~4之整數,c、d以及e分別獨立表示0~3之整數,e為2或者3時,多個環S可為相同基團,亦可為不同基團,f以及g分別獨立表示0~2之整數,並且c+d+e≧1。)(In the formula (X), A 4 and A 5 are each independently a single bond, -O-, -COO-, -OCO-, -CONH-, -CH=CH- or an alkylene group having 1 to 12 carbon atoms. , R 7 and R 8 are each independently -F or -CH 3 , and ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, Pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl, R 9 is -H , -F, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH 2 F, -OCHF 2 or -OCF 3 , a and b respectively represent an integer of 0 to 4, and c, d and e each independently represent an integer of 0 to 3. When e is 2 or 3, a plurality of rings S may be the same group or different groups. f and g respectively represent an integer of 0~2, and c+d+e≧1.)
於通式(Ⅸ)中,2個胺基鍵結於苯環碳上,2個胺基之鍵結位置關係較好的是間位或者對位。進而於「R6 -A3 -」之鍵結位置為1位時,較好的是2個胺基分別鍵結於3位與5位,或者2位與5位。In the formula (IX), two amine groups are bonded to the benzene ring carbon, and the bonding position relationship of the two amine groups is preferably a meta or a para position. Further, when the bonding position of "R 6 -A 3 -" is 1 position, it is preferred that the two amine groups are bonded to the 3 position and the 5 position, or the 2 position and the 5 position, respectively.
通式(Ⅸ)所表示之二胺,例如可列舉下述通式(Ⅸ-1)~(Ⅸ-11)所表示之二胺。Examples of the diamine represented by the formula (IX) include diamines represented by the following formulae (IX-1) to (IX-11).
[化50]
於上述通式(Ⅸ-1)、(Ⅸ-2)、(Ⅸ-7)以及(Ⅸ-8)中, R18 為氫或者碳數1~30之有機基,該些中較好的是碳數3~12之烷基或者碳數3~12之烷氧基,進而好的是碳數5~12之烷基或者碳數5~12之烷氧基。又,於上述通式(Ⅸ-3)~(Ⅸ-6)以及(Ⅸ-9)~(Ⅸ-11)中,R19 為氫或者碳數1~30之有機基,該些中較好的是碳數1~10之烷基或者碳數1~10之烷氧基,進而好的是碳數3~10之烷基或者碳數3~10之烷氧基。In the above formulae (IX-1), (IX-2), (IX-7) and (IX-8), R 18 is hydrogen or an organic group having 1 to 30 carbon atoms, and among these, The alkyl group having 3 to 12 carbon atoms or the alkoxy group having 3 to 12 carbon atoms is preferably an alkyl group having 5 to 12 carbon atoms or an alkoxy group having 5 to 12 carbon atoms. Further, in the above formulae (IX-3) to (IX-6) and (IX-9) to (IX-11), R 19 is hydrogen or an organic group having 1 to 30 carbon atoms, which is preferably. The alkyl group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms is further preferably an alkyl group having 3 to 10 carbon atoms or an alkoxy group having 3 to 10 carbon atoms.
通式(Ⅸ)所表示之二胺,進而例如可列舉下述通式(Ⅸ-12)~(Ⅸ-17)所表示之二胺。Further, examples of the diamine represented by the formula (IX) include diamines represented by the following formulae (IX-12) to (IX-17).
於上述通式(Ⅸ-12)~(Ⅸ-15)中,R20 為碳數2~30之有機基,較好的是碳數4~16之烷基,進而好的是碳數6~16之烷基。於通式(Ⅸ-16)與式(Ⅸ-17)中,R21 為碳數2~30之有機基,較好的是碳數6~20之烷基,進而好的是碳數8~20之烷基。In the above formula (IX-12) to (IX-15), R 20 is an organic group having 2 to 30 carbon atoms, preferably an alkyl group having 4 to 16 carbon atoms, and more preferably a carbon number of 6 to 6 16 alkyl. In the formula (IX-16) and the formula (IX-17), R 21 is an organic group having 2 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, and more preferably a carbon number of 8 to 8 20 alkyl.
通式(Ⅸ)所表示之二胺,進而例如可列舉下述通式 (Ⅸ-18)~(Ⅸ-38)所表示之二胺。The diamine represented by the formula (IX), for example, may be exemplified by the following formula The diamine represented by (IX-18)~(IX-38).
[化54]
[化55]
於上述通式(Ⅸ-18)、(Ⅸ-19)、(Ⅸ-22)、(Ⅸ-24)、(Ⅸ-25)、(Ⅸ-28)、(Ⅸ-30)、(Ⅸ-31)、(Ⅸ-36)以及(Ⅸ-37)中,R22 為氫或者碳數1~30之有機基,較好的是碳數1~12之烷基、碳數1~12之烷氧基,進而好的是碳數3~12之烷基或者碳數3~12之烷氧基。又,於上述通式(Ⅸ-20)、(Ⅸ-21)、(Ⅸ-23)、(Ⅸ-26)、(Ⅸ-27)、(Ⅸ-29)、(Ⅸ-32)~(Ⅸ-35)以及(Ⅸ-38)中,R23 為-H、-F、碳數1~12之烷基、碳數1~12之烷氧基、-CN、-OCH2 F、-OCHF2 或者-OCF3 ,進而好的是碳數3~12之烷基或者碳數3~12之烷氧基。於上述通式(Ⅸ-33)與(Ⅸ-34)中,A9 為碳 數1~12之亞烷基。In the above formula (IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31) And (IX-36) and (IX-37), R 22 is hydrogen or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Further, it is preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. Further, in the above formula (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (IX) -35) and (IX-38), R 23 is -H, -F, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, -CN, -OCH 2 F, -OCHF 2 Or -OCF 3 , and further preferably an alkyl group having 3 to 12 carbon atoms or an alkoxy group having 3 to 12 carbon atoms. In the above general formula (Ⅸ-33) and (Ⅸ-34) in, A 9 carbon atoms of the alkylene group having 1 to 12.
通式(Ⅸ)所表示之二胺,進而例如可列舉下式(Ⅸ-39)~(Ⅸ-48)所表示之二胺。Further, examples of the diamine represented by the formula (IX) include a diamine represented by the following formulas (IX-39) to (IX-48).
[化57]
於通式(Ⅸ)所表示之二胺(a2')中,較好的是通式(Ⅸ-1)~(Ⅸ-11)所表示之二胺,進而好的是由通式(Ⅸ-2)、(Ⅸ-4)、(Ⅸ-5)以及(Ⅸ-6)所表示之二胺。Among the diamines (a2') represented by the formula (IX), preferred are the diamines represented by the formulae (IX-1) to (IX-11), and further preferably by the formula (IX-). 2), the diamines represented by (IX-4), (IX-5), and (IX-6).
本發明中所使用的二胺(a2'),進而可列舉下述通式(XI)以及(XII)所表示之化合物。The diamine (a2') used in the present invention may furthermore be a compound represented by the following formula (XI) and (XII).
[化58]
(通式(XI)與(XII)中,R10 、R11 分別獨立為-H或者碳數1~20之烷基或烯基,A6 分別獨立為單鍵、-C(=O)-或者-CH2 -,R13 以及R14 分別獨立為-H、碳數1~20之烷基或者苯基。)(In the general formulae (XI) and (XII), R 10 and R 11 are each independently -H or an alkyl or alkenyl group having 1 to 20 carbon atoms, and A 6 is independently a single bond, -C(=O)- Or -CH 2 -, R 13 and R 14 are each independently -H, an alkyl group having 1 to 20 carbon atoms or a phenyl group.
於上述通式(XI)中,較好的是2個「NH2 -Ph-A6 -O-」(其中,Ph表示亞苯基。)中的一個鍵結於類固醇核之3位,另一個鍵結於6位。又,2個胺基分別鍵結於苯環碳上,較好的是相對於A6 之鍵結位置,鍵結於間位或者對位。In the above formula (XI), it is preferred that one of two "NH 2 -Ph-A 6 -O-" (wherein Ph represents a phenylene group) is bonded to the steroid core at the 3 position, and One key is in 6 digits. Further, the two amine groups are bonded to the benzene ring carbon, respectively, and it is preferably bonded to the meta or para position relative to the bonding position of A 6 .
通式(XI)所表示之二胺,例如可列舉下式(XI-1)~(XI-4)所表示之二胺。The diamine represented by the formula (XI) is, for example, a diamine represented by the following formulas (XI-1) to (XI-4).
[化59]
於通式(XII)中,2個「NH2 -(R14 -)Ph-A6 -O-」(其中,Ph表示亞苯基。)分別鍵結於苯環碳上,較好的是鍵結於相對於類固醇核所鍵結之碳為間位或者對位之碳上。又,2個胺基分別鍵結於苯環碳上,較好的是相對於A6 鍵結於間位或者對位。In the formula (XII), two "NH 2 -(R 14 -)Ph-A 6 -O-" (wherein Ph represents a phenylene group) are bonded to the benzene ring carbon, preferably The bond is bonded to the carbon of the meta or para position relative to the carbon to which the steroid nucleus is bonded. Further, the two amine groups are bonded to the benzene ring carbon, respectively, and it is preferably bonded to the meta or para position with respect to A 6 .
通式(XII)所表示之二胺,例如可列舉下式(XII-1)~(XII-8)所表示之二胺。Examples of the diamine represented by the formula (XII) include diamines represented by the following formulas (XII-1) to (XII-8).
[化60]
本發明中所使用的二胺(a2'),進而可列舉下述通式(XⅢ)以及(XⅣ)所表示之化合物。The diamine (a2') used in the present invention may, for example, be a compound represented by the following formula (XIII) or (XIV).
(通式(XⅢ)中,R15 為-H或者碳數1~20之烷基,該烷基中碳數2~20之烷基之任意的-CH2 -可經-O-、-CH=CH-或者-C≡C-取代,A7 分別獨立為-O-或者碳數1~6之亞烷基,A8 為單鍵或者碳數1~3之亞烷基,環T為1,4-亞苯基或者1,4-亞環己基,h為0或者1。)(In the formula (XIII), R 15 is -H or an alkyl group having 1 to 20 carbon atoms, and any -CH 2 - of the alkyl group having 2 to 20 carbon atoms in the alkyl group may be -O-, -CH =CH- or -C≡C-substituted, A 7 is independently -O- or an alkylene group having 1 to 6 carbon atoms, A 8 is a single bond or an alkylene group having 1 to 3 carbon atoms, and ring T is 1 , 4-phenylene or 1,4-cyclohexylene, h is 0 or 1.)
(通式(XⅣ)中,R16 為碳數6~22之烷基,R17 為-H或者碳數1~22之烷基, A7 分別獨立為-O-或者碳數1~6之亞烷基。)(In the formula (XIV), R 16 is an alkyl group having 6 to 22 carbon atoms, R 17 is -H or an alkyl group having 1 to 22 carbon atoms, and A 7 is independently -O- or a carbon number of 1 to 6 Alkylene.)
於上述通式(XⅢ)中,2個胺基分別鍵結於苯環碳上,較好的是相對於A7 鍵結於間位或者對位。In the above formula (XIII), the two amine groups are bonded to the benzene ring carbon, respectively, and it is preferably bonded to the meta or para position with respect to A 7 .
通式(XⅢ)所表示之二胺,例如可列舉下述通式(XⅢ-1)~(XⅢ-9)所表示之二胺。Examples of the diamine represented by the formula (XIII) include diamines represented by the following formulae (XIII-1) to (XIII-9).
[化65]
於上述通式(XⅢ-1)~(XⅢ-3)中,R24 較好的是-H、碳數1~20之烷基,於(XⅢ-4)~(XⅢ-9)中,R25 進而好的是-H、碳數1~10之烷基。In the above formula (XIII-1) to (XIII-3), R 24 is preferably -H, an alkyl group having 1 to 20 carbon atoms, and (XIII-4) to (XIII-9), R. Further preferably, 25 is -H and an alkyl group having 1 to 10 carbon atoms.
於上述通式(XⅣ)中,2個胺基分別鍵結於苯環碳上,較好的是相對於A7 鍵結於間位或者對位。In the above formula (XIV), the two amine groups are bonded to the benzene ring carbon, respectively, and it is preferably bonded to the meta or para position with respect to A 7 .
通式(XⅣ)所表示之二胺,例如可列舉下述通式(XⅣ-1)~(XⅣ-3)所表示之二胺。Examples of the diamine represented by the formula (XIV) include diamines represented by the following formulae (XIV-1) to (XIV-3).
[化66]
於上述通式(XⅣ-1)~(XⅣ-3)中,R26 為碳數2~30之有機基,該些中較好的是碳數6~20之烷基,R27 為碳數2~30之有機基,該些中進而好的是-H或者碳數1~10之烷基。In the above formula (XIV-1) to (XIV-3), R 26 is an organic group having 2 to 30 carbon atoms, and among these, an alkyl group having 6 to 20 carbon atoms and R 27 being a carbon number are preferred. Further, an organic group of 2 to 30, and more preferably a -H or an alkyl group having 1 to 10 carbon atoms.
如上所述,本發明中所使用的二胺(a2')例如可使用通式(Ⅱ)~(XⅣ)所表示之二胺,但亦可使用該些二胺以外的二胺。例如,可將具有萘結構之萘系二胺、具有茀結構之茀系二胺、或者具有矽氧烷鍵之矽氧烷系二胺等單獨使用或者與其他二胺混合使用。As described above, the diamine (a2') used in the present invention may be, for example, a diamine represented by the formulae (II) to (XIV), but a diamine other than the diamine may be used. For example, a naphthalene type diamine having a naphthalene structure, an anthracene diamine having a fluorene structure, or a decane group diamine having a decane bond may be used alone or in combination with other diamines.
矽氧烷系二胺並無特別限定,於本發明中可較好地使用下述通式(XV)所表示之矽氧烷系二胺。The oxirane-based diamine is not particularly limited, and the oxirane-based diamine represented by the following formula (XV) can be preferably used in the present invention.
(上述通式(XV)中,R3 以及R4 獨立為碳數1~3 之烷基或者苯基,R5 獨立為亞甲基、亞苯基或者經烷基取代之亞苯基,x獨立為1~6之整數,y為1~70之整數。其中,更好的是y為1~15之整數。)(In the above formula (XV), R 3 and R 4 are independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R 5 is independently a methylene group, a phenylene group or a phenylene group substituted by an alkyl group, x Independently an integer from 1 to 6, and y is an integer from 1 to 70. Among them, it is better that y is an integer from 1 to 15.)
進而好的是,本發明中所使用的二胺(a2')可使用下述通式(XⅥ-1)~(XⅥ-8)所表示之二胺。Further, the diamine (a2') used in the present invention may be a diamine represented by the following formula (XVI-1) to (XVI-8).
(上述通式(XⅥ-1)~(XⅥ-8)中,R30 以及R31 獨立為碳數3~20之烷基。)(In the above formula (XVI-1) to (XVI-8), R 30 and R 31 are independently an alkyl group having 3 to 20 carbon atoms.)
另外,本發明中可使用的二胺(a2')並不限定於本說明書之二胺,可於達成本發明之目的的範圍內使用其他各種形態的二胺。Further, the diamine (a2') which can be used in the present invention is not limited to the diamine of the present specification, and other various forms of diamine can be used within the range in which the object of the present invention is achieved.
