JP2012246225A - Silane coupling agent - Google Patents
Silane coupling agent Download PDFInfo
- Publication number
- JP2012246225A JP2012246225A JP2011117040A JP2011117040A JP2012246225A JP 2012246225 A JP2012246225 A JP 2012246225A JP 2011117040 A JP2011117040 A JP 2011117040A JP 2011117040 A JP2011117040 A JP 2011117040A JP 2012246225 A JP2012246225 A JP 2012246225A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silane coupling
- coupling agent
- methoxy
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000006087 Silane Coupling Agent Substances 0.000 title abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 13
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 19
- 125000001424 substituent group Chemical group 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 50
- -1 chlorosilyl group Chemical group 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 235000002597 Solanum melongena Nutrition 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000010703 silicon Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- JSHLOPGSDZTEGQ-UHFFFAOYSA-N 3-methoxy-4-phenylmethoxybenzaldehyde Chemical compound COC1=CC(C=O)=CC=C1OCC1=CC=CC=C1 JSHLOPGSDZTEGQ-UHFFFAOYSA-N 0.000 description 2
- INFACQKUQJGVFF-UHFFFAOYSA-N 4-hydroxy-5-methoxy-2-nitrobenzaldehyde Chemical compound COC1=CC(C=O)=C([N+]([O-])=O)C=C1O INFACQKUQJGVFF-UHFFFAOYSA-N 0.000 description 2
- 125000006043 5-hexenyl group Chemical group 0.000 description 2
- WKDLWHKMVQVRNO-UHFFFAOYSA-N 5-methoxy-2-nitro-4-phenylmethoxybenzaldehyde Chemical compound COC1=CC(C=O)=C([N+]([O-])=O)C=C1OCC1=CC=CC=C1 WKDLWHKMVQVRNO-UHFFFAOYSA-N 0.000 description 2
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 2
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- MEBLMJJIGUUIJO-UHFFFAOYSA-N 3-[(4,5-dimethoxy-2-nitrophenyl)methoxy]propyl-trimethoxysilane Chemical compound COC1=CC(COCCC[Si](OC)(OC)OC)=C([N+]([O-])=O)C=C1OC MEBLMJJIGUUIJO-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- SXNKGNZZYFNVJR-UHFFFAOYSA-N [N+](=O)([O-])C1=C(C=NN)C=C(C(=C1)O)OC Chemical compound [N+](=O)([O-])C1=C(C=NN)C=C(C(=C1)O)OC SXNKGNZZYFNVJR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- USEUJPGSYMRJHM-UHFFFAOYSA-N formaldehyde;4-methylphenol Chemical compound O=C.CC1=CC=C(O)C=C1 USEUJPGSYMRJHM-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- UCSUOYMTZRJAIH-UHFFFAOYSA-N iron(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Fe+2] UCSUOYMTZRJAIH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZZFQSVCIQZESOD-UHFFFAOYSA-N trimethoxy-[6-[(2-nitrophenyl)methoxy]hexyl]silane Chemical compound CO[Si](OC)(OC)CCCCCCOCC1=CC=CC=C1[N+]([O-])=O ZZFQSVCIQZESOD-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
Description
本発明は、疎水性から親水性に変性するシランカップリング剤、より詳しくは、光照射の前後で疎水性が大きく変化し、光照射された際に疎水性能を有する基が解離し親水性能を有するヒドロキシ基が生じる光分解性シランカップリング剤に関する。 The present invention relates to a silane coupling agent that is modified from hydrophobic to hydrophilic. More specifically, the hydrophobicity largely changes before and after light irradiation, and the group having hydrophobic performance is dissociated when irradiated with light, thereby improving the hydrophilic performance. The present invention relates to a photodegradable silane coupling agent in which a hydroxy group is generated.
疎水性から親水性に変性することができる光分解性シランカップリング剤は、特許文献１〜４に記載されているように開示されている。
しかしながら、特許文献１〜２によると精製したシランカップリング剤は材料表面に修飾した際に、光照射前の表面接触角が６０〜７０°前後のため、光照射前後の疎水性と親水性の差が少なく実用的なパターニングをするには難しかった。一方、疎水性を向上するためにフッ化アルキル鎖を有するシランカップリング剤が特許文献４に記載されているが、確かに光照射前の表面接触角は１００°前後まで上昇するが、高価な原料とフッ素化合物の環境への適性を考慮すると工業化に難があった。
Photodegradable silane coupling agents that can be modified from hydrophobic to hydrophilic are disclosed as described in Patent Documents 1 to 4.
However, according to Patent Documents 1 and 2, when the purified silane coupling agent is modified on the surface of the material, the surface contact angle before light irradiation is around 60 to 70 °, so hydrophobic and hydrophilic before and after light irradiation. There were few differences and it was difficult to perform practical patterning. On the other hand, in order to improve hydrophobicity, a silane coupling agent having an fluorinated alkyl chain is described in Patent Document 4, but the surface contact angle before light irradiation certainly increases to around 100 °, but is expensive. Considering the environmental suitability of raw materials and fluorine compounds, it was difficult to industrialize.
本発明の目的は、従来のシランカップリング剤よりも光照射前の疎水性が高いシランカップリング剤で、汎用露光機を使用できる、好ましくは３００〜４００ｎｍのような紫外線で露光できて親水性となり、ポジ型の画像形成等に応用できる安定なシランカップリング剤を提供することである。 An object of the present invention is a silane coupling agent having a higher hydrophobicity before light irradiation than that of a conventional silane coupling agent, and a general-purpose exposure machine can be used, preferably it can be exposed to ultraviolet rays such as 300 to 400 nm and is hydrophilic. Thus, it is an object of the present invention to provide a stable silane coupling agent that can be applied to positive image formation and the like.
本発明は、高い疎水性を持ち合わせた光分解性シランカップリング剤である、一般式（Ｉ）に示す化合物を提供する。 The present invention provides a compound represented by the general formula (I), which is a photodegradable silane coupling agent having high hydrophobicity.
（上式中、Ｒは、メチル基、ｔ−ブチル基、置換基を有してもよいフェニル基、又は置換基を有してもよいシクロヘキシル基を表し、ｍは、３〜１０の整数であり、ｎは、３〜９の整数であり、Ｘは、加水分解性シリル基を表す。） (In the above formula, R represents a methyl group, a t-butyl group, an optionally substituted phenyl group, or an optionally substituted cyclohexyl group, and m is an integer of 3 to 10. Yes, n is an integer of 3 to 9, and X represents a hydrolyzable silyl group.)
本発明に係るシランカップリング剤によれば、光照射前の高い疎水性を有するシランカップリング剤を提供できる。シランカップリング剤は、環境負荷の少ないフルオロ基非含有の特定置換基の採用により材料表面への導入の際に、シランカップリング剤同士が分子配向し易くなりより疎水性が高くなると考えられる。その後、汎用露光機を使用できる、好ましくは３００〜４００ｎｍのような紫外線で露光でき、その際に疎水性能を有する基が解離し親水性能を有するヒドロキシ基が生じる。したがって、光照射前後の疎水性と親水性の差が大きく、実用的なパターニングに好適である。 According to the silane coupling agent which concerns on this invention, the silane coupling agent which has high hydrophobicity before light irradiation can be provided. It is considered that the silane coupling agent is more hydrophobic because the silane coupling agent is easily molecularly oriented when introduced onto the surface of the material by adopting a specific substituent having no environmental load and containing no fluoro group. Thereafter, a general-purpose exposure machine can be used, preferably exposure with ultraviolet rays such as 300 to 400 nm. At that time, a group having hydrophobic performance is dissociated to produce a hydroxy group having hydrophilic performance. Therefore, there is a large difference between hydrophobicity and hydrophilicity before and after light irradiation, which is suitable for practical patterning.
以下に、本発明の実施の形態について詳細に説明するが、本発明は、以下の実施形態に限定されるものではない。
一般式（Ｉ）中のＸは、加水分解性シリル基を表し、ケイ素原子に結合したアルコキシ基又はクロロ基等の加水分解性基を１〜３個有する、アルコキシシリル基又はクロロシリル基等が挙げられる。例えば、各アルコキシ基の炭素数が１〜４（好ましくは１〜２）のトリアルコキシシリル基、アルキル基の炭素数が１〜４（好ましくは１〜２）で各アルコキシ基の炭素数が１〜４（好ましくは１〜２）のアルキルジアルコキシシリル基、各アルキル基の炭素数が１〜４（好ましくは１〜２）でアルコキシ基の炭素数が１〜４（好ましくは１〜２）のジアルキルアルコキシシリル基、トリクロロシリル基、アルキル基の炭素数が１〜４（好ましくは１〜２）のアルキルジクロロシリル基、各アルキル基の炭素数が１〜４（好ましくは１〜２）のジアルキルクロロシリル基が挙げられる。Ｘは、好ましくは、トリメトキシシリル基、トリエトキシシリル基、ジメトキシメチル基、ジエトキシメチル基である。
一般式（Ｉ）中のｍは、３〜１０の整数である。３以上であれば、Ｋａｒｓｔｅｄｔ触媒を用いることができ加水分解性シリル基の導入上好ましいからであり、１０以下であれば、反応性良く表面修飾できるからである。
Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.
X in the general formula (I) represents a hydrolyzable silyl group, and includes an alkoxysilyl group or a chlorosilyl group having 1 to 3 hydrolyzable groups such as an alkoxy group or a chloro group bonded to a silicon atom. It is done. For example, a trialkoxysilyl group having 1 to 4 (preferably 1 to 2) carbon atoms of each alkoxy group, a carbon number of 1 to 4 (preferably 1 to 2) of an alkyl group, and a carbon number of each alkoxy group being 1 -4 (preferably 1-2) alkyl dialkoxysilyl group, each alkyl group has 1-4 carbon atoms (preferably 1-2) and alkoxy group has 1-4 carbon atoms (preferably 1-2). A dialkylalkoxysilyl group, a trichlorosilyl group, an alkyldichlorosilyl group having 1 to 4 carbon atoms (preferably 1 to 2), and an alkyl group having 1 to 4 carbon atoms (preferably 1 to 2 carbon atoms). A dialkylchlorosilyl group is mentioned. X is preferably a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethyl group, or a diethoxymethyl group.
