TWI443167B - And a polyorganosiloxane compound as a main component - Google Patents
And a polyorganosiloxane compound as a main component Download PDFInfo
- Publication number
- TWI443167B TWI443167B TW098104138A TW98104138A TWI443167B TW I443167 B TWI443167 B TW I443167B TW 098104138 A TW098104138 A TW 098104138A TW 98104138 A TW98104138 A TW 98104138A TW I443167 B TWI443167 B TW I443167B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- decane
- compound
- decane compound
- carbon atoms
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 55
- -1 1 Chemical class 0.000 claims description 199
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 95
- 239000000853 adhesive Substances 0.000 claims description 55
- 230000001070 adhesive effect Effects 0.000 claims description 53
- 125000001424 substituent group Chemical group 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 125000005843 halogen group Chemical group 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 15
- 239000000057 synthetic resin Substances 0.000 claims description 14
- 229920003002 synthetic resin Polymers 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 125000006239 protecting group Chemical group 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 17
- 239000000758 substrate Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 125000000732 arylene group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 150000002602 lanthanoids Chemical group 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- SMLNDVNTPWRZJH-UHFFFAOYSA-N 1-chloro-4-(trimethoxymethyl)dodecane Chemical compound ClCCCC(C(OC)(OC)OC)CCCCCCCC SMLNDVNTPWRZJH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CWZQYRJRRHYJOI-UHFFFAOYSA-N 1,1,1-trimethoxydecane Chemical compound CCCCCCCCCC(OC)(OC)OC CWZQYRJRRHYJOI-UHFFFAOYSA-N 0.000 description 2
- DGZPBRFJRXDRDD-UHFFFAOYSA-N 1-chloro-4-(triethoxymethyl)dodecane Chemical compound ClCCCC(C(OCC)(OCC)OCC)CCCCCCCC DGZPBRFJRXDRDD-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- GNPSQUCXOBDIDY-UHFFFAOYSA-N 4-(trimethoxymethyl)dodecane Chemical compound C(CCCCCCC)C(C(OC)(OC)OC)CCC GNPSQUCXOBDIDY-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CYYYHNQUUHHLPD-UHFFFAOYSA-N C(#N)CCC(C(OC)(OC)OC)CCCCCCCC Chemical compound C(#N)CCC(C(OC)(OC)OC)CCCCCCCC CYYYHNQUUHHLPD-UHFFFAOYSA-N 0.000 description 2
- JZHKIUBMQMDQRG-UHFFFAOYSA-N C(=C)C(C(OC)(OC)OC)CCCCCCCC Chemical group C(=C)C(C(OC)(OC)OC)CCCCCCCC JZHKIUBMQMDQRG-UHFFFAOYSA-N 0.000 description 2
- CISZSEKPWJADRI-UHFFFAOYSA-N C(C)OCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound C(C)OCCCC(C(OC)(OC)OC)CCCCCCCC CISZSEKPWJADRI-UHFFFAOYSA-N 0.000 description 2
- MTDLVDBRMBSPBJ-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC MTDLVDBRMBSPBJ-UHFFFAOYSA-N 0.000 description 2
- RVKBRFNNOKOSTA-UHFFFAOYSA-N C(CC)C(C(Cl)(Cl)Cl)CCCCCCCC Chemical compound C(CC)C(C(Cl)(Cl)Cl)CCCCCCCC RVKBRFNNOKOSTA-UHFFFAOYSA-N 0.000 description 2
- JSGRIFNBTXDZQU-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC JSGRIFNBTXDZQU-UHFFFAOYSA-N 0.000 description 2
