CN1252137A - 用于固化环氧/多元醇树脂组合物的三元光引发剂体系 - Google Patents
用于固化环氧/多元醇树脂组合物的三元光引发剂体系 Download PDFInfo
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- CN1252137A CN1252137A CN98804068A CN98804068A CN1252137A CN 1252137 A CN1252137 A CN 1252137A CN 98804068 A CN98804068 A CN 98804068A CN 98804068 A CN98804068 A CN 98804068A CN 1252137 A CN1252137 A CN 1252137A
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- alkyl
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- aryl
- iodine
- acid
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical group C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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- 235000012222 talc Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract
公开了一种含环氧树脂和光引发剂体系的可光致固化、可加成聚合的组合物,它包括:(a)环氧树脂;(b)含羟基材料;(c)光引发剂体系,该光引发剂体系包括:(i)碘鎓盐;(ii)可见光敏化剂;(iii)电子给体化合物,相对于2.9×10-5mol/g六氟锑酸二苯基碘鎓和1.5×10-5mol/g樟脑醌的2-丁酮标准溶液,光引发剂体系的光引发电位至少约100mV。该组合物可用可见光辐照固化并适用于各种用途,包括牙用粘合剂和复合物。
Description
发明的领域
本发明涉及可光致固化、可加成聚合的含环氧树脂、含羟基材料和任选的含可自由基固化材料的组合物。该组合物含有在可见光谱的光化辐照下会活化的三元光引发剂体系。本发明还涉及使用该三元光引发剂体系固化可加成聚合的组合物的方法。
发明的背景
已知用各种阳离子引发剂体系可固化含环氧的化合物。Smith在美国专利4,256,828中公开了含环氧化物、具有羟基官能度的有机化合物和光敏的含卤配合物离子的芳香锍或碘鎓盐的可光致聚合的组合物。Hayase等的美国专利4,835,193描述了含环氧树脂和杂多酸芳香锍盐光致固化剂的可光致聚合的环氧树脂化合物。在WO 95/14716中,Neckers等描述了含有可阳离子聚合的化合物、呫吨染料或荧光酮染料、氢给体和鎓盐的可光硬化的组合物。Palazzotto等的美国专利5,545,676描述了可自由基聚合材料的加成聚合。该专利所述的光引发剂体系包括芳基碘鎓盐、敏化剂以及氧化电位小于或等于对二甲氧基苯的氧化电位的电子给体。
公布的PCT申请No.WO 96/13538描述了用于固化环氧化合物的体系,它使用含芳族碘鎓盐和敏化剂并将其置于可见光中进行固化。该申请的比较例34描述了在环氧/多元醇树脂体系中使用Palazzotto等的美国专利5,545,676所述的引发剂体系中的一种。将N,N-二甲基苄胺用作电子给体。该实验的结果表明使用这种胺电子给体延缓了树脂体系的固化。
阳离子固化树脂的供应商明确指出不要在光引发的环氧树脂中使用有机胺。这种警示的一个例子可参见Union Carbide关于Cyracure脂环环氧化物的文献中。
发明的概述
我们发现并且本发明提供一种含环氧树脂、羟基官能的化合物和光引发剂体系的可光致聚合的组合物,所述光引发剂体系含有碘鎓盐、可见光敏化剂和电子给体化合物,其中所述光引发剂体系的光引发电位大于或等于3-二甲基氨基苯甲酸在2.9×10-5摩尔/克六氟锑酸二苯基碘鎓和1.5×10-5摩尔/克樟脑醌的2-丁酮标准溶液中的光引发电位。一般来说,按2.9×10-5摩尔/克六氟锑酸二苯基碘鎓和1.5×10-5摩尔/克樟脑醌的2-丁酮标准溶液计,3-二甲基氨基苯甲酸表现出至少约115mV的光引发电位。
用波长约400-1000nm的光线辐照这些组合物可将其固化,本发明提供一种光致加成聚合的方法,它包括用波长约400-1000nm的光线将可光致聚合的组合物辐照至该组合物胶凝或硬化的步骤,所述组合物含有环氧树脂、羟基官能的材料和光引发剂体系,所述光引发剂体系含有碘鎓盐、可见光敏化剂和电子给体化合物,按2.9×10-5摩尔/克六氟锑酸二苯基碘鎓和1.5×10-5摩尔/克樟脑醌的2-丁酮标准溶液计,所述光引发剂体系的光引发电位至少约100mV。
在本申请中,术语“多元醇”和“含羟基的材料”可互换使用。
在室温和标准压力条件下本发明引发剂体系能有效地进行阳离子聚合。另外,在适当的条件下,该引发剂体系能引发阳离子和自由基聚合。这种性能使之适用于各种可光致聚合的组合物,包括含丙烯酸酯或甲基丙烯酸酯官能度的体系。使用本发明引发剂体系能显著缩短将含环氧或羟基的树脂组合物固化成不发粘的凝胶或固体所需的时间。这种胶凝时间的缩短可使树脂组合物硬化成不发粘的凝胶或固体所需的时间减少约30-70%。
发明的详细描述
本发明可光致聚合组合物对整个可见区光谱是敏感的,无需向该体系加入大量热量就可引发固化,尽管可以存在附带(incidental)量的热量。在本申请中“可见光”一词指波长约为400-1000纳米(nm)的光线。将组合物置于波长在所述光谱区范围内的光化辐照源下进行辐照,该组合物发生光致聚合。
适用于本发明组合物的可阳离子聚合的环氧树脂是具有可开环聚合的环氧乙烷环(即如下结构式的基团)的有机化合物:
这种广义地称为环氧化物的材料包括环氧化合物单体和聚合型的环氧化物,它可以是脂族的、脂环族的、芳族的或杂环的。这些材料每个分子一般平均至少具有一个可聚合的环氧基团,较好至少具有约1.5个环氧基团,最好至少具有约2个环氧基团。聚合的环氧化物包括具有环氧端基的线型聚合物(如聚氧化烯基二醇的二缩水甘油醚)、具有环氧乙烷单元主链的聚合物(如聚丁二烯多环氧化物)和具有环氧侧基的聚合物(如甲基丙烯酸缩水甘油酯聚合物或共聚物)。环氧化物可以是纯的化合物或者可以是每个分子含一个、两个或多个环氧基团的化合物的混合物。每个分子中环氧基团的“平均”数是将含环氧基团材料中环氧基团的总数除以所有含环氧的分子的总数得到的。
这些含环氧的材料可以是低分子量单体材料至高分子量聚合物的不同材料,其主链和取代基的性能可有很大的不同。例如,主链可具有不同的类型,主链上的取代基可以是基本不影响室温阳离子固化的任何基团。说明性的适用的取代基包括卤素、酯基团、醚基团、磺酸酯基团、硅氧烷基团、硝基、磷酸酯基等。含环氧的材料的分子量可约为58-100,000或更高。
合适的含环氧的材料包括那些含环氧环己烷基团的材料,如环氧环己烷羧酸酯,通常为3,4-环氧环己烷羧酸3,4-环氧环己基甲基酯,3,4-环氧-2-甲基环己烷羧酸3,4-环氧-2-甲基环己基甲基酯和己二酸二(3,4-环氧-6-甲基环己基甲酯)。对于具有这种性能的适用的环氧化物的详细情况,可参见美国专利3,117,099,该专利在此引为参考。
适用于本发明组合物的另外一些含环氧基团的材料包括下式缩水甘油醚单体:其中R’是烷基或芳基,n是1-6的整数。其例子有多元酚的缩水甘油醚,它是由多元酚与过量的氯代醇(例如表氯醇)制得的,如2,2-二(2,3-环氧丙氧基苯酚)丙烷的二缩水甘油醚。这种类型的环氧化物的其它例子描述在美国专利3,018,262(在此引为参考)和Lee和Neville的“环氧树脂手册”,McGraw-Hill Book Co.,New York(1967)中。
许多市售的环氧树脂适用于本发明。具体地说,能容易地购得的环氧化物包括环氧十八烷、表氯醇、氧化苯乙烯、氧化乙烯基环己烯、缩水甘油、甲基丙烯酸缩水甘油酯、双酚A的二环氧甘油醚(如购自Shell Chemical Co.的Epon 828、Epon 825、Epon 1004和Epon 1010,购自Dow Chemical Co.的DER-331、DER-332和DER-334)、二氧化乙烯基环己烯(如购自Union Carbide Corp.的ERL-4206)、3,4-环氧环己烯羧酸3,4-环氧环己基甲基酯(如购自Union CarbideCorp的ERL-4221或CYRACURE UVR 6110或UVR 6105)、3,4-环氧-6-甲基环己烯羧酸3,4-环氧-6-甲基环己基甲基酯(如购自Union Carbide Corp的ERL-4201)、己二酸二(3,4-环氧-6-甲基环己基甲酯)(如购自Union Carbide Corp.的ERL-4289)、二(2,3-环氧环戊基)醚(如购自Union Carbide Corp.的ERL-0400)、聚丙二醇改性的脂族环氧树脂(如购自Union Carbide Corp.的ERL-4050和ERL-4052)、二氧化二聚戊烯(如购自Union Carbide Corp.的ERL-4269)、环氧化的聚丁二烯(如购自FMC Corp.的Oxiron 2001)、含环氧官能度的硅氧烷树脂,阻燃环氧树脂(如购自Dow Chemical Co.的溴化的双酚型环氧树脂)、酚甲醛线型酚醛清漆的1,4-丁二醇二环氧甘油醚(如购自Dow Chemical Co.的DEN-431和DEN-438)、和间苯二酚二缩水甘油醚(如购自Koppers Company,Inc.的Kopoxite)、己二酸二(3,4-环氧环己酯)(如购自Union Carbide Corp.的ERL-4299或UVR-6128)、2-(3,4-环氧环己基-5,5-螺-3,4-环氧)环己烷间二噁烷(如购自Union Carbide Corp.的ERL-4234)、一氧化乙烯基环己烯1,2-环氧十六烷(如购自Union Carbide Corp.的UVR-6216)、烷基缩水甘油醚,如C8-C10烷基缩水甘油醚(如购自Shell ChemicalCo.的HELOXY Modifier 7),C12-C14烷基缩水甘油醚(如购自Shell Chemical Co.的HELOXY Modifier 8),丁基缩水甘油醚(如购自Shell Chemical Co.的HELOXYModifier 61)、羟甲苯基缩水甘油醚(如购自Shell Chemical Co.的HELOXYModifier 62),对叔丁基苯基缩水甘油醚(如购自Shell Chemical Co.的HELOXYModifier 65),多官能缩水甘油醚,如1,4-丁二醇的二缩水甘油醚(如购自ShellChemical Co.的HELOXY Modifier 67),新戊二醇的二缩水甘油醚(如购自ShellChemical Co.的HELOXY Modifier 68),环己烷二甲醇的二缩水甘油醚(如购自Shell Chemical Co.的HELOXY Modifier 107),三羟甲基乙烷三缩水甘油醚(如购自Shell Chemical Co.的HELOXY Modifier 44),三羟甲基丙烷三缩水甘油醚(如购自Shell Chemical Co.的HELOXY Modifier 48),脂族多元醇的多缩水甘油醚(如购自Shell Chemical Co.的HELOXY Modifier 84),二环氧化聚二醇(如购自Shell Chemical Co.的HELOXY Modifier 32),环氧化双酚F(如购自Ciba-Geigy Corp.的EPN-1138或GY-281),9,9-二[4-(2,3-环氧丙氧烷)-苯基]芴酮(如购自Shell Chemical Co.的Epon 1079)。