M in the general formula (I) is an integer of 3 to 10. If it is 3 or more, a Karstedt catalyst can be used, which is preferable in terms of introducing hydrolyzable silyl groups, and if it is 10 or less, surface modification can be performed with good reactivity.
一般式（Ｉ）中のＲは、メチル基、ｔ−ブチル基、置換基を有してもよいフェニル基、置換基を有してもよいシクロヘキシル基を表す。フェニル基やシクロヘキシル基が有してもよい置換基としては、好ましくは炭素数１〜４（より好ましくは１〜２）のアルキル基又はアルコキシ基であり、より好ましくは、メチル基、エチル基、メトキシ基等が挙げられる。フェニル基やシクロヘキシル基が有してもよい置換基の個数は、使用する紫外線の波長への影響が少ないので特に限定されないが、好ましくは１〜２である。
一般式（Ｉ）中のｎは３〜９の整数である。この範囲は、光分解速度の上で好ましい。
R in the general formula (I) represents a methyl group, a t-butyl group, a phenyl group which may have a substituent, or a cyclohexyl group which may have a substituent. The substituent that the phenyl group or the cyclohexyl group may have is preferably an alkyl group or an alkoxy group having 1 to 4 carbon atoms (more preferably 1 to 2), more preferably a methyl group, an ethyl group, A methoxy group etc. are mentioned. The number of substituents that the phenyl group or the cyclohexyl group may have is not particularly limited because it has little influence on the wavelength of ultraviolet rays to be used, but it is preferably 1 to 2.
N in general formula (I) is an integer of 3-9. This range is preferable in terms of the rate of photolysis.
一般式（Ｉ）の化合物は、好ましくは、下記式（１ＥＴ）〜（１２ＥＴ）で表される化合物である。 The compound of the general formula (I) is preferably a compound represented by the following formulas (1ET) to (12ET).
一般式（Ｉ）の化合物の製造方法の一例を以下に示す。 An example of a method for producing the compound of general formula (I) is shown below.
一般式（Ｉ）の化合物は、例えば、バニリンをベンジルブロミドにより保護し、ニトロ化、脱保護し、４位に特定置換基、５位にメトキシ基を有する２−ニトロベンズアルデヒドをヒドラジンと反応させ、二酸化マンガンで酸化してジアゾ化合物とし、過塩素酸の存在下、二重結合を有するアルコールと反応させてエーテルを得た後、エーテルの二重結合をＫａｒｓｔｅｄｔ’ｓ ｃａｔａｌｙｓｔを触媒として、例えば、トリメトキシシラン、トリエトキシシランと反応させることにより得られる。本発明の化合物の分離する方法は、特に限定されないが、好ましくは、本発明者らの特許文献２の段落０００７の記載と同様に、テトラメトキシシランを加えた溶出液を用いるシリカゲルカラムクロマトグラフィー法である。一般式（Ｉ）の化合物の製造方法は、これに限らず、他の公知の方法も利用できる。 The compound of the general formula (I) is obtained by, for example, protecting vanillin with benzyl bromide, nitration and deprotection, reacting 2-nitrobenzaldehyde having a specific substituent at the 4-position and a methoxy group at the 5-position with hydrazine, Oxidized with manganese dioxide to form a diazo compound, reacted with an alcohol having a double bond in the presence of perchloric acid to obtain an ether, and then the ether double bond was converted to, for example, tris by using Karstedt's catalyst as a catalyst. It can be obtained by reacting with methoxysilane or triethoxysilane. The method for separating the compound of the present invention is not particularly limited, but preferably, as in the description of paragraph 0007 of the present inventors, a silica gel column chromatography method using an eluate added with tetramethoxysilane. It is. The production method of the compound of the general formula (I) is not limited to this, and other known methods can be used.
一般式（Ｉ）の化合物と、表面にヒドロキシ基を有する材料とを反応させ、光照射することにより、材料表面にヒドロキシアルキル基を有する材料の製造できる。
ヒドロキシ基を有する材料は、反応できるヒドロキシ基が存在すれば特に限定されないが、ガラス、シリカ（ＳｉＯ2）、アルミナ（Ａｌ2Ｏ3）、タルク、クレー、アルミニウム、鉄、マイカ、アスベスト、酸化チタン、酸化鉄等が挙げられ、好ましくは、ガラス、シリカ、アルミナ、タルク、クレー、アルミニウム、鉄、マイカ、特に好ましくは、ガラス、シリカ、アルミナである。詳しくは、エヌ・ティー・エヌ社「表面処理技術ハンドブック」等を参照されたい。これらの材料の形状は、特に限定されず、シリカ粉等の粉状物、シリコンウェハ等の板状物であってもよい。
By reacting the compound of the general formula (I) with a material having a hydroxy group on the surface and irradiating with light, a material having a hydroxyalkyl group on the material surface can be produced.
The material having a hydroxy group is not particularly limited as long as a reactive hydroxy group exists, but glass, silica (SiO 2 ), alumina (Al 2 O 3 ), talc, clay, aluminum, iron, mica, asbestos, titanium oxide Iron oxide, etc., preferably glass, silica, alumina, talc, clay, aluminum, iron, mica, particularly preferably glass, silica, alumina. For details, please refer to the “Handbook of Surface Treatment Technology”, etc. The shape of these materials is not particularly limited, and may be a powdery material such as silica powder or a plate-like material such as a silicon wafer.
ヒドロキシ基を有する材料としてシリコンウェハを例にとれば、一般式（Ｉ）の化合物は、以下に示すように、シリコンウェハ表面のヒドロキシ基と反応して付着し、ＵＶ照射によりアルコールに変換される。なお、この例では、加水分解性シリル基としてトリメトキシシリル基を用いた。 Taking a silicon wafer as an example of a material having a hydroxy group, the compound of general formula (I) adheres by reacting with the hydroxy group on the surface of the silicon wafer and is converted to alcohol by UV irradiation as shown below. . In this example, a trimethoxysilyl group was used as the hydrolyzable silyl group.
一般式（Ｉ）のシランカップリング剤を材料表面に付着させる手段は、特に限定されず、通常のシランカップリング剤による表面処理と同様である。例えば、材料が粉体の場合には、一般式（Ｉ）の化合物をトルエン又はベンゼン等の溶媒に溶解し、撹拌された粉状のシリカ表面等に噴射したり、溶液中にシリカ等を入れ処理する方法が用いられる。材料がシリコンウェハ等の一定の形状を有する場合には、一般式（Ｉ）の化合物をトルエン又はベンゼン等の溶媒に溶解した溶液にシリコンウェハ等を投入し、還流又は室温での振動撹拌を行ったり、又は溶液を材料表面に薄く塗布することにより表面修飾を行うことができる。 The means for attaching the silane coupling agent of the general formula (I) to the material surface is not particularly limited, and is the same as the surface treatment with a normal silane coupling agent. For example, when the material is powder, the compound of the general formula (I) is dissolved in a solvent such as toluene or benzene and sprayed onto a stirred powdery silica surface, or silica or the like is put into the solution. A processing method is used. When the material has a certain shape such as a silicon wafer, the silicon wafer is put into a solution obtained by dissolving the compound of general formula (I) in a solvent such as toluene or benzene, and the mixture is stirred at reflux or at room temperature Alternatively, surface modification can be performed by thinly applying the solution to the material surface.
材料表面に付着した一般式（Ｉ）の化合物は、ＵＶ照射により、そのエーテル結合が切れて材料表面にヒドロキシ基を存在させることとなる。これは、トルエン又はベンゼン等の溶媒中に分散させた粉体にＵＶ照射したり、又はシリコンウェハ表面に直接ＵＶ照射すること等により行うことができる。材料表面での反応（表面修飾）と光照射を同時に行うと、光照射により生じたヒドロキシ基がシリル基と反応することとなり不都合である。
ＵＶ照射は、通常の方法が用いられるが、一例を挙げれば、超高圧水銀ランプ（ＵＳＨ−５００等）を光源とし、３００ｎｍ以下の波長はパイレックス（登録商標）製ガラスフィルターでカットして５〜６０秒照射する。好ましくは３００〜４００ｎｍのような紫外線で露光できるため、汎用露光機を使用できる。
The compound of the general formula (I) attached to the material surface breaks the ether bond by UV irradiation and causes a hydroxyl group to exist on the material surface. This can be performed by irradiating the powder dispersed in a solvent such as toluene or benzene with UV, or directly irradiating the silicon wafer surface with UV. If the reaction on the material surface (surface modification) and light irradiation are performed simultaneously, the hydroxy group generated by light irradiation reacts with the silyl group, which is inconvenient.
For UV irradiation, a normal method is used. For example, an ultrahigh pressure mercury lamp (USH-500 or the like) is used as a light source, and a wavelength of 300 nm or less is cut with a glass filter made of Pyrex (registered trademark) to 5 to 5 nm. Irradiate for 60 seconds. Since it can expose preferably by ultraviolet rays, such as 300-400 nm, a general purpose exposure machine can be used.