又,本發明中可使用的二胺(a2')可單獨使用一種或者組合兩種或兩種以上加以使用。即,兩種或兩種以上之二胺的組合可使用:上述二胺彼此的組合、上述二胺與其 他二胺的組合或者上述二胺以外之二胺彼此的組合。Further, the diamine (a2') which can be used in the present invention may be used alone or in combination of two or more. That is, a combination of two or more kinds of diamines may be used: a combination of the above diamines, the above diamine and A combination of his diamines or a combination of diamines other than the above diamines.
又,根據噴墨用墨水之用途,有時要求高透明性,於此情形時,尤其好的是使用3,3'-二胺基二苯基碸以及上述通式(XV)中y=1~15之整數的二胺。Further, depending on the use of the ink for inkjet, high transparency is sometimes required. In this case, it is particularly preferable to use 3,3'-diaminodiphenylanthracene and y=1 in the above formula (XV). A diamine of an integer of ~15.
2高分子化合物(B)2 polymer compound (B)
可進而含有於本發明之噴墨用墨水中的高分子化合物(B)為聚醯胺酸、可溶性聚醯亞胺、聚醯胺、聚醯胺醯亞胺、聚醯胺酸酯、聚酯、丙烯酸聚合物、丙烯酸酯聚合物、聚乙烯醇、聚氧乙烯等高分子化合物,但並不限定於所述化合物。較好的是聚醯胺酸或者可溶性聚醯亞胺等聚醯亞胺系高分子化合物,例如可較好地列舉特願2006-235336號中揭示之聚醯胺酸、或者此聚醯胺酸之醯亞胺化聚合物,但並不限定於所述化合物。The polymer compound (B) which can be further contained in the inkjet ink of the present invention is polyacrylic acid, soluble polyimine, polyamide, polyamidamine, polyphthalate, polyester A polymer compound such as an acrylic polymer, an acrylate polymer, polyvinyl alcohol or polyoxyethylene, but is not limited to the compound. A polyimine-based polymer compound such as a polyaminic acid or a soluble polyimine is preferable, and for example, the poly-proline which is disclosed in Japanese Patent Application No. 2006-235336, or the poly-proline is preferably used. The imidized polymer is, but not limited to, the compound.
該聚醯胺酸可藉由至少使用具有大於等於2個之酸酐基之化合物(b1)與二胺(b2)與單胺(b3)而獲得,但並不限定於利用該製法獲得的聚醯胺酸。The polyamic acid can be obtained by using at least a compound (b1) having two or more acid anhydride groups and a diamine (b2) and a monoamine (b3), but is not limited to the polyfluorene obtained by the process. Amino acid.
以下,對可用於獲得高分子化合物(B)的具有大於等於2個之酸酐基之化合物(b1)與二胺(b2)與單胺(b3)加以說明。Hereinafter, the compound (b1) and the diamine (b2) and the monoamine (b3) having two or more acid anhydride groups which can be used for obtaining the polymer compound (B) will be described.
2.1具有大於等於2個之酸酐基之化合物(b1)2.1 Compound having two or more acid anhydride groups (b1)
本發明中所使用的具有大於等於2個之酸酐基之化合物(b1)之具體例,可使用與上述可用於獲得矽醯胺酸(A)的具有大於等於2個之酸酐基之化合物(a1)相同的化合物。As a specific example of the compound (b1) having two or more acid anhydride groups used in the present invention, a compound having the acid anhydride group of 2 or more which can be used for obtaining the valine acid (A) can be used (a1). ) the same compound.
具有大於等於2個之酸酐基之化合物(b1)可與具有大於等於2個之酸酐基之化合物(a1)相同,亦可不同。又,上述揭示之具有酸酐基之化合物可單獨使用一種或者組合兩種或兩種以上使用。The compound (b1) having two or more acid anhydride groups may be the same as or different from the compound (a1) having two or more acid anhydride groups. Further, the compound having an acid anhydride group disclosed above may be used alone or in combination of two or more.
2.2二胺(b2)2.2 diamine (b2)
本發明中所使用的二胺(b2)之具體例,可使用與上述可用於獲得矽醯胺酸(A')的二胺(a2')相同的二胺。As a specific example of the diamine (b2) used in the present invention, the same diamine as the above-mentioned diamine (a2') which can be used for obtaining valine acid (A') can be used.
二胺(b2)與二胺(a2')可相同亦可不同。又,上述揭示之二胺可單獨使用一種或者組合兩種或兩種以上使用。The diamine (b2) and the diamine (a2') may be the same or different. Further, the diamines disclosed above may be used alone or in combination of two or more.
2.3單胺(b3)2.3 monoamine (b3)
本發明中所使用的單胺(b3)之具體例,可使用與上述可用於獲得矽醯胺酸(A)的單胺(a2)相同的單胺。單胺(b3)與單胺(a2)可相同亦可不同。又,上述揭示之單胺可單獨使用一種或者組合兩種或兩種以上使用。As a specific example of the monoamine (b3) used in the present invention, the same monoamine as the above-mentioned monoamine (a2) which can be used for obtaining valine acid (A) can be used. The monoamine (b3) may be the same as or different from the monoamine (a2). Further, the monoamines disclosed above may be used alone or in combination of two or more.
2.4聚醯胺酸之反應條件2.4 Polyampinic acid reaction conditions
本發明中可使用的聚醯胺酸較好的是相對於1莫耳之具有大於等於2個之酸酐基之化合物(b1),與0.05莫耳~0.8莫耳之二胺(b2)、0.4莫耳~1.9莫耳之單胺(b3)反應而獲得。又,進而好的是相對於1莫耳之具有大於等於2個之酸酐基之化合物(b1),與0.1莫耳~0.6莫耳之二胺(b2)、0.8莫耳~1.8莫耳之單胺(b3)反應而獲得。更好的是相對於1莫耳之具有大於等於2個之酸酐基之化The polyamic acid which can be used in the present invention is preferably a compound (b1) having an acid anhydride group of 2 or more with respect to 1 mole, and 0.05 to 0.8 mole of diamine (b2), 0.4. Obtained by the reaction of moles to 1.9 moles of monoamine (b3). Further, further preferably, it is a compound (b1) having an acid anhydride group of 2 or more with respect to 1 mol, and a diamine (b2) of 0.1 mol to 0.6 mol, and a molar of 1.8 mol to 1.8 mol. The amine (b3) is obtained by a reaction. More preferably, it has an acid anhydride group of 2 or more with respect to 1 mole.
合物(b1),與0.15莫耳~0.35莫耳之二胺(b2)、1.3莫耳~1.7莫耳之單胺(b3)反應而獲得。The compound (b1) is obtained by reacting with 0.15 moles to 0.35 moles of diamine (b2) and 1.3 moles to 1.7 moles of monoamine (b3).
2.4(1)反應溶劑2.4(1) Reaction solvent
本發明中可使用的用於獲得聚醯胺酸的溶劑,可使用與上述可用於獲得矽醯胺酸(A)或者矽醯胺酸(A')的溶劑相同的溶劑。反應溶劑可單獨使用,亦可用作兩種或兩種以上之混合溶劑。又,除上述反應溶劑以外,亦可混合使用其他溶劑。As the solvent for obtaining polylysine which can be used in the present invention, the same solvent as the above-mentioned solvent which can be used for obtaining glutamic acid (A) or lysine (A') can be used. The reaction solvent may be used singly or as a mixed solvent of two or more kinds. Further, in addition to the above reaction solvent, other solvents may be used in combination.
反應溶劑若相對於具有大於等於2個之酸酐基之化合物(b1)、二胺(b2)與單胺(b3)之總計100重量份,使用大於等於100重量份,則反應順利進行,故而較好。較好的是反應於0℃~100℃(較好的是8℃~70℃)下進行0.2小時~20小時(較好的是2小時~10小時)。When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the compound (b1), the diamine (b2) and the monoamine (b3) having two or more acid anhydride groups, the reaction proceeds smoothly, so that the reaction proceeds smoothly. it is good. Preferably, the reaction is carried out at from 0 ° C to 100 ° C (preferably from 8 ° C to 70 ° C) for from 0.2 hours to 20 hours (preferably from 2 hours to 10 hours).
2.4(2)添加至反應系中的順序2.4(2) Sequence added to the reaction system
另外,反應原料添加至反應系中的順序並無特別限定。即,可使用如下方法中的任一種方法:將具有大於等於2個之酸酐基之化合物(b1)與二胺(b2)與單胺(b3)同時添加至反應溶劑中的方法;將二胺(b2)與單胺(b3)溶解於反應溶劑中後添加具有大於等於2個之酸酐基之化合物(b1)的方法;先使具有大於等於2個之酸酐基之化合物(b1)與單胺(b3)反應後添加二胺(b2)的方法;先使具有大於等於2個之酸酐基之化合物(b1)與二胺(b2)反應合成共聚物後,於此共聚物中添加單胺(b3)的方法等。Further, the order in which the reaction raw material is added to the reaction system is not particularly limited. That is, any one of the following methods may be used: a method of simultaneously adding a compound (b1) having two or more acid anhydride groups and a diamine (b2) and a monoamine (b3) to a reaction solvent; (b2) a method of adding a compound (b1) having two or more acid anhydride groups after dissolving in a reaction solvent with a monoamine (b3); first, a compound (b1) having an acid anhydride group of 2 or more and a monoamine (b3) a method of adding a diamine (b2) after the reaction; after reacting a compound (b1) having two or more acid anhydride groups with a diamine (b2) to synthesize a copolymer, a monoamine is added to the copolymer ( Method of b3), etc.
2.5高分子化合物(B)之重量平均分子量2.5 Weight average molecular weight of the polymer compound (B)
重量平均分子量為1,000~20,000之高分子化合物(B)尤其對溶劑之溶解性優異,作為噴墨用墨水較好。於本發明中,為了進一步提昇高分子化合物(B)對溶劑之「溶解性」,較好的是高分子化合物(B)的重量平均分子量為1,000~10,000,更好的是1,000~7,500,進而好的是1,000~5,000,尤其好的是1,000~3,500。The polymer compound (B) having a weight average molecular weight of 1,000 to 20,000 is particularly excellent in solubility in a solvent, and is preferably used as an ink for inkjet. In the present invention, in order to further enhance the "solubility" of the polymer compound (B) with respect to the solvent, it is preferred that the polymer compound (B) has a weight average molecular weight of 1,000 to 10,000, more preferably 1,000 to 7,500. Good is 1,000~5,000, especially good is 1,000~3,500.
其原因在於:具有大於等於1,000之重量平均分子量的高分子化合物(B)不會因加熱處理而蒸發,於化學性.機械性方面穩定,具有小於等於20,000之重量平均分子量的高分子化合物(B)可提高對溶劑之溶解性,因此可增大所得塗膜之膜厚,可較好地用作噴墨用墨水。The reason is that the polymer compound (B) having a weight average molecular weight of 1,000 or more is not evaporated by heat treatment, and is chemical. The polymer compound (B) having a weight average molecular weight of 20,000 or less is stable in terms of mechanical properties, and the solubility in a solvent can be improved. Therefore, the film thickness of the obtained coating film can be increased, and it can be suitably used as an ink for inkjet.
高分子化合物(B)之重量平均分子量可藉由凝膠滲透層析(GPC)法而測定。具體而言,可藉由如下方法求得:以四氫呋喃(THF)等將所得高分子化合物(B)之濃度稀釋至約1重量百分比(wt%),使用Tosoh股份有限公司製造之管柱(column)G4000HXL、G3000HXL、G2500HXL以及G2000HXL,以THF為展開劑,藉由凝膠滲透層析(GPC)法而測定,以聚苯乙烯進行換算。The weight average molecular weight of the polymer compound (B) can be measured by a gel permeation chromatography (GPC) method. Specifically, it can be obtained by diluting the concentration of the obtained polymer compound (B) to about 1 weight percent (wt%) with tetrahydrofuran (THF) or the like, using a column manufactured by Tosoh Co., Ltd. (column) G4000HXL, G3000HXL, G2500HXL, and G2000HXL were measured by gel permeation chromatography (GPC) using THF as a developing solvent, and converted to polystyrene.
3烯基取代納迪克酸醯亞胺化合物(C)3-alkenyl substituted nadic acid ylide imine compound (C)
本發明之噴墨用墨水中所含的烯基取代納迪克酸醯亞胺化合物(C),是分子內具有至少1個烯基取代納迪克酸醯亞胺結構的化合物,較好的是使單胺、二胺、三胺或者四胺與上述式(5')所表示之烯基取代納迪克酸酐反應而The alkenyl-substituted nadic ylidene imide compound (C) contained in the inkjet ink of the present invention is a compound having at least one alkenyl-substituted nadic acid ylidene imine structure in the molecule, and it is preferred to The monoamine, diamine, triamine or tetraamine is reacted with an alkenyl-substituted nadic anhydride represented by the above formula (5')
獲得的烯基取代納迪克酸醯亞胺,更好的是上述通式(5)所表示之烯基取代納迪克酸醯亞胺化合物,但並不限定於所述化合物。The alkenyl group obtained by substituting the naphthyl group is more preferably an alkenyl group substituted with a nadic acid ylide compound represented by the above formula (5), but is not limited to the compound.
烯基取代納迪克酸醯亞胺化合物(C)中存在:n為1之烯基取代納迪克酸醯亞胺化合物(c1:以下,有時僅稱為「烯基取代納迪克酸醯亞胺」)、以及n為2之烯基取代納迪克酸醯亞胺化合物(c2:以下,有時僅稱為「雙烯基取代納迪克酸醯亞胺」)、n為3之烯基取代納迪克酸醯亞胺化合物(c3:以下,有時僅稱為「三烯基取代納迪克酸醯亞胺」)、n為4之烯基取代納迪克酸醯亞胺化合物(c4:以下,有時僅稱為「四烯基取代納迪克酸醯亞胺」)。Alkenyl-substituted nadic acid ylidene imine compound (C): n-substituted alkenyl-substituted nadic acid ylidene imine compound (c1: hereinafter, sometimes only referred to as "alkenyl-substituted nadic acid ylide" "), and n is an alkenyl group substituted with a nadic acid ylide compound (c2: hereinafter, sometimes referred to simply as "dienyl substituted nadic acid ylide"), n is an alkenyl substituted sodium of 3 Dick acid imine compound (c3: hereinafter, sometimes referred to simply as "trienyl substituted nadic acid ylide"), n is an alkenyl-substituted nadic acid ylide compound (c4: below, It is only referred to as "tetraalkenyl substituted nadic acid ylide").
3.1烯基取代納迪克酸醯亞胺(c1)3.1 alkenyl substituted nadic acid ylide (c1)
本發明中所使用的n為1之烯基取代納迪克酸醯亞胺化合物之具體例,例如可列舉以下化合物。Specific examples of the alkenyl-substituted nadic acid ruthenium imine compound in which n is 1 used in the present invention include, for example, the following compounds.
