JPWO2015088021A1 - 接着性を有する光硬化性組成物 - Google Patents
接着性を有する光硬化性組成物 Download PDFInfo
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- JPWO2015088021A1 JPWO2015088021A1 JP2015552547A JP2015552547A JPWO2015088021A1 JP WO2015088021 A1 JPWO2015088021 A1 JP WO2015088021A1 JP 2015552547 A JP2015552547 A JP 2015552547A JP 2015552547 A JP2015552547 A JP 2015552547A JP WO2015088021 A1 JPWO2015088021 A1 JP WO2015088021A1
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- Prior art keywords
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- polymer
- compound
- meth
- crosslinkable silicon
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 229920000642 polymer Polymers 0.000 claims abstract description 164
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 157
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 229920000620 organic polymer Polymers 0.000 claims abstract description 52
- 125000003277 amino group Chemical group 0.000 claims abstract description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 11
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 9
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 9
- -1 alkali metal salts Chemical class 0.000 claims description 350
- 239000012025 fluorinating agent Substances 0.000 claims description 27
- 150000004756 silanes Chemical class 0.000 claims description 21
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 19
- 229910008284 Si—F Inorganic materials 0.000 claims description 16
- 150000003377 silicon compounds Chemical class 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 14
- 229910015900 BF3 Inorganic materials 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 70
- 238000000034 method Methods 0.000 description 63
- 239000000178 monomer Substances 0.000 description 62
- 229940048053 acrylate Drugs 0.000 description 55
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 54
- 125000000217 alkyl group Chemical group 0.000 description 43
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 37
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 34
- 229920002313 fluoropolymer Polymers 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 125000003545 alkoxy group Chemical group 0.000 description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 24
- 229910052782 aluminium Inorganic materials 0.000 description 23
- 229910052731 fluorine Inorganic materials 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 125000003118 aryl group Chemical group 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 22