表面にヒドロキシ基を有する材料が、ヒドロキシ基含有ポリマーであってもよく、この場合、表面にヒドロキシルアルキル基を有するポリマーが製造できる。すなわち、一般式（Ｉ）で表される化合物をヒドロキシ基含有ポリマーと反応させ、光照射することによりヒドロキシアルキル基をポリマーに導入することができる。これを用いると、光酸発生剤を必要とせず、ポジ型の画像を形成できる。また、酸素阻害も受けず、この新規ポリマーが有機−無機複合体を形成していることから高い耐熱性も期待される。 The material having a hydroxyl group on the surface may be a hydroxy group-containing polymer, and in this case, a polymer having a hydroxylalkyl group on the surface can be produced. That is, a hydroxyalkyl group can be introduced into a polymer by reacting the compound represented by the general formula (I) with a hydroxy group-containing polymer and irradiating with light. When this is used, a positive-type image can be formed without requiring a photoacid generator. Further, since the novel polymer forms an organic-inorganic composite without being inhibited by oxygen, high heat resistance is also expected.
一般式（Ｉ）の化合物は、ベンゼン環上の置換基を選択することにより、ベンゼン環上に置換基を有しない化合物と比較して光の吸収ピークを長波長側にシフトさせることができる。例えば、ベンゼン環上に置換基を有しない化合物の吸収ピークが２４３ｎｍであるとき、ベンゼン環上に一つのメトキシ基を有する化合物の吸収ピークが３４５ｎｍとなる場合が挙げられる。この結果として、一般式（Ｉ）の化合物は、ベンゼン環上に置換基を有しない化合物より短時間の光照射により反応を完了するができる。 The compound of the general formula (I) can shift the absorption peak of light to the longer wavelength side by selecting a substituent on the benzene ring as compared with a compound having no substituent on the benzene ring. For example, when the absorption peak of a compound having no substituent on the benzene ring is 243 nm, the absorption peak of a compound having one methoxy group on the benzene ring is 345 nm. As a result, the compound of the general formula (I) can complete the reaction by light irradiation in a shorter time than a compound having no substituent on the benzene ring.
一般式（Ｉ）の化合物を付加できるポリマーとしては、ヒドロキシ基を有するポリマーが挙げられる。ヒドロキシ基の存在位置は、特に限定されず、側鎖の一部であってもよい。具体的には、ｍ−クレゾールホルムアルデヒド樹脂、ｐ−クレゾールホルムアルデヒド樹脂、ｏ−クレゾールホルムアルデヒド樹脂、ｍ−とｐ−の混合クレゾールホルムアルデヒド樹脂、フェノール/クレゾール（ｍ−、ｐ−、ｏ−、ｍ−とｐ−の混合、又はｍ−とo−の混合のいずれでもよい。）混合ホルムアルデヒド樹脂などのクレゾールホルムアルデヒド樹脂などが挙げられる。その他、レゾール型フェノール樹脂類、ポリビニルフェノール、ｔ−ブチル置換ポリビニルフェノール樹脂、ヒドロキシル基を有するポリアクリル、ポリウレタン樹脂、ポリビニルアルコール等である。 Examples of the polymer to which the compound of the general formula (I) can be added include polymers having a hydroxy group. The location of the hydroxy group is not particularly limited, and may be a part of the side chain. Specifically, m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, mixed cresol formaldehyde resin of m- and p-, phenol / cresol (m-, p-, o-, m- and Either a mixture of p- or a mixture of m- and o- may be used.) Examples include cresol formaldehyde resins such as mixed formaldehyde resins. Other examples include resol type phenol resins, polyvinyl phenol, t-butyl substituted polyvinyl phenol resin, polyacryl having a hydroxyl group, polyurethane resin, polyvinyl alcohol and the like.
一般式（Ｉ）で表される化合物をヒドロキシ基含有ポリマーと反応させ、光照射することによりヒドロキシアルキル基をポリマーに導入する反応スキームを以下に示す。なお、ｐとｑは、モル分率を示す。なお、この例では、加水分解性シリル基としてトリメトキシシリル基を用いた。 A reaction scheme for introducing a hydroxyalkyl group into a polymer by reacting the compound represented by formula (I) with a hydroxy group-containing polymer and irradiating with light is shown below. In addition, p and q show a mole fraction. In this example, a trimethoxysilyl group was used as the hydrolyzable silyl group.
以下、本発明を実施例により詳細に説明するが、本発明はこれに限定されるものではない。
［合成例１］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ３−（トリメトキシシリル）プロピルエーテル（７ＥＴ）の合成
［１−１］４−ベンジロキシ−３−メトキシベンザルデヒドの合成
２００ｍｌナスフラスコにバニリン１６．５ｇ（０．１０８ｍｏｌ）、アセトン１２０ｍｌ、Ｋ２ＣＯ３１５．０ｇ（０．１０８ｍｏｌ）を入れ、室温で２５分攪拌した。撹拌後、ベンジルブロミド１８．５ｇ（０．１０８ｍｏｌ）を加えオイルバス上６８℃で３時間還流した。その後、濃縮し、水２００ｍｌを入れクロロホルム１００ｍｌで３回抽出を行った。５％ＮａＨＣＯ３水溶液１００ｍｌで２回洗浄し無水硫酸マグネシウムで乾燥し、ろ過、濃縮し、液状残渣にヘキサンを入れ固体を析出させ濃縮し、得られた固体を７０℃に温めた酢酸エチルに溶かしヘキサンを加えて析出した固体を吸引ろ過し、その後、真空乾燥を行い白色固体１８．７ｇを得た。収量１８．７ｇ、収率７１％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ9.84 (s, 1H, -CHO), 7.45-7.31 (m, 7H, Ar-H), 6.99 (d, 1H,J=8.2 Hz, Ar-H), 5.26 (s, 2H, -O-CH 2-ph), 3.96 (s, 3H, -OCH 3)。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this.
[Synthesis Example 1] Synthesis of 4-hexyloxy-5-methoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether (7ET) [1-1] Synthesis of 4-benzyloxy-3-methoxybenzaldehyde 200 ml eggplant flask 16.5 g (0.108 mol) of vanillin, 120 ml of acetone, and 15.0 g (0.108 mol) of K 2 CO 3 were added and stirred at room temperature for 25 minutes. After stirring, 18.5 g (0.108 mol) of benzyl bromide was added and refluxed at 68 ° C. for 3 hours on an oil bath. Thereafter, the mixture was concentrated, 200 ml of water was added, and extraction was performed three times with 100 ml of chloroform. This was washed twice with 100 ml of 5% NaHCO 3 aqueous solution, dried over anhydrous magnesium sulfate, filtered and concentrated, hexane was added to the liquid residue, solid was precipitated and concentrated, and the obtained solid was dissolved in ethyl acetate warmed to 70 ° C. Hexane was added and the precipitated solid was suction filtered and then vacuum dried to obtain 18.7 g of a white solid. Yield 18.7 g, 71% yield.
1 HNMR (400MHz, CDCl 3 / TMS): δ9.84 (s, 1H, -C H O), 7.45-7.31 (m, 7H, Ar- H ), 6.99 (d, 1H, J = 8.2 Hz, Ar - H), 5.26 (s, 2H, -OC H 2 -ph), 3.96 (s, 3H, -OC H 3).
［１−２］４−ベンジロキシ−５−メトキシ−２−ニトロベンザルデヒドの合成
氷浴上で３００ｍｌナスフラスコに４−ベンジロキシ−３−メトキシベンザルデヒド１８．７ｇ（７７ｍｍｏｌ）、酢酸１４０ｍｌを入れ撹拌し、冷却後、発煙硝酸２５ｍｌを３０分かけて滴下した。３時間撹拌した後、氷浴を外し１２．５時間撹拌した。撹拌後、反応溶液を冷水２５０ｍｌの中に入れ固体を析出させ、吸引ろ過を行い、水で固体を洗浄、酢酸エチルに溶かし無水硫酸マグネシウムで乾燥、濃縮、７０℃に温めた酢酸エチルに溶かしヘキサンを加えて固体を析出させ、その後真空乾燥を行い黄色固体１４．７ｇを得た。収量１４．７ｇ、収率６７％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ10.41 (s, 1H, -CHO), 7.67 (s, 1H, Ar-H), 7.47-7.35（m, 6H, Ar-H）, 5.28 (s, 2H, -O-CH 2-ph), 4.02 (s, 3H, -OCH 3)。
[1-2] Synthesis of 4-Benzyloxy-5-methoxy-2-nitrobenzaldehyde In a 300 ml eggplant flask on an ice bath, 18.7 g (77 mmol) of 4-benzyloxy-3-methoxybenzaldehyde and 140 ml of acetic acid were added and stirred. After cooling, 25 ml of fuming nitric acid was added dropwise over 30 minutes. After stirring for 3 hours, the ice bath was removed and the mixture was stirred for 12.5 hours. After stirring, the reaction solution is poured into 250 ml of cold water to precipitate a solid, and suction filtration is performed. The solid is washed with water, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate, concentrated, dissolved in ethyl acetate warmed to 70 ° C., and hexane. To precipitate a solid, followed by vacuum drying to obtain 14.7 g of a yellow solid. Yield 14.7 g, 67% yield.
1 HNMR (400 MHz, CDCl 3 / TMS): δ 10.41 (s, 1H, —C 3 H 2 O), 7.67 (s, 1H, Ar—H), 7.47-7.35 (m, 6H, Ar—H), 5.28 (s, 2H, -OC H 2 -ph), 4.02 (s, 3H, -OC H 3 ).
