CN1103073A - 环氧丙烯酸酯 - Google Patents
环氧丙烯酸酯 Download PDFInfo
- Publication number
- CN1103073A CN1103073A CN94108125A CN94108125A CN1103073A CN 1103073 A CN1103073 A CN 1103073A CN 94108125 A CN94108125 A CN 94108125A CN 94108125 A CN94108125 A CN 94108125A CN 1103073 A CN1103073 A CN 1103073A
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- China
- Prior art keywords
- formula
- base
- following formula
- epoxy
- epoxy acrylate
- Prior art date
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- Granted
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 35
- 150000001252 acrylic acid derivatives Chemical class 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000009472 formulation Methods 0.000 claims abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 58
- 239000011347 resin Substances 0.000 claims description 58
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 22
- -1 cyclic anhydride Chemical class 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- 229920005596 polymer binder Polymers 0.000 abstract description 8
- 239000002491 polymer binding agent Substances 0.000 abstract description 8
- 238000007639 printing Methods 0.000 abstract description 5
- 239000004020 conductor Substances 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 30
- 239000002585 base Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000007795 chemical reaction product Substances 0.000 description 23
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- 238000000207 volumetry Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- 125000003700 epoxy group Chemical group 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 14
- 229920002223 polystyrene Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
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- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
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- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 4
- 238000006206 glycosylation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 206010034960 Photophobia Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