可列舉:烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-羥基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-羥基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-羥基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、 N-羥基-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-乙基己基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、以及該些的寡聚物等。There may be mentioned allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-di Carboxylimine, methallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, methallylmethyl bicyclo [2.2.1] hept-5-ene -2,3-dicarboxy quinone imine, N-hydroxy-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-hydroxy-allyl methyl bicyclic [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-hydroxy-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene amine, N-Hydroxy-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-methyl-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-methyl- Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, and the like Oligomers, etc.
又可列舉:N-(2-乙基己基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、 N-異丙烯基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、以及該些的寡聚物等。Further, N-(2-ethylhexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-allyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-isopropenyl-allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene amine, N-isopropenyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl bicyclo [2.2.1] g-5 -ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl- Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-phenyl-allyl bicyclo [2.2.1] hept-5-ene-2,3 - Dicarboxy quinone imine, and oligomers thereof and the like.
又可列舉:N-苯基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2'-羥基乙基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2'-羥基乙基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2'-羥基乙基)-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、以及該些的寡聚物等。Further, N-phenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-benzyl-allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- Benzyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-(2'-hydroxyethyl)-allyl bicyclo [2.2.1] Hg-5-ene-2,3-dicarboxyindolimine, N-(2'-hydroxyethyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(2'-hydroxyethyl)-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, and oligomers thereof .
又可列舉:N-(2',2'-二甲基-3'-羥基丙基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2',2'-二甲基-3'-羥基丙基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2',3'-二羥基丙基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2',3'-二羥基丙基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(3'-羥基-1'-丙烯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4'-羥基-環己基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、以及該些的寡聚物等。Further, N-(2',2'-dimethyl-3'-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2',2'-dimethyl-3'-hydroxypropyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N- (2',3'-Dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2',3'-dihydroxypropyl ())-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3'-hydroxy-1'-propenyl)-allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4'-hydroxy-cyclohexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine, and oligomers thereof.
又可列舉:N-(4'-羥基苯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4'-羥基苯基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4'-羥基苯基)-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4'-羥基苯基)-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(3'-羥基苯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(3'-羥基苯基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二 羧基醯亞胺、N-(對羥基苄基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{2'-(2'-羥基乙氧基)乙基}-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、以及該些的寡聚物等。Further, N-(4'-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(4'-hydroxyphenyl) -allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4'-hydroxyphenyl)-methylallylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine, N-(4'-hydroxyphenyl)-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-(3'-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3'-hydroxybenzene Base)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-{2'-(2'-hydroxyl Ethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, and oligomers thereof and the like.
又可列舉:N-{2'-(2'-羥基乙氧基)乙基}-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{2'-(2'-羥基乙氧基)乙基}-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{2'-(2'-羥基乙氧基)乙基}-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-[2'-{2'-(2"-羥基乙氧基)乙氧基}乙基]-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-[2'-{2'-(2"-羥基乙氧基)乙氧基}乙基]-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-[2'-{2'-(2"-羥基乙氧基)乙氧基}乙基]-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{4'-(4'-羥基苯基亞異丙基)苯基}-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{4'-(4'-羥基苯基亞異丙基)苯基}-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{4'-(4'-羥基苯基亞異丙基)苯基}-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、 以及該些的寡聚物等。Further, N-{2'-(2'-hydroxyethoxy)ethyl}-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarlimine, N-{2'-(2'-hydroxyethoxy)ethyl}-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-{2 '-(2'-Hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-[2'- {2'-(2"-Hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-[2 '-{2'-(2"-Hydroxyethoxy)ethoxy}ethyl]-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-[2'-{2'-(2"-Hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-{4'-(4'-hydroxyphenyl isopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine , N-{4'-(4'-hydroxyphenyl isopropylidene)phenyl}-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4'-(4'-hydroxyl Phenyl isopropyl) phenyl} - methallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (PEI) And such oligomers and the like.
又,該些烯基取代納迪克酸醯亞胺(c1)可單獨使用,亦可作為該些的混合物而使用。Further, the alkenyl-substituted nadic acid ylidene imide (c1) may be used singly or as a mixture of these.
上述烯基取代納迪克酸醯亞胺(c1)中較好的可列舉:N-甲基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-乙基己基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺等。Preferred examples of the above alkenyl-substituted nadic acid ylidene imide (c1) include N-methyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-methyl-methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- (2-Ethylhexyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine.
又可列舉:N-(2-乙基己基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧 基醯亞胺、N-異丙烯基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺等。Further, N-(2-ethylhexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-allyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-isopropenyl-allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Base imine, N-isopropenyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl bicyclo [2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-phenyl-allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, and the like.
又可列舉:N-苯基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺等。Further, N-phenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-benzyl-allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- Benzyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, and the like.
烯基取代納迪克酸醯亞胺(c1)更好的可列舉:N-甲基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、 N-甲基-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-乙基己基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺等。More preferably, the alkenyl-substituted nadic acid ylide (c1) is N-methyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N- Methyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, N-methyl-methylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-methyl-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-ethylhexyl)-allylbicyclo[2.2 .1] Hept-5-ene-2,3-dicarboxy quinone imine, and the like.
又可列舉:N-(2-乙基己基)-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺等。Further, N-(2-ethylhexyl)-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-allyl-allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-allyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-isopropenyl-allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimine, N-isopropenyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine, N-isopropenyl-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, and the like.
3.2雙烯基取代納迪克酸醯亞胺(c2)3.2 Dienyl substituted nadic acid ylide (c2)
又,本發明中所使用的n為2之烯基取代納迪克酸醯亞胺化合物之具體例,例如可列舉以下化合物。Further, specific examples of the alkenyl-substituted nadic acid ruthenium imine compound in which n is 2 used in the present invention include, for example, the following compounds.
可列舉:N,N'-亞乙基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二 羧基醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、以及該些的寡聚物等。Mention may be made of N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-ethylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-ethylidene-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'- Trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine), N,N'-docamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-docamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-cyclohexylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), and oligomers thereof and the like.
又可列舉:1,2-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙烷、1,2-雙{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙烷、1,2-雙{3'-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙烷、 雙[2'-{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙基]醚、雙[2'-{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙基]醚、1,4-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}丁烷、1,4-雙{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}丁烷、以及該些的寡聚物等。Also exemplified by 1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, 1,2- Double {3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, 1,2-double {3'-( Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy}ethane, Bis[2'-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, bis[2'-{ 3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, 1,4-double {3'-( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy}butane, 1,4-double {3'-(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine)propoxy}butane, and oligomers thereof and the like.
又可列舉:N,N'-對亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二 羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、以及該些的寡聚物等。Also exemplified are: N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-m-xylylene - bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), and Oligomers and the like.
又可列舉:2,2-雙[4'-{4'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4'-{4'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4'-{4'-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、以及該些的寡聚物等。Further, exemplified by 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenoxy}phenyl] Propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenoxy}phenyl] Propane, 2,2-bis[4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl] Propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2 .1] hept-5-ene-2,3-dicarboxyinimide)phenyl}methane, and oligomers thereof.
又可列舉:雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞 胺)苯基}醚、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、以及該些的寡聚物等。Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, double {4-(methylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine) phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl} Ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine) phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}indole, double {4-(allyl Methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene, and oligomers thereof and the like.
又可列舉:雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、1,6-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-3-羥基-己烷、1,12-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-3,6-二羥基-十二烷、1,3-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-5-羥基-環己烷、1,5-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}-3-羥基-戊烷、1,4-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-2-羥基-苯、以及該些的寡聚物等。Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)phenyl}anthracene, 1,6-bis(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-3-hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) Propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)-2-hydroxy-benzene, And such oligomers and the like.
又可列舉:1,4-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-2,5-二羥基-苯、N,N'-對(2-羥基)苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對(2-羥基)苯二甲基-雙(烯丙基甲基環[2.2.1]庚 -5-烯-2,3-二羧基醯亞胺)、N,N'-間(2-羥基)苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間(2-羥基)苯二甲基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對(2,3-二羥基)苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、以及該些的寡聚物等。Further, 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)-2,5-dihydroxy-benzene, N,N '-p-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-pair (2- Hydroxy) benzenedimethyl-bis(allylmethylcyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-p-(2,3-dihydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine), and oligomers and the like.
又可列舉:2,2-雙[4'-{4'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-2'-羥基-苯氧基}苯基]丙烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-2-羥基-苯基}甲烷、雙{3-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-4-羥基-苯基}醚、雙{3-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-5-羥基-苯基}碸、1,1,1-三{4'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)}苯氧基甲基丙烷、N,N',N"-三(亞乙基甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)三聚異氰酸酯、以及該些的寡聚物等。Also exemplified is: 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinylimine)-2'-hydroxy-benzene Oxy}phenyl]propane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)-2-hydroxy-phenyl}methane, Double {3-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-4-hydroxy-phenyl}ether, double {3-(methallyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4'-(allylmethylbicyclic [2.2.1]hept-5-ene-2,3-dicarboxy quinazomine)}phenoxymethylpropane, N,N',N"-tris(ethylene allylenylbicyclo[2.2 .1] hept-5-ene-2,3-dicarboxyinimide) a trimeric isocyanate, and oligomers thereof.
進而亦可為包含非對稱之亞烷基.亞苯基的以下化合物。Further, it may also be an asymmetric alkylene group. The following compounds of phenylene.
[化69]
又,該些雙烯基取代納迪克酸醯亞胺(c2)可單獨使用,亦可作為該些的混合物而使用。Further, these dienyl substituted nadic acid ylides (c2) may be used singly or as a mixture of these.
上述雙烯基取代納迪克酸醯亞胺(c2)較好的可列舉:N,N'-亞乙基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、 N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)等。The above dienyl substituted nadic acid ylide (c2) is preferably exemplified by N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine), N,N'-ethylidene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N' -ethylidene-bis(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-trimethylene-bis(allyl bicyclol) [2.2.1]hept-5-ene-2,3-dicarboxynonimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-double ( Allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, N'-docamethylene-bis(allyl bicyclo [2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N'- Cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) and the like.
又可列舉:N,N'-對亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、 N,N'-對苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、2,2-雙[4'-{4'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4'-{4'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4'-{4'-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷等。Also exemplified are: N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-xylylene Base-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allylmethylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine) phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine) phenoxy} phenyl] propane, bis {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) benzene Methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane, and the like.
又可列舉:雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、 雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸等。Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, double {4-(methylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine) phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl} ether, Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, bis{4-(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}indole, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine) phenyl} oxime and the like.
又可列舉:雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸等。Further, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}anthracene or the like can be mentioned.
雙烯基取代納迪克酸醯亞胺(c2)更好的可列舉:N,N'-亞乙基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯 -2,3-二羧基醯亞胺)、N,N'-亞環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-亞環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)等。More preferred examples of the dienyl substituted nadic acid ylide (c2) are: N,N'-ethylidene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'- Ethylene-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-trimethylene-bis(allylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-dodecyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-dodecamethylene-double (allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine) and the like.
又可列舉:N,N'-對亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間亞苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間亞苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-{(1-甲基)-2,4-亞苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)等。Also exemplified are: N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-m-xylylene - bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2 .1] hept-5-ene-2,3-dicarboxy quinone imine) and the like.
又可列舉:2,2-雙[4'-{4'-(烯丙基雙環[2.2.1]庚-5-烯 -2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4'-{4'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4'-{4'-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷等。Also exemplified is: 2,2-bis[4'-{4'-(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenoxy}phenyl]propane, 2,2-bis[4'-{4'-(methylallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenoxy} phenyl] propane, bis {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) Phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane, and the like.
又可列舉:雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷等。Further, exemplified by: bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, double {4-(methylallyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}methane, and the like.
3.3三烯基取代納迪克酸醯亞胺(c3)3.3 trienyl substituted nadic acid ylide (c3)
本發明中所使用的n為3之三烯基取代納迪克酸醯亞胺化合物的合成可利用如下方法進行:相對於1.0莫耳之三胺,混合3.0莫耳~5.0莫耳之烯基取代納迪克酸酐,於常溫下溶解於例如苯、甲苯、二甲苯、均三甲苯、甲基萘、四氫萘(tetralin)、氯仿、三氯乙烯、四氯乙烯、氯苯、二噁烷、四氫呋喃、六亞甲基醚、苯甲醚(anisole)、丙酮、甲基乙基酮、甲基異丁基酮、苯乙酮、N,N-二甲基甲醯胺、二甲基亞碸等任意溶劑,或者混合兩種或兩種以上的溶劑中,作為溶液攪拌保持0.5小時~30小時進行反應。於20℃~80℃下減壓乾燥除去上述溶劑,獲得醯胺酸。將上述 醯胺酸於上述溶劑中、於溶劑之沸點附近回流(reflux)0.5小時~30小時,或者將化合物本身於160℃~200℃下加熱,使之進行脫水閉環後,減壓乾燥溶劑而獲得目標化合物。可藉由核磁共振(NMR)、紅外線(IR)確認為目標化合物。The synthesis of a 3, 3-alkenyl substituted nadic acid ylidene imine compound used in the present invention can be carried out by mixing 3.0 moles to 5.0 moles of alkenyl substitution with respect to 1.0 mole of triamine. Nadickic anhydride, dissolved at room temperature, for example, benzene, toluene, xylene, mesitylene, methylnaphthalene, tetralin, chloroform, trichloroethylene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran , hexamethylene ether, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, N, N-dimethylformamide, dimethyl hydrazine, etc. The solvent may be stirred in a solvent or in a mixture of two or more solvents for 0.5 to 30 hours. The solvent was removed by drying under reduced pressure at 20 ° C to 80 ° C to obtain valine acid. Will be above The proline is refluxed in the above solvent at a boiling point of the solvent for 0.5 hours to 30 hours, or the compound itself is heated at 160 ° C to 200 ° C to cause dehydration ring closure, and the solvent is dried under reduced pressure to obtain a target. Compound. It can be confirmed as a target compound by nuclear magnetic resonance (NMR) or infrared (IR).
本發明中所使用的n為3之三烯基取代納迪克酸醯亞胺化合物之具體例,例如可列舉以下化合物。Specific examples of the n-alkenyl-substituted nadic ylidene imide compound used in the present invention are, for example, the following compounds.
三{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)三乙基}胺(TrisANITAEA)、三{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)三苯基}甲烷(TrisANITrisAM)、三{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}羥基甲烷(TrisANIPARARO)、「TrisANITAEA」之IR光譜以及1 H-NMR光譜(400 MHz)分別示於圖1以及圖2。Tris{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)triethyl}amine (TrisANITAEA), tris{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)triphenyl}methane (TrisANITrisAM), tris{4-(allylbicyclo[2.2.1]hept-5-ene-2, The IR spectrum of TrisANI PARAR, "TrisANITAEA" and the 1 H-NMR spectrum (400 MHz) are shown in Fig. 1 and Fig. 2, respectively.