［１−３］４−ヒドロキシ−５−メトキシ−２−ニトロベンザルデヒド
氷浴上で２００ｍｌナスフラスコに４−ベンジロキシ−５−メトキシ−２−ニトロベンザルデヒド１４．６ｇ（５０．９ｍｍｏｌ）、トリフルオロ酢酸９０ｍｌを入れ６０℃で１時間２０分撹拌した。その後、反応溶液を濃縮し、冷ヘキサン１００ｍｌに入れて固体を析出させ、吸引ろ過を行い、７０℃に温めた酢酸エチルに溶かしヘキサンを加えて固体を析出させ、ろ過後真空乾燥を行い暗黄色固体７．１１ｇを得た。収量７．１１ｇ、収率７１％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ10.4 (s, 1H, -CHO), 7.68 (s, 1H, Ar-H), 7.46（s, 1H, Ar-H）, 6.22 (s, 1H, Ar-OH), 4.07 (s, 3H, -OCH 3)。
[1-3] 4-Hydroxy-5-methoxy-2-nitrobenzaldehyde 14.6 g (50.9 mmol) of 4-benzyloxy-5-methoxy-2-nitrobenzaldehyde in a 200 ml eggplant flask on an ice bath, trifluoro 90 ml of acetic acid was added and stirred at 60 ° C. for 1 hour and 20 minutes. Then, the reaction solution is concentrated, put into 100 ml of cold hexane to precipitate a solid, suction filtered, dissolved in ethyl acetate warmed to 70 ° C., hexane added to precipitate the solid, filtered and vacuum dried to dark yellow 7.11 g of solid was obtained. Yield 7.11 g, 71% yield.
1 HNMR (400MHz, CDCl 3 / TMS): δ10.4 (s, 1H, -C H 2 O), 7.68 (s, 1H, Ar-H), 7.46 (s, 1H, Ar-H), 6.22 (s , 1H, Ar-OH), 4.07 (s, 3H, -OC H 3).
［１−４］４−ヘキシロキシ−５−メトキシ−２−ニトロベンザルデヒドの合成
窒素気流下で５０ｍｌ二口ナスフラスコに６−ニトロバニリン１．１０ｇ（５．５８ｍｍｏｌ）、ドライＤＭＦ５ｍｌ、Ｋ２ＣＯ３０．７９８ｇ（５．７７ｍｍｏｌ）を入れ室温で２０分撹拌し、１−ブロモヘキサン０．９６０ｇ（５．８２ｍｍｏｌ）を加えオイルバス上８５℃で９０分間加熱撹拌した。反応後、水３０ｍｌ、１Ｎ塩酸水溶液１０ｍｌを少しづつ反応液に加え、酢酸エチル５０ｍｌで３回抽出し、飽和ＮａＣｌ水溶液１００ｍｌで４回洗浄し、無水硫酸マグネシウムを加え乾燥、ろ過、濃縮、シリカゲルカラムクロマトグラフィーによる精製、真空乾燥を行い、明黄色固体１．３６ｇを得た。収量１．３６ｇ、収率８７％。
1ＨＮＭＲ(400MHz, CDCl3/TMS): δ10.45 (s, 1H, -CHO), 7.59 (s, 1H, Ar-H), 7.41（s, 1H, Ar-H）, 4.15 (t, 2H, J=6.7Hz, Ar-O-CH 2-), 4.01 (s, 3H, -OCH 3), 1.90 (quint, 2H, J=7.2Hz, Ar-CH2CH2-, 1.51-1.35 (m, 6H, -(CH 2)3CH3), 0.917 (t, 3H, J=7.1Hz, -(CH2)5CH 3)。
Synthesis of [1-4] 4-hexyloxy-5-methoxy-2-nitrobenzaldehyde In a 50 ml two-necked eggplant flask under a nitrogen stream, 1.10 g (5.58 mmol) of 6-nitrovanillin, 5 ml of dry DMF, K 2 CO 3 0.798 g (5.77 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. 0.960 g (5.82 mmol) of 1-bromohexane was added, and the mixture was heated and stirred at 85 ° C. for 90 minutes on an oil bath. After the reaction, 30 ml of water and 10 ml of 1N hydrochloric acid aqueous solution are gradually added to the reaction solution, extracted 3 times with 50 ml of ethyl acetate, washed 4 times with 100 ml of saturated NaCl aqueous solution, dried over anhydrous magnesium sulfate, filtered, concentrated, silica gel column Purification by chromatography and vacuum drying were performed to obtain 1.36 g of a light yellow solid. Yield 1.36 g, 87% yield.
1 HNMR (400 MHz, CDCl 3 / TMS): δ10.45 (s, 1H, —C 3 H 2 O), 7.59 (s, 1H, Ar—H), 7.41 (s, 1H, Ar—H), 4.15 (t , 2H, J = 6.7Hz, Ar-OC H 2- ), 4.01 (s, 3H, -OC H 3 ), 1.90 (quint, 2H, J = 7.2Hz, Ar-CH 2 CH 2- , 1.51-1.35 (m, 6H,-(C H 2 ) 3 CH 3 ), 0.917 (t, 3H, J = 7.1 Hz,-(CH 2 ) 5 C H 3 ).
［１−５］４−ヘキシロキシ−５−メトキシ−２−ニトロベンザルデヒドのヒドラゾンの合成
１００ｍｌナスフラスコに、４−へキシロキシ−５−メトキシ−２−ニトロベンザルデヒド０．６１６ｇ（２．０９ｍｍｏｌ）、ヒドラジン一水和物０．６４２ｇ（１２．８２ｍｍｏｌ）、エタノール４５ｍｌ、回転子を加え２時間還流した。反応溶液を室温に戻し、析出結晶を自然ろ過した。得られた橙黄色結晶をエタノールで軽く洗い、真空乾燥すると目的物０．６２ｇを得た。収量０．６２ｇ、収率４４％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ8.43 (s, 1H, -CH), 7.56 (s, 1H, Ar-H), 7.48 (s, 1H, Ar-H), 5.80 (s, 2H, -NH 2), 4.07 (t, 2H, Ar-O-CH 2-), 3.98 (s, 3H, -OCH 3), 1.88 (quint, J=7.4Hz, 2H, Ar-O-CH2CH 2CH2-), 1.48-1.34 (m, 6H, -(CH 2)3CH3), 0.910 (t, 3H, J=7.1Hz, -(CH2)5CH 3)。
Synthesis of [1-5] 4-hexyloxy-5-methoxy-2-nitrobenzaldehyde hydrazone In a 100 ml eggplant flask, 0.616 g (2.09 mmol) of 4-hexyloxy-5-methoxy-2-nitrobenzaldehyde, Hydrazine monohydrate (0.642 g, 12.82 mmol), ethanol (45 ml) and a rotator were added, and the mixture was refluxed for 2 hours. The reaction solution was returned to room temperature, and the precipitated crystals were naturally filtered. The obtained orange-yellow crystals were lightly washed with ethanol and vacuum dried to obtain 0.62 g of the desired product. Yield 0.62 g, yield 44%.
1 HNMR (400MHz, CDCl 3 / TMS): δ8.43 (s, 1H, -C H ), 7.56 (s, 1H, Ar- H ), 7.48 (s, 1H, Ar- H ), 5.80 (s, 2H, -N H 2 ), 4.07 (t, 2H, Ar-OC H 2- ), 3.98 (s, 3H, -OC H 3 ), 1.88 (quint, J = 7.4Hz, 2H, Ar-O-CH 2 C H 2 CH 2- ), 1.48-1.34 (m, 6H,-(C H 2 ) 3 CH 3 ), 0.910 (t, 3H, J = 7.1 Hz,-(CH 2 ) 5 C H 3 ).
［１−６］アリル ４−ヘキシロキシ−５−メトキシ−２−ニトロベンジルエーテルの合成
３００ｍｌナスフラスコに４−ヘキシロキシ−５−メトキシ−２−ニトロベンザルデヒドのヒドラゾン０．６１６ｇ（２．０９ｍｍｏｌ）、回転子、ドライクロロホルム５０ｍｌを加え撹拌した。均一溶液になったら、二酸化マンガン１．４２ｇ（１６．３ｍｍｏｌ）を少しずつ加えた。室温で１０分程撹拌した後二酸化マンガンをろ過により除去した。０．１Ｍ炭酸水素ナトリウム水溶液（５０ｍｌｘ２）で洗浄し、有機相を無水硫酸マグネシウムで乾燥した（溶液Ａ）。一方、氷浴上で３００ｍｌナスフラスコにアリルアルコール０．２４ｇ（４．１３ｍｍｏｌ）、回転子を加えＨＣｌＯ４（７０％）７滴を加えた。溶液Ａをろ過して無水硫酸マグネシウムを除去した。２００ｍｌ滴下ロートに溶液Ａを加え、３００ｍｌナスフラスコに４５分で滴下した。氷浴を除去し、室温で一晩撹拌した。飽和炭酸水素ナトリウム水溶液３０ｍｌ、蒸留水２０ｍｌを加え洗浄した。水相をクロロホルムで抽出し（１００ｍｌｘ２）、有機相を合わせ無水硫酸マグネシウムで乾燥した。ろ過後濃縮し、粗生成物を得た。粗生成物を溶出液（クロロホルム：へキサン＝４：１）でシリカゲルカラムクロマトグラフィーを行い、目的物（淡橙色結晶）０．１０ｇ（０．３０９ｍｍｏｌ）を得た。収量０．１０ｇ、収率１５％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ7.71 (s, 1H, Ar), 7,31 (s, 1H, Ar), 6.0 (m, 1H, -CH=CH2), 5.37 (m, 1H, Jtrans=16Hz, -CH=CH 2), 5.25 (m, 1H, Jcis=12Hz, -CH=CH 2), 4.92 (s, 2H, Ar-CH 2-O-), 4.16 (d, J=6.9Hz, 2H, CH 2-CH=CH2), 4.07 (t, 2H, J=6.8Hz, Ar-O-CH 2-), 3.98 (s, 3H, -OCH 3), 1.87 (quint, J=7.4Hz, 2H, Ar-O-CH2CH 2CH2-), 1.55-1.34 (m, 6H, -(CH 2)3CH3), 0.910 (t, 3H, J=7.1Hz, -(CH2)5CH 3)。
Synthesis of [1-6] allyl 4-hexyloxy-5-methoxy-2-nitrobenzyl ether 0.616 g (2.09 mmol) of 4-hydroxy-5-methoxy-2-nitrobenzaldehyde hydrazone in a 300 ml eggplant flask and rotation A child and 50 ml of dry chloroform were added and stirred. When it became a homogeneous solution, 1.42 g (16.3 mmol) of manganese dioxide was added little by little. After stirring at room temperature for about 10 minutes, manganese dioxide was removed by filtration. The organic phase was washed with 0.1 M aqueous sodium hydrogen carbonate solution (50 ml × 2) and dried over anhydrous magnesium sulfate (solution A). Meanwhile, 0.24 g (4.13 mmol) of allyl alcohol and a rotator were added to a 300 ml eggplant flask on an ice bath, and 7 drops of HClO 4 (70%) were added. Solution A was filtered to remove anhydrous magnesium sulfate. Solution A was added to a 200 ml dropping funnel and dropped into a 300 ml eggplant flask in 45 minutes. The ice bath was removed and stirred at room temperature overnight. 30 ml of a saturated aqueous sodium hydrogen carbonate solution and 20 ml of distilled water were added for washing. The aqueous phase was extracted with chloroform (100 ml × 2), and the organic phases were combined and dried over anhydrous magnesium sulfate. After filtration, it was concentrated to obtain a crude product. The crude product was subjected to silica gel column chromatography using an eluent (chloroform: hexane = 4: 1) to obtain 0.10 g (0.309 mmol) of the desired product (pale orange crystals). Yield 0.10 g, yield 15%.