- 125000004122 cyclic group Chemical group 0.000 description 22
- 239000002585 base Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 125000001424 substituent group Chemical group 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 20
- 235000019000 fluorine Nutrition 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- 238000002156 mixing Methods 0.000 description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 18
- 239000011737 fluorine Substances 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 16
- 238000003682 fluorination reaction Methods 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 15
- 229910052757 nitrogen Chemical group 0.000 description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 238000010526 radical polymerization reaction Methods 0.000 description 14
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 14
- 230000005494 condensation Effects 0.000 description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 13
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 12
- 229920001451 polypropylene glycol Polymers 0.000 description 12
- 125000003396 thiol group Chemical group [H]S* 0.000 description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 12
- 125000005843 halogen group Chemical group 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 125000006574 non-aromatic ring group Chemical group 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 7
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 7
- 0 CNc1c(*)c(*)c(*)c(*)c1* Chemical compound CNc1c(*)c(*)c(*)c(*)c1* 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 7
- 125000004104 aryloxy group Chemical group 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000004423 acyloxy group Chemical group 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical class NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 6
- 239000003504 photosensitizing agent Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 125000003302 alkenyloxy group Chemical group 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000012643 polycondensation polymerization Methods 0.000 description 5
- 125000003107 substituted aryl group Chemical group 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 5
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
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- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- HYGWNUKOUCZBND-UHFFFAOYSA-N azanide Chemical compound [NH2-] HYGWNUKOUCZBND-UHFFFAOYSA-N 0.000 description 4