IR光譜中,歸屬於烯烴C-H伸縮:3070 cm-1 、2966 cm-1 ;歸屬於芳香族C-H伸縮:2966 cm-1 ;歸屬於烷烴C-H伸縮:2938 cm-1 ;歸屬於醯亞胺C=O伸縮:1762 cm-1 、1690 cm-1 ;歸屬於C=C伸縮:1640 cm-1 ;歸屬於-CH2 -N-亞甲基剪式振動:1448 cm-1 ;歸屬於醯亞胺C-N伸縮:1382 cm-1 等。In the IR spectrum, it belongs to the olefin C-H stretching: 3070 cm -1 , 2966 cm -1 ; the aromatic C-H expansion: 2966 cm -1 ; the alkane C-H expansion: 2938 cm -1 ;醯 醯 imine C=O stretching: 1762 cm -1 , 1690 cm -1 ; belonging to C=C stretching: 1640 cm -1 ; belonging to -CH 2 -N-methylene scissor vibration: 1448 cm -1 ; belongs to the quinone imine C-N expansion: 1382 cm -1 and so on.
[化70]
1 H-NMR光譜中,歸屬於a、b、e、f、g、i、l質子(30H):2.50 pm~3.49 pm之峰;歸屬於j、k、m、n質子(12H):5.01 ppm~6.27 ppm之峰;歸屬於h質子(6H):1.25 ppm~1.76 ppm之峰等。 1 H-NMR spectrum, belonging to a, b, e, f, g, i, l proton (30H): 2.50 pm ~ 3.49 pm peak; belonging to j, k, m, n proton (12H): 5.01 Peak of ppm~6.27 ppm; attributed to h proton (6H): peak of 1.25 ppm~1.76 ppm.
「TrisANITrisAM」之IR光譜以及1 H-NMR光譜(400 MHz)分別示於圖3以及圖4。The IR spectrum and 1 H-NMR spectrum (400 MHz) of "TrisANI Tris AM" are shown in Fig. 3 and Fig. 4, respectively.
IR光譜中,歸屬於烯烴C-H伸縮:3056 cm-1 、2970 cm-1 ;歸屬於芳香族C-H伸縮:2970 cm-1 ;歸屬於烷烴C-H伸縮:2936 cm-1 ;歸屬於醯亞胺C=O伸縮:1772 cm-1 、1706 cm-1 ;歸屬於C=C伸縮:1638 cm-1 ;歸屬於醯亞胺C-N伸縮:1402 cm-1 等。In the IR spectrum, it belongs to the olefin C-H stretching: 3056 cm -1 , 2970 cm -1 ; the aromatic C-H expansion: 2970 cm -1 ; the alkane C-H expansion: 2936 cm -1 ;醯 醯 imine C=O stretching: 1772 cm -1 , 1706 cm -1 ; belonging to C=C stretching: 1638 cm -1 ; belonging to yttrium C-N stretching: 1402 cm -1 and so on.
[化71]
1 H-NMR光譜中,歸屬於a質子~d質子(12H):6.50 ppm~7.59 ppm之峰;歸屬於e、f、g、i、l質子(18H):2.25 ppm~3.73 ppm之峰;歸屬於h質子(6H):1.25 ppm~1.81 ppm;歸屬於j、k、m、n質子(12H):5.01 ppm~5.14 ppm、5.74 ppm~6.34 ppm之峰;歸屬於o質子(1H):5.30 ppm~5.60 ppm之峰等。 1 H-NMR spectrum, belonging to a proton to d proton (12H): 6.50 ppm ~ 7.59 ppm peak; belonging to e, f, g, i, l proton (18H): 2.25 ppm ~ 3.73 ppm peak; Attributable to h proton (6H): 1.25 ppm~1.81 ppm; attributed to j, k, m, n protons (12H): 5.01 ppm~5.14 ppm, 5.74 ppm~6.34 ppm peak; attributed to o proton (1H): 5.30 ppm to 5.60 ppm peak.
「TrisANIPARARO」之IR光譜以及1 H-NMR光譜(400 MHz)分別示於圖5以及圖6。The IR spectrum and 1 H-NMR spectrum (400 MHz) of "TrisANIPARARO" are shown in Fig. 5 and Fig. 6, respectively.
IR光譜中,歸屬於烯烴C-H伸縮:3056 cm-1 、2972 cm-1 ;歸屬於芳香族C-H伸縮:2972 cm-1 ;歸屬於烷烴C-H伸縮:2936 cm-1 ;歸屬於醯亞胺C=O伸縮:1776 cm-1 、1706 cm-1 ;歸屬於C=C伸縮:1636 cm-1 ;歸屬於醯亞胺C-N伸縮:1402 cm-1 等。In the IR spectrum, it belongs to the olefin C-H stretching: 3056 cm -1 , 2972 cm -1 ; the aromatic C-H expansion: 2972 cm -1 ; the alkane C-H expansion: 2936 cm -1 ;醯 醯 imine C=O stretching: 1776 cm -1 , 1706 cm -1 ; belonging to C=C stretching: 1636 cm -1 ; belonging to yttrium imine C-N stretching: 1402 cm -1 and so on.
1 H-NMR光譜中,歸屬於a質子~d質子(12H):6.98 ppm~7.53 ppm之峰;歸屬於e、f、g、i、l質子(18H):2.27 ppm~3.60 ppm之峰;歸屬於h質子(6H):1.47 ppm~1.81 ppm之峰;歸屬於j、k、m、n質子(12H):5.01 ppm~6.24 ppm之峰等。 1 H-NMR spectrum, belonging to a proton to d proton (12H): 6.98 ppm ~ 7.53 ppm peak; belonging to e, f, g, i, l proton (18H): 2.27 ppm ~ 3.60 ppm peak; Attributable to h proton (6H): peak from 1.47 ppm to 1.81 ppm; attributed to j, k, m, n protons (12H): peaks from 5.01 ppm to 6.24 ppm.
3.4四烯基取代納迪克酸醯亞胺(c4)3.4 Tetraalkenyl Substituted Nadidic Acid Imine (c4)
本發明中所使用的n為4之四烯基取代納迪克酸醯亞胺化合物的合成可利用如下方法進行:相對於1.0莫耳之四胺,混合4.0莫耳~6.0莫耳之烯基取代納迪克酸酐,於常溫下溶解於例如苯、甲苯、二甲苯、均三甲苯、甲基萘、四氫萘、氯仿、三氯乙烯、四氯乙烯、氯苯、二噁烷、四氫呋喃、六亞甲基醚、苯甲醚、丙酮、甲基乙基酮、甲基 異丁基酮、苯乙酮、N,N-二甲基甲醯胺、二甲基亞碸等任意溶劑,或者混合兩種或兩種以上的溶劑中,作為溶液攪拌保持0.5小時~30小時進行反應。於20℃~80℃下減壓乾燥除去上述溶劑,獲得醯胺酸。將上述醯胺酸於上述溶劑中、於溶劑之沸點附近回流(reflux)0.5小時~30小時,或者將化合物本身於160℃~200℃下加熱,使之進行脫水閉環後,減壓乾燥溶劑而獲得目標化合物。可藉由NMR、IR確認為目標化合物。The synthesis of a 4 tetraalkenyl substituted nadic acid ruthenium imine compound using n in the present invention can be carried out by mixing 4.0 moles to 6.0 moles of alkenyl substitution with respect to 1.0 mole of tetraamine. Nadic anhydride, dissolved at room temperature such as benzene, toluene, xylene, mesitylene, methyl naphthalene, tetrahydronaphthalene, chloroform, trichloroethylene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran, six Methyl ether, anisole, acetone, methyl ethyl ketone, methyl Any solvent such as isobutyl ketone, acetophenone, N,N-dimethylformamide, dimethyl hydrazine, or a mixture of two or more solvents, and stirred as a solution for 0.5 hour to 30 hours. Carry out the reaction. The solvent was removed by drying under reduced pressure at 20 ° C to 80 ° C to obtain valine acid. The above proline is refluxed in the above solvent at a boiling point of the solvent for 0.5 to 30 hours, or the compound itself is heated at 160 to 200 ° C to dehydrate the ring, and the solvent is dried under reduced pressure. The target compound is obtained. It can be confirmed as a target compound by NMR or IR.
本發明中所使用的n為4之四烯基取代納迪克酸醯亞胺化合物之具體例,例如可列舉以下化合物。Specific examples of the n-alkenyl-substituted nadic ylidene imide compound to be used in the present invention include, for example, the following compounds.
四{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)四苯基}甲烷(TetrakisANITAM)Tetra{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)tetraphenyl}methane (TetrakisANITAM)
「TetrakisANITAM」之IR光譜以及1 H-NMR光譜(400 MHz)分別示於圖7以及圖8。The IR spectrum and 1 H-NMR spectrum (400 MHz) of "Tetrakis ANITAM" are shown in Fig. 7 and Fig. 8, respectively.
IR光譜中,歸屬於烯烴C-H伸縮:3060 cm-1 、2972 cm-1 ;歸屬於芳香族C-H伸縮:2972 cm-1 ;歸屬於烷烴C-H伸縮:2936 cm-1 ;歸屬於醯亞胺C=O伸縮:1776 cm-1 、1706 cm-1 ;歸屬於C=C伸縮:1638 cm-1 ;歸屬於醯亞胺C-N伸縮:1404 cm-1 等。In the IR spectrum, it is attributed to olefin C-H stretching: 3060 cm -1 , 2972 cm -1 ; attributed to aromatic C-H stretching: 2972 cm -1 ; attributable to alkane C-H stretching: 2936 cm -1 ;醯 醯 imine C=O stretching: 1776 cm -1 , 1706 cm -1 ; belonging to C=C stretching: 1638 cm -1 ; belonging to yttrium imine C-N stretching: 1404 cm -1 and so on.
[化73]
1 H-NMR光譜中,歸屬於a質子~d質子(16H):6.80 ppm~7.59 ppm之峰;歸屬於e、f、g、i、l質子(24H):2.25 ppm~3.60 ppm之峰;歸屬於j、k、m、n質子(16H):5.04 ppm~6.50 ppm之峰;歸屬於h質子(8H):1.25 ppm~1.75 ppm之峰等。 1 H-NMR spectrum attributed to a proton ~ d protons (16H): 6.80 ppm ~ 7.59 Peak ppm of; attributed to e, f, g, i, l protons (24H): 2.25 ppm ~ 3.60 ppm of the peak; Attributable to j, k, m, n protons (16H): peaks from 5.04 ppm to 6.50 ppm; attributable to h protons (8H): peaks from 1.25 ppm to 1.75 ppm.
本發明之較佳烯基取代納迪克酸醯亞胺化合物(C)是具有蓬鬆結構之低分子量的醯亞胺單體,因此可溶於大部分有機溶劑中,即使以溶液狀態長時間保存亦不會產生結晶之析出或膠化而可穩定地使用。又,藉由加熱而形成立體交聯結構之聚醯亞胺,該聚醯亞胺固化物顯示良好之耐熱性、機械特性、電氣特性、耐藥品性。The preferred alkenyl-substituted nadic acid ylidene imine compound (C) of the present invention is a low molecular weight quinone imine monomer having a bulky structure, and thus is soluble in most organic solvents, even if stored in a solution state for a long period of time. It can be used stably without precipitation or gelation of crystals. Further, the polyimine which forms a three-dimensional crosslinked structure by heating exhibits good heat resistance, mechanical properties, electrical properties, and chemical resistance.
4溶劑(D)4 solvent (D)
本發明之噴墨用墨水例如可將矽醯胺酸(A)以及/或者矽醯胺酸(A'),必要時亦將高分子化合物(B)、烯基取代納迪克酸醯亞胺化合物(C)溶解於溶劑(D)中而獲得。因此,本發明之噴墨用墨水中所含的溶劑只要可溶解矽醯胺酸(A)以及/或者矽醯胺酸(A'),必要時可溶解高分子化合物(B)、烯基取代納迪克酸醯亞胺化合物(C),則並無特別限制。又,即使是單獨無法溶解矽醯胺酸(A)、矽醯胺酸(A')、以及必要時的高分子化合物(B)、烯基取代納迪克酸醯亞胺化合物(C)的溶劑,亦可藉由與其他溶劑混合,而用作噴墨用墨水中所含的溶劑(D)。The inkjet ink of the present invention may, for example, be a proline (A) and/or a proline (A'), and if necessary, a polymer compound (B) or an alkenyl group, may be substituted with a nadic acid ylide compound. (C) is obtained by dissolving in a solvent (D). Therefore, the solvent contained in the inkjet ink of the present invention can dissolve the polymer compound (B) and the alkenyl group if necessary, as long as it can dissolve the lysine (A) and/or the proline (A'). The nadic acid imide compound (C) is not particularly limited. Further, even a solvent which cannot dissolve valine acid (A), valine acid (A'), and if necessary, a polymer compound (B) or an alkenyl group substituted with a nadic acid ylide compound (C) It can also be used as a solvent (D) contained in the ink for inkjet by mixing with other solvents.
噴墨用墨水中所含的溶劑(D)之具體例,可列舉:N-甲基-2-吡咯烷酮、二甲基咪唑烷酮、N-甲基己內醯胺、N-甲基丙醯胺、N,N-二甲基乙醯胺、二甲基亞碸、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、二乙基乙醯胺、γ-丁內酯、乳酸乙酯、3-甲基-3-甲氧基丁醇、四氫萘、異佛爾酮、乙二醇單丁醚、二乙二醇單***、二乙二醇單***乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、三乙二醇單***、丙二醇單丁醚、丙二醇單甲醚乙酸酯、二丙二醇單甲醚、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙二酸二乙酯、乙醇、2-丙醇、二噁烷、乙二醇等。Specific examples of the solvent (D) contained in the inkjet ink include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, and N-methylpropionamidine. Amine, N,N-dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ- Butyrolactone, ethyl lactate, 3-methyl-3-methoxybutanol, tetrahydronaphthalene, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether Acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, 3- Methyl methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethanol, 2-propanol, dioxane, ethylene glycol, and the like.
如上所述,本發明之噴墨用墨水中所含的溶劑並無特別限制,但根據噴墨印刷機之噴墨頭的規格,其接合部件或者內部之過濾器材料有時會因所使用之溶劑之種類而產生腐蝕或者膨脹。或者,乾燥速度較快的溶劑會使噴墨頭 產生堵塞等,因此溶劑(D)的選擇非常重要。As described above, the solvent contained in the inkjet ink of the present invention is not particularly limited, but depending on the specifications of the inkjet head of the inkjet printer, the bonding member or the internal filter material may be used depending on the use. Corrosion or expansion due to the type of solvent. Or, a solvent that dries faster will make the head Blockage or the like is generated, so the choice of the solvent (D) is very important.
本發明者經努力研究之結果發現,就提昇噴墨頭之耐久性或者噴頭堵塞、墨水噴出性之方面而言,乳酸乙酯、乙二醇單丁醚、二乙二醇單***乙酸酯、二乙二醇二甲醚、二乙二醇甲基乙基醚、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、γ-丁內酯作為溶劑(D)尤其好。As a result of intensive studies, the present inventors have found that ethyl lactate, ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether acetate are used in terms of improving the durability of the ink jet head or the nozzle clogging and ink ejection properties. Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and γ-butyrolactone are particularly preferred as the solvent (D).