- BBWFBBVQVRYACB-UHFFFAOYSA-N C1(CC2C(CC1)O2)CCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C1(CC2C(CC1)O2)CCC(C(OCC)(OCC)OCC)CCCCCCCC BBWFBBVQVRYACB-UHFFFAOYSA-N 0.000 description 2
- DVARJKVNDAJOEV-UHFFFAOYSA-N CC(CCCCCCCCC)OC(Cl)Cl Chemical compound CC(CCCCCCCCC)OC(Cl)Cl DVARJKVNDAJOEV-UHFFFAOYSA-N 0.000 description 2
- UQVRNLNIGWWDQE-UHFFFAOYSA-N ClCCCC(C(OC)(OC)Cl)CCCCCCCC Chemical compound ClCCCC(C(OC)(OC)Cl)CCCCCCCC UQVRNLNIGWWDQE-UHFFFAOYSA-N 0.000 description 2
- QHBRFDRRDWKRBR-UHFFFAOYSA-N ClCCCC(C(OCC)(OCC)Cl)CCCCCCCC Chemical compound ClCCCC(C(OCC)(OCC)Cl)CCCCCCCC QHBRFDRRDWKRBR-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- IDSSAEFSKKOAFJ-UHFFFAOYSA-N 1,1,1,4-tetrachlorobutane Chemical compound ClCCCC(Cl)(Cl)Cl IDSSAEFSKKOAFJ-UHFFFAOYSA-N 0.000 description 1
- KHPNGCXABLTQFJ-UHFFFAOYSA-N 1,1,1-trichlorodecane Chemical compound CCCCCCCCCC(Cl)(Cl)Cl KHPNGCXABLTQFJ-UHFFFAOYSA-N 0.000 description 1
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- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本發明係關於將金屬及合成樹脂等牢固地接著,以某種聚有機矽氧烷化合物為主要成份之接著劑。
先前,在電子零件及半導體元件,廣泛地使用於絕緣性基材表面形成導體電路之印刷電路板。在近幾年,隨著電子機器的小型化、高機能化的要求,對印刷電路板,要求導體電路更進一步的細微化、高密度化。
為了因應如此之要求,有稱為半添加法的方法,被提案作為高精細印刷電路板之製造方法。該方法係於合成樹脂製之絕緣基板之表面進行無電電鍍銅,將無電電鍍所形成之銅箔層蝕刻去除形成電路圖案者,可精度良好地形成細微的電路圖案。
但是,在半添加法,有如下的問題。即,在於絕緣基板與電路圖案之間雖有無電電鍍之銅箔層之存在,但該本質上並不具有對對絕緣基板之接著性。因此絕緣基板表面的凹凸較大時,雖然電路圖案與絕緣基板間的接著係以銅箔層之錨定效果而良好地保持,但是使用表面平滑者作為絕緣基板時接著性並不充分,而對形成之導體電路之基板之接著強度並不充分。
因此,以提升導體電路之接著強度為目的,提案有將絕緣基板表面粗面化之方法(專利文獻1等)。該方法在以可說是在絕緣基板表面形成細微的凹凸者。
但是,藉由該方法形成更精細的電路圖案時,高密度的極細電路線受到絕緣基板表面的凹凸的影響,而有難以形成細微而高密度的導體電路之情形。
如上所述在,近幾年,要求形成於印刷電路板之電路之細微化、高密度化,期望即使在具有平滑性之絕緣基板之情形,亦不會降低接著性之電路形成技術。
與本發明關聯,已知具有梯形型構造之聚有機矽氧烷化合物,係可形成硬度、耐熱性、耐候性等優良的薄膜之高分子(專利文獻2~5等)。又,於專利文獻6揭示有,含有羥基之聚有機矽倍半氧烷化合物;具有醇性羥基之丙烯共聚物樹脂;及含有聚異氰酸酯化合物之樹脂組合物,對金屬,特別是鋁之密著性優良。
但是,於專利文獻2~6,並沒有記載具有梯形型構造之聚有機矽氧烷化合物,可成為可牢固地接著金屬或合成樹脂之接著劑。
[專利文獻1]日本特開2003-49079號公報
[專利文獻2]日本特開昭58-59222號公報
[專利文獻3]日本特開平7-70321號公報
[專利文獻4]日本特開平8-92374號公報
[專利文獻5]日本特開平6-306173號公報
[專利文獻6]日本特開平10-87834號公報
本發明之課題係在於提供,可牢固地接著金屬或合成樹脂等,以某種聚有機矽氧烷化合物為主要成份之接著劑。
本發明者們為解決上述課題專心反覆研究的結果,藉由將在於3-乙醯氧基丙基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、2-氰基乙基三甲氧基矽烷等之分子末端具有特定官能基之烷氧基矽烷化合物縮聚合而合成聚有機矽氧烷化合物。然後,發現此者之硬化物,可牢固地接著金屬或合成樹脂等,而達至完成本發明。
因此根據本發明,可提供下述(1)~(7)之接著劑。
(1)一種接著劑,其係於分子內,具有式(I)所示反覆單位之梯形型構造之聚有機矽氧烷化合物為主要成份:
式中A係表示單鍵結或連接基,R1
係表示氫原子或碳數1~6之烷基,X0
係鹵素原子、以式:OG表示之基(式中,G係表示羥基的保護基)、或氰基;R2
係表示可具有取代基之苯基,可具有取代基(去除,鹵素原子、以上述式:OG所示之基及氰基。)之碳數1~20之烷基或碳數2~20之烯基;l、m、n係分別獨立地表示0或任意自然數,惟,去除l及n同時為0之情形;又,A相互,X0
相互、R1
相互及R2
相互可互相相同或不同,l、m及n分別為2以上時,以下述(i)、(ii)及(iii)所示之反覆單位,可互相相同亦可不同:
(2)如(1)所述的接著劑,其中上述聚有機矽氧烷化合物,係於觸媒的存在下,使式:X0
-CH(R1
)-A-Si(OR3
)p
(X1
)3-p
(式中X0
、R1
及A係表示與上述相同的意思,R3
係表示碳數1~6之烷基,X1
係表示鹵素原子,p係表示0~3之任一整數。)所示之矽烷化合物(1),與式:R2
Si(OR4
)q
(X2
)3-q
(式中R2
係表示與上述相同的意思,R4
係表示碳數1~6之烷基,X2
係表示鹵素原子,q係表示0~3之任一整數。)所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之比例反應而得。
(3)一種接著劑,其係以聚有機矽氧烷化合物為主要成份,該聚有機矽氧烷化合物,係於觸媒的存在下,式:X0
-CH(R1
)-A-Si(OR3
)p
(X1
)3-p
(式中X0
、R1
及A係表示與上述相同的意思,R3
係表示碳數1~6之烷基,X1
係表示鹵素原子,p係表示0~3之任一整數。)所示之矽烷化合物(1),與式:R2
Si(OR4
)q
(X2
)3-q