还有一类环氧树脂含有丙烯酸酯或缩水甘油(如丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯)与一种或多种可共聚的乙烯基化合物的共聚物。这种共聚物的例子有1∶1苯乙烯-甲基丙烯酸缩水甘油酯、1∶1甲基丙烯酸甲酯-丙烯酸缩水甘油酯和62.5∶24∶13.5甲基丙烯酸甲酯-丙烯酸乙酯-甲基丙烯酸缩水甘油酯。
其它适用的环氧树脂是已知的,并含有如下的环氧化物,如表氯醇,环氧烷(如1,2-环氧丙烷、环氧苯乙烯),氧化烯(如氧化丁二烯),缩水甘油酯(如缩水甘油酸乙酯)。
环氧树脂的聚合物可任选地含有基本不会影响室温阳离子固化的其它官能度。
本发明还可使用各种含环氧材料的掺混物。这种掺混物的例子包括两种或多种重均分子量分布(如低分子量(低于200),中等分子量(约200-10,000)和较高分子量(高于约10,000))的含环氧的化合物。或者或另外,环氧树脂可含有不同化学性能(如脂族和芳族)或不同官能度(如极性或非极性)的含环氧材料的掺混物。如有必要,还可加入其它可阳离子聚合的聚合物,如乙烯基醚等。
适用于本发明的含羟基材料可以是羟基官能度至少为1,较好至少为2的任何有机材料。
较好的含羟基材料含有两个或多个伯或仲(即羟基直接与非芳香碳原子相连)脂族羟基。羟基可位于聚合物或共聚物的端部,或可以侧接在其上。含羟基的有机材料的分子量可由很低(如32)至很高(如一百万或更多)。合适的含羟基材料可具有低的分子量(即约32-200)、中等的分子量(即约200-10,000)或高的分子量(即高于约10,000)。在本文中,所有的分子量均为重均分子量。
含羟基的材料可含有基本不影响室温阳离子固化的其它官能度。因此,含羟基材料可具有非芳香性或可含有芳香官能度。含羟基材料可任选地在分子主链中含有杂原子,如氮、氧、硫等,只要最终含羟基材料基本不影响室温阳离子固化即可。含羟基材料可选自,例如天然的或合成的纤维素材料。当然,含羟基材料还应基本不含热不稳定的或光不稳定的材料,也就是说,该材料在所需的可光致聚合的组合物的固化过程中会遇到的低于约100℃的温度或在光化辐照光的存在下不会分解或释放出挥发性组分。
羟基官能度为1的合适的含羟基材料的代表性例子包括醇、聚氧化烯二醇的单烷基醚、烷二醇的单烷基醚和本领域已知的其它化合物。
适用的单体多羟基有机材料的代表性例子包括烷二醇(如1,2-乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇、2-乙基-1,6-己二醇、二(羟甲基)环己烷、1,18-二羟基十八烷、3-氯-1,2-丙二醇)、多羟基烷烃(如丙三醇、三羟甲基乙烷、季戊四醇、山梨醇)以及其它多羟基化合物,如N,N-二(羟乙基)苯甲酰胺、2-丁炔-1,4-二醇、4,4-二(羟甲基)二苯基砜、蓖麻油等。
适用的含羟基的聚合材料的代表性例子包括聚氧乙烯乙二醇和聚氧丙烯二醇,尤其是聚氧乙烯和聚氧丙烯二醇和三醇,其分子量约为200-10,000,相当于二元醇的羟基当量为100-5000,或三元醇的羟基当量为70-3300;聚亚丁基醚二醇如各种分子量的聚四氢呋喃(或“聚THF”);丙烯酸和甲基丙烯酸羟丙酯和羟乙酯与其它可自由基聚合的单体(如丙烯酸酯、卤代乙烯或苯乙烯)的共聚物;通过乙酸乙烯酯共聚物氢化或部分氢化形成的含侧接羟基的共聚物,含侧接的羟基的聚乙烯基乙缩醛树脂;改性的纤维素聚合物,如羟乙基化的和羟丙基化的纤维素;羟基封端的聚酯;羟基封端的聚内酯,尤其是聚己内酯;含氟聚氧化乙烯或聚氧化丙烯二醇;和羟基封端的聚二烯。
适用的市售含羟基材料包括“TERATHANE”系列聚亚丁基醚二醇,如TERATHANE 650、1000、2000和2900(购自du Pont de Nemours,Wilmington,DE),具有仲羟基基团的“PEP”系列聚氧化烯四醇,如购自Monsanto ChemicalComapny,St.Louis,MO的PEP 450、550和650;“BUTVAR”系列聚乙烯基缩醛树脂,如购自Monsanto Chemical Comapny,St.Louis,MO的BUTVAR B-72A、B-73、B-76、B-90和B-98;和购自Monsanto Chemical Company的“FORMVAR”系列树脂,如7/70、12/85、7/95S、7/95E、15/95S和15/95E;“TONE”系列聚己内酯多醇,如购自Union Carbide的“TONE”0200、0210、0230、0240、0300和0301;购自Rohm and Haas,Philadelphia,PA的“PARAPLEX U-148”脂族聚酯二醇;“MULTRON”R系列饱和聚酯多醇,如购自Mobay Chemical Co.的MULTRON R-2、R-12A、R-16、R-18、R-38、R-68和R-74等“MULTRON”R系列;当量约为100的“KLUCEL E”羟丙基化的纤维素(购自Hercules Inc.);羟基当量约为400的“Alcohol SolubleButyrate”乙酸丁酸纤维素酯(购自Eastman Kodak Co.,Rochester,NY);聚醚多醇,如聚丙二醇二醇(如购自ARCO Chemical Co.的ARCOL PPG-425、ARCOLPPG-725、ARCOL PPG-1025、ARCOL PPG2025、ARCOL PPG-3025、ARCOLPPG-4025);聚丙二醇三醇(如购自ARCO Chemical Co.的ARCOL LT-28、ARCOL LHT-42、ARCOL LHT-112、ARCOL LHT-240、ARCOL LG-56、ARCOL LG-168、ARCOL LG-650);环氧乙烷封端的聚氧化丙烯三醇或二醇(如购自ARCO Chemical Co.的ARCOL 11-27、ARCOL 11-34、ARCOL E-351、ARCOL E-452、ARCOL E-785、ARCOL E-786);环氧化的双酚A;1,2-环氧丙烷或环氧乙烷基聚醇(如购自Dow Chemical Co.的“VORANOL”聚醚聚醇)。
在本发明组合物中含羟基的有机材料的用量可在很大的范围内变化,取决于各种因素,例如含羟基材料与环氧化物的相容性,含羟基材料的当量和官能度,在最终固化的组合物中所需的物理性能,所需的光致固化速度等。
各种含羟基材料的掺混物特别适用于本发明。这种掺混物的例子包括两种或多种分子量分布(如低分子量(低于200),中等分子量(约200-10,000)和较高分子量(高于约10,000))的含羟基的化合物。或者或另外,含羟基材料可含有不同化学性能(如脂族和芳族)或不同官能度(如极性或非极性)的含羟基材料的掺混物。作为一个附加的例子,可以使用两种或多种多官能羟基材料或一种或多种单官能羟基材料与多官能羟基材料的混合物。
如有必要,该组合物还可含有可自由基聚合的材料,它包括一种或多种烯键不饱和的单体、低聚物或共聚物。合适的材料包括至少一根不饱和烯键,并能进行加成聚合。这种可自由基聚合的材料包括单、二或多丙烯酸酯或甲基丙烯酸酯酯,如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸异丙酯、丙烯酸正己酯、丙烯酸十八烷酯、丙烯酸烯丙酯、丙三醇二丙烯酸酯、丙三醇三丙烯酸酯、乙二醇二丙烯酸酯、二甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,3-丙二醇二甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、1,2,4-丁三醇三甲基丙烯酸酯、1,4-环己二醇二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、山梨醇六丙烯酸酯、二[1-(2-丙烯酰氧基)]-对乙氧基苯基二甲基甲烷、二[1-(3-丙烯酰氧基-2-羟基)]-对丙氧基苯基二甲基甲烷和三羟乙基异氰脲酸酯三甲基丙烯酸酯;分子量为200-500的聚乙二醇的二丙烯酸酯和二甲基丙烯酸酯,如美国专利4,652,274所述的丙烯酸酯单体以及如美国专利4,642,126所述的丙烯酸化的低聚物的可共聚的混合物;以及乙烯基化合物,如苯乙烯、苯二甲酸二烯丙酯、琥珀酸二乙烯酯、己二酸二乙烯酯和苯二甲酸二乙烯酯。如有必要,可使用两种或多种这些可自由基聚合材料的混合物。
如有必要,可在一个可聚合材料的分子中同时含有环氧和可自由基聚合的官能度。这种材料可由二或多环氧化物与一个或多个当量的烯键不饱和羧酸反应制得。这种材料的一个例子是UVR-6105(购自Union Carbide)与一当量的甲基丙烯酸的反应产物。具有环氧和可自由基聚合的官能度的市售材料包括“Cyclomer”系列材料,如购自Daicel Chemical,Japan的Cyclomer M100或M101。
还可在一个可聚合材料的分子中含有羟基或可自由基聚合的官能度。这种材料的例子包括丙烯酸羟烷酯和甲基丙烯酸羟烷酯,如丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙三醇一或二丙烯酸酯和甲基丙烯酸酯等。
可将环氧树脂、含羟基的材料和任选的可自由基聚合的材料与三组分或三元光引发剂体系合并。三组分的引发剂体系描述在Palazzotto等的美国专利5,545,676(在此引为参考)。光引发剂体系的第一组分是碘鎓盐,即二芳基碘鎓盐。该碘鎓盐应能溶解在单体中,最好是储存稳定的(指在敏化剂和电子给体的存在下溶解在单体中时不会自发聚合)。因此,具体碘鎓盐的选择在某种程度上取决于具体的单体、所选的敏化剂和电子给体。合适的碘鎓盐描述在美国专利3,729,313、3,741,769、3,808,006、4,250,053和4,394,403,这些文献中公开的碘鎓盐在此引为参考。碘鎓盐可以是含有一个阴离子(如Cl-、Br-、I-或C4H5SO3 -)的简单盐,或者是含有锑酸根、砷酸根、磷酸根或硼酸根的金属配合物(如SbF5OH-、AsF6 -)的盐。如有必要,可使用碘鎓盐的混合物。
适用的芳族碘鎓配盐光引发剂的例子包括:四氟硼酸二苯基碘鎓、四氟硼酸二(4-甲基苯基)碘鎓、四氟硼酸苯基-4-甲基苯基碘鎓、四氟硼酸二(4-庚基苯基)碘鎓、六氟磷酸二(3-硝基苯基)碘鎓、六氟磷酸二(4-氯苯基)碘鎓、四氟硼酸二萘基碘鎓、四氟硼酸二(4-三氟甲基苯基)碘鎓、六氟磷酸二苯基碘鎓、六氟磷酸二(4-甲基苯基)碘鎓、六氟砷酸二苯基碘鎓、四氟硼酸二(4-苯氧基苯基)碘鎓、六氟磷酸苯基-2-噻吩基碘鎓、六氟磷酸3,5-二甲基吡唑基-4-苯基碘鎓、六氟锑酸二苯基碘鎓、四氟硼酸2,2’-二苯基碘鎓、六氟磷酸二(2,4-二氯苯基)碘鎓、六氟磷酸二(4-溴苯基)碘鎓、六氟磷酸二(4-甲氧基苯基)碘鎓、六氟磷酸二(3-羧基苯基)碘鎓、六氟磷酸二(3-甲氧基羰基苯基)碘鎓、六氟磷酸二(3-甲氧基磺基苯基)碘鎓、六氟磷酸二(4-乙酰氨基苯基)碘鎓、六氟磷酸二(2-苯并噻吩基)碘鎓和六氟锑酸二苯基碘鎓。