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- 238000003776 cleavage reaction Methods 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 4
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- 238000010894 electron beam technology Methods 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
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- 150000002367 halogens Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
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- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 4
- PMOWTIHVNWZYFI-AATRIKPKSA-N trans-2-coumaric acid Chemical class OC(=O)\C=C\C1=CC=CC=C1O PMOWTIHVNWZYFI-AATRIKPKSA-N 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
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- 229910052727 yttrium Inorganic materials 0.000 description 4
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 3
- ZPQQHVQDOFHNLD-UHFFFAOYSA-N 2-(1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrimidin-4-yl)-1-phenylethanone Chemical compound C(C(=O)C1=CC=CC=C1)C1N2CCCC2NCC1 ZPQQHVQDOFHNLD-UHFFFAOYSA-N 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 3
- IVLICPVPXWEGCA-UHFFFAOYSA-N 3-quinuclidinol Chemical class C1C[C@@H]2C(O)C[N@]1CC2 IVLICPVPXWEGCA-UHFFFAOYSA-N 0.000 description 3
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
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- WACOZNZTFMHMOG-UHFFFAOYSA-N ethenyl(trifluoro)silane Chemical compound F[Si](F)(F)C=C WACOZNZTFMHMOG-UHFFFAOYSA-N 0.000 description 3
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- NGXSWUFDCSEIOO-UHFFFAOYSA-N pyrrolidin-3-amine Chemical group NC1CCNC1 NGXSWUFDCSEIOO-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 125000000213 sulfino group Chemical group [H]OS(*)=O 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- STAGZMKHHNNCKQ-UHFFFAOYSA-N tributyl(fluoro)silane Chemical compound CCCC[Si](F)(CCCC)CCCC STAGZMKHHNNCKQ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])[H] 0.000 description 1
- XVYIJOWQJOQFBG-UHFFFAOYSA-N triethoxy(fluoro)silane Chemical compound CCO[Si](F)(OCC)OCC XVYIJOWQJOQFBG-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- QYBKVVRRGQSGDC-UHFFFAOYSA-N triethyl methyl silicate Chemical compound CCO[Si](OC)(OCC)OCC QYBKVVRRGQSGDC-UHFFFAOYSA-N 0.000 description 1
- QVMRVWAOMIXFFW-UHFFFAOYSA-N triethyl(fluoro)silane Chemical compound CC[Si](F)(CC)CC QVMRVWAOMIXFFW-UHFFFAOYSA-N 0.000 description 1
- BHOCBLDBJFCBQS-UHFFFAOYSA-N trifluoro(methyl)silane Chemical compound C[Si](F)(F)F BHOCBLDBJFCBQS-UHFFFAOYSA-N 0.000 description 1