(式中R2
係表示與上述相同的意思,R4
係表示碳數1~6之烷基,X2
係表示鹵素原子,q係表示0~3之任一整數。)所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之比例反應而得。
(4)如(1)~(3)之任何一項所述的接著劑,其中上述A,係碳數1~10之亞烷基。
(5)如(1)~(4)之任何一項所述的接著劑,其中上述X0
,係氯原子、乙醯氧基或氰基。
(6)如(1)~(5)之任何一項所述的接著劑,其中接著之材料,係選自由玻璃、陶瓷、金屬及合成樹脂所組成之群之至少一種。
(7)如(6)所述的接著劑,其中上述金屬,係選自由銅、鋁、金、鉑及該等金屬之合金所組成之群之至少一種。
本發明之接著劑,可牢固地接著玻璃、陶瓷、金屬及合成樹脂等。
以下,詳細說明本發明。
1)接著劑
本發明之接著劑,其特徵係在於:以(i)於分子內,具有上述式(I)所示反覆單位之梯形型構造之聚有機矽氧烷化合物(以下,有稱為「聚有機矽氧烷化合物(I)」之情形。),或(ii)在觸媒的存在下,使式:X0
-CH(R1
)-A-Si(OR3
)p
(X1
)3-p
(式中X0
、R1
及A係表示與上述相同的意思,R3
係表示碳數1~6之烷基,X1
係表示鹵素原子,p係表示0~3之任一整數。)所示之矽烷化合物(1)與式:R2
Si(OR4
)q
(X2
)3-q
(式中R2
係表示與上述相同的意思,R4
係表示碳數1~6之烷基,X2
係表示鹵素原子,q係表示0~3之任一整數。)所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之比例反應而得之聚有機矽氧烷化合物(以下,有稱為「聚有機矽氧烷化合物(Ia)」之情形。),作為主要成份。
在於本發明之接著劑,所謂「以聚有機矽氧烷化合物(I)或聚有機矽氧烷化合物(Ia)作為主要成份」,以聚有機矽氧烷化合物(I)或聚有機矽氧烷化合物(Ia)之一種或二種以上作為含於接著劑之成份,而可在不阻礙本發明之目的範圍,含有後述之其他的添加成份之意思。
聚有機矽氧烷化合物(I)或聚有機矽氧烷化合物(Ia)在於本發明之成形材料中的含量,對接著劑全體,通常為70重量%以上,以80重量%以上為佳,以90重量%以上更佳。
上述式(I)中,A係表示單鍵結或連接基。
連接基,可舉例如,可具有取代基之亞烷基、可具有取代基之亞芳基、及可具有取代基之亞烷基與可具有取代基之亞芳基之組合等。
可具有取代基之亞烷基之亞烷基,可舉亞甲基、乙烯基、丙烯基、三亞甲基、四亞甲基、五亞甲基、環己烷基等碳數1~10之亞烷基;亞乙烯基、亞丙烯基、亞丁烯基、亞戊烯基等具有不飽和鍵結之碳數2~10之亞烷基等。
可具有取代基之亞芳基之亞芳基,可舉鄰亞苯基、間亞苯基、對亞苯基、2,6-亞萘基等。
上述亞烷基之取代基,可舉甲氧基、乙氧基等烷氧基;甲基硫代基、乙基硫代基等烷基硫代基;甲氧基羰基、乙氧基羰基等烷氧基羰基等。
上述亞芳基之取代基,可舉氰基;硝基;氟原子、氯原子、溴原子等鹵素原子;甲基、乙基等烷基;甲氧基、乙氧基等烷氧基;甲基硫代基、乙基硫代基等烷基硫代基等。
該等取代基可鍵結於亞烷基或亞芳基之任意位置、亦可鍵結有複數個相同或不同者。
可具有取代基之亞烷基與可具有取代基之亞芳基之組合,可舉將具有上述取代基之亞烷基之至少一種與具有上述取代基之亞芳基之至少一種串聯鍵結之基。具體而言,可舉下式所示之基。
該等之中,由可得對玻璃、陶瓷、金屬及合成樹脂具有優良的接著性,A以碳數1~6之亞烷基為佳,以乙烯基特別佳。
R1
係表示氫原子;甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、正己基等碳數1~6之烷基;以氫原子為佳。
X0
係表示氟原子、氯原子、溴原子、碘原子等的鹵素原子;以式:OG表示之基;或氰基。
G係表示羥基的保護基。羥基的保護基,並無特別限制,可舉已知作為羥基的保護基之習知之保護基。例如,醯系保護基;三甲基矽基、三乙基矽基、第三丁基二甲基矽基、第三丁基二苯矽基等的矽系保護基;甲氧基甲基、甲氧基乙氧基甲基、1-乙氧基乙基、四羥基芘-2-基、四羥呋喃-2-基等的縮醛系保護基;第三丁氧羰基等的烷氧基羰基系的保護基;甲基、乙基、第三丁基、辛基、芳基、三苯甲基、芐基、對甲氧基芐基、芴基、三苯甲基、二苯甲基等的醚系保護基等。該等之中,G以醯系保護基為佳。
醯系的保護基,具體而言,係以式:-C(=O)R5
表示之基。式中R5
係表示甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基等之碳數1~6之烷基;可具有取代基之苯基。
可具有R5
之取代基之苯基之取代基,可舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基、異辛基等烷基;氟原子、氯原子、溴原子等的鹵素原子;甲氧基、乙氧基等烷氧基。
該等之中,由容易取得,且可得對玻璃、陶瓷、金屬及合成樹脂具有優良的接著性之接著劑,X0
以氯原子、式:OG所示之基(式中,G係表示醯系保護基。)或氰基為佳,以氯原子、乙醯氧基或氰基特別佳。
R2
係表示可具有取代基之苯基、可具有取代基(去除鹵素原子、上述式:OG所示之基及氰基。)之碳數1~20之烷基或碳數2~20之烯基。
可具有R2
之取代基之苯基之取代基,可舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基、異辛基等烷基;甲氧基、乙氧基等烷氧基;氟原子、氯原子等的鹵素原子等。
可具有R2
之取代基之苯基之具體例,可舉苯基、2-氯苯基、4-甲基苯基、3-乙基苯基、2-甲氧基苯基等。
可具有R2
之取代基之碳數1~20之烷基之碳數1~20之烷基,可舉甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基、異辛基、正壬基、正癸基、正十二烷基等。
可具有R2
之碳數1~20之烷基之取代基,可舉縮水甘油基、縮水甘油醚氧基、環氧基、3,4-環氧環己基、丙烯醯氧基、甲基丙烯醯氧基、胇基、羧基、乙醯基乙腈基、胺基、胺基乙基胺基、苯基胺基等可具有取代基之胺基等。
碳數2~20之烯基,可舉乙烯基、異丙烯基、芳基等。
l、m、n係分別獨立地表示0或任意自然數。惟,去除l及n均為0之情形。由於在達成本發明之目的之化合物,須有式:X0
-CH(R1
)-A-(式中X0
、R1
及A係表示與上述相同的意思)所示之基。
又,A相互,X0
相互、R1
相互及R2
相互可互相相同或不同,l、m及n分別為2以上時,以下述(i)、(ii)及(iii)所示之反覆單位,可互相相同亦可不同
聚有機矽氧烷化合物(I)的反覆單位之中,必須要有(i)所示之反覆單位或(iii)所示之反覆單位。
聚有機矽氧烷化合物(I),可為僅以(i)或(iii)所示之反覆單位之一種所構成之均聚物;由(i)及/或(iii)所示之反覆單位之二種以上所構成之共聚物;由(i)及/或(iii)所示反覆單位之至少一種,及(ii)所示反覆單位所構成之共聚物等均可。再者,上述(iii)所示反覆單位亦可以上下旋轉180°的形式鍵結。
