JP7211274B2 - Water repellent composition - Google Patents
Water repellent composition Download PDFInfo
- Publication number
- JP7211274B2 JP7211274B2 JP2019112783A JP2019112783A JP7211274B2 JP 7211274 B2 JP7211274 B2 JP 7211274B2 JP 2019112783 A JP2019112783 A JP 2019112783A JP 2019112783 A JP2019112783 A JP 2019112783A JP 7211274 B2 JP7211274 B2 JP 7211274B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- methyl
- carbon atoms
- water
- chlorodimethylsilyl
- 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.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 105
- 239000000203 mixture Substances 0.000 title claims description 85
- 239000005871 repellent Substances 0.000 title claims description 64
- 230000002940 repellent Effects 0.000 title claims description 51
- 229920001296 polysiloxane Polymers 0.000 claims description 148
- -1 halide ion Chemical class 0.000 claims description 133
- 150000001875 compounds Chemical class 0.000 claims description 87
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical group C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical group C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 claims description 3
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical group [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 claims description 3
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical group C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 61
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 61
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 39
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 34
- 230000015572 biosynthetic process Effects 0.000 description 34
- 238000003786 synthesis reaction Methods 0.000 description 34
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007788 liquid Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 150000008040 ionic compounds Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000002347 octyl 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])[H] 0.000 description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- 125000003010 ionic group Chemical group 0.000 description 9
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229940125904 compound 1 Drugs 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 150000007514 bases Chemical class 0.000 description 6
- 238000006664 bond formation reaction Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- LWIGVRDDANOFTD-UHFFFAOYSA-N hydroxy(dimethyl)silane Chemical compound C[SiH](C)O LWIGVRDDANOFTD-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 229940126543 compound 14 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
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- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000005496 phosphonium group Chemical group 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
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- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- JXZIFDVIADNBTN-UHFFFAOYSA-N N-[[chloro(dimethyl)silyl]methyl]tridecan-1-amine Chemical compound C(CCCCCCCCCCCC)NC[Si](C)(C)Cl JXZIFDVIADNBTN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 239000006227 byproduct Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QUUMJKPTDWCRAB-UHFFFAOYSA-N chloro-[(2,3-dimethylimidazol-3-ium-1-yl)methyl]-dimethylsilane Chemical compound Cl[Si](C)(C)CN1C(=[N+](C=C1)C)C QUUMJKPTDWCRAB-UHFFFAOYSA-N 0.000 description 1
- LNDHTVZDTYKFLN-UHFFFAOYSA-M chloro-[(2,3-dimethylimidazol-3-ium-1-yl)methyl]-dimethylsilane chloride Chemical compound [Cl-].Cl[Si](C)(C)CN1C(=[N+](C=C1)C)C LNDHTVZDTYKFLN-UHFFFAOYSA-M 0.000 description 1
- WKOBEIUPRBJMHD-UHFFFAOYSA-N chloro-[(3-ethylimidazol-1-ium-1-yl)methyl]-dimethylsilane Chemical compound Cl[Si](C)(C)CN1C=[N+](C=C1)CC WKOBEIUPRBJMHD-UHFFFAOYSA-N 0.000 description 1
- WAGYNOFJLCZQOY-UHFFFAOYSA-M chloro-[(3-ethylimidazol-1-ium-1-yl)methyl]-dimethylsilane chloride Chemical compound [Cl-].Cl[Si](C)(C)CN1C=[N+](C=C1)CC WAGYNOFJLCZQOY-UHFFFAOYSA-M 0.000 description 1
- PQZPQHBTYZLTCQ-UHFFFAOYSA-N chloro-dimethyl-(pyridin-1-ium-1-ylmethyl)silane Chemical compound Cl[Si](C)(C)C[N+]1=CC=CC=C1 PQZPQHBTYZLTCQ-UHFFFAOYSA-N 0.000 description 1
- RCAVHHQRQUBVHH-UHFFFAOYSA-N chloro-dimethyl-[(1-methylpiperidin-1-ium-1-yl)methyl]silane Chemical compound Cl[Si](C[N+]1(CCCCC1)C)(C)C RCAVHHQRQUBVHH-UHFFFAOYSA-N 0.000 description 1
- WVLUVPHGZIZQJJ-UHFFFAOYSA-M chloro-dimethyl-[(1-methylpiperidin-1-ium-1-yl)methyl]silane chloride Chemical compound [Cl-].Cl[Si](C)(C)C[N+]1(CCCCC1)C WVLUVPHGZIZQJJ-UHFFFAOYSA-M 0.000 description 1
- WYDADNDMCRDPAJ-UHFFFAOYSA-N chloro-dimethyl-[(1-methylpyrrolidin-1-ium-1-yl)methyl]silane Chemical compound C[N+]1(CCCC1)C[Si](C)(C)Cl WYDADNDMCRDPAJ-UHFFFAOYSA-N 0.000 description 1
- ODRYIXSIPYAHJI-UHFFFAOYSA-M chloro-dimethyl-[(1-methylpyrrolidin-1-ium-1-yl)methyl]silane chloride Chemical compound [Cl-].Cl[Si](C)(C)C[N+]1(CCCC1)C ODRYIXSIPYAHJI-UHFFFAOYSA-M 0.000 description 1
- BPMKPIXZFBAVCF-UHFFFAOYSA-N chloro-dimethyl-[(2-methylpyridin-1-ium-1-yl)methyl]silane Chemical compound Cl[Si](C)(C)C[N+]1=C(C=CC=C1)C BPMKPIXZFBAVCF-UHFFFAOYSA-N 0.000 description 1
- DLZRAZABCJVFMF-UHFFFAOYSA-M chloro-dimethyl-[(2-methylpyridin-1-ium-1-yl)methyl]silane chloride Chemical compound [Cl-].Cl[Si](C)(C)C[N+]1=C(C=CC=C1)C DLZRAZABCJVFMF-UHFFFAOYSA-M 0.000 description 1
- YTDZCECYXOSECU-UHFFFAOYSA-N chloro-dimethyl-[(3-methylimidazol-3-ium-1-yl)methyl]silane Chemical compound Cl[Si](C)(C)CN1C=[N+](C=C1)C YTDZCECYXOSECU-UHFFFAOYSA-N 0.000 description 1