1 HNMR (400MHz, CDCl 3 / TMS): δ7.71 (s, 1H, Ar), 7,31 (s, 1H, Ar), 6.0 (m, 1H, -C H = CH 2 ), 5.37 (m , 1H, J trans = 16Hz, -CH = C H 2 ), 5.25 (m, 1H, J cis = 12Hz, -CH = C H 2 ), 4.92 (s, 2H, Ar-C H 2 -O-) , 4.16 (d, J = 6.9Hz, 2H, C H 2 -CH = CH 2 ), 4.07 (t, 2H, J = 6.8Hz, Ar-OC H 2- ), 3.98 (s, 3H, -OC H 3 ), 1.87 (quint, J = 7.4Hz, 2H, Ar-O-CH 2 C H 2 CH 2- ), 1.55-1.34 (m, 6H,-(C H 2 ) 3 CH 3 ), 0.910 (t , 3H, J = 7.1 Hz,-(CH 2 ) 5 C H 3 ).
［１−７］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ３−（トリメトキシシリル）プロピルエーテルの合成
２０ｍｌナスフラスコを窒素置換し、アリル ４−ヘキシロキシ−５−メトキシ−２−ニトロベンジルエーテル ０．０９５ｇ（０．２９ｍｍｏｌ）、トリメトキシシラン０．２４５ｇ（２．００ｍｍｏｌ）、Ｋａｒｓｔｅｄｔ’ｓ触媒を4滴加え、室温で終夜撹拌した。中圧カラムを用いてシリカゲルカラムクロマトグラフィーによる精製を行った。溶出液としてヘキサン：酢酸エチル：テトラメトキシシラン＝４：１：０．０５(体積比)を用い、目的物を０．０６１ｇ（０．１４ｍｍｏｌ）得た。収量０．０６１ｇ、収率４７％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ7.70 (s, 1H, Ar), 7,30 (s, 1H, Ar),4.89 (s, 2H, Ar-CH 2-O-), 4.06 (t, 2H, J=6.8Hz, Ar-O-CH 2-), 3.97 (s, 3H, Ar-OCH 3), 3.58 (s, 2H, -CH 2-O-CH2-Ar), 3.58 (s, 9H, -Si-(OCH 3)3), 1.77-1.9 (m, 4H, -Si-CH2-CH 2-CH2-,Ar-O-CH2-CH 2-),1.34-1.48 (m, 6H, -(CH 2)3-CH3), 0.91 (t,3H, J=7.1Hz, -(CH2)5CH 3), 0.72-0.76 (m, 2H, -CH 2-Si-)。
FT-IR (KBr): 1527 (NO2), 1328 (NO2), 1275 (C-O-C)。
[1-7] Synthesis of 4-hexyloxy-5-methoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether A 20 ml eggplant flask was replaced with nitrogen, and allyl 4-hexyloxy-5-methoxy-2-nitrobenzyl ether 0.095 g (0.29 mmol), 0.245 g (2.00 mmol) of trimethoxysilane and 4 drops of Karstedt's catalyst were added, and the mixture was stirred at room temperature overnight. Purification by silica gel column chromatography was performed using an intermediate pressure column. Using hexane: ethyl acetate: tetramethoxysilane = 4: 1: 0.05 (volume ratio) as an eluent, 0.061 g (0.14 mmol) of the desired product was obtained. Yield 0.061 g, 47% yield.
1 HNMR (400MHz, CDCl 3 / TMS): δ7.70 (s, 1H, Ar), 7,30 (s, 1H, Ar), 4.89 (s, 2H, Ar-C H 2 -O-), 4.06 (t, 2H, J = 6.8Hz, Ar-OC H 2- ), 3.97 (s, 3H, Ar-OC H 3 ), 3.58 (s, 2H, -C H 2 -O-CH 2 -Ar), 3.58 (s, 9H, -Si- (OC H 3 ) 3 ), 1.77-1.9 (m, 4H, -Si-CH 2 -C H 2 -CH 2- , Ar-O-CH 2 -C H 2- ), 1.34-1.48 (m, 6H,-(C H 2 ) 3 -CH 3 ), 0.91 (t, 3H, J = 7.1Hz,-(CH 2 ) 5 C H 3 ), 0.72-0.76 (m, 2H, -C H 2 -Si-).
FT-IR (KBr): 1527 (NO 2 ), 1328 (NO 2 ), 1275 (COC).
［合成例２］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ６−（トリメトキシシリル）ヘキシルエーテル（２ＥＴ）の合成
［２−１］５−ヘキセニル ４−ヘキシロキシ−５−メトキシ−２−ニトロベンジルエーテルの合成
２００ｍｌナスフラスコに合成例１−５で得られた４−ヘキシロキシ−５−メトキシ−２−ニトロベンザルデヒドのヒドラゾン０．８８ｇ（３．９ｍｍｏｌ）、回転子、ドライクロロホルム６０ｍｌを加え撹拌した。均一溶液になったら、二酸化マンガン２．８ｇ（３２ｍｍｏｌ）を少しずつ加えた。室温で１０分程撹拌した後、二酸化マンガンをろ過により除去した。０．１Ｍ炭酸水素ナトリウム水溶液（５０ｍｌｘ２）で洗浄し、有機相を無水硫酸マグネシウムで乾燥した（溶液Ａ）。
一方、氷浴上で３００ｍｌナスフラスコに５−ヘキセン−１−オール０．５ｇ（５．０ｍｍｏｌ）、回転子を加えＨＣｌＯ４（７０％）２滴を加えた。溶液Ａをろ過して無水硫酸マグネシウムを除去した。１００ｍｌ滴下ロートに溶液Ａを加え、３００ｍｌナスフラスコに３０分で滴下した。氷浴を除去し、室温で一晩撹拌した。飽和炭酸水素ナトリウム水溶液２０ｍｌ、蒸留水３０ｍｌを加え洗浄した。水相をクロロホルムで抽出し（１００ｍｌｘ２）、有機相を合わせ無水硫酸マグネシウムで乾燥した。ろ過後濃縮し、粗生成物を１．４ｇ得た。粗生成物を溶出液クロロホルムでシリカゲルカラムクロマトグラフィーを行い、目的物（橙色結晶）０．４８ｇ（１．６ｍｍｏｌ）を得た。収量０．４８ｇ、収率４１％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ7.71 (s, 1H, Ar), 7,31 (s, 1H, Ar), 5.77-5.87 (m, 1H, -CH=CH2), 5.00-5.04 (s, 1H, Jtrans=16Hz, -CH=CH 2), 4.95-4.98 (s, 1H, Jcis=8Hz, -CH=CH 2), 4.92 (s, 1H, Ar-CH 2-O-), 4.07 (t, 2H, J=6.8Hz, Ar-O-CH 2-), 3.99 (s, 3H, -OCH 3) 、3.60-3.63 (t, 2H, -O-CH 2-CH2), 2.09-2.15 (m, 2H, -CH 2-CH=CH2), 1.87 (quint, J=7.4Hz, 2H, Ar-O-CH2CH 2CH2-), 1.68-1.75 (m, 2H, -O-CH2-CH 2-), 1.34-1.58 (m, 8H, -CH2-CH 2-CH2-CH=CH2, -(CH 2)3CH3), 0.910 (t, 3H, J=7.1Hz, -(CH2)5CH 3)。
[Synthesis Example 2] Synthesis of 4-hexyloxy-5-methoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether (2ET) [2-1] 5-hexenyl 4-hexyloxy-5-methoxy-2-nitro Synthesis of benzyl ether To a 200 ml eggplant flask, add 0.88 g (3.9 mmol) of hydrazone of 4-hexyloxy-5-methoxy-2-nitrobenzaldehyde obtained in Synthesis Example 1-5, a rotor and 60 ml of dry chloroform, and stir. did. When a homogeneous solution was obtained, 2.8 g (32 mmol) of manganese dioxide was added little by little. After stirring at room temperature for about 10 minutes, manganese dioxide was removed by filtration. The organic phase was washed with 0.1 M aqueous sodium hydrogen carbonate solution (50 ml × 2) and dried over anhydrous magnesium sulfate (solution A).
On the other hand, 0.5 g (5.0 mmol) of 5-hexen-1-ol and a rotator were added to a 300 ml eggplant flask on an ice bath, and 2 drops of HClO 4 (70%) were added. Solution A was filtered to remove anhydrous magnesium sulfate. Solution A was added to a 100 ml dropping funnel and dropped into a 300 ml eggplant flask in 30 minutes. The ice bath was removed and stirred at room temperature overnight. 20 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of distilled water were added for washing. The aqueous phase was extracted with chloroform (100 ml × 2), and the organic phases were combined and dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated to obtain 1.4 g of a crude product. The crude product was subjected to silica gel column chromatography with eluent chloroform to obtain 0.48 g (1.6 mmol) of the desired product (orange crystals). Yield 0.48 g, 41% yield.
