TWI423998B - Redox-induced cationically polymerizable compositions with low cure temperature - Google Patents
Redox-induced cationically polymerizable compositions with low cure temperature Download PDFInfo
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Description
本發明係有關於一種氧化還原-引發之陽離子性可聚合組成物，其具有降低的固化溫度，及有關於一種用於降低陽離子性可聚合組成物之固化溫度之方法。This invention relates to a redox-initiated cationic polymerizable composition having a reduced curing temperature and to a method for reducing the curing temperature of a cationic polymerizable composition.
於許多製造程序中，操作速度導致較高的產量及較低的裝置費用。當使用一種黏著劑、塗層、或膠囊作為製造程序之一部份時，若是黏著劑、塗層、或膠囊可於相對地低的固化溫度下迅速地被固化，則可增加操作速度。In many manufacturing processes, operating speeds result in higher throughput and lower equipment costs. When an adhesive, coating, or capsule is used as part of the manufacturing process, the speed of operation can be increased if the adhesive, coating, or capsule can be rapidly cured at relatively low curing temperatures.
於電子封裝工業中，例如：低溫、快速(急速)固化的黏著劑及膠囊材料，為各種應用所意欲。一種常用的電子封裝模式涉及：經由一種黏著劑或膠囊材料，將半導體裝置固定於基底上。更重要的用途為：將積體電路晶片結合至金屬導線架或有機基底，及將電路包裝或組裝結合至印刷電路板，包括如：列陣包裝之黏晶、RFID包裝之黏晶、與噴墨卡帶組裝之組份黏附。對於噴墨卡帶，低溫固化之組裝可使噴射軌道之變形減至最小，並可改善印刷品質。對於感溫組份或基底，如：於RFID應用中以紙為基底的天線及於有機基質之照相機感測器，低溫的互連為非常意欲，因此於低溫下固化，以低於100℃為較佳，的可聚合組成物有其需求。In the electronic packaging industry, for example, low temperature, fast (rapid) curing adhesives and capsule materials are intended for a variety of applications. One common electronic packaging mode involves securing a semiconductor device to a substrate via an adhesive or capsule material. More important uses are: the integration of integrated circuit wafers into metal leadframes or organic substrates, and the packaging or assembly of circuit packaging to printed circuit boards, including, for example, die-packaged die-bonding, RFID-packed die bonding, and spray The component of the ink cartridge assembly is adhered. For inkjet cartridges, low temperature curing assembly minimizes distortion of the jet track and improves print quality. For temperature sensitive components or substrates, such as paper-based antennas for RFID applications and camera sensors for organic substrates, low temperature interconnects are highly desirable and therefore cure at low temperatures, below 100 ° C. Preferably, the polymerizable composition has its needs.
本發明為一種可聚合組成物，其包括：(i)一種陽離子性可聚合樹脂，(ii)一種鎓鹽，(iii)一種偶氮或過氧化物引發劑，及(iv)一種富含電子的乙烯基樹脂。The present invention is a polymerizable composition comprising: (i) a cationically polymerizable resin, (ii) a phosphonium salt, (iii) an azo or peroxide initiator, and (iv) an electron-rich Vinyl resin.
於另一實例中，本發明為一種可聚合組成物，其包括：(i)一種陽離子性可聚合樹脂，(ii)一種鎓鹽，(iii)一種偶氮或過氧化物引發劑，及(iv)一催化量或低於化學計量之富含電子的乙烯基樹脂。In another example, the invention is a polymerizable composition comprising: (i) a cationically polymerizable resin, (ii) a phosphonium salt, (iii) an azo or peroxide initiator, and Iv) A catalytic amount or less than a stoichiometric amount of an electron-rich vinyl resin.
於另一實例中，本發明為一種用於降低陽離子性可聚合樹脂之固化溫度之方法，其中樹脂的固化係藉添加一種鎓鹽與一種偶氮或過氧化物引發劑至樹脂予以催化，此方法包括：添加一種富含電子的乙烯基樹脂至包含樹脂、鎓鹽、及偶氮或過氧化物引發劑之混合物中。In another example, the invention is a method for reducing the curing temperature of a cationically polymerizable resin, wherein the curing of the resin is catalyzed by adding a cerium salt to an azo or peroxide initiator to the resin, The method comprises: adding an electron-rich vinyl resin to a mixture comprising a resin, a phosphonium salt, and an azo or peroxide initiator.
於另一實例中，本發明為一種用於降低陽離子性可聚合樹脂之固化溫度之方法，其中樹脂的固化係藉添加一種鎓鹽與一種偶氮或過氧化物引發劑至樹脂予以催化，此方法包括：添加一催化量或低於化學計量之富含電子的乙烯基樹脂至包含樹脂、鎓鹽、及偶氮或過氧化物引發劑之混合物中。In another example, the invention is a method for reducing the curing temperature of a cationically polymerizable resin, wherein the curing of the resin is catalyzed by adding a cerium salt to an azo or peroxide initiator to the resin, The method comprises adding a catalytic amount or a substoichiometric amount of an electron-rich vinyl resin to a mixture comprising a resin, a phosphonium salt, and an azo or peroxide initiator.
對於在一種富含電子的乙烯基物料之存在下，使用鎓鹽與一種偶氮引發劑的陽離子性聚合反應，其反應系統依下圖所示發生：For the cationic polymerization of a sulfonium salt with an azo initiator in the presence of an electron-rich vinyl material, the reaction system occurs as shown in the following figure:
其中R與R’為任何有機部份。Wherein R and R' are any organic moiety.
亦可使用過氧化物，藉以產生一種用於與鎓鹽反應之自由基。A peroxide can also be used to produce a free radical for reaction with the cerium salt.
於本說明書及申請專利範圍中所使用之可固化樹脂，為一種具有或不具有交聯的可聚合者，可固化與可聚合可被替換地使用，及一種陽離子性可固化樹脂或組成物為一種可聚合者。任何陽離子性可聚合樹脂可被用於前述的反應，陽離子性可聚合樹脂之實例包括：氧雜環丁烷、環氧樹脂、螺原碳酸酯、螺原酯、及苯並噁嗪、或一種包括任意這些的混合物。The curable resin used in the specification and the patent application is a polymerizable person with or without crosslinking, curable and polymerizable may be used alternatively, and a cationic curable resin or composition is An aggregator. Any cationic polymerizable resin can be used for the aforementioned reaction, and examples of the cationic polymerizable resin include: oxetane, epoxy resin, spiro orthocarbonate, spiroester, and benzoxazine, or a kind A mixture of any of these is included.