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- 239000003822 epoxy resin Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 208000013469 light sensitivity Diseases 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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Abstract
权利要求书中式III和式IV的新型环氧丙烯酸酯
和含羧基环氧丙烯酸酯是分子量较大的而且是化学
交联性的。这类新型环氧丙烯酸酯可用于光致抗蚀
剂制剂用途,尤其可用于印制线路板和印刷版材方
面。特别在导体上几乎不粘,并具有很优良的边缘遮
盖力。
Description
本发明涉及新型高分子量环氧丙烯酸酯和新型高分子量含羧基的环氧丙烯酸酯,涉及其制备方法,涉及该环氧丙烯酸酯在光致抗蚀剂制剂中的应用,並涉及该制剂,尤其在印制线路板方面的应用,一般用作阻焊抗蚀剂或用作主抗蚀剂(蚀刻抗蚀剂或电镀抗蚀剂),並涉及该制剂在印刷版材方面的应用。
已知环氧丙烯酸酯生产量很多,而且特别用于光致抗蚀剂制剂的组合物中。
用于阻焊抗蚀剂的含有环氧线型酚醛树脂与丙烯酸和环羧酸酐反应产物的制剂特别在EP0 273 729中公开报道。这类制剂可在碱性水介质中显影並有优良的耐热性和光敏性。但是其耐化学性是不能令人满意的。
EP0418011公开报道的阻焊掩膜组合物也是基于环氧甲酚酚醛树脂与丙烯酸和环二羧酐的反应产物,其中每当量环氧基使用0.4-0.9当量丙烯酸,以使最终产物在同一分子中同时含有酸基和环氧基。从而在这两种官能团之间的二次热交联反应在使用这些抗蚀剂时成为可能。但这里的问题是,且不说产品的制备(在与酸酐反应中的凝胶化危险),还存在储存的稳定性,因为:含有这种反应产品的制剂,即使在室温下也具有相当的反应性。所有上述列举的环氧丙烯酸酯相当普遍的是较低分子的。
由低分子环氧树脂和线型酚醛环氧树脂制得的经光化学固化或热固化的环氧丙烯酸酯,由于它们优良的热性能与机械性能以及由于它们的优良的耐腐蚀性化学品性能而闻名。但是用这些物系敷盖在导体上所得抗蚀剂膜的粘性和边缘遮盖性两项指标,由于其颇低的分子量而不能令人满意。因此在实际应用中往往需要添加高聚合的聚合物粘合剂来避免这些缺点。这类粘合剂通常不含丙烯酸基官能团,而且在光化学固化或热固化时並不同时起反应,即是作为“惰性”成分混入聚合物网络,因而导致网络密度的稀释,稀释特别又有害地影响加工好的抗蚀剂层的耐化学性和电性能。而且,因丙烯酸基的“稀释”而光敏性下降。添加高聚合的聚合物粘合剂,即使固含量比较低也引起这些制剂的高粘度,因此在涂敷中经常导致严重问题。
因此本发明的目的是提供多种没有上述缺点的丙烯酸酯。
在本发明的实施中达到这个目的的方法是使用新型高分子量环氧丙烯酸酯和新型高分子量含羧基的环氧丙烯酸酯,当在抗蚀剂中使用时,这些丙烯酸酯能够在没有或仅有少量别的聚合物粘合剂的情况下起作用。这些丙烯酸酯是通过所谓的“后缩水甘油基化”环氧树脂(PGER)一般与(甲基)丙烯酸反应而制得的。
Batzer和Zahir(J.Appl.Polym.Sci.19 609(1975))描述了双酚A的低分子液态二缩水甘油醚的后缩水甘油基化。US4 623 701公开了后缩水甘油基化的环氧树脂以及用多种环氧固化剂使之固化;US4 074 008公开了几种分子中含不止2个环氧基的光致交联的环氧树脂,其中至少2个环氧基产生于后缩水甘油基化反应。该分子链中的光交联性基团形成α,β-不饱和羰基系(查耳酮),该专利说明书中未描述含(甲基)丙烯酰基的衍生物。
并且众所周知,借助2+2环加成反应历程能光交联的α,β-不饱和羰基系的光敏性,与丙烯酸酯的光聚合性相比,有明显的降低。
日本公开特许平04-294352公开了通过与不饱和-羧酸、接着与不饱和多羧酸酐起反应制得的改性环氧线型酚醛树脂及其在含水光敏制剂中的应用。另外,欧洲专利申请0 292 219公开了含双酚A的环氧化合物的光敏系,该环氧化合物是用丙烯酸改性的。
具体地说,本发明提供式Ⅲ的新型环氧丙烯酸酯
式中
Q 是氢或一个下式基
R1是-H或-CH3,R2是-H,-CH3或苯基
T 是芳基双官能化合物的基,和
M 各自分别为氢或一个下式的基
R1和R2定义如上,
A 是芳基双官能化合物的基,
n 是从0到300的整数,和
L 是一个下式的基
或-O-A-OM,
但须式Ⅲ中的全部M基不可以同时是氢或一个下式的基