在适用于本发明的芳族碘鎓配盐中,六氟磷酸二芳基碘鎓和六氟锑酸二芳基碘鎓是较好的盐。这些盐是较好的原因是因为一般来说,它们能促进快速反应,在惰性有机溶剂中比其它芳族碘鎓复合离子盐具有更高的溶解性。
可根据Beringer等的美国化学会志(J.Am.Chem.Soc.)81,342(1959)所述通过复分解相应的芳族碘鎓简单盐(如硫酸氢二苯基碘鎓)制得所述芳族碘鎓配盐。因此,例如六氟硼酸二苯基碘鎓配盐可在60℃通过将含29.2g氟硼酸银、2g氟硼酸和0.5g磷酸在30ml水中的水溶液加入44g(139mmol)氯化二苯基碘鎓溶液中而制得。滤去沉淀的卤化银并浓缩滤液,得到的氟硼酸二苯基碘鎓可通过重结晶纯化。
芳族碘鎓简单盐可根据上面Beringer等所述通过各种方法制得,这些方法包括(1)在硫酸中用硫酸碘酰偶合两种芳族化合物、(2)在乙酸-乙酸酐-硫酸中,用碘酸盐偶合两种芳族化合物、(3)在酸的存在下,用丙烯酸碘偶合两种芳族化合物和(4)在酸的存在下,用另一种芳族化合物缩合碘氧基化合物、碘氧基二乙酸酯或二氧碘基化合物。硫酸氢二苯基碘鎓是用方法(3)制得的,例如在低于5℃的温度下在8小时内将35ml浓硫酸和50ml乙酸酐的混合物加入经充分搅拌的55.5ml苯、50ml乙酸酐和53.5g碘酸钾的混合物中。在0-5℃将混合物再搅拌4小时,并在室温(约25℃)搅拌48小时,用300ml乙醚处理之。浓缩后得到粗的硫酸氢二苯基碘鎓沉淀。如有必要,可对其进行重结晶纯化。
在光引发剂体系中的第二组分是敏化剂。敏化剂应能溶解在可光致聚合的组合物中,不含会影响阳离子固化的官能团并能吸收约300-1000nm波长范围内的光线。
合适的敏化剂包括下列类型的化合物:酮、香豆素染料(如氧代香豆素(ketocoumarins))、呫吨染料、吖啶染料、噻唑染料、噻嗪染料、噁嗪染料、吖嗪染料、氨基酮染料、卜啉、芳族多环烃、对位取代的氨基苯乙烯基酮化合物、氨基三芳基甲烷、部花青、squarylium染料和吡啶鎓染料。酮(如单酮或α-二酮)、氧代香豆素、氨基烷基酮和对位取代的对位氨基苯乙烯基酮化合物是较好的敏化剂。对于要求深度固化的用途(如固化高度填充的复合物),最好使用消光系数低于约1000 lmol-1cm-1,较好低于100 lmol-1cm-1的敏化剂在所需的辐照波长中进行光致聚合。α-二酮是具有这性能的一类敏化剂的例子,对于牙科用途特别适用。
作为例子,较好类型的酮敏化剂具有下述结构式:
ACO(X)bB其中X为CO或CR1R2,R1和R2可以相同或不同,它们可为氢、烷基、烷芳基或芳烷基,b为0,A和B可以相同或不同,它们可为取代(含有一个或多个不干扰的取代基)或未取代的芳基、烷基、烷芳基或芳烷基,或者A和B可以一起形成一个环结构,该结构可以是取代或未取代的脂环、芳环、杂芳环或稠芳环。
合适的上式酮包括单酮(b=0)如2,2-、4,4-或2,4-二羟基二苯酮,二-2-吡啶酮,二-2-呋喃酮,二-2-噻吩(thiophenyl)酮,苯偶姻,芴酮,查耳酮,米蚩酮,2-氟-9-芴酮,2-氯噻吨酮,苯乙酮,二苯酮,1-或2-萘乙酮,9-乙酰基蒽,2-、3-或9-乙酰基菲,4-乙酰基联苯,苯基·乙基酮,丙基苯基酮,丁基苯基酮(valerophenone),2-、3-或4-乙酰基吡啶,3-乙酰基香豆素等。合适的二酮包括芳烷基二酮如蒽醌,菲醌,邻、间和对二乙酰基苯,1,3-、1,4-、1,5-、1,6-、1,7-和1,8-二乙酰基萘,1,5-、1,8-和9,10-二乙酰基蒽等。合适的I-二酮(b=1和x=CO)包括2,3-丁二酮,2,3-戊二酮,2,3-己二酮,3,4-己二酮,2,3-庚二酮,3,4-庚二酮,2,3-辛二酮,4,5-辛二酮,苯偶酰,2,2’-、3,3’-和4,4’-二羟基苯偶酰,糠偶酰,二-3,3’-吲哚基乙二酮,2,3-莰烷二酮(樟脑醌),联乙酰,1,2-环己二酮,1,2-萘醌,苊醌(acenaphthaquinone)等。
特别好的可见光敏化剂的例子包括樟脑醌;乙二醛;联乙酰;3,3,6,6-四甲基环己二酮;3,3,7,7-四甲基-1,2-环庚二酮;3,3,8,8-四甲基-1,2-环辛二酮;3,3,18,18-四甲基-1,2-环十八烷二酮;联新戊酰;苯偶酰;糠偶酰;羟基苯偶酰;2,3-丁二酮;2,3-戊二酮;2,3-己二酮;3,4-己二酮;2,3-庚二酮;3,4-庚二酮;2,3-辛二酮;4,5-辛二酮;和1,2-环己二酮。其中,樟脑醌是最好的敏化剂。
引发剂体系的第三种组分是电子给体。一种或多种电子给体化合物应满足下述要求并且应能溶于可聚合的组合物中。电子给体的选择还应考虑其它因素,如所选用的可聚合材料、碘鎓盐和敏化剂的储存稳定性和性能。适用于本发明体系的一种类型的电子给体化合物可以选自Palazzotto等人在美国专利5,545,676中所描述的某些电子给体。此时符合Palazzotto等人所述标准的可能的电子给体化合物必须使用下述方法中的一种或两种进行测试,以确定它们是否是本发明可光致聚合的组合物的适用的电子给体。
电子给体一般是烷基芳族聚醚或烷基、芳基氨基化合物,其中芳基被一种或多种吸电子基团所取代。合适的吸电子基团的例子包括羧酸、羧酸酯、酮、醛、磺酸、磺酸根和腈基。
在本发明组合物中化合物作为电子给体的适用性可以通过测量包含该化合物的样品光引发剂体系的光引发电位加以确定。可以使用下列方法来评价光引发电位。制备含有2.9×10-5mol/g六氟锑酸二苯基碘鎓和1.5×10-5mol/g樟脑醌的2-丁酮标准溶液。然后将pH电极浸在溶液中,将pH计校准到0mV。接着使用浓度为2.9×10-5mol/g的化合物来制备标准溶液和化合物的试验溶液。使用波长约为400-500nm,强度约为200-400mW/cm2的蓝光在约1mm的距离对此试验溶液辐照约5-10秒钟。然后将pH电极浸在试验溶液中,并读取pH计上的mV读数,测定相对于标准溶液的毫伏数。适用的电子给体是那些相对于标准溶液的读数至少为100mV,并且使组合物的胶凝时间比不含电子给体的组合物短至少约30-40%的化合物。mV读数较高通常表明活性较大。
在某些情况下,上述方法的结果会有某些不确定性。这是由于所用的仪器、所使用的方法或其它因素等问题或不确定性导致的,或者有人可能希望核实具体化合物的适用性。可以在上述步骤后进行第二次试验来检验获得的结果并解决任何这种不确定性。
第二种方法包括评价与含有3-二甲基氨基苯甲酸的体系相比,含有所述化合物的引发剂体系的光引发电位。对于这种方法,制备2.9×10-5mol/g六氟锑酸二苯基碘鎓、1.5×10-5mol/g樟脑醌和2.9×10-5mol/g 3-二甲基氨基苯甲酸的2-丁酮标准溶液。然后将pH电极浸在该溶液中,将pH计校准到0mV。使用聚焦光源如牙用固化光(dental curing light)用波长约为400-500nm,强度约为200-400mW/cm2的蓝光在约1mm的距离照射标准溶液约5-10秒钟。光照射后,将pH电极浸在照射过的标准溶液中,并用pH计读取电位(mV),测得溶液的电位。而后使用2.9×10-5mol/g六氟锑酸二苯基碘鎓、1.5×10-5mol/g樟脑醌和2.9×10-5mol/g的所述化合物的2-丁酮溶液制得试验溶液。使用与标准溶液所述的相同方法来照射试验溶液并测量光引发电位。若该试验溶液的光引发电位等于或大于含3-二甲基氨基苯甲酸的标准溶液的光致电势,则该化合物是适用的电子给体。
较好的烷基、芳基胺电子给体化合物系列可用下述结构式描述:其中R1独立地为H,任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、COOH、COOC1-18烷基、(C1-18烷基)0- 1-CO-C1-18烷基、SO3R2、CN、或所取代的C1-18烷基,或任选地被一个或多个吸电子基团取代的芳基,或者R1基团可组合在一起形成一个环;Ar是被一个或多个吸电子基团取代的芳基。合适的吸电子基团包括-COOH、-COOR2、-SO3R2、-CN、-CO-C1-18烷基和-C(O)H基团。
较好的芳基烷基聚醚系列具有下述结构式:其中n=1-3,各R3独立地为H或任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、取代的芳基、-COOH、-COOC1-18烷基、-(C1-18烷基)0-1-COH、-(C1-18烷基)0-1-CO-C1-18烷基、-CO-C1-18烷基、-C(O)H或-C2-18链烯基取代的C1-18烷基,各R4可为任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、取代芳基、-COOH、-COOC1-18烷基、-(C1-18烷基)0-1-COH、-(C1-18烷基)0-1-CO-C1-18烷基、-CO-C1-18烷基、-C(O)H或-C2-18链烯基取代的C1-18烷基。
在上述各式中,烷基可为直链或支链的,而环烷基较好具有3至6个环碳原子,但可以具有高达该特定数目碳原子的其它烷基取代基。芳基可以是碳环或杂环芳基,但较好的是碳环,更好的是苯环。
较好的电子给体化合物包括4-二甲基氨基苯甲酸、4-二甲基氨基苯甲酸乙酯、3-二甲基氨基苯甲酸、4-二甲基氨基苯偶姻、4-二甲基氨基苯甲醛、4-二甲基氨基苄腈和1,2,4-三甲氧基苯。
光引发剂化合物的用量能有效地引发或提高树脂体系的固化速度。业已发现尤其是当电子给体是胺时,其用量是关键性的。太多的电子给体对固化性能是有害的。以整个组合物的树脂化合物计,敏化剂的用量较好约为0.05-5.0重量%。敏化剂的用量更好为0.10-1.0重量%。同样,碘鎓引发剂的用量较好为0.05-10.0重量%,更好为0.10-5.0重量%,最好为0.50-3.0重量%。同样,电子给体的用量较好为0.01-5.0重量%,更好为0.05-1.0重量%,最好为0.05-0.50重量%。
本发明可光致聚合的组合物可通过在“安全光”条件下简单地混合本发明组合物的各组分而制得。在制备此混合物时,若需要的话可以使用合适的惰性溶剂。可使用不会与本发明组合物组分明显发生反应的任何溶剂。合适溶剂的例子包括丙酮、二氯甲烷和乙腈。待聚合的液体材料可以作为另一种待聚合的液体或固体材料的溶剂。无溶剂的组合物可通过在进行或不进行适度加热以便溶解的情况下,将芳族碘鎓配盐和敏化剂简单地溶解在环氧树脂多元醇混合物中而制得。
本发明的组合物提供非常有用的固化速度、固化深度和贮藏寿命的综合性能。即使含有大量填料,它们也能很好地固化,并且可用于各种用途,包括图形艺术成象(例如用于色彩防护体系、可固化油墨或无银成象),印刷板(例如投影板或激光板),光刻胶,焊料掩模,电子保形涂层,涂覆磨料,磁性介质,可光致固化的粘合剂(例如用于正牙)和可光致固化的复合物(例如用于汽车车身修理或牙用技术)。
本发明的独特组合物尤其有利于牙科用途。迄今为止,丙烯酸酯和甲基丙烯酸酯化学品被广泛地用作粘合剂和牙用修补组合物。该化学品的优点在于可使用光引发剂体系用可见光进行固化,但缺点在于在聚合过程中会发生较高度的收缩。相反,发现在聚合过程中,于本发明组合物中的环氧树脂的收缩明显少于已有技术中的丙烯酸酯和甲基丙烯酸酯树脂的收缩。本发明提供一种以可接受的时间固化存在或不存在丙烯酸酯或甲基丙烯酸酯的环氧/多元醇树脂体系的体系,它使用牙科医院中已有的可见光源设备,并固化至足够的深度。