又,聚有機矽氧烷化合物(I)為共聚物時,該共聚物,可為無規共聚物、部分嵌段(共)聚合物、完全嵌段(共)聚合物等之任何一種(共)聚縮合物。
聚有機矽氧烷化合物(I)之製造方法,並無特別限制,於既定量的觸媒的存在下,使式:X0
-CH(R1
)-A-Si(OR3
)p
(X1
)3-p
所示之矽烷化合物(1)與式:R2
Si(OR4
)q
(X2
)3-q
所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之比例反應之方法為佳。
又,聚有機矽氧烷化合物(Ia),係於既定量的觸媒的存在下,使式:N≡C-CH(R1
)-A-Si(OR3
)p
(X1
)3-p
(式中R1
及A係表示與上述相同的意思,R3
係表示碳數1~6之烷基,X1
係表示鹵素原子,p係表示0~3之任一整數。)所示之矽烷化合物(1),與R2
Si(OR4
)q
(X2
)3-q
(式中R2
係表示與上述相同的意思,R4
係表示碳數1~6之烷基,X2
係表示鹵素原子,q係表示0~3之任一整數。)所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之比例反應而得。
在於上述式(1)之X0
、A、R1
及式(2)之R2
係表示與上述相同的意思。
上述式(1)中,R3
係表示與於上述R1
所例示之碳數1~6之烷基相同的碳數1~6之烷基。其中,由可經濟性、良率優良地得到目的物等之觀點,以甲基、乙基為佳。
X1
係表示氟原子、氯原子、溴原子等的鹵素原子。
p係表示0~3之任一整數。P為2以上時,以複數之式:OR3
表示之基可為相同亦可不同,(3-p)為2以上時,複數X1
相互可為相同亦可不同。
矽烷化合物(1)之具體例,可舉氯甲基三甲氧基矽烷、溴甲基三乙氧基矽烷、2-氯乙基三丙氧基矽烷、2-溴乙基三丁氧基矽烷、3-氯丙基三甲氧基矽烷、3-氯丙基三乙氧基矽烷、3-氯丙基三丙氧基矽烷、3-氯丙基三丁氧基矽烷、3-溴丙基三甲氧基矽烷、3-溴丙基三乙氧基矽烷、3-溴丙基三丙氧基矽烷、3-溴丙基三丁氧基矽烷、3-氟丙基三甲氧基矽烷、3-氟丙基三乙氧基矽烷、3-氟丙基三丙氧基矽烷、3-氟丙基三丁氧基矽烷、3-碘丙基三甲氧基矽烷、2-氯乙基三甲氧基矽烷、3-氯丙基三乙氧基矽烷、4-氯丁基三丙氧基矽烷、5-氯戊基三丙氧基矽烷、2-氯丙基三甲氧基矽烷、3-氯-3-乙醯丙基三甲氧基矽烷、3-氯-3-甲氧基羰基丙基三甲氧基矽烷、鄰(2-氯乙基)苯基三丙氧基矽烷、間(2-氯乙基)苯基三甲氧基矽烷、對(2-氯乙基)苯基三乙氧基矽烷、對(2-氟乙基)苯基三甲氧基矽烷等之X0
為鹵素原子之三烷氧基矽烷化合物類;氯甲基三氯矽烷、溴甲基溴二甲氧基矽烷、2-氯乙基二氯甲氧基矽烷、2-溴乙基二氯乙氧基矽烷、3-氯丙基三氯矽烷、3-氯丙基三溴矽烷、3-氯丙基氯二甲氧基矽烷、3-氯丙基氯二乙氧基矽烷、3-氯丙基氯二甲氧基矽烷、3-氯丙基氯二乙氧基矽烷、3-溴丙基二氯乙氧基矽烷、3-溴丙基三溴矽烷、3-溴丙基三氯矽烷、3-溴丙基氯二甲氧基矽烷、3-氟丙基三氯矽烷、3-氟丙基氯二甲氧基矽烷、3-氟丙基二氯甲氧基矽烷、3-氟丙基氯二乙氧基矽烷、3-碘丙基三氯矽烷、4-氯丁基氯二乙氧基矽烷、3-氯正丁基氯二乙氧基矽烷、3-氯-3-乙醯丙基二氯乙氧基矽烷、3-氯-3-甲氧基羰基丙基三溴矽烷等X0
為鹵素原子之鹵化矽烷化合物類;3-乙醯氧基丙基三甲氧基矽烷、3-乙醯氧基丙基三乙氧基矽烷、3-乙醯氧基丙基三丙氧基矽烷、3-乙醯氧基丙基三丁氧基矽烷、3-丙醯氧基丙基三甲氧基矽烷、3-丙烯氧基丙基三乙氧基矽烷、3-苯甲醯氧基丙基三甲氧基矽烷、3-苯甲醯氧基丙基三乙氧基矽烷、3-苯甲醯氧基丙基三丙氧基矽烷、3-苯甲醯氧基丙基三丁氧基矽烷、2-三甲基矽氧基乙基三甲氧基矽烷、3-三乙基矽氧基丙基三乙氧基矽烷、3-(2-四羥芘氧基)丙基三丙氧基矽烷、3-(2-四羥呋喃氧基)丙基三丁氧基矽烷、3-甲氧基甲基氧丙基三甲氧基矽烷、3-甲氧基乙氧基甲基氧丙基三乙氧基矽烷、3-(1-乙氧基乙基氧)丙基三丙氧基矽烷、3-(第三丁氧基碳醯氧基)丙基三甲氧基矽烷、3-第三丁氧基丙基三甲氧基矽烷、3-芐氧基丙基三乙氧基矽烷、3-三苯基甲氧丙基三乙氧基矽烷等X0
係以上述式:OG表示之基之三烷氧基矽烷化合物類;3-乙醯氧基丙基三氯矽烷、3-乙醯氧基丙基三溴矽烷、3-乙醯氧基丙基二氯甲氧基矽烷、3-乙醯氧基丙基二氯乙氧基矽烷、3-乙醯氧基丙基氯二甲氧基矽烷、3-乙醯氧基丙基氯二乙氧基矽烷、3-苯甲醯氧基丙基三氯矽烷、3-三甲基矽氧基丙基氯二甲氧基矽烷、3-三乙基矽氧基丙基二氯甲氧基矽烷、3-(2-四羥芘氧基)丙基氯二乙氧基矽烷、3-(2-四羥呋喃氧基)丙基二氯乙氧基矽烷、3-甲氧基甲基氧丙基三溴矽烷、3-甲氧基乙氧基甲基氧丙基三氯矽烷、3-(1-乙氧基乙基氧)丙基氯二甲氧基矽烷、3-第三丁氧基羰醯氧基丙基二氯甲氧基矽烷、3-第三丁氧基丙基氯二乙氧基矽烷、3-三苯甲氧基丙基二氯乙氧基矽烷、3-芐氧基丙基三溴矽烷等X0
係以上述式:OG表示之基之鹵化矽烷化合物類;氰基甲基三甲氧基矽烷、氰基甲基三乙氧基矽烷、1-氰基乙基三甲氧基矽烷、2-氰基乙基三甲氧基矽烷、2-氰基乙基三乙氧基矽烷、2-氰基乙基三丙氧基矽烷、3-氰基丙基三甲氧基矽烷、3-氰基丙基三乙氧基矽烷、3-氰基丙基三丙氧基矽烷、3-氰基丙基三丁氧基矽烷、4-氰基丁基三甲氧基矽烷、5-氰基戊基三甲氧基矽烷、2-氰基丙基三甲氧基矽烷、2-(氰基甲氧基)乙基三甲氧基矽烷、2-(2-氰基乙氧基)乙基三甲氧基矽烷、鄰(氰基甲基)苯基三丙氧基矽烷、間(氰基甲基)苯基三甲氧基矽烷、對(氰基甲基)苯基三乙氧基矽烷、對(2-氰基乙基)苯基三甲氧基矽烷等X0
為氰基之三烷氧基矽烷化合物類;氰基甲基三氯矽烷、氰基甲基溴二甲氧基矽烷、2-氰基乙基二氯甲氧基矽烷、2-氰基乙基二氯乙氧基矽烷、3-氰基丙基三氯矽烷、3-氰基丙基三溴矽烷、3-氰基丙基二氯甲氧基矽烷、3-氰基丙基二氯乙氧基矽烷、3-氰基丙基氯二甲氧基矽烷、3-氰基丙基氯二乙氧基矽烷、4-氰基丁基氯二乙氧基矽烷、3-氰基正丁基氯二乙氧基矽烷、2-(2-氰基乙氧基)乙基三氯矽烷、2-(2-氰基乙氧基)乙基二乙氧基矽烷、2-(2-氰基乙氧基)乙基二氯丙氧基矽烷、鄰(2-氰基乙基)苯基三氯矽烷、間(2-氰基乙基)苯基甲氧基二溴矽烷、對(2-氰基乙基)苯基二甲氧基氯矽烷、對(2-氰基乙基)苯基三溴矽烷等X0
為氰基之鹵化矽烷化合物類等。
矽烷化合物(1)可以一種單獨,或組合二種以上使用。
該等之中,由於可得對玻璃、陶瓷、金屬及合成樹脂具有更優良的接著性之接著劑,矽烷化合物(1)以具有3-氯丙基、3-乙醯氧基丙基、2-氰基乙基、或3-有氰基丙基之矽烷化合物為佳,以具有3-氯丙基、3-乙醯氧基丙基、或2-氰基乙基之三烷氧基矽烷化合物更佳。
上述式(2)中,R4
係表示與上述R3
相同之碳數1~6之烷基,X2
係表示與上述X1
相同之鹵素原子。
q係表示0~3之任一整數。Q為2以上時,複數以式:OR4
表示之基,‧可為相同亦可不同,(3-q)為2以上時,複數之X2
相互可為相同亦可不同。