- ASRFTLYVOSNLMT-UHFFFAOYSA-M chloro-dimethyl-[(3-methylimidazol-3-ium-1-yl)methyl]silane chloride Chemical compound [Cl-].Cl[Si](C)(C)CN1C=[N+](C=C1)C ASRFTLYVOSNLMT-UHFFFAOYSA-M 0.000 description 1
- JLVSPAMDKNZINX-UHFFFAOYSA-N chloro-dimethyl-[(3-methylpyridin-1-ium-1-yl)methyl]silane Chemical compound Cl[Si](C)(C)C[N+]1=CC(=CC=C1)C JLVSPAMDKNZINX-UHFFFAOYSA-N 0.000 description 1
- JRVSOCGEZMEIKW-UHFFFAOYSA-M chloro-dimethyl-[(3-methylpyridin-1-ium-1-yl)methyl]silane chloride Chemical compound [Cl-].Cl[Si](C)(C)C[N+]1=CC(=CC=C1)C JRVSOCGEZMEIKW-UHFFFAOYSA-M 0.000 description 1
- OVRKDTKWCPEYFH-UHFFFAOYSA-N chloro-dimethyl-[(3-octylimidazol-1-ium-1-yl)methyl]silane Chemical compound Cl[Si](C)(C)CN1C=[N+](C=C1)CCCCCCCC OVRKDTKWCPEYFH-UHFFFAOYSA-N 0.000 description 1
- SNIYIWZUQLEMTK-UHFFFAOYSA-M chloro-dimethyl-[(3-octylimidazol-1-ium-1-yl)methyl]silane chloride Chemical compound [Cl-].Cl[Si](C)(C)CN1C=[N+](C=C1)CCCCCCCC SNIYIWZUQLEMTK-UHFFFAOYSA-M 0.000 description 1
- FRRKGUHFMTUOAU-UHFFFAOYSA-N chloro-dimethyl-[(4-methylpyridin-1-ium-1-yl)methyl]silane Chemical compound Cl[Si](C)(C)C[N+]1=CC=C(C=C1)C FRRKGUHFMTUOAU-UHFFFAOYSA-N 0.000 description 1
- STMPWRLWKPSXOR-UHFFFAOYSA-M chloro-dimethyl-[(4-methylpyridin-1-ium-1-yl)methyl]silane chloride Chemical compound [Cl-].Cl[Si](C)(C)C[N+]1=CC=C(C=C1)C STMPWRLWKPSXOR-UHFFFAOYSA-M 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 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 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and 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
- C08F30/04—Homopolymers and 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
- C08F30/08—Homopolymers and 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
-
- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Combustion & Propulsion (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Description
本発明は、撥水剤組成物に関し、さらに詳述すると、分子中にオルガノポリシロキサン構造と重合性反応基およびイオン性基とを有するオルガノポリシロキサン化合物を含有し、撥水性コーティング剤等として好適な撥水剤組成物に関する。 The present invention relates to a water repellent composition, more specifically, it contains an organopolysiloxane compound having an organopolysiloxane structure, a polymerizable reactive group and an ionic group in the molecule, and is suitable as a water repellent coating agent or the like. It relates to a water repellent composition.
従来、自動車および電車等の輸送機車両や建築物等に使用されるガラス・金属・有機樹脂等の基材や繊維製品等に撥水性を付与するものとして、種々のフッ素系材料を用いた撥水剤組成物が利用されてきた。
このようなフッ素系材料としては、例えば、分子内にパーフルオロポリエーテル基またはフルオロアルキル基を含有する化合物や、これらモノマーの重合物またはこれらモノマーとその他のモノマーとの共重合物等が用いられている。
Conventionally, various fluorine-based materials have been used to impart water repellency to base materials such as glass, metals, organic resins, etc. and textile products used in transportation vehicles such as automobiles and trains, and buildings. Aqueous agent compositions have been utilized.
As such a fluorine-based material, for example, a compound containing a perfluoropolyether group or a fluoroalkyl group in the molecule, a polymer of these monomers, or a copolymer of these monomers and other monomers is used. ing.
しかし、これらのフッ素系材料を用いた撥水剤組成物は、撥水効果の一つである水接触角の値としては高値であり良好であるが、一方で水転落角の値は一般的に高値となり滑水性が悪いため、実使用上は弾いた水が基材上に留まり、それが原因となって水垢などの外観不良を生じやすいという問題がある。
また、このようなフッ素系材料は、希釈用溶剤として、大気中のオゾン層破壊の一因として挙げられ、地球環境保護の観点からその使用が制限されているようなフッ素系溶剤を使用せざるを得ないという問題があり、環境負荷の少ない代替溶剤の検討もなされているが、未だ満足すべき結果は得られていない。
However, the water repellent composition using these fluorine-based materials has a high water contact angle, which is one of the water repellent effects, and is good. Because of its high value and poor lubricating property, the repelled water remains on the base material in actual use, which tends to cause poor appearance such as limescale.
In addition, such fluorine-based materials, as solvents for dilution, are considered to be one of the causes of atmospheric ozone layer depletion. There is a problem that the solvent cannot be obtained, and although alternative solvents with less environmental impact have been investigated, satisfactory results have not yet been obtained.
そこで最近では、上述のような環境問題を引き起こす可能性のあるフッ素系溶剤を使用する必要がない、シリコーン系材料を用いた撥水剤組成物の検討が種々行われている。
シリコーン系材料を用いた撥水剤組成物としては、特定の有機溶剤可溶性シリコーン樹脂および／または有機溶剤可溶性シリコーングラフトアクリル樹脂と、金属アルコキシドと、オルガノポリシロキサンとからなる撥水剤成分に、有機溶剤と噴射ガスとが配合されたエアゾール型撥水処理剤（特許文献１参照）、両末端がアルコキシシリル基で封鎖されたオルガノポリシロキサンと、金属アルコキシドまたはその部分加水分解縮合物と、エタノールまたはイソプロパノールとが配合された撥水剤組成物（特許文献２参照）、特定のオルガノポリシロキサン樹脂と、直鎖状ジオルガノポリシロキサンと、有機チタン酸エステル等の有機金属酸エステルと、第４級アンモニウム塩構造を有する抗菌性シランと、溶剤とを含有する撥水処理剤組成物（特許文献３参照）、特定のオルガノポリシロキサン樹脂と、アルキル基およびアルコキシ基含有ポリシロキサン樹脂と、縮合触媒と、芳香族系溶剤とからなる撥水剤（特許文献４参照）などが提案されている。
Therefore, recently, various studies have been made on water repellent compositions using silicone-based materials that do not require the use of fluorine-based solvents that may cause environmental problems as described above.
As a water repellent composition using a silicone-based material, an organic An aerosol water repellent agent (see Patent Document 1) containing a solvent and propellant gas, an organopolysiloxane having both ends blocked with alkoxysilyl groups, a metal alkoxide or a partially hydrolyzed condensate thereof, ethanol or A water repellent composition containing isopropanol (see Patent Document 2), a specific organopolysiloxane resin, a linear diorganopolysiloxane, an organometallic acid ester such as an organotitanate ester, and a quaternary A water repellent agent composition containing an antibacterial silane having an ammonium salt structure and a solvent (see Patent Document 3), a specific organopolysiloxane resin, an alkyl group- and alkoxy group-containing polysiloxane resin, and a condensation catalyst. , and an aromatic solvent (see Patent Document 4).