牙用材料可加有或未加有填料,它包括下述牙用材料,例如直接美观的修复材料(例如前端和后端修复剂(restoratives)),修补物,用于口腔硬组织的粘合剂和底涂剂,密封剂,镶饰,空穴衬里,供任何类型托架(例如金属、塑料和陶瓷)使用的牙托粘合剂,齿冠和齿桥(bridge)胶接剂,人工齿冠,人工牙齿,假牙等。这些牙用材料可用于口腔中或置于天然牙齿附近。本文所用的术语“置于.....附近”是指临时或永久地放置牙用材料使之与天然牙齿粘接(例如粘合)或触摸性(例如咬合或接近)接触。本文所用的术语“复合物”是指加有填料的牙用材料。本文所用的术语“修复剂”是指置于牙齿附近后经过聚合的复合物。本文所用的术语“修补物”是指置于牙齿附近前已经成形并聚合以便用于最终用途(例如齿冠、齿桥、镶饰、镶嵌物、修饰物等)的复合物。本文所用的术语“密封剂”是指置于牙齿附近后被固化的稍带填料的复合物或不带填料的牙用材料。术语“可聚合的”是指例如通过自由基、阳离子或混合反应机理使牙用材料固化或硬化。
在某些应用中,使用填料是合适的。填料的选择会影响复合物的重要性能如其外观、射线不透性和物理及机械性能。通过调节复合物各组分的用量和相对折射率,从而改变复合物的半透明性、不透明性或珠光,可以部分地影响外观。单独的或与稀释剂单体混合的本发明的环氧树脂组合物可被制成折射率与诸如石英(折射率1.55)、亚微细粒的二氧化硅(折射率1.46)和SiO∶ZrO摩尔比为5.5∶1非透明微粒(折射率1.54)之类的填料的折射率接近或大致相同。这样,若需要的话,牙用材料的外观可以作成与天然牙齿的外观大致接近。
射线不透性是用x-射线检查复合物的能力的尺度。射线不透性探测是复合物所需的,例如,它能使牙医确定牙齿修补是否保持完好。在其它情况下,透射线的复合物可能是需要的。
加到复合物中的填料的量(在此称为“填充量”,并以牙用材料总重量重量百分数表示)将视填料、环氧树脂和该组合物其它组分的种类和复合物的最终用途而变。
对于某些牙用材料如密封剂,本发明组合物的环氧树脂可稍含填料(例如其填充量为小于约40重量%)或不含填料。牙用材料的粘度最好足够低,使其能渗入咬合牙齿表面的凹坑和裂缝中以及渗入珐琅质腐蚀区,从而有助于牙用材料的滞留。在需要高强度或耐久性的用途(例如前端或后端修复剂、修补物、齿冠和齿桥胶接剂,人工齿冠,人工牙齿和假牙)中,填充量可以高达约95重量%。对于大多数牙齿修复(dental restorative)和修补用途,填充量约为70-90重量%通常是适宜的。
填料可选自一种或多种适于混入医学用途的组合物中的任何材料,例如目前在牙齿修复组合物等中所用的填料。该填料是细分的,其最大粒径较好小于约50微米,平均粒径小于约10微米。填料可以具有单峰或多峰(例如双峰)的粒径分布。填料可以是无机材料。它也可以是不溶于可聚合树脂并且任选地含有无机填料的交联有机材料。在任何情况下填料都应是无毒的并且适用于口腔。填料可以是不透射线的、半透射线的或透射线的。
合适的无机填料的例子是天然的或合成的材料,例如石英,氮化物(如氮化硅),得自如Ce、Sb、Sn、Zr、Sr、Ba和Al的玻璃,胶体二氧化硅,长石,硼硅酸盐玻璃,高岭土,滑石,二氧化钛和锌玻璃;如在美国专利4,695,251中所述的莫氏硬度低的填料;和亚微细粒的二氧化硅颗粒(例如热解的二氧化硅如购自Degussa的“Aerosil”系列的“OX 50”、“130”、“150”和“200”二氧化硅,和购自Cabot Corp.的“Cab-O-Sil M5”)。合适的有机填料颗粒的例子包括填充或未填充的粉状聚碳酸酯、聚环氧化物等。较好的填料颗粒是石英,亚微细粒的二氧化硅和如美国专利4,503,169中所述类型的非玻璃状微粒。也可以加入金属填料如由纯金属如那些IVA、VA、VIA、VIIA、VIII、IB或IIB族金属,铝,铟和IIIB族的铊以及IVB族的锡和铅或它们的合金制成的颗粒金属填料。常规的牙用汞齐合金粉末一般是银、锡、铜和锌的混合物,也可以任选地加入。颗粒金属填料的平均粒径较好约为1-100微米,更好为1微米至约50微米。也可以考虑采用这些填料的混合物以及用有机和无机材料制成的混合填料。最好是未处理过或用硅烷醇处理过的氟铝硅酸盐玻璃。这些玻璃填料的附加好处在于在口腔环境中,在牙修补处会释放出氟化物。
填料颗粒的表面可以任选地用表面处理剂如偶合剂进行处理,以提高填料和可聚合树脂之间的粘接。偶合剂可以用反应性固化基团如丙烯酸酯、甲基丙烯酸酯、环氧化物等进行官能化。偶合剂的例子包括硅烷,如γ-甲基丙烯酰氧基丙基三甲氧基硅烷,γ-巯基丙基三乙氧基硅烷,β-(3,4-环氧环己基)乙基三甲氧基硅烷,γ-缩水甘油氧基丙基三甲氧基硅烷等。
本发明的材料还可以包含合适的助剂如加速剂、抑制剂、吸收剂、稳定剂、颜料、染料、粘度改进剂、表面张力抑制剂和润湿助剂,抗氧剂和本领域普通技术人员熟知的其它组分。
应调节牙用材料中各组分的用量和种类,以在固化前和固化后提供所需的物理和加工性能。例如,一般通过改变一种或多种聚合引发剂的种类和用量,和(若存在的话)一种或多种填料的用量和粒径分布来部分调节牙用材料的固化速度、固化稳定性、流动性、压缩强度、拉伸强度和耐用性。这种调节一般是基于对已有技术的牙用材料的经验进行的。
当将牙用材料施加到牙齿上时,牙齿可以任选地用底涂剂(如牙质或珐琅粘合剂)按本领域普通技术人员熟知的方法进行预处理。
本发明将进一步参考下述实施例进行描述,应理解下述实施例仅仅是例举性的而不以任何方式限制本发明。
实施例1
如下制得环氧树脂和含多元醇材料的储备溶液(“SL1”):将0.50克樟脑醌、1.50克六氟锑酸二苯基碘鎓(DPI SbF6)和24.50克UVR 6105脂环二环氧化物以及0.50g平均分子量为250的聚四氢呋喃二醇(pTHF-250)混合在一起,在无光状态下搅拌直至均匀。UVR 6105是具有如下分子式的脂环二环氧化物:评价各种电子给体化合物的光引发电位和提高固化速度的能力。为了评价化合物的光引发电位,如下制得引发剂储备溶液:将0.50克樟脑醌和3.00克DPI SbF6转移至250毫升的聚乙烯带螺旋盖的瓶中。将200克99.5+%2-丁酮转移至该聚乙烯瓶中,混合内容物直至均匀。形成的溶液含有约2.9×10-5摩尔的DPI SbF6/克和1.5×10-5摩尔的CPQ/克。在2.9×10-5摩尔电子给体/克SL1的浓度下评价电子给体添加剂。如下制得试样:将1.16×10-4摩尔的电子给体转移至13毫升的玻璃小瓶中,随后加入4.0g引发剂储备溶液。盖上瓶盖,并使劲摇动直至均匀。然后,根据下面步骤评价试样的的相对电位。
将半微复合pH电极(Corning 476540型)与毫伏容量的pH计(BeckmanφP/N123133)连接。在该评价中使用引发剂储备溶液作为毫伏标准。将4克引发剂储备溶液转移至13毫升玻璃小瓶中并加入微小的磁性搅拌条。将试样置于磁性搅拌器上,启动搅拌器使之缓慢搅拌试样。电极依次用水、乙醇清洗,然后用纸巾彻底擦干之。将该电极浸没在引发剂储备溶液中,将毫伏读数校正至0.00毫伏。取出电极,通过放置光波导向装置的顶部使之直接照射玻璃小瓶的底部中央,用光密度约为200mW/cm2,波长为400-500nm的Visilux牙用固化光将试样照射10秒。光照射后,盖上盖子,将试样摇动大约5秒使之完全混合。用乙醇彻底清洗电极,吸干,浸没在辐照的溶液中。按下pH计上的mV按钮直至读数稳定。得到相对于对照试样的毫伏数。对各种电子给体溶液重复上述试验。如上所述在每次操作前,用未照射的引发剂储备溶液校准电极。
还评价电子给体化合物对储备树脂溶液的固化速度的影响。如下制得约1克试样:将2.9×10-5摩尔的各种电子给体转移到1英钱的玻璃小瓶中,随后加入1.0克储备树脂溶液。将这些成份混合至均匀。将溶液移至直径6毫米、厚2.5毫米的底面直接固定有聚酯薄膜的特氟龙模具中,以测定每种试验的胶凝时间。将试样直接置于Visilux 2牙用固化光的光波导向装置的下方10毫米处。辐照试样并最长在60秒内探测形成硬凝胶的时间。结果如表1所示。在整个实施例中,“NC”指材料未固化,“NT”指材料未试验。
表1
试样 | 给体化合物 | 给体克数/树脂克数 | 胶凝时间(秒) | mV(初始)MEK | mV(光照)MEK |
1 | 无 | 无 | 25 | 0 | -25 |
2 | 4-二甲基氨基苯甲酸 | 0.0047 | 7 | -11 | 184 |
3 | 4-二甲基氨基苯甲酸乙酯 | 0.0053 | 7 | -12 | 200 |
4 | 3-二甲基氨基苯甲酸 | 0.0047 | 12 | -5 | 115 |
5 | 1,2,4,-三甲氧基苯 | 0.0053 | 7 | -3 | 233 |
6 | 4-二甲基氨基苯偶姻 | 0.0068 | 9 | -13.4 | 261 |
7 | 4-二甲基氨基苄腈 | 0.0045 | 16(顶部) | 9.7 | 266 |
8 | 4-二甲基氨基苯甲醛 | 0.0043 | 16(顶部) | 8 | 245 |
9 | 4-二甲基氨基苯乙醇 | 0.0046 | NC | -83.2 | 17 |
10 | 二甲苯胺 | 0.0043 | 20 | -55 | 54 |
11 | 2,5-二甲氧基苄醇 | 0.0049 | 25 | 30.8 | 52 |
12 | 四氢糠醇 | 0.0030 | 25 | -34 | -10 |
13 | 1,2,3-三甲氧基苯 | 0.0050 | 25 | -1.9 | 5 |
14 | 1,3,5-三甲氧基苯 | 0.0050 | 24 | 10.1 | 28 |
15 | 苄醇 | 0.0031 | 26 | -13.7 | 24 |
16 | 2,4,6-三甲基苯胺 | 0.0050 | 22 | 10 | 71.3 |
17 | N,N-二甲基苄胺 | 0.0040 | 25 | -189.7 | -170 |
18 | 三乙醇胺 | 0.0042 | NC | -171 | -162 |
19 | 二羟乙基-对-甲苯胺 | 0.0058 | NC | -180 | -98 |
20 | 4-叔丁基N,N-二甲基苯胺 | 0.0050 | 34 | NT | NT |
实施例2
如下制得环氧树脂/多元醇/丙烯酸酯树脂材料的储备液:将0.50g樟脑醌和1.50gDPI SbF6转移至玻璃瓶中,随后加入约0.20g二氯甲烷溶剂、70.56g UVR6105、9.80g Ebecryl 1830聚酯六丙烯酸酯(Radcure Specialties)和17.64g pTHF-250。在无光线的情况下将该混合物搅拌至均匀。
评价三种电子给体化合物的光引发电位及其提高环氧树脂/多元醇/丙烯酸酯树脂材料固化速度的能力。
为了评价化合物的光引发电位,如下制得引发剂储备液(SL2):将0.50g樟脑醌和3.00g DPI SbF6转移至250ml带螺旋盖的聚乙烯瓶中。将200g 99.5+%2-丁酮转移至该聚乙烯瓶中,混合内容物直至均匀。形成的溶液含有约2.9×10-5摩尔的DPI SbF6/克和1.5×10-5摩尔的CPQ/克。在2.9×10-5摩尔电子给体/克SL2的浓度下评价电子给体添加剂。如下制得试样:将1.16×10-4摩尔的电子给体转移至13毫升的玻璃小瓶中,随后加入4.0g引发剂储备溶液。盖上瓶盖,并使劲摇动直至均匀。然后,根据实施例1详细描述的步骤评价试样的的相对电位。