而且,不存在于端基Q和L中的M基的至少10mol%,最好是20-100mol%,代表前面提到的下式的基
式Ⅲ的环氧丙烯酸酯的制法是在有催化剂、阻聚剂和在升高温度的情况下,使一种式Ⅱ的后缩水甘油基化环氧树脂与一种烯属不饱和一元羧酸起反应:
式中
E 是氢或一个下式的基
F 代表式-O-A-OG或下式的基
,
G 是-H或下式的基
但须式Ⅱ中不存在于端基E和F中的G基的至少10mol%代表下式的基
A、T、和n的含义如上。
当式Ⅲ中的n是0,那么Q是-H,L是下式的基
在优选的式Ⅲ环氧丙烯酸酯中,n是一个从0到50的整数,最好是从0到30,符号A和T具有在日本公开特许平1-195056中给出的A和B的优选含意。
优选的双官能芳族化合物A和T是下式的连接基团
式中R4和R5各自分别为-H或C1-C4烷基,Z是-S-,-O-或-SO2,连接基A或T的芳族基是未被取代或被卤素或C1-C4烷基取代的基团。C1-C4烷基最好是-CH3,卤素最好是溴。
特别优选的连接基A和T各自分别具有下式
式中R4和R5的定义如上,连接基的苯基是未被取代或被溴取代的基团,最好具有下式
在本专利说明书中自始至终环氧丙烯酸酯是指环氧化合物与(甲基)丙烯酸的反应产物。
式Ⅱ的某些后缩水甘油基化环氧树脂是已知的,这些树脂可由式Ⅰ有关的已知现有的环氧树脂用缩水甘油基化反应来制备
式Ⅰ中,U是氢或下式的基
D是下式的基
或者是-O-A-OH基,符号A、T、和n的定义见式Ⅲ。另一方面,式Ⅰ现有的环氧树脂可用已知的双酚HO-A-OH加成聚合到下式的二环氧化物上来制备
式中A和T是双官能芳族化合物的基。
双酚HO-A-OH或HO-T-OH最好是已知的双酚,更具体地说是双酚A和四溴双酚A,以及在日本公开特许平1-195056中描述的双酚,最好是双酚A、双酚F、四溴双酚A和四溴双酚F。
为了制备现有环氧树脂,要用过量的上述二环氧化物,以使式Ⅰ的现有环氧树脂含有环氧端基。但是也可能使用过量的双酚HO-A-OH,从而制备含有酚端基的分子。其分子量由双酚HO-A-OH与二环氧化物摩尔比来决定。如有需要,还可添加少量高官能苯酚或环氧化合物到加成聚合中。现有环氧树脂中也可以存在特定量的起始物料(双酚HO-A-OH和/或二环氧化合物)。
式Ⅰ的现有环氧树脂含有仲羟基,该基是由酚羟基加成到环氧乙烷环
上生成的。
用已知方法来进行式Ⅱ的后缩水甘油基化环氧树脂的缩水甘油基化反应,是在有碱(例如NaOH)和催化剂和在升高温度的情况下使现有环氧树脂(Ⅰ)与过量的表氯醇起反应。
缩水甘油基化中碱的用量将取决于想要的缩水甘油化程度。在现有环氧树脂中每当量仲羟基最好使用0.1-1.2当量碱。采用过量的表氯醇借助共沸蒸馏法除水。
特别合适的催化剂是季铵盐或鏻盐,通常包括氯化四甲铵、氯化苄基三甲铵、氯化苄基三乙铵、氯化四乙铵和溴化四丁铵。
合适的反应温度是40-80℃,最好是50-65℃。
脂族羟基用缩水甘油基化反应被部分地或者完全地缩水甘油化。
式Ⅱ后缩水甘油基化环氧树脂进一步生成式Ⅲ新型环氧丙烯酸酯的反应同样用已知方法通过与下式的烯属不饱和一元羧酸起反应进行
合适的酸通常包括巴豆酸、肉桂酸、最好是丙烯酸或甲基丙烯酸或它们的混合物。R1和R2定义如上。
在反应中最好使用一种催化剂。特别合适的催化剂是金属盐诸如铬的化合物,胺诸如三乙胺或苄基二甲胺,还有铵盐诸如氯化苄基三甲铵,或者三苯膦和三苯基铋
因为式Ⅱ后缩水甘油基化环氧树脂是固态的,可向反应中添加溶剂。但溶剂必须对离析物是惰性的。合适的溶剂包括:酮诸如丙酮、甲乙酮、环己酮,酯诸如乙酸乙酯和乙酸丁酯,乙酸乙氧基乙酯或乙酸甲氧基丙酯,醚诸如二甲氧基乙烷和二噁烷,芳烃诸如甲苯、苯和二甲苯,以及二种或多种上述溶剂的混合物。
合适的温度是80-140℃,与丙烯酸的反应最好在80-120℃下进行,与甲基丙烯酸的反应最好在80-140℃下进行。
还可向反应介质中添加阻聚剂,合适的是氢醌,氢醌单甲醚和2,6-二-叔丁基-对甲酚。
向反应介质中引入空气或者氮/氧混合气是合乎需要的,因为一些上述阻聚剂只在有氧的情况下才有效。取决于烯属不饱和一元羧酸的用量,制得的式Ⅲ环氧丙烯酸酯可以是完全丙烯酸酯化的或者是部分丙烯酸酯化的。一元羧酸的用量可以是与环氧基等摩尔或者少于当量。完全反应的环氧丙烯酸酯几乎不再含环氧基。
式Ⅲ新型环氧丙烯酸酯既不需要从反应介质中离析也不需要提纯。反应溶液能够以合成中所得的形式直接使用。
部分以及完全反应的式Ⅲ产物所含的脂族羟基来自环氧基与烯属不饱和一元羧酸的反应,产物可另外含有来自离析物的脂族羟基。
完全丙烯酸酯化的式Ⅲ环氧丙烯酸酯然后就能进一步反应成含羧基的式Ⅳ环氧丙烯酸酯
式中
X 是氢或一个下式的基
R3是多元羧酸环酐除去酐基后的基
W1是氢或一个下式的基
式中符号A、T、R1、R2、R3和n的含义已给定,但须式Ⅳ中不存在于端基X和Y中的W1基的至少10mol%是一个下式的基