しかし、これらのシリコーン系材料を用いた撥水剤組成物は、一般に室温湿気硬化または加熱硬化によるものが多く、活性エネルギー線による硬化形態には適用できないといった問題がある。 However, water repellent compositions using these silicone-based materials are generally cured by moisture at room temperature or by heat, and have the problem that they cannot be cured by active energy rays.
本発明は、上記事情に鑑みなされたもので、活性エネルギー線硬化型樹脂を用いたコーティング剤に対して高い撥水性および滑水性を付与でき、かつその撥水性および滑水性の耐久性に優れる撥水剤組成物および撥水性コーティング剤を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is capable of imparting high water repellency and water slippage to a coating agent using an active energy ray-curable resin, and having excellent durability of the water repellency and water slippage. An object of the present invention is to provide a liquid agent composition and a water-repellent coating agent.
本発明者らは、上記目的を達成するため鋭意検討を行った結果、分子中にオルガノポリシロキサン構造と、重合性反応基およびイオン性基とを有する、所定のオルガノポリシロキサン化合物が、特に活性エネルギー線硬化型樹脂を含有する組成物およびコーティング剤に対して高い撥水性、滑水性を付与できるだけでなく、撥水性、滑水性の耐久性にも優れていることを見出し、本発明を完成した。 The inventors of the present invention conducted intensive studies to achieve the above object, and found that a predetermined organopolysiloxane compound having an organopolysiloxane structure, a polymerizable reactive group and an ionic group in the molecule is particularly active. The inventors have found that not only high water repellency and water sliding properties can be imparted to compositions and coating agents containing energy ray-curable resins, but also excellent durability of water repellency and water sliding properties, and the present invention has been completed. .
すなわち、本発明は、
１． （Ａ）平均構造式（１）で表されるオルガノポリシロキサン化合物を含むことを特徴とする撥水剤組成物、
Ｒ1は、それぞれ独立して、単結合、または非置換もしくは置換の炭素原子数１～２０のアルキレン基を表し、
Ｒ2およびＲ3は、それぞれ独立して、非置換もしくは置換の炭素原子数１～１０のアルキル基、または炭素原子数６～１０のアリール基を表し、
Ｙは、それぞれ独立して、重合性反応基を有する一価炭化水素基を表し、
ｐは、１～１０、ｑは、１～１０、かつ、ｐ＋ｑは、前記Ｚの価数に対応して２～２０を満たす数を表すが、前記Ｚが単結合の場合、ｐおよびｑはともに１であり、
Ａ-は、１価のアニオンを表し、
Ｑ+は、下記式（２）～（４）のいずれかで表される１価のカチオン性基を表す。
２． （Ｂ）活性エネルギー線硬化型樹脂を含む１の撥水剤組成物、
３． （Ｃ）硬化触媒を含む２の撥水剤組成物、
４． 前記Ｙの重合性反応基が、（メタ）アクリロイルオキシ基および（メタ）アクリルアミド基から選ばれる１種である１～３のいずれかの撥水剤組成物、
５． 前記Ａ-が、含フッ素アニオンまたはハロゲン化物イオンである１～４のいずれか１の撥水剤組成物、
６． 前記Ａ-が、トリフルオロメタンスルホン酸アニオン、ノナフルオロブタンスルホン酸アニオン、ビス（フルオロスルホニル）イミドアニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、テトラフルオロボレートアニオン、ヘキサフルオロホスフェートアニオン、塩化物イオン、臭化物イオンまたはヨウ化物イオンである１～５のいずれかの撥水剤組成物、
７． 前記（Ａ）オルガノポリシロキサン化合物が、平均構造式（５）で表される１～６のいずれかの撥水剤組成物、
８． １～７のいずれかの撥水剤組成物からなる撥水性コーティング剤、
９． ８の撥水性コーティング剤を用いてなる被覆層を有する撥水性硬化物品
を提供する。
That is, the present invention
1. (A) a water repellent composition comprising an organopolysiloxane compound represented by the average structural formula (1);
each R 1 independently represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms;
R 2 and R 3 each independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms;
Y each independently represents a monovalent hydrocarbon group having a polymerizable reactive group,
p is 1 to 10, q is 1 to 10, and p+q is a number that satisfies 2 to 20 corresponding to the valence of Z, but when Z is a single bond, p and q are are both 1,
A − represents a monovalent anion,
Q + represents a monovalent cationic group represented by any one of the following formulas (2) to (4).
2. (B) 1 water repellent composition containing an active energy ray-curable resin;
3. (C) two water repellent compositions containing a curing catalyst;
4. The water repellent composition according to any one of 1 to 3, wherein the polymerizable reactive group of Y is one selected from a (meth)acryloyloxy group and a (meth)acrylamide group,
5. The water repellent composition according to any one of 1 to 4, wherein A − is a fluorine-containing anion or a halide ion;
6. A - is trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, bis(fluorosulfonyl)imide anion, bis(trifluoromethanesulfonyl)imide anion, tetrafluoroborate anion, hexafluorophosphate anion, chloride ion, bromide the water repellent composition of any one of 1 to 5, which is an ion or an iodide ion;
7. The water repellent composition according to any one of 1 to 6, wherein the (A) organopolysiloxane compound is represented by the average structural formula (5);
8. a water-repellent coating agent comprising the water-repellent composition according to any one of 1 to 7;
9. A water-repellent cured article having a coating layer formed by using the water-repellent coating agent of No. 8 is provided.
本発明の撥水剤組成物は、分子中にオルガノポリシロキサン構造と重合性反応基およびイオン性基とを有している化合物を含んでいるため、従来の撥水剤組成物に比べ、高い撥水性および滑水性を付与でき、かつその撥水性、滑水性の耐久性に優れるという特性を有している。
このような特性を有する本発明のオルガノポリシロキサン化合物を含む撥水剤組成物は、特に活性エネルギー線硬化型樹脂を含有する撥水剤組成物や撥水性コーティング剤として好適に用いることができる。
Since the water repellent composition of the present invention contains a compound having an organopolysiloxane structure, a polymerizable reactive group, and an ionic group in the molecule, it is higher than conventional water repellent compositions. It has the property of being able to impart water repellency and water sliding properties and having excellent durability of the water repellency and water sliding properties.