还评价电子给体化合物对环氧/多元醇/丙烯酸酯树脂溶液的固化速度的影响。如下制得约1克试样:将2.9×10-5摩尔的各种电子给体转移到1英钱的玻璃小瓶中,随后加入1滴二氯甲烷溶剂和1.0克储备树脂溶液。将这些成份混合至均匀。将溶液移至直径6毫米、厚2.5毫米的底面直接固定有聚酯薄膜的特氟龙模具中,以测定每种试验的胶凝时间。将试样直接置于Visilux 2牙用固化光的光波导向装置的下方3厘米处。试样最长辐照120秒并探测形成软和硬凝胶的时间。结果如表2所示。
表2
电子给体化合物 | 克给体/克树脂 | 胶凝时间(秒) | mV(初始) | mV(光照) |
无 | 无 | 120 | 0 | -25 |
4-二甲基氨基苯甲酸 | 0.0047 | 30 | -11 | 184 |
4-二甲基氨基苯甲酸乙酯 | 0.0053 | 35 | -12 | 200 |
4-二甲基氨基苯偶姻 | 0.0068 | 70 | -13 | 261 |
实施例3
用如下方法制得二官能的环氧/丙烯酸酯材料:
向一个带冷凝器、带Teflon搅拌片的气动搅棒和加液漏斗的三颈树脂烧瓶中加入Epon 828二环氧化双酚A(82.9g,0.22mol)。用硫酸钙干燥管使该体系保持干燥。将该树脂反应器部分浸入加热至约100℃的油浴中,并使二环氧化物在该温度下平衡约30分钟。向该二环氧化物中加入三苯基锑(1.1g)并使之溶解约15分钟。向加液漏斗中称入甲基丙烯酸(17.2g,0.20mol),随后在约3小时内缓慢地将其加至加热的二环氧化物中。使混合物总共反应24小时,形成高粘度的液体,它包括单环氧化物/单甲基丙烯酸酯加合物和二环氧化物及二甲基丙烯酸酯的统计混合物。
实施例4
使用或不使用二苯基碘鎓盐(DPISbF6)由实施例3的反应产物如下制得两种环氧/丙烯酸酯多醇组合物:
试样I 试样2
组分 重量份 重量份
UVR 6105环氧 64.00 64.00
实施例3的产物 20.00 20.00
pTHF-250 16.60 16.60
DPISbF6 0.00 1.50
CPQ 0.50 0.50
EDMAB 0.56 0.56
用Visilux 2牙用固化光在约10mm的距离下对约2.5mm厚的试样辐照约30秒。两种试样均较软,具有挠性,难以测定BarCol硬度值。将试样在37℃的烘箱中放置24小时。试样1仍较软,而含DPISbF6的试样2变成硬的固体,BarCol硬度值约为30。该数据表明初始的胶凝归因于来自实施例3反应产物的自由基聚合,随后的聚合来自环氧树脂UVR 6105和实施例3反应产物的阳离子固化,除了自由基固化外,加入二苯基碘鎓盐或化合物能形成除自由基固化外的阳离子固化。
实施例5
在存在或不存在芳香胺的情况下在环氧树脂/多元醇组合物中评价各种二苯基碘鎓盐的作用。
组合物A(1) 重量份
UVR 6105 80.0
pTHF-250 20.0
樟脑醌 0.50
DPISbF6 1.50
组合物B(1)
UVR 6105 80.0
pTHF-250 20.0
樟脑醌 0.50
DPIPF6 1.23
组合物C(1)
UVR 6105 80.0
pTHF 20.0
樟脑醌 0.50
DPICl 0.90
以每100重量份A(1)、B(1)和C(1)0.56重量份的量将4-二甲基氨基苯甲酸乙酯(EDMAB)加入一部分上述组合物中,分别形成组合物A(2)、B(2)和C(2)。
在室温混合各组分并搅棒至均匀,制得各个组合物。用Visilux 2光源以400-500nm的波长在10mm的距离辐照2mm厚的试样,来评价每种组合物的固化速度。辐照持续120秒或持续至形成软或硬的凝胶。结果列于表3。
表3
组合物 胶凝时间(秒)
A(1) 14
B(1) 16
C(1) NC
A(2) 8
B(2) 8
C(2) NC
数据表明当组合使用胺电子给体和带-PF6或-SbF6平衡离子的碘鎓盐时,可获得加快的固化速度。当-Cl作为平衡离子时,使用或不使用电子给体EDMAB均未观察到发生固化。
实施例6
在含1.50重量%Ph2ISbF6、0.50重量%敏化剂化合物和任选的0.56重量%EDMAB的环氧/多元醇制剂中评价各种吸收可见光的敏化剂。如下制得分别含有或不含有EDMAB的溶液A和溶液B:
成分 溶液A(重量份) 溶液B(重量份)
UVR 6105 80.00 80.00
pTHF-250 20.00 20.00
DPISbF6 1.50 1.50
EDMAB - 0.56
将0.0050g敏化剂转移至2英钱的玻璃小瓶中,随后加入2滴二氯甲烷溶剂和1.0g溶液A来评价敏化剂。将组合物混合至均匀,如实施例1所述评价胶凝时间。对溶液B重复相同的步骤。表4列出了使用或不使用EDMAB的试验号、敏化剂和胶凝时间。
表4
试样号 | 敏化剂化合物(0.0050g/克树脂) | 无EDMAB的胶凝时间(秒) | 有EDMAB的胶凝时间(秒) |
1 | 无 | NC | NC |
2 | 樟脑醌 | 14 | 8 |
3 | 2-氯噻吨酮 | 25(仅表面) | 15 |
4 | 芴 | NC | 30(顶部1mm) |
5 | 糠偶酰 | 115 | 40 |
6 | 二溴荧光素 | 70 | 17 |
7 | 荧光素 | 95(仅表面) | 91(仅表面) |
8 | 乙基曙红 | 64(仅表面) | 15 |
9 | 曙红y | 19(仅表面) | 20(完全固化) |
10 | 苯甲酰基苯并香豆素 | NC | 15 |
11 | 玫瑰红 | NC | 26 |
12 | 异丙基噻吨酮 | 11(仅表面) | 20(完全固化) |
15 | 蒽醌 | 30(仅表面) | 90(完全固化) |
16 | 二乙氧基蒽 | 20(仅表面) | 40(仅表面) |
17 | 2-乙基-9,10-二甲氧基蒽 | 22(仅表面) | 45(仅表面) |
18 | 9,10-二氯蒽 | NC | NC |
19 | 二苯基异苯并呋喃 | 32 | 41 |
20 | 亚甲紫 | NC | NC |
数据表明与仅含敏化剂和DPISbF6的制剂相比,各种酮官能的敏化剂和DPISbF6及电子给体EDMAB组合在一起能更快和/或更完全地进行光致固化。
实施例7
测定EDMAB与DPISbF6的摩尔比对胶凝时间的影响。使用摩尔比为0-8.0的EDMAB/DPISbF6。将16.0gUVR 6105、4.0gpTHF-250、0.10g樟脑醌和0.30gDPISbF6混合在一起制得溶液A。该溶液含有每克树脂2.9×10-5摩尔DPISbF6。如下制得溶液B:将0.44g EDMAB转移至玻璃小瓶中,随后10g溶液A,形成含有每克树脂2.3×10-4mol EDMAB或8摩尔当量EDMAB/DPISbF6的制剂。制得1g溶液A和溶液B的混合物并按实施例1所述评价胶凝时间,但是使用的辐照距离为10mm。表5列出了试验号、溶液A和B的克数、胺与鎓盐的摩尔比和胶凝时间。
数据表明使用小至0.08当量EDMAB/鎓盐就可使固化速度明显增快。使用约0.10-1.0当量可获得完美的固化速度。再加入EDMAB使之远超过1.0当量时,结果胶凝时间接近线性增加(延迟)并降低材料硬度。
表5
试样号 | 溶液B(克)2.32×10-4摩尔EDMAB/克 | 溶液A(克)2.0×10-5摩尔鎓盐/克 | EDMAB/鎓盐的摩尔比 | 胶凝时间(秒) | 评注 |
1 | 0.00 | 1.00 | 0.00 | 18 | 硬固体 |
2 | 0.01 | 0.99 | 0.08 | 9 | 硬固体 |
3 | 0.02 | 0.98 | 0.16 | 7 | 硬固体 |
4 | 0.03 | 0.97 | 0.25 | 8 | 硬固体 |
5 | 0.05 | 0.95 | 0.40 | 8 | 硬固体 |
6 | 0.10 | 0.90 | 0.80 | 8 | 硬固体 |
7 | 0.20 | 0.80 | 1.60 | 13 | 硬固体 |
8 | 0.30 | 0.70 | 2.40 | 15 | 硬凝胶 |
9 | 0.40 | 0.60 | 3.20 | 20 | 硬凝胶 |
10 | 0.50 | 0.50 | 4.00 | 21 | 硬凝胶 |
11 | 0.60 | 0.40 | 4.80 | 25 | 软凝胶 |
12 | 0.70 | 0.30 | 5.60 | 30 | 软凝胶 |
13 | 0.80 | 0.20 | 6.40 | 35 | 软凝胶 |
14 | 0.90 | 0.10 | 7.20 | 55 | 软凝胶 |
15 | 1.00 | 0.00 | 8.00 | 60 | 软凝胶 |
数据表明,与不使用EDMAB相比,加入胺电子给体EDMAB分别在低和高浓度下会加快和减缓固化速度和性能。
实施例8
根据表5所示的组分浓度制得18个可光致固化的环氧/多元醇树脂制剂,用于2(5-1)分数阶乘设计试验。5个实验的不同之处在于:
A)%樟脑醌(CPQ),
B)%六氟锑酸二苯基碘鎓(DPISbF6),
C)%4-二甲基氨基苯甲酸乙酯(EDMAB),
D)脂族和脂环二环氧化物的比例(EPON/UVR之比),
E)%聚四氢呋喃MW250(pTHF)。
使用的脂族二环氧化物是双酚A的二缩水甘油醚(Epon 828,Shell Oil Co.);使用的脂环二环氧化物是3,4-环氧环己烷羧酸3,4-环氧环己基甲基酯(UVR-6105)。
在Visilux-2牙用固化光的连续辐照下试验制得的各种树脂溶液的胶凝时间。将未固化的树脂填入3mm厚的圆柱型Teflon BarCol Hardness模具中。接着用Visilux-2牙用固化光以1cm的距离辐照各个模具中的未固化的树脂,同时用塑料搅棒经常探测之。将树脂开始变稠并显示出软固体性能的时刻记录为以秒为单位的胶凝时间。各种树脂制剂的三次这种试验的平均值列于表6,其旁边为各树脂制剂相应的组成信息。
统计分析(YATES ANOVA)表明,当将1摩尔当量(按DPISbF6计)EDMAB加入树脂制剂中时,在统计上EDMAB明显不同于胶凝时间下降7.7秒的平均效果。
表6可见光固化环氧/多元醇树脂中含DPISbF6的环氧制剂
树脂变化 | 2(5-1)分数阶乘 | |||||||||||
变化 | (-) | 0 | (+) | |||||||||
%樟脑醌 | 敏化剂 | 0.25% | 0.50% | 0.75% | ||||||||
%DPISbF6(CD-1012) | 催化剂 | 0.50% | 1.00% | 2.00% | ||||||||
EDMAB(DPISbF6当量) | 电子给体 | (0当量) | (0.5当量) | (1当量) | ||||||||
EPON 828∶UVR-6105 | 环氧树脂 | 1∶2 | 1∶1 | 2∶1 | ||||||||
%聚四氢呋喃 | 多元醇 | 10% | 20% | 30% | ||||||||
1当量EDMAB=DPISbF6的克数(193/516) | ||||||||||||
EDMAB的摩尔重量=193 | DPISbF6的摩尔重量=516 | |||||||||||
活化的树脂中的组分百分数 | ||||||||||||