- JGHTXIKECBJCFI-UHFFFAOYSA-N trifluoro(propyl)silane Chemical compound CCC[Si](F)(F)F JGHTXIKECBJCFI-UHFFFAOYSA-N 0.000 description 1
- CJYXHAUSMDGBBU-UHFFFAOYSA-N trifluoro-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound F[Si](F)(F)CCCOCC1CO1 CJYXHAUSMDGBBU-UHFFFAOYSA-N 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- DALOGFFOSLUGET-UHFFFAOYSA-N trifluoromethoxysilane Chemical compound FC(F)(F)O[SiH3] DALOGFFOSLUGET-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 125000004933 β-carbolinyl group Chemical group C1(=NC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
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- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
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- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
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Abstract
Description
Xは水酸基または加水分解性基を示し、Xが2個以上存在するとき、それらは同一であってもよく、異なっていてもよい。aは0、1、2または3を、bは0、1または2を、それぞれ示す。またp個の下記一般式(2)におけるbは同一である必要はない。pは0〜19の整数を示す。但し、a+(bの和)≧1を満足するものとする。
また、高伸びで、低弾性率を示すゴム状硬化物を得るためには、分子中に含まれる架橋性珪素基の数は20個以下が好ましく、10個以下がより好ましく、5個以下がさらに好ましく、3個以下が特に好ましい。分子中に含まれる架橋性珪素基の数が平均して20個を超えると、硬化物が硬くなりすぎ、良好なゴム弾性挙動を発現しにくくなる。
架橋性珪素基は、有機重合体分子鎖の主鎖の末端あるいは側鎖の末端にあってもよいし、また、両方にあってもよい。特に、架橋性珪素基が分子鎖の主鎖の末端にのみあるときは、最終的に形成される硬化物に含まれる有機重合体成分の有効網目長が長くなるため、高強度、高伸びで、低弾性率を示すゴム状硬化物が得られやすくなる。
−R2−O−・・・(4)
前記一般式(4)中、R2は炭素数1〜14の直鎖状もしくは分岐アルキレン基であり、炭素数1〜14の、さらには2〜4の、直鎖状もしくは分岐アルキレン基が好ましい。
−CH2O−、−CH2CH2O−、−CH2CH(CH3)O−、−CH2CH(C2H5)O−、−CH2C(CH3)2O−、−CH2CH2CH2CH2O−
等が挙げられる。ポリオキシアルキレン系重合体の主鎖骨格は、1種類だけの繰り返し単位からなってもよいし、2種類以上の繰り返し単位からなってもよい。特にシーリング材等に使用される場合には、プロピレンオキシド重合体を主成分とする重合体から成るものが非晶質であることや比較的低粘度である点から好ましい。
原子移動ラジカル重合において用いられる(メタ)アクリル系モノマーやビニル系モノマーとしては特に制約はなく、例示した(メタ)アクリル系モノマーやビニル系モノマーをすべて好適に用いることができる。
−CH2−C(R3)(COOR4)− ・・・(5)
(式中、R3は水素原子またはメチル基、R4は炭素数1〜8のアルキル基を示す)で表される(メタ)アクリル酸エステル単量体単位と、下記一般式(6):
−CH2−C(R3)(COOR5)− ・・・(6)
(式中、R3は前記に同じ、R5は炭素数10以上のアルキル基を示す)で表される(メタ)アクリル酸エステル単量体単位からなる共重合体に、架橋性珪素基を有するポリオキシアルキレン系重合体をブレンドして製造する方法である。
前記アクリル系共重合体は、前記(a1)及び(a2)以外の単量体単位が含まれていてもよい。(a1)及び(a2)以外の単量体単位としては、たとえば、前記(メタ)アクリル酸エステル系共重合体の説明において前述した他の単量体単位を同様に用いることができる。
[前記式(VI)において、Aは直接結合又は2価の連結基であり、Q’は環状構造含有基である。直接結合とは、Q’が連結基を介することなく、Zに直接結合していることを意味する。Aにおける2価の連結基としては、例えば、それぞれ置換基を有していてもよい、アルキレン基、カルボニル基、エーテル結合、エステル結合、−CONH−基、またはこれらの組み合わせを含む2価の連結基等が挙げられ、置換基を含んでいてもよいアルキレン基やカルボニル基及びそれらの組合せが好ましい。また、Aの置換基が環状構造を有していてもよく、また、置換基同士が結合し、環状構造を形成していてもよい。該環状構造としては、例えば、Q’と同様のものが挙げられる。