A water repellent composition containing the organopolysiloxane compound of the present invention having such properties can be suitably used particularly as a water repellent composition containing an active energy ray-curable resin or a water repellent coating agent.
以下、本発明について具体的に説明する。
本発明に係る撥水剤組成物は、（Ａ）平均構造式（１）で表されるオルガノポリシロキサン化合物（以下、オルガノポリシロキサン（１）という）を含むことを特徴とする。
The present invention will be specifically described below.
The water repellent composition according to the present invention is characterized by containing (A) an organopolysiloxane compound represented by the average structural formula (1) (hereinafter referred to as organopolysiloxane (1)).
式（１）において、Ｒ1は、それぞれ独立して、単結合、または非置換もしくは置換の炭素原子数１～２０のアルキレン基を表すが、好ましくは炭素原子数１～１０のアルキレン基、より好ましくは炭素原子数１～３のアルキレン基である。
炭素原子数１～２０のアルキレン基は、直鎖状、環状、分枝状のいずれでもよく、その具体例としては、メチレン、エチレン、トリメチレン、プロピレン、ｎ－ブチレン、イソブチレン、ｎ－ペンチレン、ｎ－ヘキシレン、ヘプタメチレン、オクタメチレン、ノナメチレン、デカメチレン、ウンデカメチレン、ドデカメチレン、トリデカメチレン、テトラデカメチレン、ペンタデカメチレン、ヘキサデカメチレン、へプタデカメチレン、オクタデカメチレン、ノナデカメチレン、エイコサデシレン基等が挙げられる。
これらの中でも、直鎖状のアルキレン基が好ましく、メチレン基、エチレン基、トリメチレン基、オクタメチレン基がより好ましく、メチレン基、トリメチレン基がより一層好ましい。
なお、上記アルキレン基の水素原子の一部または全部は、炭素原子数１～１０のアルキル基、Ｆ，Ｃｌ，Ｂｒ等のハロゲン原子、シアノ基等で置換されていてもよい。
In formula (1), each R 1 independently represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more An alkylene group having 1 to 3 carbon atoms is preferred.
The alkylene group having 1 to 20 carbon atoms may be linear, cyclic or branched, and specific examples include methylene, ethylene, trimethylene, propylene, n-butylene, isobutylene, n-pentylene, n - hexylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosadecylene and the like.
Among these, linear alkylene groups are preferred, methylene groups, ethylene groups, trimethylene groups and octamethylene groups are more preferred, and methylene groups and trimethylene groups are still more preferred.
Some or all of the hydrogen atoms in the alkylene group may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, or the like, a cyano group, or the like.
Ｒ2およびＲ3は、それぞれ独立して、非置換もしくは置換の炭素原子数１～１０のアルキル基、または炭素原子数６～１０のアリール基を表すが、撥水性、滑水性およびその耐久性の観点から、好ましくは炭素原子数１～８のアルキル基、より好ましくは炭素原子数１～３のアルキル基である。
炭素原子数１～１０のアルキル基は、直鎖状、環状、分枝状のいずれでもよく、その具体例としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、ｎ－ヘプチル、ｎ－オクチル、ｎ－ノニル、ｎ－デシル基等が挙げられるが、直鎖のアルキル基が好ましく、メチル、ｎ－プロピル、ｎ－ヘキシル、ｎ－オクチル基が好ましく、メチル基がより好ましい。
炭素原子数６～１０のアリール基としては、フェニル、ナフチル基等が挙げられるが、フェニル基が好ましい。
R 2 and R 3 each independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and the from the viewpoint of , it is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
The alkyl group having 1 to 10 carbon atoms may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n -hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl groups, etc., preferably linear alkyl groups, preferably methyl, n-propyl, n-hexyl, n-octyl groups, A methyl group is more preferred.
Examples of the aryl group having 6 to 10 carbon atoms include phenyl and naphthyl groups, with the phenyl group being preferred.
なお、上述したアルキル基およびアリール基の水素原子の一部または全部は、炭素原子数１～１０のアルキル基、Ｆ，Ｃｌ，Ｂｒ等のハロゲン原子、シアノ基等で置換されていてもよく、そのような基の具体例としては、３－クロロプロピル、３，３，３－トリフルオロプロピル、２－シアノエチル、トリル、キシリル基等が挙げられるが、撥水性、滑水性およびその耐久性の観点から、３，３，３－トリフルオロプロピル基が好ましい。 Incidentally, some or all of the hydrogen atoms of the alkyl group and aryl group described above may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, a cyano group, etc. Specific examples of such groups include 3-chloropropyl, 3,3,3-trifluoropropyl, 2-cyanoethyl, tolyl, and xylyl groups. Therefore, a 3,3,3-trifluoropropyl group is preferred.
Ｙは、それぞれ独立して、重合性反応基を含有する一価炭化水素基を表す。
重合性反応基の具体例としては、（メタ）アクリロイルオキシ基、（メタ）アクリルアミド基、スチリル基、ビニル基、アルケニル基、エポキシ基、マレイミド基等が挙げられるが、これらの中でも、撥水性、滑水性およびその耐久性の観点から、（メタ）アクリロイルオキシ基、（メタ）アクリルアミド基、スチリル基、ビニル基が好ましく、（メタ）アクリロイルオキシ基、（メタ）アクリルアミド基がより好ましい。
Each Y independently represents a monovalent hydrocarbon group containing a polymerizable reactive group.
Specific examples of the polymerizable reactive group include a (meth)acryloyloxy group, a (meth)acrylamide group, a styryl group, a vinyl group, an alkenyl group, an epoxy group, and a maleimide group. From the viewpoint of water slippage and durability thereof, a (meth)acryloyloxy group, a (meth)acrylamide group, a styryl group and a vinyl group are preferable, and a (meth)acryloyloxy group and a (meth)acrylamide group are more preferable.
Ａ-は、一価のアニオンを表すが、ハロゲン化物イオン、含フッ素アニオンが好ましい。
ハロゲン化物イオンの具体例としては、塩化物イオン、臭化物イオン、ヨウ化物イオンが挙げられるが、撥水性、滑水性およびその耐久性の観点から、塩化物イオンが好ましい。
含フッ素アニオンの具体例としては、トリフルオロメタンスルホン酸アニオン、ノナフルオロブタンスルホン酸アニオン、ビス（フルオロスルホニル）イミドアニオン、ビス（トリフルオロメタンスルホニル）イミドアニオン、テトラフルオロボレートアニオン、ヘキサフルオロホスフェートアニオン等が挙げられるが、撥水性、滑水性およびその耐久性の観点から、ビス（フルオロスルホニル）イミドアニオン、ビス（トリフルオロメタンスルホニル）イミドアニオンが好ましく、ビス（トリフルオロメタンスルホニル）イミドアニオンがより好ましい。
A − represents a monovalent anion, preferably a halide ion or a fluorine-containing anion.