適合的氧雜環丁烷樹脂為那些揭示於美國專利7,034,064、6,982,338、6,953,862、6,943,258、6,753,434中者，及那些得自Toagosei公司，商品名為OXT-221、OXT-121、OXT-101、OXT-212、OXT-211、CHOX、OX-SC、PNOX-1009者，其具有結構：Suitable oxetane resins are those disclosed in U.S. Patents 7,034,064, 6,982,338, 6,953,862, 6,943,258, 6,753,434, and those available from Toagosei under the tradenames OXT-221, OXT-121, OXT-101, OXT- 212, OXT-211, CHOX, OX-SC, PNOX-1009, which has the structure:
適合的環氧樹脂包括：二酚環氧樹脂、萘環氧樹脂、及脂肪族類環氧樹脂，市售的物料包括：二酚類環氧樹脂(例如：那些以商品名EPICLON 830LVP，830CRP，835LV，850CRP販售者，可得自Dainippon印墨與化學品公司)；萘類環氧樹脂(例如：那些以商品名EPICLON HP4032販售者，可得自Dainippon印墨與化學品公司)；脂肪族環氧樹脂(例如：那些以商品名ARALDITE CY179，184，192，175，179販售者，可得自汽巴特用化學品公司，EPOXY 1234，249，206，可得自Dow公司，及EHPE-3150，可得自Daicel化學工業公司)。Suitable epoxy resins include: diphenol epoxy resins, naphthalene epoxy resins, and aliphatic epoxy resins. Commercially available materials include: diphenolic epoxy resins (eg, those under the trade name EPICLON 830LVP, 830 CRP, 835LV, 850CRP sold by Dainippon Ink and Chemicals); naphthalene epoxy (eg those sold under the trade name EPICLON HP4032, available from Dainippon Ink and Chemicals); Family of epoxy resins (for example, those sold under the trade name ARALDITE CY179, 184, 192, 175, 179, available from Gasbat Chemicals, EPOXY 1234, 249, 206, available from Dow, and EHPE -3150, available from Daicel Chemical Industries, Inc.).
其他適合的環氧樹脂包括：環脂肪族環氧樹脂，例如：3,4-環氧基-環己基甲基3,4-環氧基環己烷羧酸酯，可得自Union Carbide公司之ERL-4221及可得自Ciba-Geigy公司之ARALDITE CY-179；六氫酞酸酐之二環氧丙酯，可得自Ciba-Geigy公司之CY-184；二(3,4-環氧基環己基甲基)-己二酸酯，可得自Union Carbide公司之ERL-4229；及其他的雙酚-A類環氧樹脂、雙酚-F類環氧樹脂、環氧酚醛清漆樹脂、二苯基類環氧樹脂、萘類環氧樹脂、及二環戊二烯苯酚類環氧樹脂，皆可由不同的來源購得。Other suitable epoxy resins include: cycloaliphatic epoxy resins such as 3,4-epoxy-cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate available from Union Carbide ERL-4221 and ARALDITE CY-179 available from Ciba-Geigy; diglycidyl hexahydrophthalic anhydride available from Ciba-Geigy CY-184; bis(3,4-epoxy ring) Hexylmethyl)-adipate available from Union Carbide's ERL-4229; and other bisphenol-A epoxy resins, bisphenol-F epoxy resins, epoxy novolac resins, diphenyls Base epoxy resins, naphthalene epoxy resins, and dicyclopentadiene phenolic epoxy resins are commercially available from various sources.
螺原碳酸酯及乙烯基螺原碳酸酯之實例包括那些具有下列結構者：Examples of spiro orthocarbonate and vinyl spirocarbonate include those having the following structure:
富含電子之乙烯基螺碳酸酯之實例包括那些具有下列結構者：Examples of electron-rich vinyl spirocarbonates include those having the following structure:
螺原酯之實例包括：Examples of spiro orthoesters include:
其中Piv為三甲基乙醯基團。Wherein Piv is a trimethyl ethane group .
富含電子之乙烯基螺原酯之一實例為An example of an electron-rich vinyl spiro orthoester is
適合的苯並噁嗪包括那些包含下列結構之化合物：Suitable benzoxazines include those containing the following structures:
其中R1 與R2 為任何有機部份，包括另一苯並噁嗪結構者。Wherein R 1 and R 2 are any organic moiety, including another benzoxazine structure.
苯並噁嗪化合物之實例包括那些具有下式者：Examples of benzoxazine compounds include those having the formula:
其中R1 為二價基團，其可為：脂肪族、芳族、或一種脂肪族與芳族之併合物，及其可包含雜原子，如：氧、氮、硫、磷、或鹵素，或其可為一單鍵，或者其可為：S、S2 、SO、SO2 、O、或CO；及R2 為：氫、烷基或經取代之烷基、芳族或經取代之芳族。Wherein R 1 is a divalent group, which may be: aliphatic, aromatic, or a mixture of an aliphatic and an aromatic, and may contain a hetero atom such as oxygen, nitrogen, sulfur, phosphorus, or halogen. Or it may be a single bond, or it may be: S, S 2 , SO, SO 2 , O, or CO; and R 2 is: hydrogen, alkyl or substituted alkyl, aromatic or substituted Aromatic.
明確的適用苯並噁嗪化合物包括：Clearly applicable benzoxazine compounds include:
除如前所示之化合物外，苯並噁嗪亦可以一種聚合物的物料存在，例如於下列結構所描述：In addition to the compounds as previously indicated, the benzoxazine may also be present as a polymeric material, for example as described in the following structures:
其中R1 如前所述，n為一整數，其會隨聚合組成物所依自之苯並噁嗪改變，及每個Q為一聚合的實體，例如：聚胺基甲酸酯、聚醚、聚酯、聚(丁二烯)、或聚苯乙烯。Wherein R 1 is as defined above, n is an integer which varies with the benzoxazine from which the polymeric composition is derived, and each Q is a polymeric entity, such as a polyurethane, a polyether , polyester, poly(butadiene), or polystyrene.