设计次序 | CPQ(g) | DBISbF6(g) | EDMAB(g) | EPON828(g) | UVR 6105(g) | pTHF(250)(g) | 胶凝时间(秒) | |||||
1 | 0.25 | 0.50 | 0.00 | 23.08 | 46.17 | 30.00 | 14.3 | |||||
2 | 0.75 | 0.50 | 0.00 | 29.58 | 59.17 | 10.00 | 24.0 | |||||
3 | 0.25 | 2.00 | 0.00 | 29.25 | 58.50 | 10.00 | 46.0 | |||||
4 | 0.75 | 2.00 | 0.00 | 22.42 | 44.83 | 3.00 | 14.0 | |||||
5 | 0.25 | 0.50 | 0.19 | 29.69 | 59.37 | 10.00 | 12.6 | |||||
6 | 0.75 | 0.50 | 0.19 | 22.85 | 45.71 | 30.00 | 11.0 | |||||
7 | 0.25 | 2.00 | 0.75 | 22.33 | 44.67 | 30.00 | 18.0 | |||||
8 | 0.75 | 2.00 | 0.75 | 28.83 | 57.67 | 10.00 | 13.3 | |||||
9 | 0.25 | 0.50 | 0.00 | 59.50 | 29.57 | 10.00 | 37.3 | |||||
10 | 0.75 | 0.50 | 0.00 | 45.83 | 22.92 | 30.00 | 23.0 | |||||
11 | 0.25 | 2.00 | 0.00 | 45.17 | 22.58 | 30.00 | 23.6 | |||||
12 | 0.75 | 2.00 | 0.00 | 58.17 | 29.08 | 10.00 | 39.0 | |||||
13 | 0.25 | 0.50 | 0.19 | 46.04 | 23.02 | 30.00 | 30.6 | |||||
14 | 0.75 | 0.50 | 0.19 | 59.04 | 29.52 | 10.00 | 17.6 | |||||
15 | 0.25 | 2.00 | 0.75 | 58.00 | 29.00 | 10.00 | 26.6 | |||||
16 | 0.75 | 2.00 | 0.75 | 44.33 | 22.17 | 30.00 | 30.0 | |||||
17 | 0.50 | 1.00 | 0.19 | 39.15 | 39.16 | 20.00 | 11.3 | |||||
18 | 0.50 | 1.00 | 0.19 | 39.16 | 39.15 | 20.00 | 11.3 |
响应:胶凝时间 | ||||
VAR | 变化 | 单位 | -1值 | +1值 |
A | CPQ | % | 0.250 | 0.750 |
B | DPISbF5 | -0.301 | 0.301 | |
C | EDMAB | 0.000 | 1.000 | |
D | 828:UVR | 0.333 | 0.666 | |
E | pTHF | % | 10.000 | 30.000 |
变化 | 系数 | 标准效果 | 平方和 |
总平均 | 22.42 | ||
A | -2.32 | -4.64 | 86.0 |
B | 2.51 | 5.01 | 100.5 |
C | -3.84 | -7.69 | 236.4 |
D | 4.66 | 9.31 | 346.9 |
E | -3.24 | -6.49 | 168.4 |
AB | 0.08 | 0.16 | 0.1 |
AC | 0.33 | 0.66 | 1.8 |
AD | 1.26 | 2.51 | 25.3 |
AE | 1.26 | 2.51 | 25.3 |
BC | -0.49 | -0.99 | 3.9 |
BD | -1.17 | -2.34 | 21.9 |
BE | -1.67 | -3.34 | 44.6 |
CD | 1.58 | 3.16 | 40.0 |
CE | 5.68 | 11.36 | 516.4 |
DE | 1.58 | 3.16 | 40.0 |
中点 | -12.51 | 278.1 |
实施例9(制备例)
将200.3克去离子水称入到1000毫升硬质聚合物烧杯中,使用三氟乙酸(Aldrich Chem.Co.,Milwaukee,WI)将pH值调节至3.02。用涂覆特氟隆的磁性搅拌棒边搅拌边慢慢向水中加入9.9099克的3-缩水甘油氧丙基三甲氧基硅烷(United Chemical Technologies,Inc.,Bristol,PA)。用大约50毫升的变性乙醇清洗装过硅烷的烧杯,然后,将洗液加入水解硅烷的水溶液中。将溶液搅拌大约65分钟(水解时间),随后将200g重量比为90/10的经球磨机研磨的平均粒径为2.25-3.15微米的磨过的石英(3M Co.,Maplewood,MN,PMC-41-5300-0422-9)和市售的热解法二氧化硅Aerosil OX-50(Degussa Inc.,Frankfurt,GE)的混合物慢慢加入到硅烷处理溶液中,在室温将形成的糊浆搅拌27小时。然后,将该糊浆平均分配到三个1000毫升的聚合物烧杯中,每个烧杯在60℃的对流干燥烘箱中放置12小时。将从每个烧杯中得到的干饼重新混合,用研钵和研杵研磨,然后,在振荡器上用74微米的尼龙筛网将其筛入一个密封容器中。接着,将过筛的粉末放入一个一品脱瓶中,在80℃最后干燥2小时。经过短暂的冷却,用带有箔内衬的纸密封的金属盖将瓶密封,以降低传入或透出瓶的湿气。
实施例10
本实施例描述制造含碘鎓盐、α-二酮和任选的胺电子给体(EDMAB)的基于环氧/多元醇树脂的复合材料。
两种组合物按如下方法制备:
组合物A
UVR 6105 8.00克
pTHF250 2.00克
DPI SbF6 0.15克
樟脑醌(CPQ) 0.05克
总量 10.20克
组合物B
UVR 6105 8.00克
pTHF250 2.00克
DPI SbF6 0.15克
樟脑醌 0.05克
EDMAB 0.05克
总量 10.20克
每种组合物都是在室温下将组份混合、并搅拌直至均匀而制得的。
两种复合材料还可如下制得:将7.50克实施例9中的填料分别与2.50克组合物A和2.50克组合物B进行混合。用刮刀调拌试样直至获得均匀的厚胶糊。
复合物A
组合物A 2.50克
实施例9的填料 7.50克
总量 10.00克
复合物B
组合物B 2.50克
实施例9的填料 7.50克
总量 10.00克
根据下面步骤,通过测定2毫米厚试样的BarCol A硬度评价试样的光致聚合性能。在一块2毫米厚的Teflon块料上放置一层透明的聚对苯二甲酸乙二醇酯(PET)薄膜,所述块料带有一个直径约6毫米穿透该块料厚度方向的圆柱形孔,使得该模具的圆柱形开孔的一端被PET膜覆盖。在该Teflon模具中填入试样,并在模具的顶部放置另一层PET薄膜以覆盖糊浆试样。用手压PET膜,形成约2毫米厚的试样。将光源棒直接置于在模具顶面覆盖试样的PET膜上,用Visilux 2光源照射试样30秒。制备三组试样,每个试样重复三次,分别于25℃储藏5分钟、20分钟和24小时,于37℃储藏20分钟和24小时。储藏完毕,移走PET膜,使用装有压头的Barber-Coleman压机(一种手动便携式硬度试验仪;GYZJ934-1型;购自Barber Coleman CompanyIndustrial Instruments Division,LovasPark,IN)测量模具底面和顶面的硬度。对每个受试试样,在每个试样的顶面和底面均读数三次。将每种组合物和储藏条件的读数进行平均。硬度值为0表示聚合是有限的或没有发生。底面硬度值显著低于顶面硬度值表示固化深度有限。结果列于下表7。
表7
Barcol硬度
25℃ 37℃
试样 受试面 5分钟 20分钟 24小时 20分钟 24小时
组合物A 顶面 48 58 67 66 70(无EDMAB) 底面 18 40 67 62 67
组合物B 顶面 54 54 56 64 56
(EDMAB) 底面 52 53 63 67 63
数据表明:当25℃下后固化5分钟时,与不含EDMAB的复合物A相比,含电子给体EDMAB的复合物B的顶面和底面硬度更高。这表明助催化剂EDMAB能明显提高环氧/多元醇复合物的固化速率。
实施例11
本实施例描述了制备含碘鎓盐、α-二酮和任选的胺电子给体的基于环氧/多元醇/甲基丙烯酸酯树脂的复合材料。
如下制得两种组合物:
组合物A
UVR 6105 7.20克
pTHF250 1.80克
Ebecryl 1830 1.00克
DPI SbF6 0.15克
樟脑醌 0.05克
总量 10.20克
组合物B
UVR 6105 7.20克
pTHF250 1.80克
Ebecryl 1830 1.00克
DPI SbF6 0.15克
樟脑醌 0.05克
对二甲基氨基苯甲酸乙酯 0.05克
总量 10.20克
每种组合物都是在室温下将组份混合、并搅拌直至均匀而制得的。
两种复合材料还可如下制得:将7.50克实施例9中的填料分别与2.50克组合物A和2.50克组合物B进行混合。用刮刀调拌试样直至获得均匀的厚胶糊。
复合物A(无EDMAB)
组合物A 2.50克
实施例9的填料 7.50克
总量 10.00克
复合物B(EDMAB)
组合物B 2.50克
实施例9的填料 7.50克
总量 10.00克
根据实施例9所述的步骤,通过测定2毫米厚的试样的BarCol A硬度来评价试样的光致聚合性能。结果列于下表8。
表8
Barcol硬度
25℃ 37℃
样品 受试面 5分钟 20分钟 24小时 20分钟 24小时
组合物A 顶面 45 39 66 58 70(无EDMAB) 底面 0 0 58 17 59
组合物B 顶面 47 54 64 60 64
(EDMAB) 底面 37 53 64 59 59
数据表明:当在25℃后固化5分钟或20分钟或更长时间、或在37℃后固化20分钟,与不含EDMAB的复合物A相比,含EDMAB电子给体的复合物B表现出更高的底面聚合程度。对于厚的环氧/多元醇/丙烯酸酯复合物,电子给体EDMAB能增加固化速度。
实施例12
由表8所示的5种可光致固化的环氧/多元醇树脂制剂制得补牙糊浆。各种补牙糊浆的填料是由95重量%磨细的石英填料(3微米APS)和5重量%热解法二氧化硅OX-50(Degussa Inc.)的混合物制得的。将两种二氧化硅基填料在一个1000ml的烧杯中混匀,随后在pH为3-3.5的5%(按填料重量计)3-缩水甘油氧丙基三甲氧基硅烷的水解溶液中形成糊浆并放置过夜。在60℃将糊浆块放置12小时,粉碎并用74微米的尼龙筛网过筛。在80℃干燥2小时后,以8-10g为一批将填料人工拌入所述树脂,使填料含量为82.0%或82.5%。
形成的糊浆在1/8”ID Lexan管中用两束Visilux-2牙用固化光辐照80秒并在37℃的蒸馏水中后固化24小时以后,测定其压缩强度和径向拉伸强度。
表9在环氧/多元醇树脂中含DPISbF6的光致固化的环氧制剂
每100g组合物中的重量 | 压缩强度(MPa)24小时 | 径向拉伸强度(MPa)24小时 | 硅烷处理过的石英的重量% | |||||