前記Q’における環状構造は、単環及び複数の環のいずれもよく、また、単素環式及び複素環式のいずれでもよいが、ビニル基やカルボニル基、イミノ基等の官能基を含んでいることが好ましく、芳香族性を示す環状構造を有していることがより好ましい。前記Q’としては、例えば、それぞれ置換基を有していてもよい、アリール基,アリールオキシ基,窒素や酸素、硫黄等のヘテロ原子を1種以上含む複素環基,カルボニル基が結合した環状構造を含む基やこれらの組合せ及びこれらの縮合環等が挙げられる。また、置換基がさらに環状構造を有していてもよい。また、Aの置換基とQ’とが結合していてもよい。]
(式(7)において、R50はそれぞれ独立して、置換あるいは非置換の炭素原子数1〜20の炭化水素基、またはR80SiO−(R80はそれぞれ独立に、炭素原子数1〜20の置換あるいは非置換の炭化水素基、又はフッ素原子である)で示されるオルガノシロキシ基のいずれかを示す。dは1〜3のいずれかであり、dが3であることが好ましい。R50及びR80が複数存在する場合、それらは同じであっても異なっていてもよい。)
(式(8)中、R50及びdはそれぞれ式(7)と同じであり、X’はそれぞれ独立して水酸基又はフッ素以外の加水分解性基であり、eは0〜2のいずれかであり、fは0〜2のいずれかであり、d+e+fは3である。R50及びX’が複数存在する場合、それらは同じであっても異なっていてもよい。)
また、合成の容易さからフルオロジメチルシリル基、ジフルオロメチルシリル基、トリフルオロシリル基、フルオロメトキシメチルシリル基、フルオロエトキシメチルシリル基、フルオロメトキシエチルシリル基、フルオロジメトキシシリル基、フルオロジエトキシシリル基、ジフルオロメトキシシリル基、ジフルオロエトキシシリル基がより好ましく、安定性の観点からフルオロジメチルシリル基、ジフルオロメチルシリル基、トリフルオロシリル基などのフッ素以外に加水分解性基を持たないケイ素基がさらに好ましく、硬化性の高さからは、ジフルオロメチルシリル基、ジフルオロメトキシシリル基、ジフルオロエトキシシリル基、トリフルオロシリル基など、ケイ素基上に2個ないし3個のフッ素が置換したケイ素基が好ましく、トリフルオロシリル基が最も好ましい。
−SiR50 3−qX’q ・・・(9)
(式(9)中、R50及びX’はそれぞれ式(8)と同じであり、qは1〜3のいずれかである。)
ハロシリル基のフッ素化に使用されるフッ素化剤の具体例としては、特に限定されず、例えば、AgBF4、SbF3、ZnF2、NaF、KF、CsF、NH4F、CuF2、NaSiF6、NaPF6、NaSbF6、NaBF4、Me3SnF、KF(HF)1.5〜5などが挙げられる。
ヒドロシリル基のフッ素化に使用されるフッ素化剤の具体例としては、特に限定されず、例えば、AgF、PF5、Ph3CBF4、SbF3、NOBF4、NO2BF4などが挙げられる。
シロキサン結合を有する化合物はBF3などにより開裂し、フルオロシリル基が得られる。
有機重合体中のSiF結合の位置も特に制限はなく、重合体分子内のいずれの部位にあっても効果を発揮し、主鎖または側鎖の末端であれば−SiRn 2F、重合体の主鎖に組み込まれていれば、−SiRnF−または≡SiF(Rnはそれぞれ独立に、任意の基)の形で表される。
主鎖又は側鎖の末端にSi−F結合を有する有機重合体としては、前述した式(8)で示されるフルオロシリル基を有する重合体が好適である。フルオロシリル基が重合体の主鎖中に組み込まれたものの例としては、−Si(CH3)F−、−Si(C6H5)F−、−SiF2−、≡SiFなどが挙げられる。
(イ)分子中に水酸基、エポキシ基やイソシアネート基等の官能基を有する重合体に、この官能基に対して反応性を示す官能基およびフルオロシリル基を有する化合物を反応させる方法。たとえば、末端に水酸基を有する重合体とイソシアネートプロピルジフルオロメチルシランを反応させる方法や、末端にSiOH基を有する重合体とジフルオロジエトキシシランを反応させる方法が挙げられる。
(ロ)分子中に不飽和基を含有する重合体に、フルオロシリル基を有するヒドロシランを作用させてヒドロシリル化する方法。たとえば、末端にアリル基を有する重合体に、ジフルオロメチルヒドロシランを反応させる方法が挙げられる。
(ハ)不飽和基を含有する重合体に、メルカプト基およびフルオロシリル基を有する化合物を反応させる方法。たとえば、末端にアリル基を有する重合体に、メルカプトプロピルジフルオロメチルシランを反応させる方法が挙げられる。
フッ素化剤としては、例えば、前述したフッ素化剤が挙げられ、中でも、BF3エーテル錯体、BF3アルコール錯体、BF3二水和物は活性が高く、効率よくフッ素化が進行し、さらに副生成物に塩等が生じず、後処理が容易であるためにより好ましく、BF3エーテル錯体が特に好ましい。
さらに、BF3エーテル錯体によるフッ素化は、加熱しなくても反応が進行するが、より効率よくフッ素化を行なうためには、加熱することが好ましい。加熱温度としては50℃以上150℃以下が好ましく、60℃以上130℃がより好ましい。50℃以下であると反応が効率よく進行せず、フッ素化に時間がかかる場合がある。150℃以上であるとフッ素化ポリマーが分解する虞がある。BF3錯体によるフッ素化において、用いる重合体(X)の種類によっては着色が起こる場合があるが、着色の抑制の点から、BF3アルコール錯体、BF3二水和物を用いることが好ましい。
これら塩基は単独で用いてもよく、2種以上組み合わせて用いてもよい。
グアニジン系化合物としては、グアニジン、1,1,3,3−テトラメチルグアニジン、1−ブチルグアニジン、1−フェニルグアニジン、1−o−トリルグアニジン、1,3−ジフェニルグアニジンなどを挙げることができる。
ビグアニド系化合物としては、ブチルビグアニド、1−o−トリルビグアニドや1−フェニルビグアニドを挙げることができる。