鎓鹽之實例包括：碘鹽、鋶鹽、偶氮鹽、銨鹽、或為一種包括這些鹽之混合物。於一實例中，鎓鹽為一種具式Examples of the onium salt include an iodide salt, a phosphonium salt, an azo salt, an ammonium salt, or a mixture including these salts. In one example, the barium salt is a type
之碘鹽，其中R為各自獨立地選自：苯基、鹵素苯基(例如：氯苯基)、及C1 -C20 烷基苯基(例如：十二烷基苯基)，X為任意適合的抗衡陰離子，例如：鹵素陰離子、CF3 SO3 - 、C6 H5 SO3 - 、NO3 - 、AsF6 - 、SbF6 - 、FeCl4 - 、SbCl6 - 、BF4 - 、PF6 - 、及(C6 H5 )B- 。The iodide salt, wherein each R is independently selected from: phenyl, halo-phenyl (e.g.: chlorophenyl), and C 1 -C 20 alkylphenyl group (e.g.: dodecylphenyl), X is Any suitable counter anion, for example: halogen anion, CF 3 SO 3 - , C 6 H 5 SO 3 - , NO 3 - , AsF 6 - , SbF 6 - , FeCl 4 - , SbCl 6 - , BF 4 - , PF 6 - , and (C 6 H 5 )B - .
市售之錪鹽包括：(對-異丙基苯基)(對-甲基苯基)碘四(五氟苯基)硼酸酯，得自Gelest公司之RHODORSIL 2074，及雙十二烷基苯基錪六氟銻酸酯，得自General Electric公司之UV 9380。鎓鹽以一有效數量使用，於一實例中，有效數量範圍為樹脂總量之0.1至10重量%。Commercially available sulfonium salts include: (p-isopropylphenyl) (p-methylphenyl) iodine tetrakis(pentafluorophenyl) borate, RHODORSIL 2074 from Gelest Corporation, and dodecyl group Phenylphosphonium hexafluoroantimonate, available from General Electric Company, UV 9380. The onium salt is used in an effective amount, and in one example, the effective amount ranges from 0.1 to 10% by weight based on the total amount of the resin.
偶氮引發劑之實例包括如：偶氮異丁腈、2,2’-偶氮二丙烷、2,2’-偶氮二(2-甲基丁烷腈)、及m,m’-偶氮氧基苯乙烯。市售的偶氮引發劑為那些得自Wako Specialty公司，例如以下列商品名販售者：VA-044、VA-057、VA-085、V-70、VF-096、V-65、V-601、V-59、V-40、VF-096、V-30，及那些得自Akzo Nobel公司，以下列商品名販售者：PERKADOX ACCN、PERKADOX AIBN、PERKADOX AMBN-GR，及那些得自杜邦公司，以下列商品名販售者：VAZO-52、VAZO-64、VAZO-67、及VAZO-88。偶氮引發劑以一有效數量使用，於一實例中，有效數量範圍為樹脂總量之0.1至10重量%。Examples of the azo initiator include, for example, azoisobutyronitrile, 2,2'-azodipropane, 2,2'-azobis(2-methylbutanenitrile), and m,m'-couple. Nitrostyrene. Commercially available azo initiators are those available from Wako Specialty, Inc., for example, under the trade names VA-044, VA-057, VA-085, V-70, VF-096, V-65, V- 601, V-59, V-40, VF-096, V-30, and those from Akzo Nobel, sold under the following trade names: PERKADOX ACCN, PERKADOX AIBN, PERKADOX AMBN-GR, and those from DuPont The company sells the following trade names: VAZO-52, VAZO-64, VAZO-67, and VAZO-88. The azo initiator is used in an effective amount, and in one example, the effective amount ranges from 0.1 to 10% by weight based on the total amount of the resin.
過氧化物引發劑之實例包括那些可購自Akzo Noble公司，例如那些以商品名PERKADOX及TRIGONOX販售者。其他的過氧化物引發劑為適合，其條件為：可與乙烯基樹脂產生自由基，以用於與鎓鹽反應。過氧化物之實例包括：苯醯過氧化物、十二烷醯過氧化物、辛烷醯過氧化物、過辛酸丁酯、二枯基過氧化物、乙醯過氧化物、對氯苯醯過氧化物、及二-三級丁基二過酞酸酯。過氧化物引發劑以一有效數量使用，於一實例中，有效數量範圍為樹脂總含量之0.1至10重量%。Examples of peroxide initiators include those commercially available from Akzo Noble, such as those sold under the tradenames PERKADOX and TRIGONOX. Other peroxide initiators are suitable provided that they can generate free radicals with the vinyl resin for reaction with the phosphonium salt. Examples of the peroxide include: phenylhydrazine peroxide, dodecane oxime peroxide, octane oxime peroxide, butyl peroctoate, dicumyl peroxide, acetam peroxide, p-chlorobenzoquinone Peroxide, and di-tertiary butyl diperonate. The peroxide initiator is used in an effective amount, and in one example, the effective amount ranges from 0.1 to 10% by weight based on the total resin content.
富含電子的乙烯基樹脂實例包括：乙烯醚、螺環乙烯醚、苯乙烯類(包含一苯乙烯部份之化合物)、肉桂基類(於本說明書與申請專利範圍中：包含一肉桂基部份之化合物)、N-乙烯醯胺、及N-乙烯胺。Examples of the electron-rich vinyl resin include: vinyl ether, spirovinyl ether, styrene (a compound containing a styrene moiety), and a cinnamyl group (in the present specification and claims: a base of a cinnamon base) Parts of the compound), N-vinylamine, and N-vinylamine.