進而,墨水之表面張力對噴墨用墨水之塗佈性的影響較大,因此較好的是將墨水之表面張力調整為20 mN/m~45 mN/m,更好的是27 mN/m~42 mN/m,進而好的是30 mN/m~40 mN/m。表面張力若為20 mN/m~45 mN/m之範圍,則墨水噴出口之墨水彎液面(ink meniscus)變得穩定,墨水之噴出良好。Further, since the surface tension of the ink has a large influence on the coatability of the ink for inkjet, it is preferred to adjust the surface tension of the ink to 20 mN/m to 45 mN/m, more preferably 27 mN/m. ~42 mN/m, and preferably 30 mN/m~40 mN/m. When the surface tension is in the range of 20 mN/m to 45 mN/m, the ink meniscus of the ink discharge port becomes stable, and the ink is ejected well.
為了將表面張力調整為20 mN/m~45 mN/m之範圍,溶劑選擇較為重要。可使用一種表面張力為20 mN/m~45 mN/m之範圍的溶劑,而若混合使用表面張力較大之溶劑(例如,γ-丁內酯:43 mN/m)以及表面張力較小之溶劑(例如,二乙二醇甲基乙基醚:24 mN/m或者乙二醇單丁醚:32 mN/m),則可利用溶劑組成而對表面張力進行微調整,故而較好。In order to adjust the surface tension to a range of 20 mN/m to 45 mN/m, solvent selection is important. A solvent having a surface tension of 20 mN/m to 45 mN/m can be used, and a solvent having a large surface tension (for example, γ-butyrolactone: 43 mN/m) and a small surface tension can be used. When the solvent (for example, diethylene glycol methyl ethyl ether: 24 mN/m or ethylene glycol monobutyl ether: 32 mN/m), the surface tension can be finely adjusted by the solvent composition, which is preferable.
又,N-甲基甲醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、二乙基乙醯胺、N-甲基丙醯胺、N,N,N',N'-四甲基脲、2-吡咯烷酮、N-甲基-2-吡咯烷酮、ε-己內醯胺、N-甲基己內醯胺、胺甲酸酯等醯胺系溶劑是矽醯胺酸(A)、矽醯胺酸(A') 或者高分子化合物(B)、烯基取代納迪克酸醯亞胺化合物(C)的良溶劑,故而可較好地使用,但另一方面該些溶劑會影響噴墨頭之耐久性,因此需要注意。Further, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethyl Ethyl amide, diethyl acetamide, N-methyl propyl amide, N, N, N', N'-tetramethyl urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε- The amide-based solvents such as caprolactam, N-methyl caprolactam, and carbamate are lysine (A) and proline (A'). Further, since the polymer compound (B) or the alkenyl group is a good solvent for the nadic acid ylidene imide compound (C), it can be preferably used. However, these solvents affect the durability of the ink jet head, and therefore, note.
較好的是,於本發明之噴墨用墨水中所含的溶劑(D)中完全不含醯胺系溶劑,或者至多相對於溶劑(D)之總重量而含有小於等於20 wt%。It is preferred that the solvent (D) contained in the inkjet ink of the present invention contains no guanamine-based solvent at all, or at most 20% by weight or less based on the total weight of the solvent (D).
該些溶劑可僅使用一種,亦可混合兩種或兩種以上使用。These solvents may be used alone or in combination of two or more.
5本發明之噴墨用墨水中的矽醯胺酸(A)、矽醯胺酸(A')、高分子化合物(B)以及烯基取代納迪克酸醯亞胺化合物(C)的濃度5 Concentration of lysine (A), proline (A'), polymer compound (B) and alkenyl substituted nadic acid ylide compound (C) in the inkjet ink of the present invention
本發明中,噴墨用墨水中之矽醯胺酸(A)以及矽醯胺酸(A')之總濃度並無特別限定,較好的是1 wt%~99 wt%,更好的是10 wt%~80 wt%,進而好的是22 wt%~70 wt%。若為所述濃度範圍,則噴墨1次所得的膜厚最適宜,噴***度高,故而較好。In the present invention, the total concentration of the lysine (A) and the lysine (A') in the ink for inkjet is not particularly limited, and is preferably from 1 wt% to 99 wt%, more preferably 10 wt% to 80 wt%, and further preferably 22 wt% to 70 wt%. In the case of the above concentration range, the film thickness obtained by one ejection of ink is most suitable, and the ejection precision is high, which is preferable.
本發明中,噴墨用墨水中之高分子化合物(B)的濃度並無特別限定,較好的是0 wt%~50 wt%,更好的是0 wt%~25 wt%。若為所述濃度範圍,則作為絕緣膜時可賦予良好之特性,故而較好。In the present invention, the concentration of the polymer compound (B) in the ink for inkjet is not particularly limited, but is preferably 0 wt% to 50 wt%, more preferably 0 wt% to 25 wt%. If it is the said concentration range, since it can provide favorable characteristics as an insulating film, it is preferable.
本發明中,噴墨用墨水中之烯基取代納迪克酸醯亞胺化合物(C)的濃度並無特別限定,較好的是0 wt%~50 wt%,更好的是0 wt%~25 wt%。若為所述濃度範圍,則作為絕緣膜時可賦予良好之特性,故而較好。In the present invention, the concentration of the alkenyl-substituted nadic acid ylidene imine compound (C) in the ink for inkjet is not particularly limited, and is preferably 0 wt% to 50 wt%, more preferably 0 wt%. 25 wt%. If it is the said concentration range, since it can provide favorable characteristics as an insulating film, it is preferable.
於用作噴墨用墨水之情形時,矽醯胺酸(A)以及/或者矽醯胺酸(A')、高分子化合物(B)以及烯基取代納迪克酸醯亞胺化合物(C)之濃度越高,所得聚醯亞胺膜之膜厚越厚,故而較好,但另一方面,黏度亦存在變高之傾向,因此有時會出現無法自噴墨印刷機噴出的問題。本發明者們經努力研究之結果發現,若尤其為上述濃度範圍,則可較好地用作可形成膜厚較厚之聚醯亞胺膜的噴墨用墨水。For use as an inkjet ink, valeric acid (A) and/or proline (A'), polymer compound (B) and alkenyl substituted nadic acid ylide compound (C) The higher the concentration, the thicker the film thickness of the obtained polyimide film, but the viscosity tends to be higher. Therefore, there is a problem that the inkjet printer cannot be ejected. As a result of intensive studies, the present inventors have found that, particularly in the above concentration range, it can be suitably used as an inkjet ink which can form a polyimide film having a thick film thickness.
6於本發明之噴墨用墨水中添加的添加劑6 Additives added to the inkjet ink of the present invention
本發明之噴墨用墨水是藉由混合矽醯胺酸(A)以及/或者矽醯胺酸(A'),必要時亦混合高分子化合物(B)、烯基取代納迪克酸醯亞胺化合物(C),必要時亦混合溶劑(D)而獲得。The inkjet ink of the present invention is obtained by mixing a proline (A) and/or a proline (A'), and if necessary, a polymer compound (B), an alkenyl group, and a naphthyl imide. The compound (C) is obtained by mixing the solvent (D) as necessary.
進而,根據所需特性,本發明之噴墨用墨水可藉由如下方法獲得:視需要選擇添加環氧樹脂、丙烯酸系樹脂、界面活性劑、抗靜電劑、偶合劑、偏苯三甲酸等環氧固化劑、胺基矽化合物、pH值調整劑、防銹劑、防腐劑、防黴劑、抗氧化劑、還原抑制劑、蒸發促進劑、螯合化劑、水溶性聚合物、顏料、染料等添加劑,將該些均勻混合溶解。Further, according to the desired characteristics, the inkjet ink of the present invention can be obtained by adding an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, a trimellitic acid or the like as needed. Oxygen curing agent, amine hydrazine compound, pH adjuster, rust inhibitor, preservative, mold inhibitor, antioxidant, reduction inhibitor, evaporation promoter, chelating agent, water soluble polymer, pigment, dye, etc. Additives, which are uniformly mixed and dissolved.
6(1)環氧樹脂6(1) epoxy resin
本發明之噴墨用墨水可進而含有環氧樹脂。本發明之噴墨用墨水中所含的環氧樹脂若具有環氧乙烷(oxirane)或者環氧丙烷(oxetane),則並無特別限定,較好的是具有大於等於2個之環氧乙烷的化合物。The inkjet ink of the present invention may further contain an epoxy resin. The epoxy resin contained in the inkjet ink of the present invention is not particularly limited as long as it has oxirane or oxetane, and preferably has two or more epoxy acrylates. a compound of an alkane.
本發明中,噴墨用墨水中之環氧樹脂的濃度並無特別限定,較好的是0.1 wt%~20 wt%,更好的是1 wt%~10 wt%。若為所述濃度範圍,則由噴墨用墨水形成之塗膜的耐熱性、耐藥品性、平坦性良好。In the present invention, the concentration of the epoxy resin in the ink for inkjet is not particularly limited, but is preferably 0.1 wt% to 20 wt%, more preferably 1 wt% to 10 wt%. When it is the said concentration range, the coating film formed from the inkjet ink is favorable in heat resistance, chemical-resistance, and flatness.
環氧樹脂例如可列舉:雙酚A型環氧樹脂、縮水甘油酯型環氧樹脂、脂環式環氧樹脂、具有環氧乙烷之單體的聚合物、以及具有環氧乙烷之單體與其他單體的共聚物等。Examples of the epoxy resin include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a polymer having a monomer of ethylene oxide, and a single having ethylene oxide. a copolymer of a body and other monomers, and the like.
具有環氧乙烷之單體的具體例可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己酯以及(甲基)丙烯酸甲基縮水甘油酯。Specific examples of the monomer having ethylene oxide include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.
又,與具有環氧乙烷之單體進行共聚合之其他單體的具體例,可列舉:(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、苯乙烯、甲基苯乙烯、氯甲基苯乙烯、(甲基)丙烯酸(3-乙基-3-環氧丙基)甲酯、N-環己基順丁烯二醯亞胺以及N-苯基順丁烯二醯亞胺等。Further, specific examples of the other monomer copolymerized with the monomer having ethylene oxide include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (meth)acrylic acid (3-ethyl-3- Epoxypropyl)methyl ester, N-cyclohexylmethyleneimine, and N-phenyl maleimide.
具有環氧乙烷之單體之聚合物以及具有環氧乙烷之單體與其他單體之共聚物的較佳具體例,可列舉:聚甲基丙烯酸縮水甘油酯、甲基丙烯酸甲酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸苄酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸正丁酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸2-羥基乙酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯 酸(3-乙基-3-環氧丙基)甲酯-甲基丙烯酸縮水甘油酯共聚物以及苯乙烯-甲基丙烯酸縮水甘油酯共聚物。若本發明之噴墨用墨水含有該些環氧樹脂,則由噴墨用墨水形成之塗膜的耐熱性良好,故而較好。Preferred examples of the polymer of the monomer having ethylene oxide and the copolymer of the monomer having ethylene oxide and other monomers include polyglycidyl methacrylate and methyl methacrylate- Glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-A Glycidyl acrylate copolymer, methacryl Acid (3-ethyl-3-epoxypropyl)methyl ester-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer. When the inkjet ink of the present invention contains these epoxy resins, the coating film formed of the inkjet ink is excellent in heat resistance, which is preferable.
本發明之噴墨用墨水中可含有的環氧樹脂之具體例可列舉:商品名「Epikote 807」、「Epikote 815」、「Epikote 825」、「Epikote 827」、「Epikote 828」、「Epikote 190P」、「Epikote 191P」(以上,油化殼牌環氧(Yuka Shell Epoxy)股份有限公司製造),商品名「Epikote 1004」、「Epikote 1256」(以上,日本環氧樹脂股份有限公司製造),商品名「Araldite CY177」、商品名「Araldite CY184」(日本汽巴-嘉基(Ciba-Geigy)股份有限公司製造),商品名「Celloxide 2021P」、「Celloxide 3000」、「EHPE-3150」(Daicel化學工業股份有限公司製造),商品名「Techmore VG3101L」(三井化學股份有限公司製造),N,N,N',N'-四縮水甘油基-間二甲苯二胺,1,3-雙(N,N-二縮水甘油基胺甲基)環己烷,N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷等。Specific examples of the epoxy resin which can be contained in the inkjet ink of the present invention include "Epikote 807", "Epikote 815", "Epikote 825", "Epikote 827", "Epikote 828", and "Epikote 190P". "Epikote 191P" (above, manufactured by Yuka Shell Epoxy Co., Ltd.), trade name "Epikote 1004", "Epikote 1256" (above, manufactured by Nippon Epoxy Co., Ltd.), "Araldite CY177", trade name "Araldite CY184" (manufactured by Ciba-Geigy Co., Ltd.), trade name "Celloxide 2021P", "Celloxide 3000", "EHPE-3150" (Daicel Chemistry) Manufactured by Industrial Co., Ltd., trade name "Techmore VG3101L" (manufactured by Mitsui Chemicals, Inc.), N, N, N', N'-tetraglycidyl-m-xylenediamine, 1,3-double (N) , N-diglycidylamine methyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.
該些中,若使用商品名「Araldite CY184」、商品名「Celloxide 2021P」、商品名「Techmore VG3101L」、商品名「Epikote 828」,則所得之聚醯亞胺膜之平坦性尤其良好,故而較好。In the above, when the trade name "Araldite CY184", the trade name "Celloxide 2021P", the trade name "Techmore VG3101L", and the trade name "Epikote 828" are used, the flatness of the obtained polyimide film is particularly good, so that it is good.
環氧樹脂可僅使用一種,亦可混合兩種或兩種以上使用。The epoxy resin may be used singly or in combination of two or more.
6(2)丙烯酸系樹脂6(2) acrylic resin
噴墨用墨水可進而含有丙烯酸系樹脂。噴墨用墨水中所含的丙烯酸系樹脂只要具有丙烯醯基或甲基丙烯醯基,則並無特別限定。The ink for inkjet may further contain an acrylic resin. The acrylic resin contained in the inkjet ink is not particularly limited as long as it has an acrylonitrile group or a methacrylium group.
噴墨用墨水中之丙烯酸系樹脂的濃度並無特別限定,較好的是0.1 wt%~20 wt%,更好的是1 wt%~10 wt%。若為所述濃度範圍,則由噴墨用墨水形成之塗膜的耐熱性、耐藥品性、平坦性良好。The concentration of the acrylic resin in the inkjet ink is not particularly limited, but is preferably 0.1% by weight to 20% by weight, more preferably 1% by weight to 10% by weight. When it is the said concentration range, the coating film formed from the inkjet ink is favorable in heat resistance, chemical-resistance, and flatness.
丙烯酸系樹脂例如可列舉:具有羥基之單官能聚合性單體、不具有羥基之單官能聚合性單體、二官能(甲基)丙烯酸酯、以及大於等於三官能之多官能(甲基)丙烯酸酯等。Examples of the acrylic resin include a monofunctional polymerizable monomer having a hydroxyl group, a monofunctional polymerizable monomer having no hydroxyl group, a difunctional (meth)acrylate, and a trifunctional polyfunctional (meth)acrylic acid or more. Ester and the like.
具有羥基之單官能聚合性單體的具體例,可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、或者1,4-環己烷二甲醇單(甲基)丙烯酸酯等。其中,就所形成之膜的柔軟性而言,尤其好的是丙烯酸4-羥基丁酯、1,4-環己烷二甲醇單丙烯酸酯。Specific examples of the monofunctional polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or 1,4-cyclohexanedimethanol mono(meth)acrylate or the like. Among them, 4-hydroxybutyl acrylate and 1,4-cyclohexane dimethanol monoacrylate are particularly preferable in terms of flexibility of the formed film.