R52及びR53は、互いに独立して、水素、C1−C18アルキル、C3−C18アルケニル、C3−C18アルキニル又はフェニルであり、そしてもしR52が水素又はC1−C18アルキルであれば、R53は、更に、基−CO−R64(式中、R64は、C1−C18アルキル又はフェニルである)であるか;或いは、R51とR53は、カルボニル基及びR53が結合しているC原子と一緒になって、ベンゾシクロペンタノン基を形成する。
R54およびR56は、一緒になって、非置換であるか、または1個以上のC1〜C4アルキル基によって置換されているC2〜C12アルキレンブリッジを形成する。R55およびR57は、一緒になって、R54およびR56とは独立して、非置換であるか、または1個以上のC1〜C4アルキル基によって置換されているC2〜C12アルキレンブリッジを形成する。R54とR56が、一緒になって、C3アルキレン橋を形成し、R55とR57が、一緒になって、プロピレン又はペンチレンであることが好ましい。
R66は炭素原子数1〜12のアルキル基;−OH、−炭素原子数1〜4のアルコキシ、−CNもしくは−COO(炭素原子数1〜4のアルキル)で置換された炭素原子数2〜4のアルキル基を表すか、または、R66は炭素原子数3〜5のアルケニル基、炭素原子数5〜12のシクロアルキル基またはフェニル−炭素原子数1〜3のアルキル基を表す。R67は炭素原子数1〜12のアルキル基;または−OH、−炭素原子数1〜4のアルコキシ基、−CNもしくは−COO(炭素原子数1〜4のアルキル)で置換された炭素原子数2〜4のアルキル基を表すかまたはR67は炭素原子数3〜5のアルケニル基、炭素原子数5〜12のシクロアルキル基、フェニル−炭素原子数1〜3のアルキル基、または、未置換であるかまたは炭素原子数1〜12のアルキル基、炭素原子数1〜4のアルコキシ基もしくは−COO(炭素原子数1〜4のアルキル)によって置換されたフェニル基を表すか、あるいはR67はRR66と一緒になって炭素原子数1〜7のアルキレン基、フェニル−炭素原子数1〜4のアルキレン基、o−キシリレン基、2−ブテニレン基または炭素原子数2もしくは3のオキサアルキレン基を表すか、あるいはR66およびR67は一緒になって−O−、−S−もしくは−CO−で中断され得る炭素原子数4〜7のアルキレン基を表すか、またはR66およびR67は一緒になってOH、炭素原子数1〜4のアルコキシ基もしくは−COO(炭素原子数1〜4のアルキル)で置換され得る炭素原子数3〜7のアルキレン基を表す。R66およびR67が複数存在する場合それらは同じであっても異なっていてもよい。
Y1は下記式(v)で示される2価の基、−N(R68)−又は−N(R68)−R69−N(R68)−で示される2価の基を表し、R68は炭素原子数1〜8のアルキル基、炭素原子数3〜5のアルケニル基、フェニル−炭素原子数1〜3のアルキル基、炭素原子数1〜4のヒドロキシアルキル基もしくはフェニル基を表し、R69は1もしくはそれ以上の−O−または−S−により中断され得る枝分かれしていないまたは枝分かれした炭素原子数2〜16のアルキレン基を表す。
Y2は炭素原子数1〜6のアルキレン基、シクロヘキシレン基もしくは直接結合を表す。
R70〜R72は、それぞれ互いに独立に、水素、C1〜C18アルキル、C3〜C18アルケニル、C3〜C18アルキニルもしくはフェニルであり;またはR70とR71および/もしくはR72とR71が、互いに独立にC2〜C12アルキレン架橋を形成しているか;あるいはR70〜R72が、結合している窒素原子とともに、P1、P2、P<t/4>型のホスファゼン塩基を、または、下記構造式(a)、(b)、(c)、(d)、(e)、(f)もしくは(g)の基を形成している。
R73およびR74は、それぞれ独立に、水素原子、炭素数1〜20のアルキル基又はハロゲン原子、炭素数1〜20のアルコキシ基、ニトロ基、カルボキシル基、水酸基、メルカプト基、炭素数1〜20のアルキルチオ基、炭素数1〜20のアルキルシリル基、炭素数1〜20のアシル基、アミノ基、シアノ基、炭素数1〜20のアルキル基、フェニル基、ナフチル基、フェノキシ基及びフェ二ルチオ基の群から選ばれる基で置換されていてもよいフェニル基を表し、R73及びR74は互いに結合して環構造を形成していてもよい。
前記光塩基発生剤(D)の配合割合は特に制限はないが、(A)架橋性珪素基含有有機重合体100質量部に対して、0.01〜50質量部が好ましく、0.1〜40質量部がより好ましく、0.5〜30質量部がさらに好ましい。
前記三フッ化ホウ素のアミン錯体の市販品としては、例えば、エアプロダクツジャパン株式会社製のアンカー1040、アンカー1115、アンカー1170、アンカー1222、BAK1171等が挙げられる。
これらの中でも、多価フルオロ化合物のアルカリ金属塩における多価フルオロ化合物成分としては、テトラフルオロホウ酸又はヘキサフルオロリン酸が好ましい。また、多価フルオロ化合物のアルカリ金属塩におけるアルカリ金属としては、リチウム、ナトリウム及びカリウムからなる群から選ばれる一種以上のアルカリ金属であることが好ましい。
前記シランカップリング剤としては、例えば、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有シラン類;γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルトリエトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルメチルジメトキシシラン、1,3−ジアミノイソプロピルトリメトキシシラン等のアミノ基含有シラン類;N−(1,3−ジメチルブチリデン)−3−(トリエトキシシリル)−1−プロパンアミン、N−(1,3−ジメチルブチリデン)−3−(トリメトキシシリル)−1−プロパンアミン等のケチミン型シラン類;γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン等のメルカプト基含有シラン類;ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリロイルオキシプロピルトリメトキシシラン、γ−アクリロイルオキシプロピルメチルジメトキシシラン等のビニル型不飽和基含有シラン類;γ−クロロプロピルトリメトキシシラン等の塩素原子含有シラン類;γ−イソシアネートプロピルトリエトキシシラン、γ−イソシアネートプロピルメチルジメトキシシラン等のイソシアネート含有シラン類;ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、デシルトリメトキシシラン等のアルキルシラン類;フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン等のフェニル基含有シラン類等が挙げられるが、これらに限定されるものではない。