適合的乙烯醚樹脂包括例如：聚(丁二烯)、聚(碳酸酯)、聚(胺基甲酸酯)、聚(醚)、聚(酯)、單純的碳氫化合物、及包含下列官能的單純碳氫化合物，如：羰基、羧基、醯胺、胺基甲酸酯、脲、酯、或醚，其亦包含乙烯醚官能者。適合的市售乙烯醚樹脂包括：環己烷-二甲醇二乙烯醚、十二烷基乙烯醚、環己基乙烯醚、2-乙基己基乙烯醚、二丙二醇二乙烯醚、己二醇二乙烯醚、十八烷基乙烯醚、及丁二醇二乙烯醚，可得自國際特殊產品公司(ISP)；以商品名VECTOMER 4010、4020、4030、4040、4051、4210、4220、4230、4060、5015販售之乙烯醚，得自Sigma-Aldrich公司。Suitable vinyl ether resins include, for example, poly(butadiene), poly(carbonate), poly(urethane), poly(ether), poly(ester), simple hydrocarbons, and the following functional groups. A simple hydrocarbon such as a carbonyl group, a carboxyl group, a guanamine, a urethane, a urea, an ester, or an ether, which also contains a vinyl ether functional group. Suitable commercially available vinyl ether resins include: cyclohexane-dimethanol divinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether Ether, octadecyl vinyl ether, and butanediol divinyl ether, available from International Special Products Corporation (ISP); under the trade names VECTOMER 4010, 4020, 4030, 4040, 4051, 4210, 4220, 4230, 4060, The vinyl ether sold in 5015 was obtained from Sigma-Aldrich.
適合的螺環乙烯醚包括例如那些具有下列結構者：Suitable spirovinyl ethers include, for example, those having the following structure:
適合的苯乙烯樹脂包括例如那些揭示於美國專利6,953,862、6,908,969、6,908,957、6,809,155、6,803,406、6,716,992、6,441,213、6,441,121、6,307,001、6,300,456中者，及那些市售的苯乙烯、經取代的苯乙烯類、二乙烯苯、二苯基乙烯、及任何其他的樹脂，其具有苯乙烯官能者(於後稱為苯乙烯類)，此類樹脂可為例如：聚酯、胺基甲酸酯、脲。苯乙烯類樹脂之實例包括具有下列結構之化合物，其中R為一種脂肪族或芳族碳氫化合物，包括那些具有雜原子者。Suitable styrenic resins include, for example, those disclosed in U.S. Patent Nos. 6,953,862, 6,908,969, 6,908,957, 6,809,155, 6,803,406, 6,716,992, 6,441,213, 6,441, 121, 6, 307, 001, 6,300, 456, and those commercially available styrene, substituted styrenes, Ethylene benzene, diphenylethylene, and any other resin having a styrene function (hereinafter referred to as styrene), and such a resin may be, for example, a polyester, a urethane, or a urea. Examples of the styrenic resin include compounds having the following structure, wherein R is an aliphatic or aromatic hydrocarbon, including those having a hetero atom.
適合的肉桂基樹脂包括例如那些揭示於美國專利6,943,258、6,753,434、6,716,992、6,908,969、6,908,957、6,809,155、6,803,406、6,753,434、6,570,032、6,441,121、6,307,001、6,300,456中者，肉桂基化合物可為任何小分子、寡聚、或聚合的物料，其包含一肉桂基官能，以結構式Suitable cinnamyl-based resins include those disclosed, for example, in U.S. Patent Nos. 6,943,258, 6,753,434, 6,716,992, 6,908,969, 6,908,957, 6,809,155, 6,803,406, 6,753,434, 6,570,032, 6,441,121, 6,307,001, 6,300,456, the cinnamyl compound can be any small molecule, oligomeric, Or a polymeric material comprising a cinnamyl function, in the structural formula
予以代表者，於後稱為肉桂基類。Representatives are referred to as cinnamon bases.
適合的市售N-乙烯醯胺樹脂包括例如：N-乙烯-吡咯啶酮、N-乙烯甲醯胺、及N-乙烯己內酯。Suitable commercially available N-vinylamine resins include, for example, N-vinyl-pyrrolidone, N-vinylformamide, and N-vinylcaprolactone.
適合的市售N-乙烯胺包括例如：N-乙烯咔唑、N-乙烯吡咯、及N-乙烯咪唑、及2-甲基-N-乙烯咪唑。Suitable commercially available N-vinylamines include, for example, N-vinylcarbazole, N-vinylpyrrole, and N-vinylimidazole, and 2-methyl-N-vinylimidazole.
於另一實例中，本發明為一種方法，用於聚合包含一種或多種陽離子性可聚合單體之陽離子性可聚合組成物，其包括：於一種鎓鹽、一種偶氮或過氧化物引發劑之存在下，將陽離子性可聚合組成物與一種富含電子的乙烯基樹脂反應，此種陽離子性可聚合組成物之組份與先前本說明書中所述者同。In another example, the invention is a method for polymerizing a cationically polymerizable composition comprising one or more cationically polymerizable monomers, comprising: a phosphonium salt, an azo or peroxide initiator The cationically polymerizable composition is reacted with an electron-rich vinyl resin in the presence of a component of such a cationic polymerizable composition as previously described in the specification.
於另一實例中，本發明為一種方法，用於聚合包含一種或多種陽離子性可聚合單體之陽離子性可聚合組成物，其包括：於一種鎓鹽、一種偶氮或過氧化物引發劑之存在下，將陽離子性可聚合組成物與一催化量或低於化學計量之富含電子的乙烯基樹脂反應，此種陽離子性可聚合組成物之組份與先前本說明書中所述者同。In another example, the invention is a method for polymerizing a cationically polymerizable composition comprising one or more cationically polymerizable monomers, comprising: a phosphonium salt, an azo or peroxide initiator The cationically polymerizable composition is reacted with a catalytic amount or less than a stoichiometric amount of an electron-rich vinyl resin in the presence of a component of such a cationic polymerizable composition as previously described in the specification. .
於另一實例中，本發明為一種方法，用於降低包含一種或多種陽離子性可聚合單體、一種鎓鹽、及一種偶氮或過氧化物引發劑之陽離子性可聚合組成物之固化溫度，此方法包括：添加一種富含電子的乙烯基樹脂至陽離子性可聚合組成物，此種陽離子性可聚合組成物之組份與先前本說明書中所述者同。In another example, the invention is a method for reducing the curing temperature of a cationically polymerizable composition comprising one or more cationically polymerizable monomers, a phosphonium salt, and an azo or peroxide initiator The method comprises: adding an electron-rich vinyl resin to the cationic polymerizable composition, the components of such a cationic polymerizable composition being the same as those previously described in the specification.