Specific examples of halide ions include chloride ions, bromide ions, and iodide ions, but chloride ions are preferred from the viewpoint of water repellency, water sliding property, and durability.
Specific examples of fluorine-containing anions include trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, bis(fluorosulfonyl)imide anion, bis(trifluoromethanesulfonyl)imide anion, tetrafluoroborate anion, hexafluorophosphate anion, and the like. Bis(fluorosulfonyl)imide anion and bis(trifluoromethanesulfonyl)imide anion are preferred, and bis(trifluoromethanesulfonyl)imide anion is more preferred, from the viewpoint of water repellency, water slippage and durability thereof.
一方、Ｑ+は、下記式（２）～（４）のいずれかで表される１価のカチオン性基を表すが、式（３）で表される基が好ましい。 On the other hand, Q + represents a monovalent cationic group represented by any one of formulas (2) to (4) below, preferably a group represented by formula (3).
式（２）で表されるアンモニウム基（以下、アンモニウム基（２）という。）において、Ｒ4～Ｒ6は、それぞれ独立して、炭素原子数１～２０、好ましくは炭素原子数１～１２のアルキル基、炭素原子数６～２０のアリール基または炭素原子数７～２０のアラルキル基を表す。
炭素原子数１～２０のアルキル基は、直鎖状、環状、分枝状のいずれでもよく、その具体例としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、ｎ－ヘプチル、ｎ－オクチル、ｎ－ノニル、ｎ－デシル、ウンデシル、ドデシル、イコシル基等が挙げられるが、撥水性、滑水性およびその耐久性の観点から、直鎖状のアルキル基が好ましく、ｎ－ブチル、ｎ－ヘキシル、ｎ－オクチル、ｎ－ノニル、ｎ－デシル、ウンデシル、ドデシル、イコシル基がより好ましく、ｎ－ブチル基、ｎ－オクチル基がより一層好ましく、ｎ－オクチル基がさらに好ましい。
炭素原子数６～２０のアリール基の具体例としては、フェニル、ナフチル基等が挙げられる。
炭素原子数７～２０のアラルキル基の具体例としては、ベンジル基等が挙げられる。
In the ammonium group represented by formula (2) (hereinafter referred to as ammonium group (2)), each of R 4 to R 6 independently has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. , an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n -hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, icosyl groups and the like. are preferred, n-butyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and icosyl groups are more preferred, n-butyl and n-octyl groups are even more preferred, n-octyl groups are more preferred.
Specific examples of aryl groups having 6 to 20 carbon atoms include phenyl and naphthyl groups.
Specific examples of aralkyl groups having 7 to 20 carbon atoms include benzyl group and the like.
また、アンモニウム基（２）において、Ｒ4とＲ5は互いに結合し、下記式（２ａ）で表される置換基を有していてもよいピロリジン環、下記式（２ｂ）で表される置換基を有していてもよいピペリジン環または下記式（２ｃ）で表される置換基を有していてもよいピリジン環を形成してもよい。ただし、Ｒ4とＲ5が末端で互いに結合してピリジン環を形成する場合は、下記式（２ｃ）に示されるように、Ｒ6は存在しない。 Further, in the ammonium group (2), R 4 and R 5 are bonded to each other, a pyrrolidine ring optionally having a substituent represented by the following formula (2a), a substituent represented by the following formula (2b) A piperidine ring optionally having a group or a pyridine ring optionally having a substituent represented by the following formula (2c) may be formed. However, when R 4 and R 5 combine at their terminals to form a pyridine ring, R 6 does not exist as shown in formula (2c) below.
式（２ａ）、（２ｂ）および（２ｃ）において、Ｒa、ＲbおよびＲcは、それぞれ炭素原子数１～２０、好ましくは炭素原子数１～６のアルキル基を表し、これらの具体例としては、上記Ｒ4～Ｒ6で例示した基と同様のものが挙げられる。
ｍは０～８、好ましくは０～４の整数、ｎは０～１０、好ましくは０～５の整数、ｏは０～５の整数である。
In formulas (2a), (2b) and (2c), R a , R b and R c each represent an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and specific examples thereof Examples include the same groups as those exemplified for R 4 to R 6 above.
m is an integer of 0-8, preferably 0-4; n is an integer of 0-10, preferably 0-5; o is an integer of 0-5.
式（３）で表されるホスホニウム基（以下、ホスホニウム基（３）という。）において、Ｒ7～Ｒ9は、それぞれ独立して、炭素原子数１～２０のアルキル基、炭素原子数６～２０のアリール基または炭素原子数７～２０のアラルキル基である。これらアルキル基、アリール基、アラルキル基の具体例および好適例としては、上記Ｒ4～Ｒ6で例示した基と同様のものが挙げられる。 In the phosphonium group represented by formula (3) (hereinafter referred to as phosphonium group (3)), R 7 to R 9 are each independently an alkyl group having 1 to 20 carbon atoms, It is an aryl group of 20 or an aralkyl group of 7 to 20 carbon atoms. Specific and preferred examples of these alkyl, aryl and aralkyl groups are the same as those exemplified for R 4 to R 6 above.
また、ホスホニウム基（３）においても、Ｒ7とＲ8は互いに結合し、下記式（３ａ）で表される置換基を有していてもよいホスホラン環、下記式（３ｂ）で表される置換基を有していてもよいホスホリナン環または下記式（３ｃ）で表される置換基を有していてもよいホスホリン環を形成してもよい。ただし、Ｒ7とＲ8が互いに結合してホスホリン環を形成する場合は、下記式（３ｃ）に示されるように、Ｒ9は存在しない。 Also in the phosphonium group (3), R 7 and R 8 are bonded to each other, and a phosphorane ring optionally having a substituent represented by the following formula (3a), represented by the following formula (3b) An optionally substituted phosphorinane ring or an optionally substituted phosphorine ring represented by the following formula (3c) may be formed. However, when R 7 and R 8 combine with each other to form a phospholine ring, R 9 does not exist as shown in the following formula (3c).
式（３ａ）、（３ｂ）および（３ｃ）において、Ｒd、ＲeおよびＲfは、それぞれ炭素原子数１～２０、好ましくは炭素原子数１～６のアルキル基を表し、これらの具体例としては、上記Ｒ4～Ｒ6で例示した基と同様のものが挙げられる。
ｐは０～８、好ましくは０～４の整数、ｑは０～１０、好ましくは０～５の整数、ｒは０～５の整数である。
In formulas (3a), (3b) and (3c), R d , R e and R f each represent an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and specific examples thereof Examples include the same groups as those exemplified for R 4 to R 6 above.
p is an integer of 0-8, preferably 0-4; q is an integer of 0-10, preferably 0-5; r is an integer of 0-5.