1 HNMR (400MHz, CDCl 3 / TMS): δ7.71 (s, 1H, Ar), 7,31 (s, 1H, Ar), 5.77-5.87 (m, 1H, -C H = CH 2 ), 5.00 -5.04 (s, 1H, J trans = 16Hz, -CH = C H 2 ), 4.95-4.98 (s, 1H, J cis = 8Hz, -CH = C H 2 ), 4.92 (s, 1H, Ar-C H 2 -O-), 4.07 (t, 2H, J = 6.8Hz, Ar-OC H 2- ), 3.99 (s, 3H, -OC H 3 ), 3.60-3.63 (t, 2H, -OC H 2 -CH 2 ), 2.09-2.15 (m, 2H, -C H 2 -CH = CH 2 ), 1.87 (quint, J = 7.4Hz, 2H, Ar-O-CH 2 C H 2 CH 2- ), 1.68 -1.75 (m, 2H, -O-CH 2 -C H 2- ), 1.34-1.58 (m, 8H, -CH 2 -C H 2 -CH 2 -CH = CH 2 ,-(C H 2 ) 3 CH 3), 0.910 (t, 3H, J = 7.1Hz, - (CH 2) 5 C H 3).
［２−２］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ６−（トリメトキシシリル）ヘキシルエーテルの合成
２０ｍｌナスフラスコを窒素置換し、５−ヘキセニル４−ヘキシロキシ−５−メトキシ−２−ニトロベンジルエーテル ２．９５ｇ（１０．０ｍｍｏｌ）、トリメトキシシラン１．４７ｇ（１２ｍｍｏｌ）、Ｋａｒｓｔｅｄｔ触媒を４滴加え、室温で終夜撹拌した。中圧カラムを用いてシリカゲルカラムクロマトグラフィーによる精製を行った。溶出液としてヘキサン：酢酸エチル：テトラメトキシシラン＝４：１：０．０５(体積比)を用い、目的物を１．４ｇ（３．３５ｍｍｏｌ）得た。収量１．４ｇ、収率３４％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ7.71 (s, 1H, Ar), 7,31 (s, 1H, Ar), 4.89 (s, 2H, Ar-CH 2-O-),4.06 (t, 2H, J=6.8Hz, Ar-O-CH 2-), 3.99 (s, 3H, Ar-OCH 3), 3.58-3.61 (s, 2H, -O-CH 2-CH2-), 3.57 (s, 9H, -Si(OCH 3)3), 1.87 (quint, J=7.4Hz, 2H, Ar-O-CH2CH 2CH2-),
1.4-1.7 (m, 14H, -CH2-(CH 2)4-CH2-,-(CH 2)3CH3), 0.91 (t,3H, J=7.1Hz, -(CH2)5CH 3), 0.63-0.67 (m, 2H, -CH 2-Si-)。
FT-IR (KBr): 1525 (NO2), 1328 (NO2), 1276 (C-O-C)。
[2-2] Synthesis of 4-hexyloxy-5-methoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether A 20 ml eggplant flask was purged with nitrogen, and 5-hexenyl 4-hexyloxy-5-methoxy-2-nitro was synthesized. 4.95 g (10.0 mmol) of benzyl ether, 1.47 g (12 mmol) of trimethoxysilane and 4 drops of Karstedt catalyst were added and stirred at room temperature overnight. Purification by silica gel column chromatography was performed using an intermediate pressure column. Hexane: ethyl acetate: tetramethoxysilane = 4: 1: 0.05 (volume ratio) was used as an eluent to obtain 1.4 g (3.35 mmol) of the desired product. Yield 1.4 g, yield 34%.
1 HNMR (400MHz, CDCl 3 / TMS): δ7.71 (s, 1H, Ar), 7,31 (s, 1H, Ar), 4.89 (s, 2H, Ar-C H 2 -O-), 4.06 (t, 2H, J = 6.8Hz, Ar-OC H 2- ), 3.99 (s, 3H, Ar-OC H 3 ), 3.58-3.61 (s, 2H, -OC H 2 -CH 2- ), 3.57 (s, 9H, -Si (OC H 3 ) 3 ), 1.87 (quint, J = 7.4Hz, 2H, Ar-O-CH 2 C H 2 CH 2- ),
1.4-1.7 (m, 14H, -CH 2- (C H 2 ) 4 -CH 2 -,-(C H 2 ) 3 CH 3 ), 0.91 (t, 3H, J = 7.1Hz,-(CH 2 ) 5 C H 3 ), 0.63-0.67 (m, 2H, -C H 2 -Si-).
FT-IR (KBr): 1525 (NO 2 ), 1328 (NO 2 ), 1276 (COC).
［合成例３］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル １０−（トリメトキシシリル）デシルエーテル（１０ＥＴ）の合成
［３−１］９−デセニル ４−ヘキシロキシ−５−メトキシ−２−ニトロベンジルエーテルの合成
５００ｍｌナスフラスコに４−ヘキシロキシ−５−メトキシ−２−ニトロベンザルデヒドのヒドラゾン４．３３ｇ（１９．２ｍｍｏｌ）、回転子、ドライクロロホルム３００ｍｌを加え撹拌した。均一溶液になったら、二酸化マンガン１３．９ｇ（１５８．７ｍｍｏｌ）を少しずつ加えた。室温で１０分程撹拌した後、二酸化マンガンをろ過により除去した。０．１Ｍ炭酸水素ナトリウム水溶液（５０ｍｌｘ２）で洗浄し、有機相を無水硫酸マグネシウムで乾燥した（溶液Ａ）。一方、氷浴上で５００ｍｌナスフラスコに９−デセン−１−オール３．８ｇ（２４．６ｍｍｏｌ）、回転子を加えＨＣｌＯ４（７０％）１０滴を加えた。溶液Ａをろ過して無水硫酸マグネシウムを除去した。２００ｍｌ滴下ロートに溶液Ａを加え、５００ｍｌナスフラスコに４５分で滴下した。氷浴を除去し、室温で一晩撹拌した。飽和炭酸水素ナトリウム水溶液２０ｍｌ、蒸留水３０ｍｌを加え洗浄した。水相をクロロホルムで抽出し（１００ｍｌｘ２）、有機相を合わせ無水硫酸マグネシウムで乾燥した。ろ過後濃縮し、粗生成物を得た。粗生成物を溶出液クロロホルムでシリカゲルカラムクロマトグラフィーを行い、目的物（橙色結晶）２．８５ｇ（８．１ｍｍｏｌ）を得た。収量２．８５ｇ、収率４２％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ7.71 (s, 1H, Ar), 7,32 (s, 1H, Ar), 5.78-5.84 (m, 1H, -CH=CH2), 4.98-5.00 (s, 1H, Jtrans=8Hz, -CH=CH 2), 4.92-4.94 (s, 1H, Jcis=8Hz, -CH=CH 2), 4.89 (s, 2H, Ar-CH 2-O-),4.07 (t, 2H, J=6.8Hz, Ar-O-CH 2-), 3.99 (s, 3H, -OCH 3) 、3.58-3.61 (t, 2H, -O-CH 2-CH2), 2.01-2.06 (m, 2H, -CH 2-CH=CH2), 1.87 (quint, J=7.4Hz, 2H, Ar-O-CH2CH 2CH2-), 1.66-1.69 (m, 2H, -O-CH2-CH 2-), 1.31-1.55 (m, 16H, -CH2-(CH 2)5-CH2-CH=CH2, -(CH 2)3CH3), 0.910 (t, 3H, J=7.1Hz, -(CH2)5CH 3)。
[Synthesis Example 3] Synthesis of 4-hexyloxy-5-methoxy-2-nitrobenzyl 10- (trimethoxysilyl) decyl ether (10ET) [3-1] 9-decenyl 4-hexyloxy-5-methoxy-2-nitro Synthesis of benzyl ether To a 500 ml eggplant flask, 4.33 g (19.2 mmol) of hydrazone of 4-hexyloxy-5-methoxy-2-nitrobenzaldehyde, a rotor and 300 ml of dry chloroform were added and stirred. When a homogeneous solution was obtained, 13.9 g (158.7 mmol) of manganese dioxide was added little by little. After stirring at room temperature for about 10 minutes, manganese dioxide was removed by filtration. The organic phase was washed with 0.1 M aqueous sodium hydrogen carbonate solution (50 ml × 2) and dried over anhydrous magnesium sulfate (solution A). On the other hand, 3.8 g (24.6 mmol) of 9-decen-1-ol and a rotor were added to a 500 ml eggplant flask on an ice bath, and 10 drops of HClO 4 (70%) was added. Solution A was filtered to remove anhydrous magnesium sulfate. Solution A was added to a 200 ml dropping funnel and dropped into a 500 ml eggplant flask in 45 minutes. The ice bath was removed and stirred at room temperature overnight. 20 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of distilled water were added for washing. The aqueous phase was extracted with chloroform (100 ml × 2), and the organic phases were combined and dried over anhydrous magnesium sulfate. After filtration, it was concentrated to obtain a crude product. The crude product was subjected to silica gel column chromatography with eluent chloroform to obtain 2.85 g (8.1 mmol) of the desired product (orange crystals). Yield 2.85 g, 42% yield.