不具有羥基之單官能聚合性單體的具體例,可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己酯、(甲基)丙烯酸甲基縮水甘油酯、3-甲基-3-(甲基)丙烯醯氧基甲基環氧丙烷、3-乙基-3-(甲基)丙烯醯氧基甲基環氧丙烷、3-甲基-3-(甲基)丙烯醯氧基乙基環氧丙烷、3-乙基-3-(甲基)丙烯醯氧基乙基環氧丙烷、對乙烯基苯基-3-乙基環氧丙-3-基甲醚、2-苯基-3-(甲基)丙烯醯氧基甲基環氧丙烷、2-三氯甲基-3-(甲基)丙烯醯氧基甲基環氧丙烷、4-三氯甲基-2-(甲基)丙烯醯氧基甲基環氧丙烷、(甲基)丙烯 酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、苯乙烯、甲基苯乙烯、氯甲基苯乙烯、(甲基)丙烯酸(3-乙基-3-環氧丙基)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)丙烯醯胺、(甲基)丙烯酸三環[5.2.1.02,6 ]癸酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸異莰酯、(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、N-丙烯醯嗎啉、(甲基)丙烯酸5-四氫糠氧基羰氧戊酯、月桂醇之環氧乙烷加成物之(甲基)丙烯酸酯、(甲基)丙烯酸、丁烯酸、α-氯丙烯酸、肉桂酸、順丁烯二酸、反丁烯二酸、伊康酸、甲基順丁烯二酸、甲基反丁烯二酸、ω-羧基聚己內酯單(甲基)丙烯酸酯、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、順丁烯二酸單[2-(甲基)丙烯醯氧基乙基]酯、或者環己烯-3,4-二羧酸單[2-(甲基)丙烯醯氧基乙基]酯等。Specific examples of the monofunctional polymerizable monomer having no hydroxyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate. Ester, 3-methyl-3-(methyl)propenyloxymethyl propylene oxide, 3-ethyl-3-(methyl) propylene methoxymethyl propylene oxide, 3-methyl-3 -(Methyl)acryloxyethyl propylene oxide, 3-ethyl-3-(methyl) propylene oxiranyl ethyl propylene oxide, p-vinyl phenyl-3-ethyl epoxide - 3-methyl methyl ether, 2-phenyl-3-(methyl) propylene methoxymethyl propylene oxide, 2-trichloromethyl-3-(methyl) propylene methoxymethyl propylene oxide, 4-trichloromethyl-2-(methyl)propenyloxymethyl propylene oxide, (meth)acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate Isopropyl ester, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, styrene , methyl styrene, chloromethyl styrene, (meth)acrylic acid (3- Ethyl-3-epoxypropyl)methyl ester, N-cyclohexylmethyleneimine, N-phenyl maleimide, vinyl toluene, (meth) acrylamide, ( Methyl)acrylic acid tricyclo[5.2.1.0 2,6 ]decyl ester, dicyclopentenyloxyethyl (meth)acrylate, isodecyl (meth)acrylate, phenyl (meth)acrylate, glycerol (Meth) acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, N-propylene hydrazinomorph, (meth)acrylic acid 5-tetrahydrofurfuryloxycarbonyloxypentoxide, lauryl alcohol (meth) acrylate, (meth) acrylate, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, ethylene oxide adducts, Methyl maleic acid, methyl fumaric acid, ω-carboxy polycaprolactone mono (meth) acrylate, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, Maleic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, or cyclohexene-3,4-dicarboxylic acid mono [2-(methyl) propylene methoxyethyl] ester Wait.
二官能(甲基)丙烯酸酯之具體例,可列舉:雙酚F環氧乙烷改質二丙烯酸酯、雙酚A環氧乙烷改質二丙烯酸酯、異三聚氰酸環氧乙烷改質二丙烯酸酯、聚乙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、季戊四醇二丙烯酸酯、季戊四醇二丙烯酸酯單硬脂酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,4-環己烷二甲醇二丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二丙烯 酸酯、三羥甲基丙烷二丙烯酸酯、或者二季戊四醇二丙烯酸酯等。Specific examples of the difunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, and isomeric cyanuric acid ethylene oxide. Modified diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, 1,4-butanediol diacrylate, 1,6- Hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4-cyclohexanedimethanol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol dipropylene An acid ester, trimethylolpropane diacrylate, or dipentaerythritol diacrylate.
大於等於三官能之多官能(甲基)丙烯酸酯的具體例,可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、表氯醇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(甲基)丙烯酸酯、表氯醇改質甘油三(甲基)丙烯酸酯、二甘油四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、烷基改質二季戊四醇五(甲基)丙烯酸酯、烷基改質二季戊四醇四(甲基)丙烯酸酯、烷基改質二季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯、環氧乙烷改質磷酸三(甲基)丙烯酸酯、三聚異氰酸三[(甲基)丙烯醯氧基乙基]酯、己內酯改質三聚異氰酸三[(甲基)丙烯醯氧基乙基]酯、或者胺基甲酸酯(甲基)丙烯酸酯等。Specific examples of the trifunctional polyfunctional (meth) acrylate are: trimethylolpropane tri(meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate Ester, propylene oxide modified trimethylolpropane tri(meth) acrylate, epichlorohydrin modified trimethylolpropane tri(meth) acrylate, di-trimethylolpropane tetra(methyl) Acrylate, glycerol tri(meth) acrylate, epichlorohydrin modified glycerol tri(meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (methyl) Acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol III ( Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, ethylene oxide modified tris(meth) acrylate, trimeric isocyanide Tris[(methyl)propenyloxyethyl]ester, caprolactone modified trimeric isocyanate tris[(methyl)propene oxime An oxyethyl] ester, or a urethane (meth) acrylate or the like.
該些丙烯酸系樹脂可僅使用一種,亦可混合兩種或兩種以上使用。These acrylic resins may be used alone or in combination of two or more.
6(3)界面活性劑6(3) surfactant
於期望提高噴墨用墨水之塗佈性時,可添加實現此目的之界面活性劑。於本發明之噴墨用墨水中添加的界面活性劑的具體例,可列舉:商品名「Byk-300」、「Byk-306」、「Byk-335」、「Byk-310」、「Byk-341」、「Byk-344」、「Byk-370」 (BYK Chemie股份有限公司製造)等矽系界面活性劑;商品名「Byk-354」、「Byk-358」、「Byk-361」(BYK Chemie股份有限公司製造)等丙烯酸系界面活性劑;商品名「DFX-18」、「ftergent 250」、「ftergent 251」(Neos股份有限公司製造)等氟系界面活性劑。When it is desired to improve the coatability of the ink for inkjet, a surfactant which achieves the object can be added. Specific examples of the surfactant added to the inkjet ink of the present invention include "Byk-300", "Byk-306", "Byk-335", "Byk-310", and "Byk-". 341", "Byk-344", "Byk-370" An anthraquinone surfactant such as BYK Chemie Co., Ltd.; an acrylic surfactant such as "Byk-354", "Byk-358", "Byk-361" (manufactured by BYK Chemie Co., Ltd.); A fluorine-based surfactant such as "DFX-18", "ftergent 250", or "ftergent 251" (manufactured by Neos Co., Ltd.).
該些界面活性劑可僅使用一種,亦可混合兩種或兩種以上使用。These surfactants may be used alone or in combination of two or more.
界面活性劑是用以提高對基礎基板的濡濕性、流平性或者塗佈性,較好的是相對於噴墨用墨水100重量份,添加0.01重量份~1重量份而加以使用。The surfactant is used to improve the wettability, leveling property, or coatability of the base substrate, and is preferably used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the inkjet ink.
6(4)抗靜電劑6 (4) antistatic agent
於本發明之噴墨用墨水中添加的抗靜電劑並無特別限定,可使用眾所周知的抗靜電劑。具體而言可列舉:氧化錫、氧化錫.氧化銻複合氧化物、氧化錫.氧化銦複合氧化物等金屬氧化物或者四級銨鹽等。The antistatic agent to be added to the inkjet ink of the present invention is not particularly limited, and a well-known antistatic agent can be used. Specifically, it can be mentioned: tin oxide, tin oxide. Cerium oxide composite oxide, tin oxide. A metal oxide such as an indium oxide composite oxide or a quaternary ammonium salt.
該些抗靜電劑可僅使用一種,亦可混合兩種或兩種以上使用。These antistatic agents may be used alone or in combination of two or more.
抗靜電劑是用以防止靜電,較好的是相對於噴墨用墨水100重量份,添加0.01重量份~1重量份而加以使用。The antistatic agent is for preventing static electricity, and is preferably used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the ink for inkjet.
6(5)偶合劑6(5) coupling agent
於本發明之噴墨用墨水中添加的偶合劑並無特別限定,可使用眾所周知的偶合劑。添加之偶合劑較好的是矽烷偶合劑,具體而言可列舉:三烷氧基矽烷化合物或者二烷氧基矽烷化合物等。較好的例如可例示:γ-乙烯基丙基 三甲氧基矽烷、γ-乙烯基丙基三乙氧基矽烷、γ-丙烯醯基丙基甲基二甲氧基矽烷、γ-丙烯醯基丙基三甲氧基矽烷、γ-丙烯醯基丙基甲基二乙氧基矽烷、γ-丙烯醯基丙基三乙氧基矽烷、γ-甲基丙烯醯基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯基丙基三甲氧基矽烷、γ-甲基丙烯醯基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-胺基乙基-γ-亞胺基丙基甲基二甲氧基矽烷、N-胺基乙基-γ-胺基丙基三甲氧基矽烷、N-胺基乙基-γ-胺基丙基二乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基甲基二甲氧基矽烷、N-苯基-γ-胺基丙基甲基二乙氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-巰基丙基甲基二乙氧基矽烷、γ-巰基丙基三乙氧基矽烷、γ-異氰酸酯丙基甲基二乙氧基矽烷、γ-異氰酸酯丙基三乙氧基矽烷等。該些中,可列舉γ-乙烯基丙基三甲氧基矽烷、γ-丙烯醯基丙基三甲氧基矽烷、γ-甲基丙烯醯基丙基三甲氧基矽烷、γ-異氰酸酯丙基三乙氧基矽烷等。The coupling agent to be added to the inkjet ink of the present invention is not particularly limited, and a well-known coupling agent can be used. The coupling agent to be added is preferably a decane coupling agent, and specific examples thereof include a trialkoxy decane compound or a dialkoxy decane compound. Preferably, for example, γ-vinylpropyl is exemplified: Trimethoxy decane, γ-vinyl propyl triethoxy decane, γ-propylene propyl propyl methyl dimethoxy decane, γ-acryl propyl propyl trimethoxy decane, γ-propylene decyl propyl Methyldiethoxy decane, γ-propylene propyl propyl triethoxy decane, γ-methyl propylene propyl propyl methyl dimethoxy decane, γ-methyl propylene propyl propyl trimethoxide Base decane, γ-methyl propylene propyl propyl methyl diethoxy decane, γ-methyl propylene propyl propyl triethoxy decane, γ-glycidoxy propyl methyl dimethoxy decane , γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-aminopropyl Methyldimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropyltriethoxydecane, N-Amino B Base-γ-iminopropylmethyldimethoxydecane, N-aminoethyl-γ-aminopropyltrimethoxydecane, N-aminoethyl-γ-aminopropyldi Ethoxy decane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropylmethyl Dimethoxy decane, N-phenyl-γ-aminopropylmethyldiethoxy decane, γ-mercaptopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, Γ-mercaptopropylmethyldiethoxydecane, γ-mercaptopropyltriethoxydecane, γ-isocyanate propylmethyldiethoxydecane, γ-isocyanatepropyltriethoxydecane, and the like. Among these, γ-vinylpropyltrimethoxydecane, γ-acrylonitrilepropyltrimethoxydecane, γ-methylpropenylpropyltrimethoxydecane, and γ-isocyanatepropyltriethyl can be cited. Oxydecane, etc.
該些偶合劑可僅使用一種,亦可混合兩種或兩種以上 使用。These coupling agents may be used alone or in combination of two or more. use.
偶合劑較好的是相對於噴墨用墨水100重量份,添加0.01重量份~3重量份而加以使用。The coupling agent is preferably used in an amount of 0.01 part by weight to 3 parts by weight based on 100 parts by weight of the ink for inkjet.
6(6)環氧固化劑6(6) epoxy curing agent
於本發明之噴墨用墨水中添加的環氧固化劑並無特別限定,可使用眾所周知的環氧固化劑。具體而言可列舉:有機酸二醯肼化合物、咪唑以及咪唑的衍生物、雙氰胺(dicyandiamide)、芳香族胺、多元羧酸、多元羧酸酐等。更具體而言可列舉:雙氰胺等雙氰胺類,己二酸二醯肼、1,3-雙(肼基羧乙基)-5-異丙基乙內醯脲(1,3-bis(hydrazino carboethyl)-5-isopropyl hydantoin)等有機酸二醯肼,2,4-二胺基-6-[2'-乙基咪唑基-(1')]-乙基三嗪、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等咪唑衍生物,鄰苯二甲酸酐、偏苯三甲酸酐、1,2,4-環己烷三羧酸-1,2-酐等酸酐等。The epoxy curing agent to be added to the inkjet ink of the present invention is not particularly limited, and a known epoxy curing agent can be used. Specific examples thereof include diterpene compounds of organic acids, derivatives of imidazoles and imidazoles, dicyandiamides, aromatic amines, polycarboxylic acids, polycarboxylic anhydrides, and the like. More specifically, dicyandiamides such as dicyandiamide, diammonium adipate, and 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin (1,3-) Bis(hydrazino carboethyl)-5-isopropyl hydantoin), such as diterpene, 2,4-diamino-6-[2'-ethylimidazolyl-(1')]-ethyltriazine, 2- Imidazole derivatives such as phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, phthalic anhydride, trimellitic anhydride, 1,2 An acid anhydride such as 4-cyclohexanetricarboxylic acid-1,2-anhydride or the like.
其中,較好的是透明性良好的偏苯三甲酸、1,2,4-環己烷三羧酸-1,2-酐。Among them, preferred are trimellitic acid having good transparency and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride.
該些環氧固化劑可僅使用一種,亦可混合兩種或兩種以上使用。These epoxy curing agents may be used alone or in combination of two or more.
環氧固化劑較好的是相對於噴墨用墨水100重量份,添加0.2重量份~5重量份而加以使用。The epoxy curing agent is preferably used in an amount of 0.2 part by weight to 5 parts by weight based on 100 parts by weight of the ink for inkjet.
6(7)胺基矽化合物6(7)Aminoguanidine compound
可於本發明之噴墨用墨水中添加胺基矽化合物。胺基矽化合物可列舉:對胺基苯基三甲氧基矽烷、對胺基苯基 三乙氧基矽烷、間胺基苯基三甲氧基矽烷、間胺基苯基三乙氧基矽烷、胺基丙基三甲氧基矽烷、胺基丙基三乙氧基矽烷等。An amine sulfonium compound can be added to the inkjet ink of the present invention. The amine ruthenium compound may, for example, be p-aminophenyltrimethoxydecane or p-aminophenyl. Triethoxy decane, m-aminophenyl trimethoxy decane, m-aminophenyl triethoxy decane, aminopropyl trimethoxy decane, aminopropyl triethoxy decane, and the like.