R1、R2和R3的含义已给定。
因为完全反应的式Ⅲ环氧丙烯酸酯几乎不再含环氧基,这些丙烯酸酯能与多元羧酸环酐起反应。在这种情况下,脂族羟基与环酐起反应来实现开环和形成半酯。在此反应中,对每个反应的羟基来说形成一个键合到树脂上的羧酸。此反应包括使式Ⅲ的环氧丙烯酸酯与环酐起反应,在没有或者有催化剂和有阻聚剂的情况下,在升高温度的情况下反应。式Ⅱ化合物的羟基被完全或者部分丙烯酸酯化同时有酐的开环。因此环氧丙烯酸酯不再含环氧基是有利的,否则产生凝胶化。酸酐的用量与羟基等摩尔或者少于当量。该反应自身是已知的。
合适的多元羧酸酐通常包括琥珀酐、马来酐、戊二酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、3-甲基-和4-甲基六氢邻苯二甲酸酐、3-乙基-和4-乙基六氢邻苯二甲酸酐、3-甲基-,3-乙基-,4-甲基-和4-乙基四氢邻苯二甲酸酐、衣康酸酐、邻苯二甲酸酐、和1,2,4-苯酸三酐。优选的酸酐是琥珀酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐和邻苯二甲酸酐。
合适的催化剂通常包括胺诸如三乙胺,苄基二甲铵,吡啶或二甲氨基吡啶,或三苯膦,或金属盐诸如铬或锆化合物。
如果需要,可向反应介质中添加一种溶剂,因为式Ⅲ的环氧丙烯酸酯是呈固体状态。但溶剂对于环酐必须是惰性的,所以含羟基的溶剂是不合适的。所列举的与烯属不饱和一元羧酸反应有关的溶剂能够合适地使用。
合适的反应温度是60-140℃,合适的阻聚剂通常是氢醌、氢醌单甲醚和2,6-二叔丁基对二甲酚。
向反应介质中引入干空气或氮氧混合气是合乎需要的。在本发明的一个优选的实施方案中,式Ⅲ的环氧丙烯酸酯不经离析在同一反应器中进一步反应成羧基改性的式Ⅳ的衍生物。
式Ⅳ的新型含羧基环氧丙烯酸酯的分离与提纯通常是不必要的。反应溶液能够以合成中所得的形式接着使用。
由于分子中存在着不饱和基,式Ⅲ环氧丙烯酸酯和式Ⅳ含羧基的丙烯酸酯是热和光化学交联性的。因此这些丙烯酸酯作为丙烯酸酯成分使用並应用于光致抗蚀剂制剂中,用已知方法制造阻焊抗蚀剂或主抗蚀剂,所得抗蚀剂层具有增强的热、机械、电和化学性能。其制造方法的例子可见瑞士专利申请2005/93-4(1993.07.02)中公开的“光聚合性组合物”。由此制备的抗蚀剂制剂特别用于印制线路板方面作为阻焊抗蚀剂或主抗蚀剂,以及印刷版材方面。它们还适于生产胶印版、柔性印刷版,书刊印刷版和丝网印刷制剂。合适的显影剂是水系以及水-有机系或有机系。由于式Ⅳ化合物中羧基的存在,上述各物系特别适于制备可碱水显影的光致抗蚀剂。
与含聚合物粘合剂的制剂中的低分子环氧丙烯酸酯相比,使人意想不到的是,含有高分子量环氧丙烯酸酯而不添加这种聚合物粘合剂的制剂导致光敏性的增强而不是衰减,此外还不发生粘性的增加。此外,用该制剂作为阻焊抗蚀剂还导致导体的边缘复盖得到改进。因为在这类制剂中没有另外的聚合物粘合剂,就出现了更多的优点,这些优点是涉及由此制备的抗蚀剂组合物的热、机械和电性能,特别是耐化学品性能。式Ⅲ的新型环氧丙烯酸酯和式Ⅳ的含羧基环氧丙烯酸酯的玻璃化温度有所提高。
用下列一些非限制性实施例举例说明本发明。
制备实施例
a)后缩水甘油酯化的环氧树脂(PGER)
实施例1:所用的装置要适合于氯化四甲铵(TMAC)的缩水甘油化反应並有可能用过量表氯醇作为减压下分离水的共沸剂。该装置包括一个有搅拌器、温度计的5000ml反应器、效率高的多盘管冷凝器和两个带有压力平衡管的滴液漏斗。连接到该装置上的有水分离器(供上层水相和真空下排气用)和带气压计的水喷射泵。油浴用于加热。
把1000g环氧树脂Araldite GT 7004(CIBA:环氧值1.36mol/kg树脂:羟值2.71mol)和1700ml(21.68mol)表氯醇借助加热溶于反应器中。把这样得到的均相溶液加热到约80℃,並有效地搅拌,小心地施加水喷射真空以使表氯醇猛烈地回流。反应器中的温度下降,设定到恒温约55℃並在整个反应中保持此温度。这开始需要110-120mbar的压力,将近反应结束可能必须稍微降低。油浴温度是恒定的105-110℃。当表氯醇恒定地在55℃下回流时,把29.80g(0.136mol)氯化四甲铵50%水溶液从第一滴液漏斗快速添加。然后从第二滴液漏斗在两小时期间滴加195.20g(2.44mol)NaOH的50%水溶液,同时从反应体系中除去由共沸蒸馏从50%溶液产生的反应水和表氯醇。内部温度保持在55-58℃並维持足够的回流来保证从反应混合物中快速去水。滴加完毕之后,使反应混合物在55℃下保持2小时同时从体系中脱除水分。撤消真空並通过添加碎干冰接着添加10-20ml冰醋酸来中和该悬浮液。添加2000ml乙酸甲氧基丙酯之后,用减压蒸馏除去溶剂和表氯醇。向残余物中添加另外2000ml乙酸甲氧基丙酯,在助滤器(Hyflo)上过滤所得的悬浮液,同时经常地擦刮滤器床层表面。将所得透明淡黄色滤液在旋转蒸发器中于高达120℃的浴温下浓缩。用乙酸甲氧基丙酯把这样得到的透明黄色树脂稀释成一种50%固含量的溶液,产出2316g几乎无色的式Ⅱ后缩水甘油化环氧树脂的50%溶液,其中