また、前記アミノ基含有シラン類と前記のシラン類を含むエポキシ基含有化合物、イソシアネート基含有化合物、(メタ)アクリロイル基含有化合物とを反応させて、アミノ基を変性した変性アミノ基含有シラン類を用いてもよい。
数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により下記条件で測定した。本発明において、該測定条件でGPCにより測定し、標準ポリエチレングリコールで換算した最大頻度の分子量を数平均分子量と称する。
・分析装置:Alliance(Waters社製)、2410型示差屈折検出器(Waters社製)、996型多波長検出器(Waters社製)、Milleniamデータ処理装置(Waters社製)
・カラム:Plgel GUARD+5μmMixed−C×3本(50×7.5mm,300×7.5mm:PolymerLab社製)
・流速:1mL/分
・換算したポリマー:ポリエチレングリコール
・測定温度:40℃
・GPC測定時の溶媒:THF
NMR及びIRの測定は、下記測定装置を用いて行った。
FT−NMR測定装置:日本電子(株)製JNM−ECA500(500MHz)
FT−IR測定装置:日本分光(株)製FT−IR460Plus
フラスコに2−ニトロベンジルアルコール15.3部とトルエン344部を加え、約113℃で60分間還流した。その後、3−イソシアネートプロピルトリエトキシシラン24.7部を滴下し、5時間撹拌し、合成物(下記式(XV)で示される光によりアミノ基を生成する架橋性珪素基含有化合物。以下光アミノシラン発生化合物B1と称する)を得た。該光アミノシラン発生化合物B1のIRスペクトル測定の結果、−N=C=O結合は検出されなかった。
攪拌装置、窒素ガス導入管、温度計および環流冷却器を備えたフラスコに、エチレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテート−グライム錯体触媒の存在下、プロピレンオキシドを反応させ、ポリオキシプロピレントリオールを得た。得られたポリオキシプロピレントリオールにナトリウムメトキシドのメタノール溶液を添加し、加熱減圧下メタノールを留去してポリオキシプロピレントリオールの末端水酸基をナトリウムアルコキシドに変換し、ポリオキシアルキレン系重合体M1を得た。
攪拌装置、窒素ガス導入管、温度計および環流冷却器を備えたフラスコに、エチレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテート−グライム錯体触媒の存在下、プロピレンオキシドを反応させ、ポリオキシプロピレントリオールを得た。得られたポリオキシプロピレントリオールにナトリウムメトキシドのメタノール溶液を添加し、加熱減圧下メタノールを留去してポリオキシプロピレントリオールの末端水酸基をナトリウムアルコキシドに変換し、ポリオキシアルキレン系重合体M2を得た。
撹拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、酢酸エチルを40.00g、メチルメタクリレート70.00g、2−エチルヘキシルメタクリレート(東京化成工業(株)製)30.00g、3−メタクリロキシプロピルトリメトキシシラン(商品名:KBM503、信越化学工業(株)製)12.00g、及び金属触媒としてチタノセンジクライド0.10gを仕込みフラスコ内に窒素ガスを導入しながらフラスコの内容物を80℃に加熱した。ついで、充分に窒素ガス置換した3−メルカプトプロピルトリメトキシシラン4.30gを撹拌下にフラスコ内に一気に添加した。3−メルカプトプロピルトリメトキシシラン4.30gを添加後、撹拌中のフラスコ内の内容物の温度が80℃に維持できるように、加熱及び冷却を4時間行った。さらに、充分に窒素ガス置換した3−メルカプトプロピルトリメトキシシラン4.30gを撹拌下に5分かけてフラスコ内に追加添加した。3−メルカプトプロピルトリメトキシシラン4.30g全量を追加添加後、撹拌中のフラスコ内の内容物の温度が90℃に維持できるように、さらに冷却及び加温を行いながら、反応を4時間行った。合計で8時間5分間の反応後、反応物の温度を室温に戻し、反応物にベンゾキノン溶液(95%THF溶液)を20.00g添加して重合を停止し、トリメトキシシリル基を有する(メタ)アクリル系重合体A3を得た。ピークトップ分子量は4000、分子量分布は2.4であった。H1−NMR測定により含有されるトリメトキシシリル基は1分子あたり2.00個であった。
攪拌装置、窒素ガス導入管、温度計および環流冷却器を備えた新しいフラスコに、分子量約2,000のポリオキシプロピレンジオールを開始剤とし、亜鉛ヘキサシアノコバルテート−グライム錯体触媒の存在下、プロピレンオキシドを反応させて得られた水酸基価換算分子量14500、かつ分子量分布1.3のポリオキシプロピレンジオールを得た。得られたポリオキシプロピレンジオールにナトリウムメトキシドのメタノール溶液を添加し、加熱減圧下メタノールを留去してポリオキシプロピレンジオールの末端水酸基をナトリウムアルコキシドに変換し、ポリオキシアルキレン系重合体M3を得た。