該些胺基矽化合物可僅使用一種,亦可混合兩種或兩種以上使用。These amine-based ruthenium compounds may be used alone or in combination of two or more.
胺基矽化合物是用以提高與基板的密著性,較好的是相對於噴墨用墨水100重量份,添加0.05重量份~2重量份而加以使用。The amine ruthenium compound is used to improve the adhesion to the substrate, and is preferably added in an amount of 0.05 part by weight to 2 parts by weight based on 100 parts by weight of the ink for inkjet.
7噴墨用墨水之黏度7 inkjet ink viscosity
於本發明中,噴墨用墨水之黏度並無特別限定,於常溫下進行噴射之情形時,就提昇藉由噴墨塗佈方法之噴***度之方面而言,較好的是1 mPa.s~50 mPa.s(25℃),更好的是5 mPa.s~30 mPa.s(25℃),進而好的是8 mPa.s~20 mPa.s(25℃)。In the present invention, the viscosity of the ink for inkjet is not particularly limited, and when it is sprayed at a normal temperature, the ejection accuracy by the inkjet coating method is improved, preferably 1 mPa. s~50 mPa. s (25 ° C), more preferably 5 mPa. s~30 mPa. s (25 ° C), and thus good is 8 mPa. s~20 mPa. s (25 ° C).
於加熱噴墨頭進行噴射之情形時,於加熱溫度(矽醯胺酸不會固化之溫度,較好的是40℃~120℃)下為1 mPa.s~50 mPa.s,較好的是5 mPa.s~30 mPa.s,更好的是8 mPa.s~20 mPa.s。In the case of heating the ink jet head for spraying, it is 1 mPa at a heating temperature (temperature at which valerine does not cure, preferably 40 ° C to 120 ° C). s~50 mPa. s, preferably 5 mPa. s~30 mPa. s, better is 8 mPa. s~20 mPa. s.
8聚醯亞胺膜8 polyimine film
藉由噴墨將本發明之噴墨用墨水塗佈於基板表面,以加熱板或者烘箱等進行加熱處理,可形成整面或者預定圖案狀(線狀等)之聚醯亞胺膜。又,本發明之聚醯亞胺膜的形成並不侷限於加熱處理,亦可為紫外線(UV)處理或者離子束、電子束、伽瑪射線(gamma ray)等處理。The inkjet ink of the present invention is applied onto the surface of the substrate by inkjet, and is heat-treated by a hot plate or an oven to form a polyimide film having a whole surface or a predetermined pattern (linear shape, etc.). Further, the formation of the polyimide film of the present invention is not limited to the heat treatment, and may be an ultraviolet (UV) treatment or an ion beam, an electron beam, a gamma ray or the like.
先前,於形成圖案狀之聚醯亞胺膜之情形時是使用光微影技術,而此技術需要使用光阻材料、顯像液、蝕刻液、剝離液等多種大量化學藥品,並且需要煩瑣的製程。相對於此,使用本發明之噴墨用墨水而形成的圖案狀聚醯亞胺膜具有如下特徵:由於是藉由噴墨印刷而僅於需要之部分進行描繪,因此材料使用量絕對的少,且不使用光罩,故而可多品種大量生產,且製造所需製程數少。Previously, in the case of forming a patterned polyimide film, photolithography has been used, and this technique requires the use of various chemicals such as photoresist materials, developing liquids, etching liquids, and stripping liquids, and requires cumbersome Process. On the other hand, the patterned polyimide film formed using the inkjet ink of the present invention is characterized in that the amount of material used is absolutely small because it is drawn only by a portion required by inkjet printing. Moreover, the reticle is not used, so that it can be mass-produced in a variety of varieties, and the number of processes required for manufacturing is small.
8.1藉由噴墨方法之噴墨用墨水之塗佈8.1 Coating of inkjet ink by inkjet method
根據墨水之噴出方法,噴墨塗佈方法存在各種類型。例如可列舉:壓電元件型、氣泡噴墨(bubble jet)(註冊商標)型、連續噴射型、靜電感應(static induction)型等。藉由適當選擇墨水中所含的各成分,可將本發明之墨水藉由各種方法進行噴射,從而可將噴墨用墨水塗佈為預先設定之圖案狀。There are various types of inkjet coating methods depending on the ink ejection method. For example, a piezoelectric element type, a bubble jet (registered trademark) type, a continuous injection type, a static induction type, and the like can be cited. By appropriately selecting the respective components contained in the ink, the ink of the present invention can be ejected by various methods, and the ink for inkjet can be applied to a predetermined pattern.
使用本發明之墨水進行塗佈的更好之噴出方法為壓電元件型。此壓電元件型之噴頭為按需式(on-demand)噴墨塗佈噴頭,該噴頭具備:具有多個噴嘴之噴嘴形成基板、與噴嘴對向配置之壓電材料、具有導電材料之壓力產生元件、於此壓力產生元件之周圍充斥的墨水,藉由施加電壓而使壓力產生元件移位,從而使墨水之小液滴自噴嘴噴出。A better ejection method for coating using the ink of the present invention is a piezoelectric element type. The piezoelectric element type head is an on-demand inkjet coating head having a nozzle forming substrate having a plurality of nozzles, a piezoelectric material disposed opposite the nozzle, and a pressure of a conductive material. The generating element, the ink filled around the pressure generating element, is displaced by the application of a voltage, so that small droplets of ink are ejected from the nozzle.
噴墨塗佈裝置並不限定於塗佈噴頭與墨水收容部兩者分開的裝置,亦可使用這兩者不可分離之一體化的裝置。又,墨水收容部不僅有以相對於塗佈噴頭可分離或者不可分離之方式與噴頭一體化並搭載於托架上的形態,亦有設 置於裝置之固定部位,經由墨水供給部件例如管子,對塗佈噴頭供給墨水的形態。The inkjet coating device is not limited to a device in which the coating head and the ink containing portion are separated, and an integrated device in which the two are inseparable may be used. Further, the ink accommodating portion is not only integrated with the head so as to be separable or inseparable from the coating head, but is also mounted on the bracket, and is also provided. The ink is supplied to the coating head via an ink supply member such as a tube at a fixed portion of the device.
又,於墨盒中設置用以對塗佈噴頭作用較好之負壓之構成之情形時,可採用於墨盒之墨水收納部中配置吸收體的形態,或者具有可撓性墨水收容袋、以及對此收容袋作用擴張其內容積之方向之推施力之彈簧部的形態等。塗佈裝置可採用如上所述之串行(serial)塗佈方式,其他亦可採用於整個對應塗佈媒體之整幅之範圍內排列塗佈元件而成的行式印表機(line printer)的形態。Further, in the case where a configuration for providing a negative pressure to the coating head is provided in the ink cartridge, the ink container may be disposed in the ink containing portion of the ink cartridge, or may have a flexible ink containing bag, and This storage bag acts to expand the shape of the spring portion of the pushing force in the direction in which the internal volume is accumulated. The coating device may adopt a serial coating method as described above, and other line printers may be used in which the coating elements are arranged over the entire range of the corresponding coating medium. Shape.
8.2溶劑乾燥8.2 Solvent drying
使用上述噴墨塗佈方法,藉由噴墨於基板上塗佈本發明之噴墨用墨水後,例如藉由使用加熱板或者烘箱等之加熱使溶劑(D)氣化等而將溶劑(D)除去,即進行乾燥,藉此可形成矽醯胺酸(A)以及/或者矽醯胺酸(A')之膜。於噴墨用墨水進而含有高分子化合物(B)、烯基取代納迪克酸醯亞胺化合物(C)之情形時,可形成矽醯胺酸(A)以及/或者矽醯胺酸(A')、高分子化合物(B)以及烯基取代納迪克酸醯亞胺化合物(C)之複合膜。After the inkjet ink of the present invention is applied onto a substrate by inkjet coating by the above-described inkjet coating method, the solvent (D) is vaporized by heating using a hot plate or an oven or the like, for example, to obtain a solvent (D). The film is removed by drying, whereby a film of proline (A) and/or amic acid (A') can be formed. When the inkjet ink further contains a polymer compound (B) or an alkenyl group substituted with a nadic acid ruthenium imine compound (C), proline (A) and/or proline (A' can be formed. A polymer compound (B) and an alkenyl group-substituted composite film of the nadic acid ylide compound (C).
加熱條件根據各成分之種類以及調配比例而有所不同,較好的是矽醯胺酸(A)以及矽醯胺酸(A')不會固化之溫度,通常為70℃~120℃,於使用烘箱之情形時於5分鐘~15分鐘形成乾燥膜,於使用加熱板之情形時於1分鐘~5分鐘形成乾燥膜。The heating conditions vary depending on the type of each component and the blending ratio, and it is preferred that the temperature at which the valine acid (A) and the proline (A') are not cured is usually 70 ° C to 120 ° C. When an oven is used, a dried film is formed at 5 minutes to 15 minutes, and when a hot plate is used, a dried film is formed at 1 minute to 5 minutes.
8.3聚醯亞胺膜之形成8.3 Formation of polyimine film
形成矽醯胺酸(A)以及/或者矽醯胺酸(A')之膜,或者矽醯胺酸(A)以及/或者矽醯胺酸(A')、高分子化合物(B)以及烯基取代納迪克酸醯亞胺化合物(C)之複合膜後,為了使矽醯胺酸(A)以及/或者矽醯胺酸(A')進行醯亞胺化.矽部位之固化,較好的是於150℃~350℃,更好的是200℃~300℃下進行加熱處理,藉此可獲得聚醯亞胺膜(於使用烘箱之情形時進行30分鐘~90分鐘,於使用加熱板之情形時進行5分鐘~30分鐘)。另外,於高分子化合物(B)為聚醯胺酸或者聚醯胺酸酯等之情形時,亦同時進行藉由加熱處理之醯亞胺化反應。Forming a membrane of proline (A) and/or proline (A'), or proline (A) and/or proline (A'), polymer (B) and alkenyl After the composite film of the Nadick acid ylidene imine compound (C) is substituted, in order to imidize the valine (A) and/or valine (A'). The curing of the crucible portion is preferably carried out at 150 ° C to 350 ° C, more preferably at 200 ° C to 300 ° C, whereby a polyimide film can be obtained (for 30 minutes in the case of using an oven) 90 minutes, 5 minutes to 30 minutes when using a hot plate). Further, when the polymer compound (B) is a polyglycolic acid or a polyglycolate or the like, the oxime imidization reaction by heat treatment is simultaneously performed.
於膜形成為圖案狀之情形時,形成圖案狀之聚醯亞胺膜。於本說明書中,若未特別言及,則認為聚醯亞胺膜包括圖案狀之聚醯亞胺膜。When the film is formed into a pattern, a patterned polyimide film is formed. In the present specification, the polyimine film is considered to include a patterned polyimide film unless otherwise specified.
如此獲得之聚醯亞胺膜是耐熱性、電絕緣性優異的絕緣膜。又,於原料之噴墨用墨水含有環氧樹脂之情形時,成為較為強韌、耐藥品性、平坦性、密著性以及耐濺射性優異的絕緣膜,故而較好。The polyimide film obtained in this way is an insulating film excellent in heat resistance and electrical insulation. In addition, when the inkjet ink of the raw material contains an epoxy resin, it is preferable because it is an insulating film which is excellent in toughness, chemical resistance, flatness, adhesion, and sputter resistance.
9薄膜基板9 film substrate
本發明之薄膜基板是以如下方式而獲得:例如於藉由噴墨等方法形成有配線之聚醯亞胺薄膜等基板上,藉由噴墨塗佈方法以整面或者預定圖案狀(線狀等)塗佈本發明之噴墨用墨水,其後乾燥該基板,進而進行加熱而形成聚醯亞胺膜。The film substrate of the present invention is obtained, for example, on a substrate such as a polyimide film having a wiring formed by an inkjet method or the like, and is formed in a whole surface or a predetermined pattern by an inkjet coating method (linear The inkjet ink of the present invention is applied, and then the substrate is dried and further heated to form a polyimide film.
10電子零件10 electronic parts
例如,於預先形成有配線之聚醯亞胺薄膜等薄膜基板上,藉由噴墨塗佈方法塗佈本發明之噴墨用墨水,其後乾燥該薄膜基板,進而進行加熱,藉此可形成由具有絕緣性之聚醯亞胺膜被覆之可撓性電子零件。For example, the inkjet ink of the present invention is applied onto a film substrate such as a polyimide film having a wiring formed in advance by an inkjet coating method, and then the film substrate is dried and further heated to form a film. A flexible electronic component covered with an insulating polyimide film.
以下,藉由實施例以及比較例說明本發明,但本發明並不限定於該些實施例。Hereinafter, the present invention will be described by way of examples and comparative examples, but the invention is not limited to the examples.
實施例以及比較例中所使用的具有大於等於2個之酸酐基之化合物(a1)、單胺(a2)、具有1個酸酐基之化合物(a1')、二胺(a2')、具有大於等於2個之酸酐基之化合物(b1)、二胺(b2)、單胺(b3)、烯基取代納迪克酸醯亞胺(C)、以及溶劑(D)之名稱記為略號。以下敍述中使用此略號。The compound (a1) having two or more acid anhydride groups used in the examples and the comparative examples, the monoamine (a2), the compound (a1') having one acid anhydride group, and the diamine (a2') have a larger than The name of the compound (b1), the diamine (b2), the monoamine (b3), the alkenyl-substituted nadic acid ylide (C), and the solvent (D) equal to two acid anhydride groups are designated as the abbreviations. This abbreviation is used in the following description.