1 HNMR (400MHz, CDCl 3 / TMS): δ7.71 (s, 1H, Ar), 7,32 (s, 1H, Ar), 5.78-5.84 (m, 1H, -C H = CH 2 ), 4.98 -5.00 (s, 1H, J trans = 8Hz, -CH = C H 2 ), 4.92-4.94 (s, 1H, J cis = 8Hz, -CH = C H 2 ), 4.89 (s, 2H, Ar-C H 2 -O-), 4.07 (t, 2H, J = 6.8Hz, Ar-OC H 2- ), 3.99 (s, 3H, -OC H 3 ), 3.58-3.61 (t, 2H, -OC H 2 -CH 2 ), 2.01-2.06 (m, 2H, -C H 2 -CH = CH 2 ), 1.87 (quint, J = 7.4Hz, 2H, Ar-O-CH 2 C H 2 CH 2- ), 1.66 -1.69 (m, 2H, -O-CH 2 -C H 2- ), 1.31-1.55 (m, 16H, -CH 2- (C H 2 ) 5 -CH 2 -CH = CH 2 ,-(C H 2 ) 3 CH 3 ), 0.910 (t, 3H, J = 7.1 Hz,-(CH 2 ) 5 C H 3 ).
［３−２］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル １０−（トリメトキシシリル）デシルエーテルの合成
２０ｍｌナスフラスコを窒素置換し、９−デセニル ４−ヘキシロキシ−５−メトキシ−２−ニトロベンジルエーテル ２．９５ｇ（１０．０ｍｍｏｌ）、トリメトキシシラン１．４７ｇ（１２ｍｍｏｌ）、Karstedt触媒を4滴加え、室温で終夜撹拌した。中圧カラムを用いてシリカゲルカラムクロマトグラフィーによる精製を行った。溶出液としてヘキサン：酢酸エチル：テトラメトキシシラン＝４：１：０．０５(体積比)を用い、目的物を１．４ｇ（３．３５ｍｍｏｌ）得た。収量１．５ｇ、収率５６％。
1ＨＮＭＲ (400MHz, CDCl3/TMS): δ7.71 (s, 1H, Ar), 7,32 (s, 1H, Ar), 4.90 (s, 2H, Ar-CH 2-O-),4.06 (t, 2H, J=6.8Hz, Ar-O-CH 2-), 3.99 (s, 3H, Ar-OCH 3) 3.58-3.61 (s, 2H, -O-CH 2-CH2-), 3.57 (s, 9H, -Si-(OCH 3)3), 1.87 (quint, J=7.4Hz, 2H, Ar-O-CH2CH 2CH2-),
1.65-1.72 (m, 2H, -CH2-CH 2-CH2-),1.34-1.48 (m, 6H, -(CH 2)3-CH3), 0.91 (t,3H, J=7.1Hz, -(CH2)5CH 3), 0.62-0.66 (m, 2H, -CH 2-Si-)。
[3-2] Synthesis of 4-hexyloxy-5-methoxy-2-nitrobenzyl 10- (trimethoxysilyl) decyl ether A 20 ml eggplant flask was purged with nitrogen, and 9-decenyl 4-hexyloxy-5-methoxy-2-nitro was synthesized. 4.95 g (10.0 mmol) of benzyl ether, 1.47 g (12 mmol) of trimethoxysilane and 4 drops of Karstedt catalyst were added, and the mixture was stirred at room temperature overnight. Purification by silica gel column chromatography was performed using an intermediate pressure column. Hexane: ethyl acetate: tetramethoxysilane = 4: 1: 0.05 (volume ratio) was used as an eluent to obtain 1.4 g (3.35 mmol) of the desired product. Yield 1.5 g, 56% yield.
1 HNMR (400MHz, CDCl 3 / TMS): δ7.71 (s, 1H, Ar), 7,32 (s, 1H, Ar), 4.90 (s, 2H, Ar-C H 2 -O-), 4.06 (t, 2H, J = 6.8Hz, Ar-OC H 2- ), 3.99 (s, 3H, Ar-OC H 3 ) 3.58-3.61 (s, 2H, -OC H 2 -CH 2- ), 3.57 ( s, 9H, -Si- (OC H 3 ) 3 ), 1.87 (quint, J = 7.4Hz, 2H, Ar-O-CH 2 C H 2 CH 2- ),
1.65-1.72 (m, 2H, -CH 2 -C H 2 -CH 2- ), 1.34-1.48 (m, 6H,-(C H 2 ) 3 -CH 3 ), 0.91 (t, 3H, J = 7.1 Hz,-(CH 2 ) 5 C H 3 ), 0.62-0.66 (m, 2H, -C H 2 -Si-).
［応用例１］シランカップリング剤（２ＥＴ)のアルカリ可溶性樹脂への導入
ビニルフェノールとスチレンの共重合体であるＣＳＴ−７０（丸善石油化学社製）（２．０ｇ）、ＣＳＴ−１５（丸善石油化学社製）（２．０ｇ）、シランカップリング剤として、４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ６−（トリメトキシシリル）ヘキシルエーテル（２ＥＴ）（０．３５ｇ）、トルエン（２０ｍｌ）を７０℃で一時間加熱した。トルエン濃縮後、ＰＳＦ２８０３（群栄化学工業社製）（５．０ｇ）、ＰＳＦ２８０７（群栄化学工業社製）（３．０ｇ）、オイルブルー６１３（０．１ｇ）、ＭＥＫ（１６０ｍｌ）を加え、室温撹拌した。ろ過後、親水化処理したアルミ板に回転塗布し、その後７０℃で一時間乾燥機で乾燥させた。露光には超高圧水銀ランプ（５００Ｗ）を用いて、３６５ｎｍ、１００ｍＷ／ｃｍ２の条件で約６０秒間程照射した。その後、アルカリ現像液にて現像をし、ポジ型の画像を得た。
[Application Example 1] Introduction of silane coupling agent (2ET) into alkali-soluble resin CST-70 (manufactured by Maruzen Petrochemical Co., Ltd.) (2.0 g), CST-15 (Maruzen), which is a copolymer of vinylphenol and styrene Petrochemical Co., Ltd. (2.0 g), 4-hexyloxy-5-methoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether (2ET) (0.35 g), toluene (20 ml) as a silane coupling agent ) At 70 ° C. for 1 hour. After toluene concentration, PSF2803 (manufactured by Gunei Chemical Industry Co., Ltd.) (5.0 g), PSF2807 (manufactured by Gunei Chemical Industry Co., Ltd.) (3.0 g), oil blue 613 (0.1 g), MEK (160 ml) were added, Stir at room temperature. After filtration, it was spin-coated on a hydrophilized aluminum plate and then dried in a dryer at 70 ° C. for 1 hour. For the exposure, an ultra-high pressure mercury lamp (500 W) was used for irradiation for about 60 seconds under conditions of 365 nm and 100 mW / cm 2 . Thereafter, development was performed with an alkali developer to obtain a positive image.
［応用例２］シランカップリング剤（７ＥＴ)のアルカリ可溶性樹脂への導入
シランカップリング剤として４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ３−（トリメトキシシリル）プロピルエーテル（７ＥＴ）（０．３５ｇ）を用いた以外は応用例１と同様にして、ポジ型の画像を得た。
Application Example 2 Introduction of Silane Coupling Agent (7ET) into Alkali-Soluble Resin 4-Hexyloxy-5-methoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether (7ET) (0 .35 g) was used in the same manner as in Application Example 1 to obtain a positive image.
［応用例３］シランカップリング剤（１０ＥＴ)のアルカリ可溶性樹脂への導入
シランカップリング剤として４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル １０−（トリメトキシシリル）デシルエーテル（１０ＥＴ）（０．３５ｇ）を用いた以外は応用例１と同様にして、ポジ型の画像を得た。
Application Example 3 Introduction of Silane Coupling Agent (10ET) into Alkali-Soluble Resin 4-Hexyloxy-5-methoxy-2-nitrobenzyl 10- (trimethoxysilyl) decyl ether (10ET) (0 .35 g) was used in the same manner as in Application Example 1 to obtain a positive image.
応用例１〜３では、光酸発生剤を必要とせず、コントラストの高いポジ型の画像を形成できた。また、必要に応じた性能を出すために、反応させるポリマーを選択することにより容易に光反応性ポリマーを合成でき、且つ酸素阻害等も受けず、この新規ポリマーが有機−無機複合体を形成していることから高い耐熱性も期待できる。 In Application Examples 1 to 3, a photoacid generator was not required, and a positive image with high contrast could be formed. In addition, in order to obtain the performance as required, it is possible to easily synthesize a photoreactive polymer by selecting a polymer to be reacted, and this new polymer forms an organic-inorganic composite without being subjected to oxygen inhibition. Therefore, high heat resistance can be expected.
［応用例４］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ６−（トリメトキシシリル）ヘキシルエーテル（２ＥＴ）を用いたシリコンウェハの表面修飾
シランカップリング剤として４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ６−（トリメトキシシリル）ヘキシルエーテル（２ＥＴ）の無水トルエン溶液に、シリコンウェハを投入し、窒素雰囲気下で１時間還流して、表面修飾を行った。得られた修飾ウェハをクロロホルムで１０分間超音波洗浄し、超高圧水銀灯（５００Ｗ）を光源としてパイレックス（登録商標）ガラスフィルターを通して光照射し表面をヒドロキシ基に変換した。接触角計（協和界面科学社製ＣＡ−Ａ）を用い、液滴法（静的接触角）、ＪＩＳ Ｒ３２５７：９９に基づき、それぞれのウェハの接触角を測定し、表面状態の変化を評価すると、光照射時間３０秒でヒドロキシ基への変換を終了したことがわかった。光照射の時間と接触角との関係を図１、照射前後の接触角の差を表１に示す。
[Application Example 4] Surface modification of silicon wafer using 4-hexyloxy-5-methoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether (2ET) 4-hexyloxy-5-methoxy- as a silane coupling agent A silicon wafer was put into an anhydrous toluene solution of 2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether (2ET), and the surface was modified by refluxing for 1 hour in a nitrogen atmosphere. The obtained modified wafer was ultrasonically cleaned with chloroform for 10 minutes, and irradiated with light through a Pyrex (registered trademark) glass filter using an ultrahigh pressure mercury lamp (500 W) as a light source to convert the surface into hydroxy groups. Using a contact angle meter (CA-A manufactured by Kyowa Interface Science Co., Ltd.), measuring the contact angle of each wafer based on the droplet method (static contact angle), JIS R3257: 99, and evaluating the change in the surface state It was found that the conversion to a hydroxy group was completed after a light irradiation time of 30 seconds. FIG. 1 shows the relationship between the time of light irradiation and the contact angle, and Table 1 shows the difference in contact angle before and after irradiation.