於另一實例中，本發明為一種方法，用於降低包含一種或多種陽離子性可聚合單體、一種鎓鹽、及一種偶氮或過氧化物引發劑之陽離子性可聚合組成物之固化溫度，此方法包括：添加一催化量或低於化學計量之富含電子的乙烯基樹脂至陽離子性可聚合組成物，此種陽離子性可聚合組成物之組份與先前本說明書中所述者同。In another example, the invention is a method for reducing the curing temperature of a cationically polymerizable composition comprising one or more cationically polymerizable monomers, a phosphonium salt, and an azo or peroxide initiator The method comprises: adding a catalytic amount or a substoichiometric amount of an electron-rich vinyl resin to the cationic polymerizable composition, the component of the cationic polymerizable composition being the same as previously described in the specification .
於另一實例中，本發明為一種二部份陽離子性可聚合組成物，一部份包括陽離子性可聚合單體與一種鎓鹽，及第二部份包括陽離子性可聚合單體與一種偶氮或過氧化物引發劑，第一部份、或第二部份、或二者包含一種富含電子的乙烯基樹脂，這些部份之組份先前已敘述於本說明書中，此二部份可在緊接於配方前予以機械地混合。In another example, the invention is a two-part cationic polymerizable composition, a portion comprising a cationically polymerizable monomer and a phosphonium salt, and a second portion comprising a cationic polymerizable monomer and an even The nitrogen or peroxide initiator, the first part, or the second part, or both comprise an electron-rich vinyl resin, the components of which are previously described in this specification, the two parts It can be mechanically mixed immediately before the formulation.
於另一實例中，本發明為一種二部份陽離子性可聚合組成物，一部份包括陽離子性可聚合單體與一種鎓鹽，及第二部份包括陽離子性可聚合單體與一種偶氮或過氧化物引發劑，第一部份、或第二部份、或二者包含一催化量或低於化學計量之富含電子的乙烯基樹脂，這些部份之組份先前已敘述於本說明書中，此二部份可在緊接於配方前予以機械地混合。In another example, the invention is a two-part cationic polymerizable composition, a portion comprising a cationically polymerizable monomer and a phosphonium salt, and a second portion comprising a cationic polymerizable monomer and an even a nitrogen or peroxide initiator, the first part, or the second part, or both comprising a catalytic amount or less than a stoichiometric amount of an electron-rich vinyl resin, the components of which have been previously described In this specification, the two parts can be mechanically mixed immediately before the formulation.
這些二部份聚合反應可同時地或各自獨立地發生，依所選擇之特殊偶氮或過氧化物引發劑、及引發劑分解與生成引發自由基物料之溫度而定。使用適當選擇的引發劑，陽離子性可聚合物料之陽離子性聚合反應及乙烯基單體之自由基聚合反應皆可在低於100℃下發生。These two-part polymerizations can occur simultaneously or independently, depending on the particular azo or peroxide initiator selected, and the temperature at which the initiator decomposes and forms the initiating free radical material. Both the cationic polymerization of the cationic polymerizable material and the free radical polymerization of the vinyl monomer can occur at less than 100 ° C using an appropriately selected initiator.
於其他實例中，一種或多種陽離子性可聚合單體之聚合反應，其中聚合反應混合物另外包括一種鎓鹽、一種偶氮或過氧化物引發劑、及一種富含電子的乙烯基樹脂，可於下者之存在下進行：一種或多種其他的乙烯基單體，如：丙烯酸酯、甲基丙烯酸酯、馬來醯亞胺、馬來酸酯、或富馬酸酯、或一種這些的混合物(亦即：非典型地被稱為富含電子之乙烯基單體)。於此聚合反應中，偶氮或過氧化物引發劑會引發這些其他乙烯基單體之自由基聚合反應。陽離子性可聚合物料之陽離子性聚合反應及這些乙烯基單體之自由基聚合反應可同時地或各自獨立地發生，依所選擇之特殊偶氮或過氧化物引發劑、及引發劑分解與生成引發自由基物料之溫度而定，於任何案例中，可選擇引發劑以使固化於100℃或更低溫下發生。In other examples, the polymerization of one or more cationically polymerizable monomers, wherein the polymerization mixture additionally comprises a phosphonium salt, an azo or peroxide initiator, and an electron-rich vinyl resin. In the presence of one or more other vinyl monomers, such as acrylates, methacrylates, maleimides, maleates, or fumarates, or a mixture of these ( That is: atypically referred to as an electron-rich vinyl monomer). In this polymerization, an azo or peroxide initiator initiates the free radical polymerization of these other vinyl monomers. The cationic polymerization of the cationic polymerizable material and the radical polymerization of these vinyl monomers can occur simultaneously or independently, depending on the particular azo or peroxide initiator selected, and the decomposition and generation of the initiator. Depending on the temperature at which the free radical material is initiated, in any case, an initiator may be selected to allow curing to occur at 100 ° C or lower.
於其他實例中，一種或多種陽離子性可聚合單體之聚合反應，其中聚合反應混合物另外包括一種鎓鹽、一種偶氮或過氧化物引發劑、及一種富含電子的乙烯基樹脂，可於下者之存在下進行：低於化學計量的一種或多種其他的乙烯基單體，如：丙烯酸酯、甲基丙烯酸酯、馬來醯亞胺、馬來酸酯、或富馬酸酯、或一種這些的混合物。於此實例中，陽離子性聚合反應之引發經由一種陽離子性大引發劑，其產生係藉自由基聚合反應，隨後經氧化反應，如下列反應圖解所顯示。此二聚合反應程序為相互依賴，欲產生大引發劑時，富含電子的乙烯基樹脂相較於其他乙烯基樹脂，應存在些微的過量。此實例於二部份的系統中運作良好，其中一部份包含陽離子性可聚合單體，及第二部份包含富含電子的乙烯基樹脂與其他的乙烯基樹脂。In other examples, the polymerization of one or more cationically polymerizable monomers, wherein the polymerization mixture additionally comprises a phosphonium salt, an azo or peroxide initiator, and an electron-rich vinyl resin. Conducted in the presence of one or more other vinyl monomers, such as acrylates, methacrylates, maleimides, maleates, or fumarates, or A mixture of these. In this example, the initiation of the cationic polymerization is via a cationic macroinitiator which is produced by free radical polymerization followed by an oxidation reaction as shown in the following reaction scheme. The two polymerization procedures are interdependent. When a large initiator is to be produced, the electron-rich vinyl resin should be slightly excessive compared to other vinyl resins. This example works well in two parts of the system, one part comprising a cationic polymerizable monomer and the second part comprising an electron-rich vinyl resin and other vinyl resins.