具有大於等於2個之酸酐基之化合物(a1)、(b1)Compounds (a1) and (b1) having an acid anhydride group of 2 or more
ODPA:3,3',4,4'-二苯基醚四羧酸二酐BTDA:3,3',4,4'-二苯基酮四羧酸二酐6FDA:4,4'-六氟亞丙基雙鄰苯二甲酸二酐ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride BTDA: 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride 6FDA: 4,4'-six Fluorinated bisphthalic dianhydride
單胺(a2)、(b3)Monoamine (a2), (b3)
APSE:3-胺基丙基三乙氧基矽烷APSE: 3-Aminopropyltriethoxydecane
具有1個酸酐基之化合物(a1')Compound having one anhydride group (a1')
TESA:三乙氧基矽烷基丙基琥珀酸酐TESA: triethoxydecyl propyl succinic anhydride
二胺(a2')、(b2)Diamine (a2'), (b2)
DDS:3,3'-二胺基二苯基碸PDA:對苯二胺DDS: 3,3'-diaminodiphenylphosphonium PDA: p-phenylenediamine
7HHP:5-[((正庚基環己基)乙基環己基)苯基]甲基-1,3-二胺基苯7HB:1,1-雙[4-(4-胺基苄基)苯基]-4-正庚基環己烷BAPP:2,2-雙[4-(4-胺基苯氧基)苯基]丙烷7HHP: 5-[((n-heptylcyclohexyl)ethylcyclohexyl)phenyl]methyl-1,3-diaminobenzene 7HB: 1,1-bis[4-(4-aminobenzyl) Phenyl]-4-n-heptylcyclohexane BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane
烯基取代納迪克酸醯亞胺(c1)Alkenyl substituted nadic acid ylide (c1)
ANIM:N-甲基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺ANIM: N-methyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine
雙烯基取代納迪克酸醯亞胺(c2)Dienyl substituted nadic acid ylide (c2)
BANIM:雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷BANIM: bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane
三烯基取代納迪克酸醯亞胺(c3)Trienyl substituted nadic acid ylide (c3)
TrisANITAEA:三{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)三乙基}胺TrisANITrisAM:三{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)三苯基}甲烷TrisANIPARARO:三{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}羥基甲烷TrisANITAEA: tris{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)triethyl}amine TrisANITrisAM: tris{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)triphenyl}methane TrisANIPARARO: tris{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} hydroxymethane
四烯基取代納迪克酸醯亞胺(c4)Tetraalkenyl substituted nadic acid ylide (c4)
TetrakisANITAM:四{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)四苯基}甲烷TetrakisANITAM: Tetra{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)tetraphenyl}methane
溶劑(D)Solvent (D)
EDM:二乙二醇甲基乙基醚GBL:γ-丁內酯NMP:N-甲基-2-吡咯烷酮EDM: Diethylene glycol methyl ethyl ether GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone
[實施例1]噴墨用墨水(1)[Example 1] Inkjet ink (1)
於具備攪拌機以及原料投入供應口之200 ml之三口燒瓶中,供應如下所述之原料,於乾燥氮氣流、室溫下攪拌3 hr,獲得透明之矽醯胺酸(A)30 wt%溶液。直接將該溶液用作噴墨用墨水(1)。The raw material as described below was supplied to a 200 ml three-necked flask equipped with a stirrer and a raw material supply port, and stirred under a nitrogen stream at room temperature for 3 hr to obtain a transparent lysine (A) 30 wt% solution. This solution was directly used as an ink for inkjet (1).
該溶液之黏度為10.8 mPa.s(25℃),表面張力(25℃)為33 mN/m。溶液之黏度是以E型黏度計(TOKYO KEIKI製造之VISCONIC ELD)進行測定。表面張力是藉由懸滴法以界面張力計(協和界面科學股份有限公司製造之Drop Master500)進行測定。The viscosity of the solution is 10.8 mPa. s (25 ° C), surface tension (25 ° C) is 33 mN / m. The viscosity of the solution was measured by an E-type viscosity meter (VISCONIC ELD manufactured by TOKYO KEIKI). The surface tension was measured by a hanging drop method using an interfacial tensiometer (Drop Master 500 manufactured by Kyowa Interface Science Co., Ltd.).
[實施例2]噴墨用墨水(2)[Example 2] Inkjet ink (2)
於具備溫度計、攪拌機、原料投入供應口以及氮氣導入口之500 ml之四口燒瓶中,供應如下所述之原料,於乾燥氮氣流、40℃下攪拌5 hr,獲得淡黃色透明之聚醯胺酸(B)之50 wt%溶液。In a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material supply port, and a nitrogen inlet, the following materials were supplied, and the mixture was stirred under a dry nitrogen stream at 40 ° C for 5 hr to obtain a pale yellow transparent polyamine. 50 wt% solution of acid (B).
該溶液之黏度為586 mPa.s。以GPC測定之重量平均分子量為2,100。聚醯胺酸之重量平均分子量以如下方式求得:以聚醯胺酸之濃度成為約1 wt%之方式將所得聚醯胺酸以四氫呋喃(THF)進行稀釋,使用GPC裝置:日本分光股份有限公司製造,JASCO GULLIVER 1500(智能 差示折射計(intelligent differential refractometer)RI-1530),以上述稀釋液為展開劑,藉由GPC法進行測定,以聚苯乙烯進行換算。管柱是將Tosoh股份有限公司製造之管柱(column)G4000HXL、G3000HXL、G2500HXL以及G2000HXL這4根以該順序連接而加以使用,於管柱溫度40℃、流速1.0 ml/min之條件下進行測定。The viscosity of the solution is 586 mPa. s. The weight average molecular weight measured by GPC was 2,100. The weight average molecular weight of polylysine is determined by diluting the obtained polyglycine in tetrahydrofuran (THF) in such a manner that the concentration of polyglycine becomes about 1 wt%, using a GPC apparatus: Japan Specimen Limited Made by the company, JASCO GULLIVER 1500 (smart An intelligent differential refractometer (RI-1530) was measured by a GPC method using the above diluent as a developing solvent, and converted into polystyrene. The pipe string is connected by using four columns of columns G4000HXL, G3000HXL, G2500HXL, and G2000HXL manufactured by Tosoh Co., Ltd. in this order, and is measured at a column temperature of 40 ° C and a flow rate of 1.0 ml/min. .
如下述般供應實施例1之矽醯胺酸(A)溶液與該聚醯胺酸(B)溶液,攪拌2 hr,獲得固體成分濃度30 wt%溶液。將該溶液用作噴墨用墨水(2)。該溶液之黏度為12.9 mPa.s(25℃),表面張力(25℃)為31.7 mN/m。The solution of the proline (A) solution of Example 1 and the solution of the polyaminic acid (B) were supplied as follows, and stirred for 2 hr to obtain a solution having a solid concentration of 30 wt%. This solution was used as an ink for inkjet (2). The viscosity of the solution is 12.9 mPa. s (25 ° C), surface tension (25 ° C) was 31.7 mN / m.
[實施例3]噴墨用墨水(3)[Example 3] Inkjet ink (3)
如下述般供應實施例1之矽醯胺酸(A)溶液與烯基取代納迪克酸醯亞胺(C),攪拌至固體成分完全溶解,獲得矽醯胺酸(A)/烯基取代納迪克酸醯亞胺(C)之40 wt%溶液。將該溶液用作噴墨用墨水(3)。該溶液之黏度為18.1 mPa.s(25℃),表面張力(25℃)為31.8 mN/m。The solution of the proline (A) solution of Example 1 and the alkenyl group substituted with the nadic acid ylide (C) were supplied as follows, and the mixture was stirred until the solid component was completely dissolved to obtain a proline (A)/alkenyl substituted sodium. A 40 wt% solution of dick acid imine (C). This solution was used as an ink for inkjet (3). The viscosity of the solution is 18.1 mPa. s (25 ° C), surface tension (25 ° C) was 31.8 mN / m.
[實施例4][Example 4]
將實施例1中製備之噴墨用墨水(1)用作噴墨墨水,以FUJIFILM Dimatix公司製造之噴墨塗佈裝置DMP-2831,於1.5 mm厚之玻璃環氧樹脂雙面敷銅板上設定為1點寬且點距40微米,進行長5 cm之線塗佈。噴墨頭之加熱器設定為30℃,壓電電壓為16 V,驅動頻率為5 kHz。將基板以80℃之加熱板乾燥5分鐘後,以230℃之烘箱加熱30分鐘,獲得形成為線狀之聚醯亞胺之絕緣膜。The inkjet ink (1) prepared in Example 1 was used as an inkjet ink, and was set on a 1.5 mm thick glass epoxy double-sided copper plate by an inkjet coating device DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd. A line length of 5 cm was applied to a width of 1 point and a pitch of 40 micrometers. The heater of the ink jet head was set to 30 ° C, the piezoelectric voltage was 16 V, and the driving frequency was 5 kHz. The substrate was dried on a hot plate at 80 ° C for 5 minutes, and then heated in an oven at 230 ° C for 30 minutes to obtain an insulating film of a polyimine formed into a linear shape.
以光學顯微鏡觀察所得聚醯亞胺膜之線寬以及該線寬之均勻性,測定膜厚。膜厚以如下方式測定:使用KLA-Tencor Japan股份有限公司製造之觸針式膜厚計α-step 200,將3處之測定值之平均值作為膜厚。將其結果示於表1。線具有充分之厚度。The line width of the obtained polyimide film and the uniformity of the line width were observed with an optical microscope, and the film thickness was measured. The film thickness was measured by using a stylus type film thickness meter α-step 200 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of the measured values at three places was taken as the film thickness. The results are shown in Table 1. The wire has sufficient thickness.
[實施例5][Example 5]
將實施例2中製備之噴墨用墨水(2)用作噴墨墨水,以與實施例4相同之條件獲得聚醯亞胺之絕緣膜。The inkjet ink (2) prepared in Example 2 was used as an inkjet ink, and an insulating film of polyimide was obtained under the same conditions as in Example 4.
以與實施例4相同之條件對所得聚醯亞胺膜進行評價。將其結果示於表1。線具有充分之厚度。The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The wire has sufficient thickness.
[實施例6][Embodiment 6]
將實施例3中製備之噴墨用墨水(3)用作噴墨墨水, 將點距設為20微米,除此以外以與實施例4相同之條件獲得聚醯亞胺之絕緣膜。The inkjet ink (3) prepared in Example 3 was used as an inkjet ink, An insulating film of polyimine was obtained under the same conditions as in Example 4 except that the dot pitch was set to 20 μm.
以與實施例4相同之條件對所得聚醯亞胺膜進行評價。將其結果示於表1。線具有充分之厚度。The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The wire has sufficient thickness.
[比較例1]噴墨用墨水(4)[Comparative Example 1] Inkjet ink (4)
如下述般供應實施例2之聚醯胺酸(B)50%溶液,於乾燥氮氣流、室溫下加以攪拌,獲得淡黃色透明之聚醯胺酸(B)之25 wt%溶液。將該溶液用作噴墨用墨水(4)。該溶液之黏度為12.3 mPa.s,表面張力(25℃)為33.2 mN/m。The polyamine acid (B) 50% solution of Example 2 was supplied as follows, and stirred under a nitrogen stream at room temperature to obtain a 25 wt% solution of pale yellow transparent polyamine (B). This solution was used as an ink for inkjet (4). The viscosity of the solution is 12.3 mPa. s, surface tension (25 ° C) is 33.2 mN / m.
[比較例2][Comparative Example 2]
將比較例1中製備之噴墨用墨水(4)用作噴墨墨水,除此之外以與實施例4相同之條件獲得聚醯亞胺之絕緣膜。An insulating film of polyimine was obtained under the same conditions as in Example 4 except that the inkjet ink (4) prepared in Comparative Example 1 was used as an inkjet ink.
以與實施例4相同之條件對所得聚醯亞胺膜進行評價。將其結果示於表1。線不具有超過1微米之程度的厚度。The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The wire does not have a thickness of more than 1 micron.
[實施例7]噴墨用墨水(5)之製備以及聚醯亞胺絕緣膜之形成[Example 7] Preparation of inkjet ink (5) and formation of polyimide film
如下述般供應原料,除此之外以依據實施例1之方法製備噴墨墨水,測定黏度。The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.
進而,以依據實施例4之方法形成聚醯亞胺絕緣膜。Further, a polyimide film was formed in accordance with the method of Example 4.
[實施例8]噴墨用墨水(6)之製備以及聚醯亞胺絕緣膜之形成[Example 8] Preparation of inkjet ink (6) and formation of polyimide film
如下述般供應原料,除此之外以依據實施例1之方法製備噴墨墨水,測定黏度。The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.
進而,以依據實施例4之方法形成聚醯亞胺絕緣膜。Further, a polyimide film was formed in accordance with the method of Example 4.
[實施例9]噴墨用墨水(7)之製備以及聚醯亞胺絕緣膜之形成[Example 9] Preparation of inkjet ink (7) and formation of polyimide film
如下述般供應原料,除此之外以依據實施例1之方法製備噴墨墨水,測定黏度。The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.
進而,以依據實施例4之方法形成聚醯亞胺絕緣膜。Further, a polyimide film was formed in accordance with the method of Example 4.
[實施例10]噴墨用墨水(8)之製備以及聚醯亞胺絕緣膜之形成[Example 10] Preparation of inkjet ink (8) and formation of polyimide film
如下述般供應原料,除此之外以依據實施例1之方法製備噴墨墨水,測定黏度。The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.
進而,以依據實施例4之方法形成聚醯亞胺絕緣膜。Further, a polyimide film was formed in accordance with the method of Example 4.
[實施例11]噴墨用墨水(9)之製備以及聚醯亞胺絕緣膜之形成[Example 11] Preparation of inkjet ink (9) and formation of polyimide film
如下述般供應原料,除此之外以依據實施例1之方法製備噴墨墨水,測定黏度。The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.
進而,以依據實施例4之方法形成聚醯亞胺絕緣膜。Further, a polyimide film was formed in accordance with the method of Example 4.
[實施例12]噴墨用墨水(10)之製備以及聚醯亞胺絕緣膜之形成[Example 12] Preparation of inkjet ink (10) and formation of polyimide film
如下述般供應原料,除此之外以依據實施例1之方法製備噴墨墨水,測定黏度。The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.
進而,以依據實施例4之方法形成聚醯亞胺絕緣膜。Further, a polyimide film was formed in accordance with the method of Example 4.
[實施例13]噴墨用墨水(11)之製備以及聚醯亞胺絕緣膜之形成[Example 13] Preparation of inkjet ink (11) and formation of polyimide film
如下述般供應原料,除此之外以依據實施例1之方法製備噴墨墨水,測定黏度。The raw material was supplied as follows, except that the inkjet ink was prepared in accordance with the method of Example 1, and the viscosity was measured.
對於實施例7~實施例13,以與實施例4相同之條件對所得聚醯亞胺膜進行評價。將其結果示於表2。線具有充分之厚度。The obtained polyimine membranes were evaluated under the same conditions as in Example 4 for Examples 7 to 13. The results are shown in Table 2. The wire has sufficient thickness.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope is subject to the definition of the scope of the patent application attached.
[產業上之可利用性][Industrial availability]
本發明之活用法例如可列舉:可撓性配線基板用絕緣膜、使用此絕緣膜之電子零件。Examples of the active use of the present invention include an insulating film for a flexible wiring board and an electronic component using the insulating film.
圖1為「TrisANITAEA」之IR光譜。Figure 1 shows the IR spectrum of "TrisANITAEA".
圖2為「TrisANITAEA」之1 H-NMR光譜。Fig. 2 is a 1 H-NMR spectrum of "TrisANITAEA".
圖3為「TrisANITrisAM」之IR光譜。Figure 3 shows the IR spectrum of "TrisANITrisAM".
圖4為「TrisANITrisAM」之1 H-NMR光譜。Fig. 4 is a 1 H-NMR spectrum of "TrisANITrisAM".
圖5為「TrisANIPARARO」之IR光譜。Figure 5 shows the IR spectrum of "TrisANIPARARO".
圖6為「TrisANIPARARO」之1 H-NMR光譜。Fig. 6 is a 1 H-NMR spectrum of "TrisANIPARARO".
圖7為「TetrakisANITAM」之IR光譜。Figure 7 shows the IR spectrum of "Tetrakis ANITAM".
圖8為「TetrakisANITAM」之1 H-NMR光譜。Fig. 8 is a 1 H-NMR spectrum of "Tetrakis ANITAM".
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