G 约90mol%下式的基
10mol%-H,
n 平均值2。
这一溶液可直接用来与丙烯酸反应。此溶液的分析数据是:
1.分析(固含量):49.5%;
2.环氧值(滴定法):1.46mol/kg/(→2.81mol/kg固体树脂);
3.Cl含量(固体树脂):0.40%Cl总量;0.23%Cl可水解;
4.GPC(凝胶渗透色谱 MW=10678;Mn=2138。聚苯乙烯校准):
如果想要获得固体树脂,可用甲基·异丁基酮替代乙酸甲氧基丙酯作为溶剂,用来精制时稀释树脂,在旋转蒸发器中浓缩之后的残余物可趁热倾倒在扁钢盘中並在150℃高真空中干燥几个小时。
实施例2:按照实施例1所述方法,使555g Araldite GT 7004(CIBA;环氧值1.36mol/kg树脂;羟值1.50mol),705ml表氯醇(9.00mol),16.40g氯化四甲铵50%水溶液和66.00g氢氧化钠50%水溶液(0.83mol)起反应。滴加NaOH溶液和进一步反应45分钟同时脱水之后,借助约85mbar的真空蒸馏除去大部分表氯醇。然后添加600ml甲基·异丁基酮,用干冰和乙酸中和反应混合物,並用另外500ml甲基·异丁基酮稀释反应混合物。在助滤器(Hyflo)上过滤悬浮液,在旋转蒸发器中除掉溶剂,把残余物趁热倾倒在钢盘中在150℃高真空下干燥几个小时。所得淡黄色固体树脂(473g)有下列分析数据:
1.环氧值(滴定法):2.39mol/kg树脂:
2.Cl含量:0.33%Cl总量;0.17%Cl可水解;
3.羟值(滴定法):1.22mol/kg;
4.GPC(聚苯乙烯校准):Mw=10721:Mn=2330。
实施例3:按照实施例1所述方法,使1525 g Araldite B41(CIBA;环氧值2.66mol/kg树脂;羟值1.01mol),712ml表氯醇(9.09mol),18.48g氯化四甲铵50%水溶液和89.00g氢氧化钠50%水溶液(1.11mol)起反应,产物以固体树脂形式分离出。
所得几乎无色的固体树脂(515g)有下列分析数据:
1.环氧值(滴定法):3.48mol/kg;
2.Cl含量:0.21%Cl总量;<0.05%Cl可水解;
3.GPC(聚苯乙烯校准):Mw=2374;Mn=935。
实施例4:按照实施例1所述方法,使1435 g Araldite GT6071(CIBA;环氧值2.18mol/kg树脂:羟值1.00mol),470ml表氯醇(6.00mol),11.00g氯化四甲铵50%水溶液和88.00g氢氧化钠50%水溶液(1.10mol)起反应,产物以固体树脂形式分离出。
所得淡黄色固体树脂(390g)有下列分析数据:
1.环氧树脂(滴定法):3.55mol/kg;
2.Cl含量:0.82%Cl总量;0.60%Cl可水解;
3.GPC(聚苯乙烯校准):Mw=6948;Mn=1376。
固体树脂与式Ⅱ相符,其中A、T、E和F的含义见实施例1,n是一个约1.0的平均值,G是100mol%的
实施例5:按照实施例1所述的方法,使1000g Araldite GT6097(CIBA;环氧值0.60mol/kg树脂;羟值3.175mol),1996ml表氯醇(25.40mol),35.20g氯化四甲铵50%水溶液和228.60g氢氧化钠50%水溶液(2.86mol)起反应,产物以约50%乙酸甲氧基丙酯溶液的形式分离出。
此溶液(2283g)有下列分析数据:
1.固含量:48.30%;
2.环氧值(滴定法):1.17mol/kg;
3.Cl含量:0.63%Cl总量;0.30%Cl可水解;
4.GPC(聚苯乙烯校准):Mw=16759;Mn=3382。
溶液中的固体树脂与式Ⅱ相符,其中A、T、E和F的含义见实施例1,n是一个约5.3的平均值,G是90mol%的
实施例6:按照实施例1所述的方法,使500g Araldite GT7097(CIBA;环氧值0.58mol/kg树脂;羟值1.60mol),753ml表氯醇(9.60mol),17.54g氯化四甲铵50%水溶液和115.20g氢氧化钠50%水溶液(1.44mol)起反应,产物以约45%乙酸甲氧基丙酯溶液的形式分离出。
此溶液(1200g)有下列分析数据:
1.固含量:44.50%
2.环氧值(滴定法):1.19mol/kg
3.Cl含量:0.70%Cl总量;0.45%Cl可水解;
4.GPC(聚苯乙烯校准):Mw=23091:Mn=4270