適合的丙烯酸酯及甲基丙烯酸酯樹脂包括那些具有一般結構Suitable acrylate and methacrylate resins include those having a general structure
者，其中n為1至6，R1 為-H或-CH3 ，及X2 為一芳族或脂肪族基團。X2 實體之實例包括：聚(丁二烯)、聚(碳酸酯)、聚(胺基甲酸酯)、聚(醚)、聚(酯)、單純的碳氫化合物、及單純的碳氫化合物包含下列官能者，如：羰基、羧基、醯胺、胺基甲酸酯、脲、酯、或醚。已有商品之物料包括：(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二烷酯、(甲基)丙烯酸烷基酯、(甲基)丙烯酸十三烷酯、(甲基)丙烯酸正硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸異冰片酯、二(甲基)丙烯酸1,4-丁二醇酯、二(甲基)丙烯酸1,6-己二醇酯、二(甲基)丙烯酸1,9-壬二醇酯、(甲基)丙烯酸過氟辛基乙酯、二(甲基)丙烯酸1,10-癸二醇酯、壬基苯酚聚(甲基)丙烯酸丙氧酯、及聚丙烯酸戊氧基四氫糠酯，可得自Kyoeisha化學公司、聚丁二烯胺基甲酸酯二甲基丙烯酸酯(CN302，NTX6513)、及聚二甲基丙烯酸丁二烯酯(CN301，NTX6039、PRO6270)，可得自Sartomer公司、聚碳酸酯胺基甲酸酯二丙烯酸酯(ARTRESIN UN9200A)，可得自Negami化學工業公司、丙烯酸化之脂肪族胺基甲酸酯寡聚物(EBECRYL 230，264，265，270，284，4830，4833，4834，4835，4866，4881，4883，8402，8800-20R，8803，8804)，可得自Radcure Specialities公司、聚酯丙烯酸酯寡聚物(EBECRYL 657，770，810，830，1657，1810，1830)，可得自Radcure Specialities公司、及環氧丙烯酸酯樹脂(CN104，111，112，115，116，117，118，119，120，124，136)，可得自Sartomer公司。於一實例中，丙烯酸酯樹脂係選自群組包括：丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯酸十二烷酯、(甲基)丙烯酸十二烷酯、具有丙烯酸酯官能的聚(丁二烯)、及具有甲基丙烯酸酯官能的聚(丁二烯)。Wherein n is from 1 to 6, R 1 is -H or -CH 3 , and X 2 is an aromatic or aliphatic group. Examples of X 2 entities include: poly(butadiene), poly(carbonate), poly(urethane), poly(ether), poly(ester), simple hydrocarbon, and pure hydrocarbon The compound contains the following functional groups such as a carbonyl group, a carboxyl group, a guanamine, a urethane, a urea, an ester, or an ether. Commercially available materials include: butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid N-dodecyl ester, alkyl (meth)acrylate, tridecyl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Hydroquinone ester, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, di(meth)acrylic acid 1,6 - hexanediol ester, 1,9-nonanediol di(meth)acrylate, perfluorooctylethyl (meth)acrylate, 1,10-decanediol di(meth)acrylate, fluorenyl Phenol poly(meth)acrylic acid propoxylate, and polyacrylic acid pentyl tetrahydrofurfuryl ester, available from Kyoeisha Chemical Co., polybutadienyl methacrylate dimethacrylate (CN302, NTX6513), and Polybutylene dimethacrylate (CN301, NTX6039, PRO6270) available from Sartomer, polycarbonate urethane diacrylate (ARTRESIN UN9200A), available from Negami Chemical Industries, Inc., acrylated Aliphatic Carbamate oligomers (EBECRYL 230, 264, 265, 270, 284, 4830, 4833, 4834, 4835, 4866, 4881, 4883, 8402, 8800-20R, 8803, 8804), available from Radcure Specialities , Polyester acrylate oligomers (EBECRYL 657, 770, 810, 830, 1657, 1810, 1830) available from Radcure Specialities, Inc., and epoxy acrylate resins (CN104, 111, 112, 115, 116, 117) , 118, 119, 120, 124, 136), available from Sartomer Corporation. In one example, the acrylate resin is selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, dodecyl acrylate, dodecyl (meth) acrylate, poly acrylate-functional poly( Butadiene), and poly(butadiene) having methacrylate functionality.
適合的馬來醯亞胺樹脂包括那些具有下列一般結構者：Suitable maleimide resins include those having the following general structure:
其中n為1至3，及X1 為一脂肪族或芳族基團，X1 實體之實例包括：聚(丁二烯)、聚(碳酸酯)、聚(胺基甲酸酯)、聚(醚)、聚(酯)、單純的碳氫化合物、及單純的碳氫化合物包含下列官能者，如：羰基、羧基、醯胺、胺基甲酸酯、脲、酯、或醚，這些類型之樹脂已有商品，可得自例如：Dainippon印墨及化學品公司。Wherein n is from 1 to 3, and X 1 is an aliphatic or aromatic group, and examples of the X 1 entity include: poly(butadiene), poly(carbonate), poly(urethane), poly (ether), poly(ester), simple hydrocarbons, and simple hydrocarbons containing the following functional groups such as carbonyl, carboxyl, decylamine, urethane, urea, ester, or ether. Resins are commercially available from, for example, Dainippon Ink and Chemicals.