式（４）で表されるイミダゾリウム基（以下、イミダゾリウム基（４）という。）において、Ｒ10は炭素原子数１～２０のアルキル基、炭素原子数６～２０のアリール基または炭素原子数７～２０のアラルキル基を表し、Ｒ11～Ｒ13は、それぞれ独立して、水素原子、炭素原子数１～２０のアルキル基、炭素原子数６～２０のアリール基または炭素原子数７～２０のアラルキル基を表す。これらアルキル基、アリール基、アラルキル基の具体例および好適例としては、上記Ｒ4～Ｒ6で例示した基と同様のものが挙げられる。 In the imidazolium group represented by formula (4) (hereinafter referred to as imidazolium group (4)), R 10 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom represents an aralkyl group having a number of 7 to 20, and each of R 11 to R 13 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryl group having 7 to 20 carbon atoms; represents 20 aralkyl groups. Specific and preferred examples of these alkyl, aryl and aralkyl groups are the same as those exemplified for R 4 to R 6 above.
また、式（１）中、Ｚは、単結合またはオルガノポリシロキサン構造を含む２～２０価の基を表す。
Ｚのオルガノポリシロキサン構造を含む基は特に限定されるものではなく、その中に直鎖状構造、分岐状構造、または架橋構造を有していてもよい。
より具体的には、Ｄ単位（Ｒ2
2ＳｉＯ2/2単位）、Ｔ単位（Ｒ2ＳｉＯ3/2単位）およびＱ単位（ＳｉＯ4/2単位）からなるオルガノポリシロキサン構造が挙げられる（式中、Ｒ2は、上記と同じ意味を表す）。
これらの単位は、それぞれ単独（Ｄ単位のみ、Ｔ単位のみ、またはＱ単位のみ）であってもよく、複数単位の組み合わせからなるものであってもよいが、撥水性および滑水性並びにそれらの耐久性の観点から、Ｄ単位を含むオルガノポリシロキサン構造が好ましく、Ｄ単位単独のオルガノポリシロキサン構造がより好ましい。
In formula (1), Z represents a divalent to 20-valent group containing a single bond or an organopolysiloxane structure.
The group of Z containing an organopolysiloxane structure is not particularly limited, and may have a linear structure, a branched structure, or a crosslinked structure therein.
More specifically, an organopolysiloxane structure consisting of D units (R 2 2 SiO 2/2 units), T units (R 2 SiO 3/2 units) and Q units (SiO 4/2 units) can be mentioned ( In the formula, R 2 has the same meaning as above).
Each of these units may be a single unit (only D unit, only T unit, or only Q unit) or may be a combination of multiple units. From the viewpoint of properties, an organopolysiloxane structure containing D units is preferred, and an organopolysiloxane structure containing only D units is more preferred.
式（１）におけるｐは、Ｙの重合性反応基を含有する一価炭化水素基の数を表し、ｑは、イオン性基の数を表す。
一分子あたりのｐの平均は１～１０であるが、１～５が好ましく、１～２がより好ましく、１がより一層好ましい。ｐが１未満であると、重合性反応基が不足することにより、耐久性に劣る。一方、ｐが１０を超えると、反応点が多くなり過ぎるため、化合物や組成物の保存安定性が悪化したり、撥水性、滑水性が悪化したりする。
また、一分子あたりのｑの平均は１～１０であるが、１～５が好ましく、１～２がより好ましく、１がより一層好ましい。ｑが１未満であると、イオン性基が不足することにより撥水性、滑水性に劣る。一方、ｑが１０を超えると、イオン性基が多くなり過ぎるため、化合物や組成物の保存安定性が悪化したり、本発明のオルガノポリシロキサン化合物を含有する硬化物の物理特性が悪化したりすることがある。
p in formula (1) represents the number of monovalent hydrocarbon groups containing polymerizable reactive groups of Y, and q represents the number of ionic groups.
The average p per molecule is 1 to 10, preferably 1 to 5, more preferably 1 to 2, and even more preferably 1. When p is less than 1, the polymerizable reactive groups are insufficient, resulting in poor durability. On the other hand, when p exceeds 10, the number of reaction sites becomes too large, so that the storage stability of the compound or composition is deteriorated, and the water repellency and water slippage are deteriorated.
The average q per molecule is 1 to 10, preferably 1 to 5, more preferably 1 to 2, and even more preferably 1. When q is less than 1, the ionic groups are insufficient, resulting in poor water repellency and water slippage. On the other hand, if q exceeds 10, the number of ionic groups will be too large, and the storage stability of the compound or composition will deteriorate, or the physical properties of the cured product containing the organopolysiloxane compound of the present invention will deteriorate. I have something to do.
本発明において、ｐとｑの合計値は、Ｚで表されるオルガノポリシロキサン構造を含む基の価数に対応する。一分子あたりのＺの価数の平均は上述のとおり２～２０であるが、２～１０が好ましく、２～４がより好ましく、２がより一層好ましい。Ｚの価数が２未満であると、重合性反応基およびイオン性基が不足することにより、撥水性、滑水性およびその耐久性に劣る。一方、Ｚの価数が２０を超えると、重合性反応基およびイオン性基が多くなり過ぎるため、化合物や組成物の保存安定性が悪化したり、撥水性、滑水性が悪化したりする。
なお、Ｚが単結合の場合、Ｚの両側のＳｉとＯが直接結合する態様となるため、ｐ，ｑはともに１となる。
In the present invention, the total value of p and q corresponds to the valence of the group represented by Z containing the organopolysiloxane structure. The average valence of Z per molecule is 2 to 20 as described above, preferably 2 to 10, more preferably 2 to 4, and even more preferably 2. When the valence of Z is less than 2, the polymerizable reactive group and the ionic group are insufficient, resulting in poor water repellency, water sliding property and durability thereof. On the other hand, if the valence of Z exceeds 20, the number of polymerizable reactive groups and ionic groups will be too large, resulting in poor storage stability, water repellency, and water slippage of the compound or composition.
When Z is a single bond, both p and q are 1 because Si and O on both sides of Z are directly bonded.
本発明の撥水剤組成物に含まれるオルガノポリシロキサン化合物としては、平均構造式が下記式（５）で表される、Ｚとして単結合またはＤ単位単独のオルガノポリシロキサン構造を有するものが好ましく、このような化合物を用いることで、さらに良好な撥水性、滑水性およびその耐久性が発揮される。 The organopolysiloxane compound contained in the water repellent composition of the present invention preferably has an organopolysiloxane structure in which Z is a single bond or a single D unit, and whose average structural formula is represented by the following formula (5). By using such a compound, even better water repellency, water slipperiness and durability thereof can be exhibited.