溶液中的固体树脂与式Ⅱ相符,其中A、T、E和F的含义见实施例1,n是一个约5.5的平均值,G是90mol%的
实施例7:按照实施例1所述的方法,使400g Araldite GT6099(CIBA;环氧值0.41mol/kg树脂;羟值1.32mol),1038ml表氯醇(11.88mol),14.08g氯化四甲铵50%水溶液和95.04g氢氧化钠50%水溶液(1.19mol)起反应,产物以约45%乙酸甲氧基丙酯溶液的形式分离出。
此溶液(915g)有下列分析数据:
1.固含量:45.60%;
2.环氧值(滴定法):1.16mol/kg;
3.Cl含量:0.42%Cl总量;0.24%Cl可水解;
4.GPC(聚苯乙烯校准):Mw=57017;Mn=5604。
溶液中的固体树脂与式Ⅱ相符,其中A、T、E和F的含义见实施例1,n是一个约8.0的平均值,G是90mol%的
和10mol%的-H。
实施例8:按照实施例1所述的方法,使1171g Araldite固体树脂(CIBA;溴化环氧树脂;环氧值1.85mol/kg树脂;羟值2.26mol),1416ml表氯醇(18.10mol),24.80g氯化四甲铵50%水溶液和162.60g氢氧化钠50%水溶液(2.03mol)起反应,产物以固体树脂形式分离出。
此固体树脂(1050g)有下列分析数据:
1.环氧值(滴定法):2.40mol/kg
2.氯含量:0.45%Cl总量;0.22%Cl可水解;
3.GPC(聚苯乙烯校准):Mw=3189;Mn=1235。
固体树脂与式Ⅱ相符,其中
E和F含义见实施例1,n为约1.0,G是90mol%的
b)PGER部分或全部丙烯酸酯化的环氧丙烯酸酯
实施例9:所用的装置包括一个安装有搅拌器、滴液漏斗、温度计、回流冷凝器和空气入口管的5000ml反应器。为了阻滞丙烯酸酯的聚合,反应期间在液面下引入一股弱空气流。用恒温控制的油浴进行加热。把2316.5g实施例1反应产物的45%乙酸甲氧基丙酯溶液(2.965mol环氧基),3.80g氢醌单甲醚和5.20ml三乙胺装填入反应器中。随着搅拌,将反应混合物加热到95℃。同时引入一股弱空气流,在1小时期间于95℃下添加213.70g丙烯酸(2.965mol),使反应混合物在这一温度下保持25小时。借助测量环氧值来监控此反应;在反应完成后其环氧值小于0.08mol/kg。反应产物经冷却可不经另外提纯而再使用。
1.固含量:54%;
2.酸值(滴定法):0.03mol/kg;
3.粘度(Brookfield)25℃ 1970mPa.S;
4.GPC(聚苯乙烯校准):Mw=8889;Mn=2256。
固体树脂与式Ⅲ相符,其中A和T的含义见实施例1,
n的值约2.0,M是90mol%的
和10mol%的-H。
实施例10:所用装置包括一个安装有搅拌器、滴液漏斗、温度计、回流冷凝器和空气入口管的2000ml反应器。为了阻滞丙烯酸酯的聚合,反应期间在液面下引入一股弱空气流。用恒温控制的油浴实现加热。把下列各成分装填在反应器中并在室温下搅拌直到获得均相溶液为止:1018.60g实施例1反应产物的50%乙酸甲氧基丙酯溶液(1.422mol环氧基,滴定);102.46g丙烯酸(1.442mol);1.53g氢醌单甲醚;20.38ml Nuosynchromium5(ex HARCROS,Durham Chemicals,Durham DH31QX,GB)10%乙酸甲氧基丙酯溶液。
将反应混合物加热到110℃並同时搅拌保持这一温度同时引入一股弱空气流达7小时。借助酸或环氧滴定来监控此反应。7小时后的酸滴定值是0.05mol/kg。冷却后取出反应产物,可不经提纯而进一步使用。反应产物(1080g)有下列分析数据:
1.固含量:53.3%;
2.环氧值(滴定法):0.02mol/kg;
3.GPC(聚苯乙烯校准):Mw=12168;Mn=2602。
固体树脂与实施例9的化学结构相符。
实施例11:
使用实施例10的方法和装置(500ml),使200g实施例1的反应产物50%乙酸甲氧基丙酯溶液(0.292mol环氧基),10.52g丙烯酸(0.146mol),0.33g氢醌单甲基醚和20.00mlNuosynchromium5的1%乙酸甲氧基丙酯溶液起反应。在100℃下3小时后使反应终止。当时的酸滴定指出<0.02mol/kg。反应产物(210g)有下列分析数据:
1.固含量:46%;
2.环氧值(滴定法):0.71mol/kg;
3.GPC(聚苯乙烯校准):Mw=11036;Mn=2352。
固体树脂与式Ⅲ相符,其中A和T的含义见实施例1,
n是2,M是90mol%的
实施例12:使用实施例11的装置。按照实施例10所述的方法,使200g实施例5的反应产物50%乙酸甲氧基丙酯溶液(0.236mol环氧基),17.00g丙烯酸(0.236mol),0.33g氢醌单甲醚和0.54g三苯膦起反应。在100℃下14小时后使反应终止。由酸滴定得0.09mol酸/kg。反应产物(210g)有下列分析数据:
1.固含量:54%;
2.环氧值(滴定法):0.10mol/kg;
3.GPC(聚苯乙烯校准):Mw=19493;Mn=3075。
固体树脂与式Ⅲ相符,其中A和T的含义见实施例1,Q、L和M的含义见实施例9,n是约5.3。
实施例13:使用实施例11的装置。按照实施例10所述的方法,使100g实施例5的反应产物48.3%乙酸甲氧基丙酯溶液(0.117mol环氧基),8.85g丙烯酸(0.123mol),0.15g氢醌单甲醚和1.15ml Nuosynchromium 5的10%乙酸甲氧基丙酯溶液起反应。反应在110℃下7小时后完成。由酸滴定得0.06mol/kg。此反应产物(210g)有下列分析数据:
环氧值(滴定法):0.020mol/kg。
产物与实施例12的式子相符。
实施例14:使用实施例10的装置(1000ml)。按照实施例10所述的方法,使720g实施例5的反应产物50%乙酸甲氧基丙酯溶液(0.828mol环氧基),29.83g丙烯酸(0.414mol),1.11g氢醌单甲醚和37.00ml Nuosynchromium 5的2%乙酸甲氧基丙酯溶液起反应。反应在100℃下5小时后完成。由酸滴定得<0.02mol酸/kg。此反应产物有下列分析数据:
1.固含量:50.3%;
2.环氧值(滴定法):0.65mol/kg;
3.GPC(聚苯乙烯校准):Mw=38840;Mn=4226。
产物与式Ⅲ相符,其中A和T的含义见实施例1,Q、L和M的含义见实施例11,n是约5.3。
c)完全丙烯酸酯化的PGER的含羧基的环氧丙烯酸酯
实施例15:所用装置包括一个安装有搅拌器、温度计、回流冷凝器和空气入口管的5000ml反应器。为了阻滞丙烯酸酯的聚合,反应期间在液面下引入一股弱空气流。用恒温控制的油浴进行加热。把2171g实施例9的反应产物(2.61mol羟基)装填在反应器中,随着搅拌,添加196.08g琥珀酐(1.96mol)。然后添加7.4ml苄基二甲胺,将反应混合物加热到110℃,同时引入一股干空气流並保持此温度达4小时。然后添加另外7.4ml苄基二甲胺,在此温度下搅拌持续4小时。均相淡黄色反应产物经冷却后可不经另外提纯而进一步使用。此反应产物有下列分析数据:
1.固含量:55%;
2.酸值(滴定法):0.88mol/kg;
3.GPC(聚苯乙烯校准):Mw=8525;Mn=2237。
固体树脂与式Ⅳ相符,其中A和T的含义见实施例1,
R3-CH2-CH2-
n 2.0.
实施例16:使用实施例15中所述的装置(500ml)。把实施例13的反应产物(0.117ml羟基)和5.854g(0.0585mol)琥珀酸酐装填在反应器中,将混合物加热到110℃,保持此温度达7小时,同时引入一股弱空气流。均相反应产物可不经另外提纯而进一步使用。此反应产物有下列分析数据:
1.固含量:61.7%;
2.酸值(滴定法):0.66mol/kg。
固体树脂与实施例15的结构相符,n是约5.3。
应用实施例
一般操作:所用的涂敷基材是洗净的敷铜层压板或者加工好的带电路图形的印制电路板。抗蚀剂制剂的制法是把列于实施例中的各成分混合、溶解,或必要时过滤。全部操作在保护性黄光下进行。
为了测试起见,可用金属绕丝涂敷器把制剂涂敷在印制电路板上,对较大系列则使用落帘式涂布法或辊涂法以及丝网印刷法。
烘干是在一个循环空气烘箱中进行的。曝光装置是一个带有5000W高压汞灯辐射源(掺杂卤化金属)的商品装置。显影在市售的连续显影装置中进行。感光度和分辨率的评价法是经由Stouffer式灰梯尺和分辨率梯尺曝光,然后从显影后的抗蚀剂图象来评价所得结果。
涂敷实施例
配方1.1包含一种用羧基改性的新型丙烯酸酯:
53.00g 实施例15的反应产物(55%乙酸甲氧基丙酯溶液);
19.00g CN965(丙烯酸酯;Craynor销售);
3.00g Irgacure 907(光引发剂;CIBA AG,Basel);
1.50g Quantacure ITX(异丙基噻吨铜;敏化剂);
0.15g Orasol blue GN(染料;CIBA AG,Basel);
28.95g 乙酸甲氧基丙酯
配方1.2含有高聚合的粘合剂和不含新型丙烯酸酯的对照实施例:
97.20g Scripset 550 E溶液(30%乙酸甲氧基丙酯溶液;聚合物粘合剂由Monsanto销售;为苯乙烯/马来酸共聚物);
19.00g CN965;
3.00g Irgacure 907;
1.50g Quantacure ITX;
0.15g Orasol blue GN
结果:
配方1.1 配方1.2
固含量 50% 43.7%
粘度25℃(Epprecht) 600mPa.s 7600mPa.s