矽烷化合物(2)之具體例,可舉具有:苯基三甲氧基矽烷、4-甲氧基苯基三甲氧基矽烷、2-氯苯基三甲氧基矽烷、苯基三乙氧基矽烷、2-甲氧基苯基三乙氧基矽烷、苯基二甲氧基乙氧基矽烷、苯基二乙氧甲氧基矽烷苯基三氯矽烷、苯基氯二甲氧基矽烷、苯基二氯甲氧基矽烷、苯基三溴矽烷、苯基氯甲氧基乙氧基矽烷、4-甲氧基苯基三氯矽烷、2-氯苯基三氯矽烷、苯基三氯矽烷、2-乙氧基苯基三氯矽烷等可具有取代基之苯基矽烷化合物類;甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、正丙基三甲氧基矽烷、正丁基三乙氧基矽烷、異丁基三甲氧基矽烷、正戊基三乙氧基矽烷、正己基三甲氧基矽烷、異辛基三乙氧基矽烷、十二烷基三甲氧基矽烷、甲基二甲氧基乙氧基矽烷、甲基二乙氧甲氧基矽烷甲基三氯矽烷、甲基氯二甲氧基矽烷、甲基二氯甲氧基矽烷、甲基二氯甲氧基矽烷、甲基三溴矽烷、甲基氯二乙氧基矽烷、乙基三氯矽烷、乙基氯二甲氧基矽烷、乙基二氯甲氧基矽烷、乙基三溴矽烷、正丙基三氯矽烷、正丙基氯二甲氧基矽烷、正丙基二氯甲氧基矽烷等烷基矽烷化合物類;縮水甘油基三甲氧基矽烷、縮水甘油基三乙氧基矽烷、縮水甘油基三丙氧基矽烷、縮水甘油基三丁氧基矽烷、縮水甘油基三氯矽烷、縮水甘油氯二甲氧基矽烷、縮水甘油二氯甲氧基矽烷、縮水甘油氯二乙氧基矽烷、縮水甘油二氯乙氧基矽烷、縮水甘油基三溴矽烷,3-縮水甘油醚氧基丙基三甲氧基矽烷、3-縮水甘油醚氧基丙基三乙氧基矽烷、3-縮水甘油醚氧基丙基三丙氧基矽烷、3-縮水甘油醚氧基丙基三丁氧基矽烷、3-縮水甘油醚氧基丙基三氯矽烷、3-縮水甘油醚氧基丙基氯二甲氧基矽烷、3-縮水甘油醚氧基丙基二氯甲氧基矽烷、3-縮水甘油醚氧基丙基氯二乙氧基矽烷、3-縮水甘油醚氧基丙基二氯乙氧基矽烷、3-縮水甘油醚氧基丙基三溴矽烷,2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三丙氧基矽烷、2-(3,4-環氧環己基)乙基三丁氧基矽烷,3-丙烯醯氧丙基三甲氧基矽烷、3-丙烯醯氧丙基三乙氧基矽烷、3-丙烯醯氧丙基三丙氧基矽烷、3-丙烯醯氧丙基三丁氧基矽烷,3-甲基丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷、3-甲基丙烯醯氧丙基三丙氧基矽烷、3-甲基丙烯醯氧丙基三丁氧基矽烷、3-甲基丙烯醯氧丙基三氯矽烷、3-甲基丙烯醯氧丙基氯二甲氧基矽烷、3-甲基丙烯醯氧丙基二氯甲氧基矽烷、3-甲基丙烯醯氧丙基氯二乙氧基矽烷、3-甲基丙烯醯氧丙基二氯乙氧基矽烷、3-甲基丙烯醯氧丙基三溴矽烷,3-[(2-胺基乙基)胺基]丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-苯基胺基丙基三甲氧基矽烷、3-羧丙基三甲氧基矽烷,3-胇基丙基三甲氧基矽烷、3-胇基丙基三乙氧基矽烷、3-胇基丙基三丙氧基矽烷、3-胇基丙基三丁氧基矽烷、3-胇基丙基三氯矽烷、3-胇基丙基氯二甲氧基矽烷、3-胇基丙基二氯甲氧基矽烷、3-胇基丙基氯二乙氧基矽烷、3-胇基丙基二氯乙氧基矽烷、3-有胇基丙基三溴矽烷等取代基之烷基矽烷化合物類;乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三丙氧基矽烷、乙烯基三丁氧基矽烷、丙烯基三甲氧基矽烷等烯基矽烷化合物類等。
矽烷化合物(2)可以一種單獨,或組合二種以上使用。
矽烷化合物(1)與矽烷化合物(2)之使用比例,以莫耳比可設定於[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之任意範圍,以20:80~70:30為佳,以25:75~60:40更加佳。藉由以如此之範圍,使用矽烷化合物(1)、矽烷化合物(2),可產率良好地製造可得接著性優良的硬化物之聚有機矽氧烷化合物。
用於矽烷化合物(1)與矽烷化合物(2)之反應之觸媒,以酸觸媒或鹼觸媒均可。
酸觸媒,可舉鹽酸、硫酸、硝酸、磷酸等的無機酸;甲基磺酸、三氟甲基磺酸、苯磺酸、對甲苯磺酸、醋酸、三氟醋酸等的有機酸。
鹼觸媒,可舉三甲胺、三乙胺、二異丙胺鋰、雙(三甲矽)醯胺化鋰、吡啶、1,8-二氮雜雙環[5.4.0]十一碳-7-烯、苯胺、甲基吡啶、1,4-二氮雜雙環[2.2.2]辛烷、咪唑等的有機鹼;氫氧化四甲基銨、氫氧化四乙基銨等有機鹽氫氧化合物;甲氧基鈉、乙氧基鈉、第三丁氧基鈉、第三氫氧化鈉、氫氧化鉀、氫氧化鈣等金屬氫氧化物;碳酸鈉、碳酸鉀、碳酸鎂等的金屬碳酸鹽;碳酸氫鈉、碳酸氫鉀等金屬碳酸氫鹽等。
觸媒的使用量,對矽烷化合物(1)或矽烷化合物(1)及矽烷化合物(2)(以下,有僅稱為「矽烷化合物」之情形。)之總莫耳量,通常為0.1mol%~10mol%,以1mol%~5mol%之範圍為佳。
使矽烷化合物(1)與矽烷化合物(2)反應之方法,並無特別限制,例如可舉於矽烷化合物(1)與矽烷化合物(2)之溶劑溶液添加觸媒,以既定溫度攪拌之方法。
使用的溶劑,可按照使用之矽烷化合物之種類適宜選擇。例如水;苯、甲苯、二甲苯等的芳香烴類;醋酸甲酯、醋酸乙酯、醋酸丙酯、丙酸甲酯等的酯類;丙酮、甲基乙基酮、甲基異丁基酮、甲基環己酮醇等酮類;甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇等醇類等。該等溶劑可以一種單獨,或混合二種以上使用。
該等之中,以水、芳香烴類及該等之混合溶劑為佳,以水與甲苯之混合溶劑特別佳。使用水與甲苯時,水與甲苯的比例(容積比)以1:9~9:1為佳,以7:3~3:7更佳。
溶劑的使用量,以溶劑每1公升,矽烷化合物之總莫耳量,通常為0.1mol~10mol,以成為0.5mol~10mol之量為佳。
使矽烷化合物反應時之溫度,通常係由0℃至使用之溶劑之沸點之溫度範圍,以20℃~100℃之範圍為佳。反應溶劑之沸點之溫度範圍,以20℃~100℃之範圍為佳。反應溫度過低,則有縮合反應的進行並不充分之情形。另一方面,反應溫度過高,則有難以抑制凝膠化。反應,通常在30分鐘至20小時完成。
反應結束之後,使用之酸觸媒時,藉由對反應溶液添加碳酸氫鈉等的鹼性水溶液,使用鹼觸媒時,對反應溶液添加鹽酸等酸進行中和,此時所產生的鹽藉由過濾或水洗等去除,得到目的之聚有機矽氧烷化合物(I)及聚有機矽氧烷化合物(Ia)(以下,有將該等總稱為「聚有機矽氧烷化合物(I)等」之情形。)。
所得聚有機矽氧烷化合物(I)等是否具有梯形型構造,例如可藉由對反應生成物進行紅外線吸收光譜測定或X射線繞射測定等確認。
所得聚有機矽氧烷化合物(I)等之重量平均分子量(Mw),通常為1,000~30,000,以1,500~10,000之範圍為佳。數目平均分子量,係例如以SEC(體積排阻層析)以聚苯乙烯換算求得。
又,聚有機矽氧烷化合物(I)等的分子量分佈(Mw/Mn),並無特別限制,通常為1.0~3.0,以1.1~2.0之範圍為佳。
本發明之接著劑,其特徵在於:含有聚有機矽氧烷化合物(I)等之一種或二種以上。本發明之接著劑,可為僅由聚有機矽氧烷化合物(I)所構成者,亦可係對聚有機矽氧烷化合物(I),以不阻礙本發明之目的之範圍,含有其他成份之組合物。