式（５）において、Ｒ14およびＲ15は、それぞれ独立して、非置換もしくは置換の炭素原子数１～２０のアルキル基、または炭素原子数６～１０のアリール基を表し、これらアルキル基、アリール基の具体例としては、上記Ｒ2～Ｒ6で例示した基と同様のものが挙げられる。
中でも、アルキル基としては、撥水性、滑水性およびその耐久性の観点から、直鎖状のアルキル基が好ましく、炭素原子数１～３のアルキル基がより好ましく、メチル基がより一層好ましい。また、アリール基としては、フェニル基が好ましい。
ｍは、０以上の数を表すが、撥水性、滑水性およびその耐久性の観点から、０～１，０００が好ましく、３～１００がより好ましく、６～５０がより一層好ましい。
In formula (5), R 14 and R 15 each independently represent an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms, and these alkyl groups, Specific examples of the aryl group include the same groups as exemplified for R 2 to R 6 above.
Among them, the alkyl group is preferably a linear alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group, from the viewpoint of water repellency, water slippage and durability thereof. Moreover, as an aryl group, a phenyl group is preferable.
Although m represents a number of 0 or more, it is preferably 0 to 1,000, more preferably 3 to 100, and even more preferably 6 to 50, from the viewpoint of water repellency, water sliding property and durability thereof.
本発明の撥水剤組成物に含まれるオルガノポリシロキサン化合物の重量平均分子量は、特に限定されるものではないが、当該化合物を含む硬化性組成物を硬化させて得られる硬化物に、十分な撥水性および滑水性並びにそれらの耐久性を付与することを考慮すると、重量平均分子量５００～１０万が好ましく、７００～１万がより好ましく、１，０００～５，０００がより一層好ましい。本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算値である。 The weight average molecular weight of the organopolysiloxane compound contained in the water repellent composition of the present invention is not particularly limited, but the cured product obtained by curing the curable composition containing the compound has a sufficient molecular weight. Considering imparting water repellency and water slipperiness and durability thereof, the weight average molecular weight is preferably 500 to 100,000, more preferably 700 to 10,000, and even more preferably 1,000 to 5,000. The weight average molecular weight in the present invention is a polystyrene conversion value obtained by gel permeation chromatography (GPC).
上記オルガノポリシロキサン化合物（１）の具体例としては、下記構造式で表されるもの等が挙げられるが、これらに限定されるものではない。
なお、下記におけるシリコーン平均組成中のＴＦＳＩ-はビス（トリフルオロメタンスルホニル）イミドアニオンを表す。
Specific examples of the organopolysiloxane compound (1) include, but are not limited to, those represented by the following structural formulas.
TFSI − in the silicone average composition below represents a bis(trifluoromethanesulfonyl)imide anion.
なお、本発明の撥水剤組成物に含まれるオルガノポリシロキサン化合物は、溶剤を含んだ状態で用いてもよい。
溶剤としては、オルガノポリシロキサン化合物（１）の溶解能を有していれば特に限定されるものではないが、溶解性および揮発性等の観点から、トルエン、キシレン等の芳香族系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；テトラヒドロフラン等のエーテル系溶剤；アセトニトリル等のニトリル系溶剤が好ましく、中でも、メチルエチルケトン、メチルイソブチルケトン、アセトニトリルがより好ましい。
溶剤の添加量は、オルガノポリシロキサン化合物（１）１００質量部に対して、１００～２０，０００質量部が好ましく、２００～１０，０００質量部がより好ましい。
The organopolysiloxane compound contained in the water repellent composition of the present invention may be used in a state containing a solvent.
The solvent is not particularly limited as long as it has the ability to dissolve the organopolysiloxane compound (1), but from the viewpoint of solubility and volatility, aromatic solvents such as toluene and xylene; methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran; and nitrile solvents such as acetonitrile.
The amount of the solvent to be added is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass, per 100 parts by mass of the organopolysiloxane compound (1).
上記オルガノポリシロキサン化合物（１）は、下記平均構造式（６）で表される、重合性反応基およびシラノール性水酸基を有するオルガノポリシロキサン化合物（以下、シラノール性水酸基含有オルガノポリシロキサン化合物（６）という）と、式（７）で表される、シラノール性水酸基と反応し得る官能基およびイオン性基を有する化合物（以下、イオン性化合物（７）という）とを反応させて得ることができる。
より具体的には、シラノール性水酸基含有オルガノポリシロキサン化合物（６）のシラノール性水酸基と、イオン性化合物（７）の脱離基との間で、脱アルコール反応、脱ハロゲン化水素反応および脱水反応のいずれかの反応形態によりシロキサン結合を形成する反応を行う。
The organopolysiloxane compound (1) is an organopolysiloxane compound having a polymerizable reactive group and a silanol hydroxyl group represented by the following average structural formula (6) (hereinafter referred to as a silanol hydroxyl group-containing organopolysiloxane compound (6) ) and a compound represented by formula (7) having a functional group capable of reacting with a silanol hydroxyl group and an ionic group (hereinafter referred to as ionic compound (7)).
More specifically, a dealcoholization reaction, a dehydrohalogenation reaction and a dehydration reaction occur between the silanol hydroxyl group of the silanol hydroxyl group-containing organopolysiloxane compound (6) and the leaving group of the ionic compound (7). Perform a reaction to form a siloxane bond by any one of the reaction modes.
Ｘの炭素原子数１～１０のアルコキシ基において、その中のアルキル基は、直鎖状、環状、分枝状のいずれでもよく、その具体例としては、メトキシ、エトキシ、ｎ－プロポキシ、イソプロポキシ、ｎ－ブトキシ、ｔ－ブトキシ、ｎ－ペントキシ、ｎ－ヘキシルオキシ、ｎ－へプチルオキシ、ｎ－オクチルオキシ、ｎ－ノニルオキシ、ｎ－デシルオキシ基等が挙げられるが、反応性の観点から、炭素原子数１～３のアルコキシ基が好ましく、メトキシ基、エトキシ基がより好ましく、メトキシ基がより一層好ましい。
ハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子等が挙げられるが、反応性の観点から、塩素原子が好ましい。
In the alkoxy group having 1 to 10 carbon atoms for X, the alkyl group therein may be linear, cyclic or branched, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy , n-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy groups and the like. An alkoxy group having numbers 1 to 3 is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred.
Halogen atoms include chlorine, bromine, and iodine atoms, with chlorine atoms being preferred from the viewpoint of reactivity.