干层厚度 12μm 12μm
烘干条件 5min.80℃ 5min.80℃
曝光 150mJ/cm2150mJ/cm2
显影 1%Na2CO3,35℃ 1%Na2CO3,35℃
最后可见的灰梯尺级数 6 无图象:被显影洗掉
含有新型丙烯酸酯的配方1.1制剂比配方1.2尽管固含量明显地高,但粘度却明显地低。另外,与配方1.2(产生图象的感光度太低)对照,配方1.1制剂的感光度(Stouffer灰梯度尺级数6)高很多。
Claims (8)
2、按照权利要求1式Ⅲ的环氧丙烯酸酯,其中R1是氢或甲基,R2是氢、甲基或苯基。
6、按照权利要求5式Ⅳ的含羧基的环氧丙烯酸酯的制备方法,该法包括在没有或者有催化剂、阻聚剂和在升高温度的情况下使一种权利要求1式Ⅲ的环氧丙烯酸酯与一种多元羧酸的环酐起反应。
7、按照权利要求1式Ⅲ的环氧丙烯酸酯在光致抗蚀剂制剂中作为丙烯酸酯成分的应用。
8、按照权利要求5式Ⅳ的含羧基的环氧丙烯酸酯在光致抗蚀剂制剂中作为丙烯酸酯成分的应用。
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CN (1) | CN1064055C (zh) |
AT (1) | ATE233287T1 (zh) |
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JP3190251B2 (ja) * | 1995-06-06 | 2001-07-23 | 太陽インキ製造株式会社 | アルカリ現像型のフレキシブルプリント配線板用光硬化性・熱硬化性樹脂組成物 |
KR100737723B1 (ko) * | 2001-07-27 | 2007-07-10 | 주식회사 동진쎄미켐 | 감광성 수지 조성물 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101450992B (zh) * | 2007-12-07 | 2010-12-22 | 比亚迪股份有限公司 | 一种聚合物及其制备方法和含有该聚合物的导电胶 |
CN104311511A (zh) * | 2014-09-17 | 2015-01-28 | 济南圣泉集团股份有限公司 | 一种低水解氯衣康酸环氧树脂的制备方法 |
CN104311511B (zh) * | 2014-09-17 | 2017-02-15 | 济南圣泉集团股份有限公司 | 一种低水解氯衣康酸环氧树脂的制备方法 |
CN105330820A (zh) * | 2015-11-27 | 2016-02-17 | 苏州市明大高分子科技材料有限公司 | 一种非对称结构改性环氧丙烯酸酯树脂及其连续法合成方法 |
CN105330820B (zh) * | 2015-11-27 | 2018-08-07 | 浙江瑞通光电材料有限公司 | 一种非对称结构改性环氧丙烯酸酯树脂及其连续法合成方法 |
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DE59410248D1 (de) | 2003-04-03 |
US6747101B2 (en) | 2004-06-08 |
EP1295900A2 (de) | 2003-03-26 |
EP1295900B1 (de) | 2006-12-06 |
JP2004004813A (ja) | 2004-01-08 |
JP3548969B2 (ja) | 2004-08-04 |
US20040072969A1 (en) | 2004-04-15 |
KR100341619B1 (ko) | 2002-11-23 |
US6784221B2 (en) | 2004-08-31 |
CA2127203C (en) | 2006-04-25 |
DE59410446D1 (de) | 2007-01-18 |
CN1064055C (zh) | 2001-04-04 |
KR950003280A (ko) | 1995-02-16 |
EP1295900A3 (de) | 2004-01-28 |
ATE233287T1 (de) | 2003-03-15 |
EP0632078A1 (de) | 1995-01-04 |
EP0632078B1 (de) | 2003-02-26 |
TW268011B (zh) | 1996-01-11 |
JPH0770281A (ja) | 1995-03-14 |
CA2127203A1 (en) | 1995-01-03 |
US20020019500A1 (en) | 2002-02-14 |
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