其他適合的馬來醯亞胺樹脂包括，但非限制性：固態的芳族二馬來醯亞胺(BMI)樹脂，特別是那些具有下列結構者：Other suitable maleated imine resins include, but are not limited to, solid aromatic dimaleimide (BMI) resins, particularly those having the following structure:
其中Q為一芳族基團。適合的具有芳族架橋基團之二馬來醯亞胺樹脂已有商品，可得自例如：Sartomer公司(美國)或HOS-技術公司(奧地利)。Wherein Q is an aromatic group. Suitable dimaleimide resins having aromatic bridging groups are commercially available, for example, from Sartomer (USA) or HOS-Technologies (Austria).
其他適合的馬來醯亞胺樹脂包括：Other suitable maleic imine resins include:
其中C36 代表一包含36個碳原子之線性或分支的碳氫化合物鏈(具有或不具有環狀的部份);Wherein C 36 represents a linear or branched hydrocarbon chain of 36 carbon atoms (with or without a cyclic moiety);
適合的富馬酸酯及馬來酸酯包括如：馬來酸二辛酯、馬來酸二丁酯、富馬酸二辛酯、及富馬酸二丁酯。Suitable fumarates and maleates include, for example, dioctyl maleate, dibutyl maleate, dioctyl fumarate, and dibutyl fumarate.
於所有的實例中，陽離子性可聚合組成物可另外包括一種其他單官能及/或多官能的陽離子性可聚合樹脂，及/或一種反應性陽離子性可聚合稀釋劑。In all of the examples, the cationically polymerizable composition may additionally comprise one other monofunctional and/or polyfunctional cationic polymerizable resin, and/or one reactive cationic polymerizable diluent.
於所有的實例中，陽離子性可聚合組成物可另外包括一種填料，適合的非傳導性填料之實例包括：氧化鋁、氫氧化鋁、二氧化矽、熔凝的二氧化矽、煅製的二氧化矽、蛭石、雲母、矽礦石、碳酸鈣、二氧化鈦、砂、玻璃、硫酸鋇、鋯、碳黑、有機填料、及經鹵化的乙烯聚合物，如：四氟乙烯、三氟乙烯、氟亞乙烯、氟乙烯、氯亞乙烯、及氯乙烯。適合的傳導性填料之實例包括：碳黑、石墨、金、銀、銅、鉑、鈀、鎳、鋁、碳化矽、氮化硼、鑽石、及氧化鋁。In all of the examples, the cationically polymerizable composition may additionally include a filler, and examples of suitable non-conductive fillers include: alumina, aluminum hydroxide, cerium oxide, fused cerium oxide, and fumed two. Cerium oxide, vermiculite, mica, strontium ore, calcium carbonate, titanium dioxide, sand, glass, barium sulfate, zirconium, carbon black, organic fillers, and halogenated ethylene polymers such as tetrafluoroethylene, trifluoroethylene, fluorine Ethylene, vinyl fluoride, vinylidene chloride, and vinyl chloride. Examples of suitable conductive fillers include: carbon black, graphite, gold, silver, copper, platinum, palladium, nickel, aluminum, tantalum carbide, boron nitride, diamond, and alumina.
填料細粒可為範圍自奈米尺寸至數毫米之任何適當尺寸，適當的填料尺寸可由施行者決定，但是通常於20奈米至100微米之範圍內，對於任何特殊終端用途，此尺寸之選擇在精於此方面技藝者之專業內。填料可存在任何有效量，典型地，有效量為組成物總量之10至90重量%。一種組成物中可使用多於一種填料類型，填料可為經或未經表面處理者。The filler fines can be of any suitable size ranging from nanometer size to a few millimeters, and suitable filler sizes can be determined by the practitioner, but typically range from 20 nanometers to 100 micrometers, for any particular end use, the choice of this size In the profession of the craftsman. The filler may be present in any effective amount, typically an effective amount of from 10 to 90% by weight of the total composition. More than one type of filler can be used in one composition, and the filler can be either with or without surface treatment.
其他的物料，如：增黏劑、染料、顏料、及流變改質劑，可依所欲添加藉以修飾最終的性能，這些物料及所需的數量在精於此方面技藝者之專業內。Other materials, such as tackifiers, dyes, pigments, and rheology modifiers, can be added as needed to modify the final properties, and the materials and quantities required are within the skill of those skilled in the art.
於那些案例中，其中陽離子性可聚合單體非環氧基時，藉添加一種環氧樹脂或一種自由基抑制劑，組成物之使用壽命可被延長。作為一種增加使用壽命之添加劑時，環氧樹脂之存在量為樹脂總量之1至90重量%，適合的環氧樹脂為那些先前揭示於本說明書中者。於那些案例中，其中藉使用一種自由基抑制劑以延長使用壽命者，自由基抑制劑之存在量為10ppm至2000ppm，適合的自由基抑制劑包括例如：氫醌、甲基氫醌、三級丁基兒茶酚、苯噻嗪、及NPAL，具有下列結構：In those cases where the cationically polymerizable monomer is a non-epoxy group, the useful life of the composition can be extended by the addition of an epoxy resin or a free radical inhibitor. As an additive for increasing the service life, the epoxy resin is present in an amount of from 1 to 90% by weight based on the total amount of the resin, and suitable epoxy resins are those previously disclosed in the present specification. In those cases, where a free radical inhibitor is used to extend the service life, the free radical inhibitor is present in an amount from 10 ppm to 2000 ppm. Suitable free radical inhibitors include, for example, hydroquinone, methylhydroquinone, tertiary Butyl catechol, phenothiazine, and NPAL have the following structure:
實例1。富含電子的乙烯基化合物對於陽離子性可聚合組成物之固化溫度之影響Example 1. Effect of electron-rich vinyl compounds on the curing temperature of cationic polymerizable compositions
製備一種陽離子性可聚合組成物作為控制樣品，其包含：具有前示於本說明書中結構之氧雜環丁烷(OXT-221)、一種錪鹽(RHODORSIL-2074)、及一種偶氮引發劑(VAZO-52)。製備其他的聚合組成物，其包含：控制組成物、及催化數量的乙烯基醚I、乙烯基醚II、或一種苯乙烯化合物，其具有下示的結構。將組成物樣品固化，並記錄其最高點(peak)溫度(T最高點 )，其他相同組成物之樣品被儲存於室溫下，記錄結膠時間藉以測定使用壽命。A cationic polymerizable composition was prepared as a control sample comprising: oxetane (OXT-221) having the structure shown in the present specification, a sulfonium salt (RHODORSIL-2074), and an azo initiator (VAZO-52). Other polymeric compositions are prepared comprising: a controlled composition, and a catalytic amount of vinyl ether I, vinyl ether II, or a styrene compound having the structure shown below. The composition sample was cured, and its peak temperature (T highest point ) was recorded. Samples of other identical compositions were stored at room temperature, and the gelation time was recorded to determine the service life.