CPQ(g) | DPISbF6(g) | EDMAB(g) | EPON828(g) | UVR-6105(g) | pTHF(250)(g) | |||
(n=5)* | (n=5)* | |||||||
0.75 | 0.50 | 0.00 | 30.00 | 60.00 | 10.00 | 247(10) | 69.5(18) | 82.0 |
0.25 | 0.50 | 0.00 | 60.0 | 30.00 | 10.00 | 233(11) | 60.7(8.6) | 82.0 |
0.75 | 2.00 | 0.75 | 53.33 | 26.67 | 20.00 | 259(7) | 70.2(5.0) | 82.0 |
0.50 | 1.00 | 0.19 | 42.50 | 42.50 | 15.00 | 262(6) | 75.6(1.7) | 82.0 |
0.50 | 1.00 | 0.19 | 42.50 | 42.50 | 15.00 | 312(7) | 82.7(9.4) | 82.5 |
*括号中的数据是5次(n)试验值的标准偏差。
实施例13(制备例)
根据下列步骤制得二官能的脂族环氧/丙烯酸酯材料。
将UVR 6105脂环二环氧化物(109.6g,0.44mol)转移至一个带有冷凝器、带Teflon搅拌叶片的气动搅棒和加液漏斗的250ml三颈烧瓶中,用硫酸钙干燥管使体系保持干燥。将该树脂反应器部分浸入一个加热至约100℃的油浴中,使二氧化物平衡约30分钟。向该二氧化物中移入三苯基锑(0.3g)并使之溶解约15分钟。向加液漏斗中称入甲基丙烯酸(8.6g,0.11mol),随后在约3小时内将其缓慢地加入缓慢加热的二氧化物中。使混合物总共反应24小时,形成粘度稍高于原料的液体。因此二官能环氧/丙烯酸酯材料的约1/4环氧官能团与不饱和酸发生反应。下面将制得的树脂称为UVR 1/4。
实施例14
本实施例描述21种基于环氧/甲基丙烯酸酯树脂的复合材料,它们含有不同量的UVR1/4(参见实施例13)、UVR 6105(脂环二环氧化物)、pTHF 250(脂族二醇)、HPMA(甲基丙烯酸3-羟基丙酯)、DPISbF6(碘鎓盐)、CPQ(樟脑醌,一种α-二酮)和EDMAB(对二甲基氨基苯甲酸乙酯,一种胺电子给体)。
如下表10所示制得21种树脂组合物。各种组合物是在室温将组分混合并搅拌均匀而制得的。
还通过将3.0g石英填料OX-50分别与6.0g表10中所列的组合物混合后制得21种复合材料。用刮刀调拌试样直至得到厚度均匀的糊浆。
根据下面步骤,通过测定2毫米厚试样的BarCol A硬度评价试样的光致聚合性能。在一块2毫米厚的Teflon块料上放置一层透明的聚对苯二甲酸乙二醇酯(PET)薄膜,所述块料带有一个直径约6毫米穿透该块料厚度方向的圆柱形孔,使得该模具的圆柱形开孔的一端被PET膜覆盖。在该Teflon模具中填入试样,并在模具的顶部放置另一层PET薄膜以覆盖糊浆试样。用手压PET膜,形成约2毫米厚的试样。将光源棒直接置于在模具顶面覆盖试样的PET膜上,用Visilux 2光源照射试样60秒。制备三组试样,每个试样重复三次,分别于25℃储藏10分钟和24小时,于37℃储藏24小时。储藏完毕,移走PET膜,使用装有压头的Barber-Coleman压机(一种手动便携式硬度试验仪;GYZJ 934-1型;购自BarberColeman CompanyIndustrial Instruments Division,Lovas Park,IN)测量模具底面和顶面的硬度。对每个受试试样,在每个试样的顶面和底面均读数三次。将每种组合物和储藏条件的读数进行平均。硬度值为0表示聚合是有限的或没有发生。底面硬度值显著低于顶面硬度值表示固化深度有限。结果列于下表10。
表10
试样组成 | Barcol硬度试验 | |||||||||
试样 | UVR1/4 | UVR6105 | pTHF250 | HPMA | CPQ | DPISbF6 | EDMAB | 10分钟室温顶面/底面 | 24小时 室温顶面/底面 | 24小时37℃顶面/底面 |
a | 1.82 | 7.58 | 0.50 | 0.10 | 0.05 | 0.125 | 0.01 | 33/0 | 66/56 | 44/33 |
b | 7.58 | 1.62 | 0.50 | 0.10 | 0.05 | 0.125 | 0.01 | 0/0 | 36/24 | 52/46 |
c | 1.54 | 6.38 | 1.74 | 0.34 | 0.05 | 0.125 | 0.01 | 53/52 | 59/50 | 37/55 |
d | 6.38 | 1.54 | 1.74 | 0.34 | 0.05 | 0.125 | 0.01 | 57/53 | 57/54 | 57/59 |
e | 1.82 | 7.58 | 0.33 | 0.26 | 0.05 | 0.125 | 0.01 | 62/57 | 40/57 | 63/62 |
f | 7.58 | 1.82 | 0.33 | 0.26 | 0.05 | 0.125 | 0.01 | 0/0 | 47/19 | 56/56 |
g | 1.52 | 6.38 | 1.15 | 0.93 | 0.05 | 0.125 | 0.01 | 48/32 | 54/48 | 57/57 |
h | 6.38 | 1.53 | 1.15 | 0.93 | 0.05 | 0.125 | 0.01 | 27/26 | 51/32 | 58/56 |
I | 4.29 | 4.30 | 0.99 | 0.47 | 0.05 | 0.125 | 0.01 | 17/0 | 55/51 | 52/58 |
j | 4.29 | 4.30 | 0.93 | 0.47 | 0.05 | 0.125 | 0.01 | 38/19 | 53/46 | 59/61 |
k | 4.29 | 4.30 | 0.93 | 0.47 | 0.05 | 0.125 | 0.01 | 20/0 | 51/43 | 58/57 |
l | 4.29 | 4.30 | 0.93 | 0.47 | 0.05 | 0.125 | 0.01 | 16/0 | 52/50 | 59/58 |
m | 0.00 | 8.80 | 0.93 | 0.47 | 0.05 | 0.125 | 0.01 | 55/45 | 53/60 | 63/61 |
n | 6.60 | 0.00 | 0.93 | 0.47 | 0.05 | 0.125 | 0.01 | 0/0 | 43/44 | 55/57 |
o | 5.00 | 5.00 | 0.00 | 0.00 | 0.05 | 0.125 | 0.01 | 0/0 | 26/17 | 51/49 |
p | 3.77 | 3.77 | 1.64 | 0.82 | 0.05 | 0.125 | 0.01 | 52/30 | 54/53 | 59/59 |
q | 4.30 | 4.90 | 1.40 | 0.00 | 0.05 | 0.125 | 0.01 | 55/50 | 52/56 | 57/57 |
r | 4.30 | 4.30 | 0.70 | 0.70 | 0.05 | 0.125 | 0.01 | 0/0 | 41/43 | 55/53 |
s | 4.30 | 4.30 | 0.83 | 0.47 | 0.05 | 0.125 | 0.01 | 18/0 | 44/95 | 54/54 |
t | 4.30 | 4.90 | 0.99 | 0.47 | 0.05 | 0.125 | 0.01 | 34/28 | 39/39 | 57/54 |
u | 0.00 | 8.00 | 2.00 | 0.00 | 0.05 | 0.125 | 0.01 | 63/54 | 61/62 | 65/63 |
本实施例证明含二官能的环氧/丙烯酸酯材料和/或二官能的环氧材料以及任选地含有羟基官能的丙烯酸酯的组合物与多元醇一起形成具有所需固化性能的树脂。这些组合物表现出良好的初始固化性能,或者经初始固化后通过随时间的硬化证实了“活的(living)”固化体系。
上述说明、实施例和数据对本发明组合物的制备和使用提供了完整的描述。在上面说明中引用的美国专利在本说明书中引为参考。由于在不脱离本发明的精神和范围的情况下,可以列举出许多本发明实例,因此本发明范围包括在所附的权利要求书中。
Claims (31)
1.一种可光致聚合的组合物,它包括:
(a)环氧树脂;
(b)含羟基的材料;和
(c)光引发剂体系,所述光引发剂体系包括:
(i)碘鎓盐;
(ii)可见光敏化剂;和
(iii)电子给体化合物,其中所述光引发剂体系的光引发电位大于或等于3-二甲基氨基苯甲酸在2.9×10-5mol/g六氟锑酸二苯基碘鎓和1.5×10-5mol/g樟脑醌的2-丁酮标准溶液中的光引发电位。
2.如权利要求1所述的组合物,其特征在于所述电子给体化合物具有下列结构式:其中R1独立地为H,任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、COOH、COOC1-18烷基、(C1-18烷基)0- 1-CO-C1-18烷基、SO3H、CN、或卤素基团所取代的C1-18烷,或任选地被一个或多个吸电子基团取代的芳基,其中R2是H,任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、COOH、COOC1-18烷基、(C1-18烷基)0-1-CO-C1-18烷基、SO3H、CN或卤素基团,或任选地被一个或多个吸电子基团取代的芳基所取代的C1-18烷基,或者R1基团可组合在一起形成一个环;Ar是被一个或多个吸电子基团取代的芳基。
3.如权利要求2所述的组合物,其特征在于所述芳基基团被一个或多个羧酸、羧酸酯、酮、醛、磺酸、磺酸根或腈基团所取代。
4.如权利要求2所述的组合物,其特征在于所述芳基被一个或多个选自-COOH、-COO-C1-18烷基、-SO3R2、-CN、-CO-C1-18烷基和-C(O)H基团所取代,其中R2是H,任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、COOH、COOC1-18烷基、(C1-18烷基)0-1-CO-C1-18烷基、SO3H、CN或卤素基团,或任选地被一个或多个吸电子基团取代的芳基所取代的C1-18烷基。
5.如权利要求1所述的组合物,其特征在于所述电子给体化合物选自4-二甲基氨基苯甲酸、4-二甲基氨基苯甲酸乙酯、3-二甲基氨基苯甲酸、4-二甲基氨基苯偶姻、4-二甲基氨基苯甲醛、4-二甲基氨基苄腈和1,2,4-三甲氧基苯。
6.如权利要求1所述的组合物,其特征在于所述电子给体化合物是烷基、芳基聚醚。
7.如权利要求1所述的组合物,其特征在于所述电子给体化合物是具有下述结构式的烷基、芳基聚醚:其中n=1-3,各R3独立地为H或任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、取代的芳基、-COOH、-COOC1-18烷基、-(C1-18烷基)0-1-COH、-(C1-18烷基)0-1-CO-C1-18烷基、-CO-C1-18烷基、-C(O)H或-C2-18链烯基取代的C1-18烷基,或者各R3基团一起形成一个环,各R4可为任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、取代芳基、-COOH、-COOC1-18烷基、-(C1-18烷基)0-1-COH、-(C1-18烷基)0-1-CO-C1-18烷基、-CO-C1-18烷基、-C(O)H或-C2-18链烯基取代的C1-18烷基。