得られた末端にメチルジメトキシシリル基を有するポリオキシアルキレン系重合体A4の分子量をGPCにより測定した結果、ピークトップ分子量は15000、分子量分布1.3であった。H1−NMR測定により末端のメチルジメトキシシリル基は1分子あたり1.7個であった。
フラスコに9−(ヒドロキシメチル)アントラセン20.8部とトルエン344部を加え、約113℃で60分間還流した。その後、3−イソシアネートプロピルトリエトキシシラン24.7部を滴下し、5時間撹拌し、合成物(光によりアミノ基を生成する架橋性珪素基含有化合物。以下光アミノシラン発生化合物B2と称する)を得た。該光アミノシラン発生化合物B2のIRスペクトル測定の結果、−N=C=O結合は検出されなかった。
フラスコにベンゾイン21.2部とトルエン344部を加え、約113℃で60分間還流した。その後、3−イソシアネートプロピルトリエトキシシラン24.7部を滴下し、5時間撹拌し、合成物(光によりアミノ基を生成する架橋性珪素基含有化合物。以下光アミノシラン発生化合物B3と称する)を得た。該光アミノシラン発生化合物B3のIRスペクトル測定の結果、−N=C=O結合は検出されなかった。
フラスコに4−ニトロベンジルアルコール15.3部とトルエン344部を加え、約113℃で60分間還流した。その後、3−イソシアネートプロピルトリエトキシシラン24.7部を滴下し、5時間撹拌し、合成物(光によりアミノ基を生成する架橋性珪素基含有化合物。以下光アミノシラン発生化合物B4と称する)を得た。該光アミノシラン発生化合物B4のIRスペクトル測定の結果、−N=C=O結合は検出されなかった。
表1に示す配合割合にて、攪拌機、温度計、窒素導入口、モノマー装入管および水冷コンデンサーを装着した300mLのフラスコに、合成例2〜4で得た重合体A1〜A3、光アミノシラン発生化合物B1、光ラジカル発生剤及びフッ素化ポリマーC1を入れ、撹拌し、溶解させた。また。表1に示す配合割合にて、別の100mLのナスフラスコに光塩基発生剤及びプロピレンカーボネートを入れ、撹拌し、溶解させ、この溶液の全量を先ほど量り取った300mLフラスコへ投入し、減圧撹拌を行い、光硬化性組成物を得た。
*1)光塩基発生剤:BASFジャパン(株)製、商品名「Irgacure379」。
*2)光塩基発生剤:サンアプロ(株)製、商品名「SA−2」。
*3)アルミニウムキレート化合物:川研ファインケミカル(株)製、商品名「アミノキレートD」、アルミニウムモノアセチルアセトネートビス(エチルアセトアセテート)。
*4)光ラジカル発生剤:BASFジャパン(株)製、商品名「ダロキュア1173」、開裂型光ラジカル発生剤。
*5)エポキシ基含有シラン類:信越化学工業(株)製、商品名「信越シリコーンKBM−403」、3−グリシドキシプロピルトリメトキシシラン。
直径20mm、高さ7mmの円筒形容器に厚みが7mmになるように光硬化性組成物を注ぎ、UV未照射及びUV照射[照射条件:メタルハライドランプ(照度:330mW/cm2)、積算光量:3000mJ/cm2]後直ちに、暗室下23℃RH50%の環境下において、30秒ごとに指触にて表面がべたつかなくなるまでの時間(TFT)を測定した。また、可使時間について、UV未照射のTFTが1日以上を◎、2時間以上1日未満を○、2時間未満を×として評価した。結果を表1に示した。
被着材[アルミニウム(硫酸アルマイト処理)]に、ガラス棒を用いて光硬化性組成物を厚さ100μmになるように塗布し、UV照射[照射条件:メタルハライドランプ(照度:330mW/cm2)、積算光量:3000mJ/cm2]を行った。照射後直ちに、25mm×25mmの面積で被着材[アルミニウム(硫酸アルマイト処理)]を張り合わせ、目玉クリップ小により圧締し23℃,50%RH下で1日間及び7日間養生した。
前記養生後、JIS K6850 剛性被着材の引張りせん断接着強さ試験方法に準拠し、試験速度50mm/分で測定した。また、接着面の破壊状態を目視にて確認した。接着性について、下記評価基準にて評価した。結果を表1に示した。
◎:せん断強度が2.5MPa以上であり且つ破壊状態が凝集破壊または薄層凝集破壊。
○:せん断強度が2.5MPa以上。
×:せん断強度が2.5MPa未満。
表1に示す如く配合を変更した以外は実施例1と同様の方法により組成物を調製し、測定を行った。結果を表1に示した。
Claims (6)
- (A)架橋性珪素基含有有機重合体、並びに
(B)光により、第一級アミノ基および第二級アミノ基からなる群から選択される1種以上のアミノ基を生成する架橋性珪素基含有化合物、
を含むことを特徴とする接着性を有する光硬化性組成物。 - (C)Si−F結合を有するケイ素化合物をさらに含むことを特徴とする請求項1記載の光硬化性組成物。
- (D)前記(B)架橋性珪素基含有化合物以外の他の光塩基発生剤をさらに含むことを特徴とする請求項1又は2記載の光硬化性組成物。
- 前記(A)架橋性珪素基含有有機重合体が、架橋性珪素基含有ポリオキシアルキレン系重合体及び架橋性珪素基含有(メタ)アクリル系重合体からなる群から選択される1種以上であることを特徴とする請求項1〜3のいずれか1項記載の光硬化性組成物。
- (E)三フッ化ホウ素、三フッ化ホウ素の錯体、フッ素化剤及び多価フルオロ化合物のアルカリ金属塩からなる群から選択される1種以上のフッ素系化合物をさらに含むことを特徴とする請求項1〜4のいずれか1項記載の光硬化性組成物。
- (F)エポキシ基含有シラン類をさらに含むことを特徴とする請求項1〜5のいずれか1項記載の光硬化性組成物。
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