又,本發明之接著劑,雖係以具有梯形型構造的聚有機矽氧烷化合物(I)為主要成份者,惟在不阻礙本發明之目的之範圍,亦可含有無規型構造或籠型構造之聚有機矽氧烷化合物。
聚有機矽氧烷化合物(I)等在本發明之接著劑中的含量,對接著劑全體,通常為60重量%以上,以80重量%以上為佳,以90重量%以上更佳。
其他的成份,可舉氧化防止劑、紫外線吸收劑、光穩定劑、稀釋劑、矽烷偶合劑、硬化劑等。
氧化防止劑,係為防止加熱時之氧化惡化而添加者。
氧化防止劑,可舉例如,酚系、硫系、磷系氧化防止劑等。
酚系氧化防止劑之具體例,可舉2,6-二第三丁基對甲酚、二丁基羥基甲苯、丁基化羥基茴香醚、2,6-二第三丁基對乙基酚、硬脂基-β-(3,5-第三丁基-4-羥基苯基)丙酸酯等的單酚類;2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、2,2’-亞甲基雙(4-乙基-6-第三丁基酚)、4,4’-硫代雙(3-甲基-6-第三丁基酚)、4,4’-亞丁基雙(3-甲基-6-第三丁基酚)、3,9-雙[1,1-二甲基-2-{β-(3-第三丁基-4-羥基5-甲基苯基)丙醯氧基}乙基]2,4,8,10-四氧雜螺[5,5]十一烷等雙酚類;1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-第三丁基-4-羥基芐基)苯、四-[亞甲基-3-(3’,5’-二第三丁基-4’-羥基苯基)丙酸酯]甲烷、雙[3,3’-雙-(4’-羥基-3’-第三丁基苯基)丁酸]二醇酯、1,3,5-三(3’,5’-第三丁基-4’-羥基芐基)-S-三嗪-2,4,6-(1H,3H,5H)三酮、生育醇等的高分子型酚類。
硫系氧化防止劑,可舉二月桂基-3,3’-硫代二丙酸酯、肉荳蔻基-3,3’-硫代二丙酸酯、二硬脂基-3,3’-硫代二丙酸酯等。
磷系氧化防止劑,可舉磷酸三苯酯、磷酸二苯基異癸酯、磷酸苯基二異癸酯、磷酸三(壬基苯基)酯、磷酸二異癸基季戊四醇酯、磷酸三(2,4-第三丁基苯基)酯、磷酸環狀新戊烷四基雙(十八烷基)酯、磷酸環狀新戊烷四基雙(2,4-第三丁基苯基)酯、磷酸環狀新戊烷四基雙(2,4-第三丁基-4-甲基苯基)酯、磷酸氫雙[2-第三丁基-6-甲基-4-{2-(十八烷基氧羰基)乙基}苯基]酯等的磷酸酯類;9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-(3,5-二第三丁基-4-羥基芐基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-癸氧基-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物等之氧雜磷雜菲氧化物類。
該等氧化防止劑可以一種單獨,或組合二種以上使用。氧化防止劑之使用量,對聚有機矽氧烷化合物100重量部,以0.01~10重量部為佳。
紫外線吸收劑係以提升接著劑之耐候性為目的而添加。
紫外線吸收劑,可舉例如柳酸苯酯、柳酸對第三丁基苯酯、柳酸對辛基苯酯等柳酸類;2,4-二羥二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、2-羥基-4-十二烷氧二苯甲酮、2,2’-二羥-4-甲氧基二苯甲酮、2,2’-二羥-4,4’-二甲氧基二苯甲酮、2-羥基-4-甲氧基-5-硫基二苯甲酮等二苯甲酮類;2-(2’-羥基-5’-甲基苯基)苯併三唑、2-(2’-羥基-5’-第三丁基苯基)苯併三唑、2-(2’-羥基-3’,5’-二第三丁基苯基)苯併三唑、2-(2’-羥基-3’-第三丁基-5’-甲基苯基)-5-氯苯併三唑、2-(2’-羥基-3’,5’-二第三丁基苯基)-5-氯苯併三唑、2-(2’-羥基-3’,5’-二第三戊基苯基)苯併三唑、2-{(2’-羥基-3’,3",4",5",6"-四氫鄰苯二甲醯亞胺甲基)-5’-甲基苯基}苯併三唑等之苯併三唑類;雙(2,2,6,6-四甲基-4-哌啶基)癸二酸鹽、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)[{3,5-雙(1,1-二甲基乙基)-4-羥基苯基}甲基]丁基丙二酸酯等的受阻胺類等。
該等紫外線吸收劑可以一種單獨,或組合二種以上使用。紫外線吸收劑的使用量,對聚有機矽氧烷化合物100重量部,以0.01~10重量部為佳。
光穩定劑係以提升接著劑之耐光性為目的而添加。
光穩定劑,可舉例如聚[{6-(1,1,3,3,-四甲基丁基)胺基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶)亞胺基}六亞甲基{(2,2,6,6-四甲基4-哌啶)亞胺基}]等之受阻胺類。
該等光穩定劑可以一種單獨,或組合二種以上使用。光穩定劑之使用量,對聚有機矽氧烷化合物100重量部,以0.01~10重量部為佳。
稀釋劑係為調整接著劑黏度而添加。
稀釋劑,可舉例如,甘油縮水甘油醚、丁二醇縮水甘油醚、縮水甘油基苯胺、新戊二醇縮水甘油醚、環己烷二甲醇縮水甘油醚、亞烷基二縮水甘油醚、聚二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、甘油基三縮水甘油醚、4-乙烯基環己烯一氧化物、乙烯基環己烯二氧化物、甲基化乙烯基環己烯二氧化物等。該等稀釋劑可以一種單獨,或組合二種以上使用。
矽烷偶合劑係以進一步提升接著劑與被黏著體之密著性而添加。
矽烷偶合劑,可舉例如,3-縮水甘油醚氧基丙基三甲氧基矽烷、3-縮水甘油醚氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等。
硬化劑,可舉例如,酸酐、芳香族胺、酚樹脂等。
酸酐,可舉四羥苯二甲酸酐、甲基四羥苯二甲酸酐、六羥苯二甲酸酐、甲基六羥苯二甲酸酐、降莰烷-2,3-二羧酸酐、甲基降莰烷-2,3-二羧酸酐、環己烷-1,2,4-三羧酸、環己烷-1,3,5-三羧酸、環己烷-1,3,4-三羧酸-3,4-酐、馬來酐、苯二甲酸酐、琥珀酸酐、十二烷基琥珀酸酐、均苯四甲酸二酐、苯偏三甲酸酐等。
芳香族胺,可舉咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-胇基甲基苯並咪唑、2-乙基咪唑-4-二硫代羧酸、2-甲基咪唑-4-羧酸、1-(2-胺基乙基)-2-甲基咪唑、1-(2-氰基乙基)-2-甲基咪唑、2-苯基-4,5-二羥甲基咪唑、苯並咪唑、2-乙基-4-硫代甲醯咪唑等的咪唑類;吡唑、3-胺基-4-氰基-吡唑等的吡唑類;1,2,4-三唑、2-胺基-1,2,4-三唑、1,2-二胺基-1,2,4-三唑、1-胇基-1,2,4-三唑等的三唑類;2-胺基三嗪、2,4-二胺基-6-(6-(2-(2甲基-1-咪唑基)乙基)三嗪、2,4,6-三胇基均三嗪-三鈉鹽等。
本發明之接著劑,亦可包含硬化劑,但即使不使用硬化劑,亦可順利地進行硬化。由於使用硬化劑可能會成為惡化的原因,故在長期維持優良的接著性,不包含硬化劑較佳。
本發明之接著劑,可藉由例如對聚有機矽氧烷化合物(I)等,根據所望調合混合上述成份之一種或二種以上而製造。