8.如权利要求1所述的组合物,其特征在于所述碘鎓盐是芳基碘鎓盐。
9.如权利要求1所述的组合物,其特征在于所述碘鎓盐包括氯化二苯基碘鎓、六氟磷酸二苯基碘鎓、六氟锑酸二(4-氯苯基)碘鎓盐、四氟硼酸二萘基碘鎓、四氟硼酸二苯基碘鎓、四氟硼酸二苯基碘鎓或其混合物。
10.如权利要求1所述的组合物,其特征在于所述敏化剂化合物包括酮。
11.如权利要求1所述的组合物,其特征在于所述敏化剂化合物包括α-二酮。
12.如权利要求1所述的组合物,其特征在于所述敏化剂化合物包括苯并二氢呋喃酮、氨基芳基酮或对位取代的氨基苯乙烯基酮化合物。
13.如权利要求1所述的组合物,其特征在于所述敏化剂化合物包括樟脑醌。
14.如权利要求1所述的组合物,其特征在于用可见光辐照后在60秒内所述组合物固化成不发粘的凝胶。
15.如权利要求1所述的组合物,其特征在于所述环氧树脂包括脂环族环氧化物或二环氧化物。
16.如权利要求1所述的组合物,其特征在于所述环氧树脂包括双酚A二环氧化物。
17.如权利要求1所述的组合物,其特征在于所述环氧树脂含有不饱和烯键。
18.如权利要求1所述的组合物,其特征在于它还包括烯键不饱和化合物。
19.如权利要求16所述的组合物,其特征在于所述烯键不饱和化合物是丙烯酸酯或甲基丙烯酸酯。
20.如权利要求16所述的组合物,其特征在于所述烯键不饱和化合物包括丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸异丙酯、丙烯酸正己酯、丙烯酸十八烷酯、丙烯酸烯丙酯、丙三醇二丙烯酸酯、丙三醇三丙烯酸酯、乙二醇二丙烯酸酯、二甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,3-丙二醇二甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、1,2,4-丁三醇三甲基丙烯酸酯、1,4-环己二醇二丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、山梨醇六丙烯酸酯或其混合物。
21.一种可光致聚合的组合物,它包括:
(a)环氧树脂;
(b)含羟基的材料;
(c)光引发剂体系,所述光引发剂体系包括:
(i)六氟锑酸二芳基碘鎓或六氟磷酸二芳基碘鎓;
(ii)樟脑醌;和
(iii)具有下列结构式的电子给体:其中R1独立地为H,任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、COOH、COOC1-18烷基、(C1-18烷基)0- 1-CO-C1-18烷基、SO3H、CN、或卤素基团所取代的C1-18烷基,或任选地被一个或多个吸电子基团取代的芳基,其中R2是H,任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、COOH、COO1-18烷基、(C1-18烷基)0-1-CO-C1-18烷基、SO3H、CN或卤素基团,或任选地被一个或多个吸电子基团取代的芳基所取代的C1-18烷基,或者R1基团可组合在一起形成一个环;Ar是被一个或多个吸电子基团取代的芳基。
22.一种可光致聚合的组合物,它包括:
(a)环氧树脂;
(b)含羟基的材料;和
(c)光引发剂体系,所述光引发剂体系包括:
(i)六氟锑酸二芳基碘鎓或六氟磷酸二芳基碘鎓;
(ii)樟脑醌;和
(iii)具有下列结构式的电子给体:其中n=1-3,各R3独立地为H或任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、取代的芳基、-COOH、-COOC1-18烷基、-(C1-18烷基)0-1-COH、-(C1-18烷基)0-1-CO-C1-18烷基、-CO-C1-18烷基、-C(O)H或-C2-18链烯基取代的C1-18烷基,或者各R3基团一起形成一个环,各R4可为任选地被一个或多个卤素、-CN、-OH、-SH、C1-18烷氧基、C1-18烷硫基、C3-18环烷基、芳基、取代芳基、-COOH、-COOC1-18烷基、-(C1-18烷基)0-1-COH、-(C1-18烷基)0-1-CO-C1-18烷基、-CO-C1-18烷基、-C(O)H或-C2-18链烯基取代的C1-18烷基。
23.一种光致聚合的方法,包括用波长约400-1000nm的光线将可光致聚合的组合物辐照至所述组合物胶凝或硬化的步骤,所述组合物包括:
(a)环氧树脂;
(b)含羟基的材料;和
(c)光引发剂体系,所述光引发剂体系包括:
(i)碘鎓盐;
(ii)可见光敏化剂;和
(iii)电子给体化合物,相对于2.9×10-5mol/g六氟锑酸二苯基碘鎓和1.5×10-5mol/g樟脑醌的2-丁酮标准溶液,所述光引发剂体系的光引发电位至少约100mV。
24.如权利要求23所述的方法,其特征在于所述组合物还包括烯键不饱和化合物。
25.一种可光致聚合的牙用组合物,它包括:
(a)环氧树脂;
(b)含羟基的材料;和
(c)光引发剂体系,所述光引发剂体系包括:
(i)碘鎓盐;
(ii)可见光敏化剂;和
(iii)电子给体化合物,相对于2.9×10-5mol/g六氟锑酸二苯基碘鎓和1.5×10-5mol/g樟脑醌的2-丁酮标准溶液,所述光引发剂体系的光引发电位至少约100mV。
26.如权利要求25所述的组合物,其特征在于所述组合物是牙用粘合剂。
27.如权利要求25所述的组合物,其特征在于所述组合物是牙用复合材料。
28.如权利要求25所述的组合物,其特征在于所述组合物是牙用密封剂。
29.如权利要求25所述的组合物,其特征在于所述组合物是正牙粘合剂。
30.如权利要求1所述的组合物,其特征在于所述组合物是图象艺术成象组合物。
31.如权利要求1所述的组合物,其特征在于所述组合物选自光刻胶,焊料掩模,电子保形涂层,涂覆磨料和磁性介质组合物。
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US08/840,093 US5998495A (en) | 1997-04-11 | 1997-04-11 | Ternary photoinitiator system for curing of epoxy/polyol resin compositions |
US08/840,093 | 1997-04-11 |
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EP (1) | EP0974078B1 (zh) |
JP (1) | JP4009754B2 (zh) |
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- 1998-03-06 WO PCT/US1998/004458 patent/WO1998047047A1/en active IP Right Grant
- 1998-03-06 KR KR1019997009365A patent/KR20010006281A/ko not_active Application Discontinuation
- 1998-03-06 CN CN98804068A patent/CN1252137A/zh active Pending
- 1998-03-06 JP JP54388598A patent/JP4009754B2/ja not_active Expired - Fee Related
- 1998-03-06 AU AU66903/98A patent/AU744316B2/en not_active Ceased
- 1998-03-06 EP EP98909015A patent/EP0974078B1/en not_active Expired - Lifetime
- 1998-03-06 CA CA002285317A patent/CA2285317C/en not_active Expired - Fee Related
- 1998-03-06 DE DE69815520T patent/DE69815520T2/de not_active Expired - Lifetime
-
1999
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CN100584301C (zh) * | 2006-10-04 | 2010-01-27 | 中国科学院长春应用化学研究所 | 一种可见光固化纳米复合树脂牙体修复材料及制备方法 |
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CN111491802A (zh) * | 2017-12-21 | 2020-08-04 | 上阿尔萨斯大学 | 通过红光至近红外辐照诱导的自由基聚合的热扩增 |
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CN112867748A (zh) * | 2018-09-27 | 2021-05-28 | 上阿尔萨斯大学 | 超快环醚-胺光加聚及其用途 |
CN112867748B (zh) * | 2018-09-27 | 2024-03-08 | 上阿尔萨斯大学 | 超快环醚-胺光加聚及其用途 |
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AU744316B2 (en) | 2002-02-21 |
NO994955D0 (no) | 1999-10-11 |
CA2285317A1 (en) | 1998-10-22 |
WO1998047047A1 (en) | 1998-10-22 |
KR20010006281A (ko) | 2001-01-26 |
AU6690398A (en) | 1998-11-11 |
US5998495A (en) | 1999-12-07 |
US6187833B1 (en) | 2001-02-13 |
JP4009754B2 (ja) | 2007-11-21 |
BR9807971A (pt) | 2000-03-08 |
DE69815520T2 (de) | 2004-04-29 |
EP0974078A1 (en) | 2000-01-26 |
CA2285317C (en) | 2009-09-08 |
DE69815520D1 (de) | 2003-07-17 |
NO994955L (no) | 1999-10-11 |
EP0974078B1 (en) | 2003-06-11 |
NO314041B1 (no) | 2003-01-20 |
JP2001520759A (ja) | 2001-10-30 |
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