［応用例５］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ３−（トリメトキシシリル）プロピルエーテル（７ＥＴ）を用いたシリコンウェハの表面修飾
シランカップリング剤として４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル ３−（トリメトキシシリル）プロピルエーテル（７ＥＴ）を用いた以外は応用例４と同様にして、表面をヒドロキシ基に変換したシリコンウェハを得た。
接触角計（協和界面科学社製ＣＡ−Ａ）を用い、液滴法（静的接触角）、ＪＩＳ Ｒ３２５７：９９に基づき、それぞれのウェハの接触角を測定し、表面状態の変化を評価すると、光照射時間３０秒でヒドロキシ基への変換を終了したことがわかった。光照射の時間と接触角との関係を図２、照射前後の接触角の差を表１に示す。
[Application Example 5] Surface modification of silicon wafer using 4-hexyloxy-5-methoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether (7ET) 4-Hexyloxy-5-methoxy- as a silane coupling agent A silicon wafer having a surface converted to a hydroxy group was obtained in the same manner as in Application Example 4 except that 2-nitrobenzyl 3- (trimethoxysilyl) propyl ether (7ET) was used.
Using a contact angle meter (CA-A manufactured by Kyowa Interface Science Co., Ltd.), measuring the contact angle of each wafer based on the droplet method (static contact angle), JIS R3257: 99, and evaluating the change in the surface state It was found that the conversion to a hydroxy group was completed after a light irradiation time of 30 seconds. FIG. 2 shows the relationship between the light irradiation time and the contact angle, and Table 1 shows the difference in contact angle before and after the irradiation.
［応用例６］４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル １０−（トリメトキシシリル）デシルエーテル（１０ＥＴ）を用いたシリコンウェハの表面修飾
シランカップリング剤として４−ヘキシロキシ−５−メトキシ−２−ニトロベンジル １０−（トリメトキシシリル）デシルエーテル（１０ＥＴ）を用いた以外は応用例４と同様にして、表面をヒドロキシ基に変換したシリコンウェハを得た。
接触角計（協和界面科学社製ＣＡ−Ａ）を用い、液滴法（静的接触角）、ＪＩＳ Ｒ３２５７：９９に基づき、それぞれのウェハの接触角を測定し、表面状態の変化を評価すると、光照射時間３０秒でヒドロキシ基への変換を終了したことがわかった。照射前後の接触角の差を表１に示す。
[Application Example 6] Surface modification of silicon wafer using 4-hexyloxy-5-methoxy-2-nitrobenzyl 10- (trimethoxysilyl) decyl ether (10ET) 4-hexyloxy-5-methoxy- as a silane coupling agent A silicon wafer having a surface converted to a hydroxy group was obtained in the same manner as in Application Example 4 except that 2-nitrobenzyl 10- (trimethoxysilyl) decyl ether (10ET) was used.
Using a contact angle meter (CA-A manufactured by Kyowa Interface Science Co., Ltd.), measuring the contact angle of each wafer based on the droplet method (static contact angle), JIS R3257: 99, and evaluating the change in the surface state It was found that the conversion to a hydroxy group was completed after a light irradiation time of 30 seconds. Table 1 shows the difference in contact angle before and after irradiation.
[比較例１]４，５‐ジメトキシ−２−ニトロベンジル ３−（トリメトキシシリル）プロピルエーテル（比較化合物１）を用いたシリコンウェハの表面修飾
４，５‐ジメトキシ−２−ニトロベンジル ３−（トリメトキシシリル）プロピルエーテル（比較化合物１）を用いた以外は応用例４と同様にして、表面をヒドロキシ基に変換したシリコンウェハを得た。
接触角計（協和界面科学社製ＣＡ−Ａ）を用い、液滴法（静的接触角）、ＪＩＳ Ｒ３２５７：９９に基づき、それぞれのウェハの接触角を測定し、表面状態の変化を評価すると、光照射時間３０秒でヒドロキシ基への変換を終了したことがわかった。照射前後の接触角の差を表１に示す。
[Comparative Example 1] Surface modification of silicon wafer with 4,5-dimethoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether (Comparative Compound 1) 4,5-dimethoxy-2-nitrobenzyl 3- ( A silicon wafer having a surface converted to a hydroxy group was obtained in the same manner as in Application Example 4 except that trimethoxysilyl) propyl ether (Comparative Compound 1) was used.
Using a contact angle meter (CA-A manufactured by Kyowa Interface Science Co., Ltd.), measuring the contact angle of each wafer based on the droplet method (static contact angle), JIS R3257: 99, and evaluating the change in the surface state It was found that the conversion to a hydroxy group was completed after a light irradiation time of 30 seconds. Table 1 shows the difference in contact angle before and after irradiation.
[比較例２]２−ニトロベンジル３−（トリメトキシシリル）へキシルエーテル（比較化合物２）を用いたシリコンウェハの表面修飾
２−ニトロベンジル３−（トリメトキシシリル）へキシルエーテル（比較化合物２）を用いた以外は応用例４と同様にして、表面をヒドロキシ基に変換したシリコンウェハを得た。
接触角計（協和界面科学社製ＣＡ−Ａ）を用い、液滴法（静的接触角）、ＪＩＳ Ｒ３２５７：９９に基づき、それぞれのウェハの接触角を測定し、表面状態の変化を評価すると、変換の終了まで２０分程度を要したことがわかった。照射前後の接触角の差を表１に示す。
[Comparative Example 2] Surface modification of silicon wafer using 2-nitrobenzyl 3- (trimethoxysilyl) hexyl ether (Comparative Compound 2) 2-nitrobenzyl 3- (trimethoxysilyl) hexyl ether (Comparative Compound 2) ) Was used in the same manner as in Application Example 4 except that a silicon wafer having a surface converted to a hydroxy group was obtained.
Using a contact angle meter (CA-A manufactured by Kyowa Interface Science Co., Ltd.), measuring the contact angle of each wafer based on the droplet method (static contact angle), JIS R3257: 99, and evaluating the change in the surface state It was found that it took about 20 minutes to complete the conversion. Table 1 shows the difference in contact angle before and after irradiation.
Claims (3)
で表される化合物。 The following general formula (I)
A compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011117040A JP2012246225A (en) | 2011-05-25 | 2011-05-25 | Silane coupling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011117040A JP2012246225A (en) | 2011-05-25 | 2011-05-25 | Silane coupling agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2012246225A true JP2012246225A (en) | 2012-12-13 |
Family
ID=47467051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011117040A Withdrawn JP2012246225A (en) | 2011-05-25 | 2011-05-25 | Silane coupling agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2012246225A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3326971A4 (en) * | 2015-07-21 | 2019-02-06 | Universitat Politècnica de València | Antimicrobial, insecticidal and acaricidal system |
-
2011
- 2011-05-25 JP JP2011117040A patent/JP2012246225A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3326971A4 (en) * | 2015-07-21 | 2019-02-06 | Universitat Politècnica de València | Antimicrobial, insecticidal and acaricidal system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4948813B2 (en) | Method for producing ketimine structure-containing alkoxysilane | |
| US7999127B2 (en) | Siloxane monomers and oligomers | |
| JP4156858B2 (en) | Silane coupling agent | |
| JPH04202196A (en) | Texiltrialkoxysilane | |
| JP4644339B2 (en) | Silane coupling agent | |
| JP2012246225A (en) | Silane coupling agent | |
| JP2701103B2 (en) | Fluorine-containing organosilicon compound and method for producing the same | |
| JP2008255062A (en) | Organosilicon compound, method for producing the same, photopolymerizable composition and inorganic material | |
| JPH0770325A (en) | Production of polyorganosilane | |
| JPH0517487A (en) | New silane compound and its production | |
| JPH082911B2 (en) | 1,3-Bis (p-hydroxybenzyl) -1,1,3,3-tetramethyldisiloxane and method for producing the same | |
| JP6202431B2 (en) | Cage-type silsesquioxane derivatives | |
| JP2008239634A (en) | Organic silicon resin having alcoholic hydroxy group, and method for producing the same | |
| JPH01275586A (en) | Fluorine-containing silane coupling agent and production thereof | |
| JPS6313446B2 (en) | ||
| Hayase et al. | Photopolymerization of cyclohexene oxide by use of o‐nitrobenzyl triphenylsilyl ether/aluminum compound catalyst. Dependence of catalyst activity on the structure of the silyl ether | |
| WO2005044828A1 (en) | Method for producing cyclic organic silicon compound and organic silicon resin having alcoholic hydroxyl group | |
| JPH02117682A (en) | Production of 1,3-bis(hydroxyphenyl)disiloxane derivative | |
| JP3087597B2 (en) | Silicon-containing phenol compound | |
| JP2599313B2 (en) | Siloxane compound having tetrahydrophthalic anhydride group and method for producing the same | |
| JP4433563B2 (en) | Organosilicon compound | |
| JP3571445B2 (en) | Method for producing silyl enol ether | |
| JP4316230B2 (en) | Oxetane compounds having a carboxyl group | |
| JP3650156B2 (en) | Process for producing trialkylsilyltrialkylsiloxymethylene compounds | |
| JPH11171891A (en) | Production of silicon compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20140805 |