本發明之接著劑之接著對象之材料,並無特別限定,鈉玻璃、耐熱誠硬質玻璃等玻璃類;矽晶圓等的陶瓷;鐵、銅、鋁、金、銀、鉑、鉻、鈦及該等金屬之合金、不銹鋼(SUS302、SUS304、SUS304L、SUS309等)等的金屬類;聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚乙烯、聚丙烯、聚氯乙烯、聚偏氯乙烯、聚乙烯醇、乙烯-醋酸乙烯酯共聚物、聚苯乙烯、聚碳酸酯、聚甲基戊烯、聚碸、聚醚醚酮、聚醚碸、聚苯硫醚、聚醚醯亞胺、聚醯亞胺、氟樹脂、聚醯胺、丙烯酸樹脂、原冰片烯系樹脂、環烯烴樹脂、玻璃環氧樹脂等有機‧無機複合樹脂等為佳。
藉由使用本發明之接著劑,可將接著對象之材料相互,具體而言,可將上述玻璃相互、陶瓷相互、金屬相互、合成樹脂相互、玻璃與陶瓷、玻璃與金屬、玻璃與合成樹脂、陶瓷與金屬、陶瓷與合成樹脂、金屬與合成樹脂等牢固地接著。
即,將本發明之接著劑塗佈於接著對象材料之一方或雙方的接著面乾燥後,使接著劑硬化,可將接著對象材料牢固地接著。
為使接著劑硬化,只要根據需要在加壓下,以既定溫度(100~200℃)加熱即可。
根據本發明之接著劑,即使是使用表面平滑之絕緣基板,於其表面形成金屬所構成之導體電路之情形,所形成之導體電路,可對基板具有充分的接著強度。
又,本發明之接著劑,由於透明性亦優良,特別是可良好地使用作為光學用接著劑。例如有用於作為將發光二極體等的半導體元件,固著於導線架、陶瓷盒、基板等時之接著劑。
[實施例]
以下,以實施例更加詳細地說明本發明。
但是,本發明並不應有任何受限於以下實施例。
再者,於下述實施例,使用如下者作為矽烷化合物。
(1)矽烷化合物(1)
1A:3-氯丙基三甲氧基矽烷(東京化成工業公司製)
1B:3-乙醯氧基丙基三甲氧基矽烷(AZMAX公司製)
1C:2-氰基乙基三甲氧基矽烷(AZMAX公司製)
(2)矽烷化合物(2)
2A:苯基三甲氧基矽烷(東京化成工業公司製)
(實施例1~8)
藉由以下所示之製造方法A或製造方法B,製造如下述第1表所示,接著劑1~8。
製造方法A:於放入攪拌子之200ml水滴瓶,放入第1表所示,矽烷化合物(1)、矽烷化合物(2)、作為溶劑之甲苯20ml及蒸餾水10ml後,將全體以室溫攪拌,加入磷酸(關東化學社製)0.10g(1mmol)作為觸媒,以同溫進一歩持續攪拌16小時。之後,對反應混合物加入飽和碳酸氫鈉水溶液使之中和。對此加入醋酸乙酯100ml將有機物萃取。
將有機物以蒸餾水清洗2次之後,以無水硫酸鎂乾燥,將硫酸鎂過濾後,將濾液滴入多量的正己烷中,使之再沈澱,將沈澱物以傾析分離。將所得沈澱物以四羥呋喃(THF)溶解回收,以減壓濃縮機餾除THF,藉由真空乾燥得到聚有機矽氧烷化合物。將此物作為接著劑。
製造方法B:於放入攪拌子之200ml水滴瓶,放入第1表所示,矽烷化合物(1)、矽烷化合物(2)、甲苯20ml、蒸餾水10ml之後、將全體以室溫攪拌,加入磷酸(關東化學社製)0.10g(1mmol)作為觸媒,以同溫進一歩持續攪拌16小時。之後,對反應混合物加入飽和碳酸氫鈉水溶液使之中和,靜置後,將甲苯及水以傾析去除。
將殘留物以蒸餾水清洗2次之後,加入2-丁酮100ml使之溶解,對所得溶液加入無水硫酸鎂乾燥,將硫酸鎂過濾後,將濾液滴入多量的正己烷中,使之再沈澱,將沈澱物濾取。將所得沈澱物以四羥呋喃(THF)溶解回收,以減壓濃縮機餾除THF,藉由真空乾燥得到聚有機矽氧烷化合物。將此物作為接著劑。
於第1表表示,在於實施例1~8之製造方法所使用之矽烷化合物(1)之種類及使用量、使用之矽烷化合物(2)之種類及使用量,並且於第1表一併表示所聚有機矽氧烷化合物之重量平均分子量(Mw)。
[表1]
又,將實施例1~8所得之聚有機矽氧烷化合物之IR光譜數據[傅立葉轉換紅外線光譜儀(以FT-IR,Perkin-Elmer公司製,Spectrum one測定]示於第2表
[表2]
(比較例1)
於20ml的玻璃製樣品管,加入3,4-環氧環己基甲基3,4-環氧環己烷羧酸酯(Aldrich製)2g、2,2-雙(4-縮水甘油醚氧基苯基)丙烷(東京化成工業公司製)1g、4-甲基環己烷-1,2-二羧酸酐(東京化成工業公司製)3g、及三苯膦(關東化學公司製)0.03g,將全體充分地混合,得到環氧樹脂組合物。將此物作為接著劑9。
(接著力測試)
於各種被著體上,固定開有直徑3mm之孔之厚度1mm之矽膠橡膠片。於該孔分別灌入實施例1~8及比較例1所得之接著劑1~9,以140℃加熱處理6小時使之硬化。之後,將矽膠橡膠片剝離,將被著體與接著劑之剪接著力,以粘合力測試機(系列4000、DAGE公司製)測定。於第3表表示其結果。
[表3]
由第3表,可知實施例1~8之接著劑,對各種接著對象材料(被著體)具有很強的接著力(無被著體依存性)。另一方面,確認到比較例1的接著劑9有被著體依存性。
Claims (7)
- 一種接著劑,於分子內,具有式(I)所示反覆單位之梯形型構造之聚有機矽氧烷化合物為主要成份
式中A係表示單鍵結或連接基,R1 係表示氫原子或碳數1~6之烷基,X0 係鹵素原子、以式:OG表示之基(式中,G係表示羥基的保護基)、或氰基;R2 係表示可具有取代基之苯基,可具有取代基(去除,鹵素原子、以上述式:OG所示之基及氰基。)之碳數1~20之烷基或碳數2~20之烯基;l、m、n係分別獨立地表示0或任意自然數,惟,去除l及n同時為0之情形;又,A相互,X0 相互、R1 相互及R2 相互可互相相同或不同,l、m及n分別為2以上時,以下述(i)、(ii)及(iii)所示之反覆單位,可互相相同亦可不同: 其中上述聚有機矽氧烷化合物,係於觸媒的存在下,使式:X0 -CH(R1 )-A-Si(OR3 )p (X1 )3-p (式中X0 、R1 及A係表示與上述相同的意思,R3 係表示碳數1~6之烷基,X1 係表示鹵素原子,p係表示0~3之任一整數。)所示之矽烷化合物(1),與式:R2 Si(OR4 )q (X2 )3-q (式中R2 係表示與上述相同的意思,R4 係表示碳數1~6之烷基,X2 係表示鹵素原子,q係表示0~3之任一整數。)所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之比例反應而得。 - 如申請專利範圍第1項所述的接著劑,其中上述聚有機矽氧烷化合物,係於觸媒的存在下,使式:X0 -CH(R1 )-A-Si(OR3 )p (X1 )3-p (式中X0 、R1 及A係表示與上述相同的意思,R3 係表示碳數1~6之烷基,X1 係表示鹵素原子,p係表示0~3之任一整數。)所示之矽烷化合物(1),與式:R2 Si(OR4 )q (X2 )3-q (式中R2 係表示與上述相同的 意思,R4 係表示碳數1~6之烷基,X2 係表示鹵素原子,q係表示0~3之任一整數。)所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~70:30之比例反應而得。