組成物之配方及結果記錄於表1中，其結果顯示：於一種錪鹽及一種偶氮引發劑之存在下，添加乙烯基醚至陽離子性可聚合之氧雜環丁烷可降低組成物之固化溫度(比較項目1控制樣品與項目2)。增加錪鹽之量自1莫耳%至2莫耳%(項目3)可增加結膠時間，不會影響固化溫度。只使用乙烯基醚時具有最低的固化溫度，但具有短的結膠時間(項目5)。二官能的苯乙烯類化合物，另一富含電子的乙烯基化合物，類似乙烯基醚般可降低固化溫度(項目6)。將等溫差示掃瞄量熱法施行於二個樣品：於項目2中所示之樣品在85℃下固化約45秒，具有一最高點溫度為76℃，及於項目5中所示之樣品，在85℃下固化約30秒，具有一最高點溫度為65℃。The composition and results of the composition are reported in Table 1. The results show that the addition of a vinyl ether to the cationically polymerizable oxetane in the presence of an onium salt and an azo initiator reduces the composition. Curing temperature (compare item 1 control sample with item 2). Increasing the amount of barium salt from 1 mole % to 2 mole % (item 3) can increase the gelation time without affecting the curing temperature. It has the lowest cure temperature when only vinyl ether is used, but has a short gel time (item 5). A difunctional styrenic compound, another electron-rich vinyl compound, lowers the curing temperature like a vinyl ether (Item 6). The isothermal differential scanning calorimetry was applied to two samples: the sample shown in item 2 was cured at 85 ° C for about 45 seconds, with a maximum point temperature of 76 ° C, and the sample shown in item 5. Cured at 85 ° C for about 30 seconds with a maximum point temperature of 65 ° C.
實例2。環氧樹脂或自由基抑制劑對於陽離子性可聚合組成物之使用壽命之影響Example 2. Effect of Epoxy Resin or Free Radical Inhibitor on the Service Life of Cationic Polymerizable Compositions
為了改良組成物之使用壽命，添加環氧樹脂或一種自由基抑制劑至配方。製備一種控制樣品之陽離子性可聚合組成物，其包含：具有前示結構之氧雜環丁烷(OXT-221)、一種錪鹽(RHODORSIL)、一種偶氮引發劑(VAZO-52)、及乙烯基醚I或II，其具有前示的結構，將環氧樹脂或甲基氫酉昆(MeHQ)加至其中作為一種自由基抑制劑。所使用的環氧樹脂為一種環脂肪族環氧樹脂，得自Dow化學品公司，以商品名CYRACURE UVR6128販售，或為環氧樹脂，得自Hexion化學品公司，以商品名EPON 834販售。In order to improve the service life of the composition, an epoxy resin or a free radical inhibitor is added to the formulation. Preparing a cationic polymerizable composition for controlling a sample comprising: oxetane (OXT-221) having the structure shown above, an onium salt (RHODORSIL), an azo initiator (VAZO-52), and Vinyl ether I or II having the structure shown above, to which an epoxy resin or methylhydroquinone (MeHQ) is added as a radical inhibitor. The epoxy resin used is a cycloaliphatic epoxy resin available from Dow Chemical Company under the trade name CYRACURE UVR 6128 or epoxy resin, available from Hexion Chemical Company under the trade name EPON 834. .
組成物組份及結果記錄於表2中，其顯示：添加環氧樹脂至組成物可穩定配方及改善結膠時間(項目2與3)。無氧雜環丁烷及含有催化數量乙烯基醚之環氧樹脂系統，顯示一最高點溫度為95℃並具有良好的使用壽命(項目4)。自乙烯基醚I改變至乙烯基醚II會些微地增加結膠時間(項目5)，顯示使用壽命可能依所使用之乙烯基醚類型而定。使用自由基抑制劑可改善配方之使用壽命，雖然伴隨了最高點溫度之增加，其對應於所使用抑制劑之數量(項目6，7，8，9)。The composition components and results are reported in Table 2, which shows that the addition of epoxy resin to the composition stabilizes the formulation and improves the gel time (items 2 and 3). Anoxetane and an epoxy resin system containing a catalytic amount of vinyl ether showed a maximum temperature of 95 ° C and a good service life (Item 4). The change from vinyl ether I to vinyl ether II slightly increased the gel time (item 5), indicating that the service life may depend on the type of vinyl ether used. The use of free radical inhibitors improves the useful life of the formulation, although it is accompanied by an increase in the highest point temperature, which corresponds to the amount of inhibitor used (items 6, 7, 8, 9).
實例3。過氧化物引發劑對於陽離子性可聚合組成物之固化溫度之影響Example 3. Effect of peroxide initiator on curing temperature of cationic polymerizable composition
偶氮引發劑於分解時可釋出氮氣，此於需要低除氣的應用中為不欲，成功地以過氧化物取代偶氮引發劑乃依所選擇的過氧化物而定。依先前實例般製備陽離子性可聚合組成物，惟以苯醯過氧化物及一種以商品名TRIGONOX-23販售之過氧化物商品取代偶氮引發劑，組成物之配方及其結果記錄於表3中，數據顯示：作為一種引發劑，(TRIGONOX)過氧化物較苯醯過氧化物更為有效。The azo initiator releases nitrogen upon decomposition, which is undesirable in applications requiring low outgassing, and the successful replacement of the azo initiator with a peroxide depends on the peroxide selected. The cationic polymerizable composition was prepared as in the previous examples except that the azo initiator was replaced by a phenylhydrazine peroxide and a peroxide commercial sold under the trade name TRIGONOX-23. The composition of the composition and the results thereof are recorded in the table. 3, the data shows: as an initiator, (TRIGONOX) peroxide is more effective than phenylhydrazine peroxide.
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