- 一種接著劑,以聚有機矽氧烷化合物為主要成份,該聚有機矽氧烷化合物係於觸媒的存在下,式:X0 -CH(R1 )-A-Si(OR3 )p (X1 )3-p (式中X0 、R1 及A係表示與上述相同的意思,R3 係表示碳數1~6之烷基,X1 係表示鹵素原子,p係表示0~3之任一整數。)所示之矽烷化合物(1),與式:R2 Si(OR4 )q (X2 )3-q (式中R2 係表示與上述相同的意思,R4 係表示碳數1~6之烷基,X2 係表示鹵素原子,q係表示0~3之任一整數。)所示之矽烷化合物(2),以矽烷化合物(1)與矽烷化合物(2)之莫耳比[矽烷化合物(1)]:[矽烷化合物(2)]=5:95~100:0之比例反應而得。
- 如申請專利範圍第1至3項中任一項所述的接著劑,其中上述A係碳數1~10之亞烷基。
- 如申請專利範圍第1至3項中任一項所述的接著劑,其中上述X0 係氯原子、乙醯氧基或氰基。
- 如申請專利範圍第1至3項中任一項所述的接著劑,其中接著之材料係選自由玻璃、陶瓷、金屬及合成樹脂所組成之群之至少一種。
- 如申請專利範圍第6項所述的接著劑,其中上述金屬係選自由銅、鋁、金、鉑及該等金屬之合金所組成之群之至少一種。
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| JPH06306173A (ja) | 1993-04-26 | 1994-11-01 | Showa Denko Kk | 反応性ポリオルガノシロキサン |
| JPH0770321A (ja) | 1993-09-01 | 1995-03-14 | Showa Denko Kk | 反応性ポリメチルシルセスキオキサン |
| JPH0892374A (ja) | 1994-09-19 | 1996-04-09 | Showa Denko Kk | ポリシルセスキオキサン及びそのビニル重合体 |
| JPH09278901A (ja) * | 1996-02-16 | 1997-10-28 | Kanegafuchi Chem Ind Co Ltd | シルセスキオキサンラダーポリマー予備硬化物及びそれを用いた成形体作製方法 |
| JPH1087834A (ja) | 1996-09-10 | 1998-04-07 | Showa Denko Kk | ポリオルガノシルセスキオキサン、その製造方法並びに該化合物を含有する樹脂組成物 |
| JP4187941B2 (ja) * | 2001-03-14 | 2008-11-26 | リンテック株式会社 | ホウ素含有ポリオルガノシルセスキオキサン及び接着剤組成物 |
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| JP2003238923A (ja) * | 2002-02-19 | 2003-08-27 | Lintec Corp | 粘接着剤形成用組成物、粘接着剤及び粘接着シート |
| SG102047A1 (en) * | 2002-05-02 | 2004-02-27 | Dso Nat Lab | Ladder-like silicone polymers |
| JP4566577B2 (ja) * | 2003-09-08 | 2010-10-20 | リンテック株式会社 | ポリシルセスキオキサングラフト重合体、その製造方法及び粘着剤 |
| JP4963781B2 (ja) * | 2004-02-25 | 2012-06-27 | リンテック株式会社 | ポリシルセスキオキサングラフト共重合体の製造方法、粘着剤および粘着シート |
| WO2006033148A1 (ja) | 2004-09-22 | 2006-03-30 | Lintec Corporation | ポリシルセスキオキサングラフト重合体、その製造方法及び粘着剤 |
| US8080604B2 (en) * | 2007-03-02 | 2011-12-20 | Lintec Corporation | Adhesive containing ladder-type polysilsesquioxane and adhesive sheet |
-
2009
- 2009-02-10 TW TW098104138A patent/TWI443167B/zh active
- 2009-02-12 CN CN201410360464.3A patent/CN104212409B/zh active Active
- 2009-02-12 KR KR1020157023610A patent/KR101732296B1/ko active Active
- 2009-02-12 KR KR1020177003875A patent/KR20170018490A/ko not_active Withdrawn
- 2009-02-12 US US12/918,127 patent/US8357261B2/en active Active
- 2009-02-12 WO PCT/JP2009/052272 patent/WO2009104505A1/ja not_active Ceased
- 2009-02-12 JP JP2009554279A patent/JP5568314B2/ja active Active
- 2009-02-12 CN CN200980105638.9A patent/CN101965387B/zh active Active
- 2009-02-12 KR KR1020107018333A patent/KR101581974B1/ko active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US20110054139A1 (en) | 2011-03-03 |
| CN101965387A (zh) | 2011-02-02 |
| US8357261B2 (en) | 2013-01-22 |
| WO2009104505A1 (ja) | 2009-08-27 |
| JPWO2009104505A1 (ja) | 2011-06-23 |
| KR101581974B1 (ko) | 2015-12-31 |
| TW200946627A (en) | 2009-11-16 |
| KR20170018490A (ko) | 2017-02-17 |
| CN104212409B (zh) | 2016-08-24 |
| JP5568314B2 (ja) | 2014-08-06 |
| KR101732296B1 (ko) | 2017-05-02 |
| CN104212409A (zh) | 2014-12-17 |
| CN104232016A (zh) | 2014-12-24 |
| KR20150107888A (ko) | 2015-09-23 |
| KR20100120156A (ko) | 2010-11-12 |
| CN101965387B (zh) | 2015-01-07 |
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