上記シラノール性水酸基含有オルガノポリシロキサン化合物（６）の具体例としては、下記構造式で表されるもの等が挙げられるが、これらに限定されるものではない。 Specific examples of the silanol hydroxyl group-containing organopolysiloxane compound (6) include, but are not limited to, those represented by the following structural formulas.
一方、イオン性化合物（７）の具体例としては、トリブチル｛（クロロジメチルシリル）メチル｝アンモニウム クロリド、トリブチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（フルオロスルホニル）イミド、トリブチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリヘキシル｛（クロロジメチルシリル）メチル｝アンモニウムクロリド、トリヘキシル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（フルオロスルホニル）イミド、トリヘキシル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝アンモニウム クロリド、トリオクチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（フルオロスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリデシル｛（クロロジメチルシリル）メチル｝アンモニウム クロリド、トリデシル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（フルオロスルホニル）イミド、トリデシル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリドデシル｛（クロロジメチルシリル）メチル｝アンモニウム クロリド、トリドデシル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（フルオロスルホニル）イミド、トリドデシル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－１－メチルピロリジニウム クロリド、１－｛（クロロジメチルシリル）メチル｝－１－メチルピロリジニウム ビス（フルオロスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－１－メチルピロリジニウム ビス（トリフルオロメタンスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－１－メチルピペリジニウム クロリド、１－｛（クロロジメチルシリル）メチル｝－１－メチルピペリジニウム ビス（フルオロスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－１－メチルピペリジニウム ビス（トリフルオロメタンスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝ピリジニウム クロリド、１－｛（クロロジメチルシリル）メチル｝ピリジニウム ビス（フルオロスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝ピリジニウム ビス（トリフルオロメタンスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－２－メチルピリジニウム クロリド、１－｛（クロロジメチルシリル）メチル｝－２－メチルピリジニウム ビス（フルオロスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－２－メチルピリジニウム ビス（トリフルオロメタンスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－３－メチルピリジニウム クロリド、１－｛（クロロジメチルシリル）メチル｝－３－メチルピリジニウム ビス（フルオロスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－３－メチルピリジニウム ビス（トリフルオロメタンスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－４－メチルピリジニウム クロリド、１－｛（クロロジメチルシリル）メチル｝－４－メチルピリジニウム ビス（フルオロスルホニル）イミド、１－｛（クロロジメチルシリル）メチル｝－４－メチルピリジニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム クロリド、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリヘキシル｛（クロロジメチルシリル）メチル｝ホスホニウム クロリド、トリヘキシル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリヘキシル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム クロリド、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１－メチルイミダゾリウム クロリド、３－｛（クロロジメチルシリル）メチル｝－１－メチルイミダゾリウム ビス（フルオロスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１－メチルイミダゾリウム ビス（トリフルオロメタンスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１－エチルイミダゾリウム クロリド、３－｛（クロロジメチルシリル）メチル｝－１－エチルイミダゾリウム ビス（フルオロスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１－エチルイミダゾリウム ビス（トリフルオロメタンスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１－オクチルイミダゾリウム クロリド、３－｛（クロロジメチルシリル）メチル｝－１－オクチルイミダゾリウム ビス（フルオロスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１－オクチルイミダゾリウム ビス（トリフルオロメタンスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１，２－ジメチルイミダゾリウム クロリド、３－｛（クロロジメチルシリル）メチル｝－１，２－ジメチルイミダゾリウム ビス（フルオロスルホニル）イミド、３－｛（クロロジメチルシリル）メチル｝－１，２－ジメチルイミダゾリウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム クロリド、トリブチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリブチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム クロリド、トリオクチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリオクチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム クロリド、トリブチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリブチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム クロリド、トリオクチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリオクチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛（メトキシジメチルシリル）メチル｝ホスホニウム クロリド、トリブチル｛（メトキシジメチルシリル）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリブチル｛（メトキシジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（メトキシジメチルシリル）メチル｝ホスホニウム クロリド、トリオクチル｛（メトキシジメチルシリル）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリオクチル｛（メトキシジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛（エトキシジメチルシリル）メチル｝ホスホニウム クロリド、トリブチル｛（エトキシジメチルシリル）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリブチル｛（エトキシジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（エトキシジメチルシリル）メチル｝ホスホニウム クロリド、トリオクチル｛（エトキシジメチルシリル）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリオクチル｛（エトキシジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛（ジメチルシラノール）メチル｝ホスホニウム クロリド、トリブチル｛（ジメチルシラノール）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリブチル｛（ジメチルシラノール）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（ジメチルシラノール）メチル｝ホスホニウム クロリド、トリオクチル｛（ジメチルシラノール）メチル｝ホスホニウム ビス（フルオロスルホニル）イミド、トリオクチル｛（ジメチルシラノール）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド等が挙げられるが、これらに限定されるものではない。 On the other hand, specific examples of the ionic compound (7) include tributyl{(chlorodimethylsilyl)methyl}ammonium chloride, tributyl{(chlorodimethylsilyl)methyl}ammonium bis(fluorosulfonyl)imide, tributyl{(chlorodimethylsilyl) Methyl}ammonium bis(trifluoromethanesulfonyl)imide, trihexyl{(chlorodimethylsilyl)methyl}ammonium chloride, trihexyl{(chlorodimethylsilyl)methyl}ammonium bis(fluorosulfonyl)imide, trihexyl{(chlorodimethylsilyl)methyl}ammonium Bis(trifluoromethanesulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}ammonium chloride, trioctyl{(chlorodimethylsilyl)methyl}ammonium bis(fluorosulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}ammonium bis(trifluoro) romethanesulfonyl)imide, tridecyl{(chlorodimethylsilyl)methyl}ammonium chloride, tridecyl{(chlorodimethylsilyl)methyl}ammonium bis(fluorosulfonyl)imide, tridecyl{(chlorodimethylsilyl)methyl}ammonium bis(trifluoromethanesulfonyl) imide, tridodecyl{(chlorodimethylsilyl)methyl}ammonium chloride, tridodecyl{(chlorodimethylsilyl)methyl}ammonium bis(fluorosulfonyl)imide, tridodecyl{(chlorodimethylsilyl)methyl}ammonium bis(trifluoromethanesulfonyl)imide, 1 -{(chlorodimethylsilyl)methyl}-1-methylpyrrolidinium chloride, 1-{(chlorodimethylsilyl)methyl}-1-methylpyrrolidinium bis(fluorosulfonyl)imide, 1-{(chlorodimethylsilyl) methyl}-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-{(chlorodimethylsilyl)methyl}-1-methylpiperidinium chloride, 1-{(chlorodimethylsilyl)methyl}-1-methyl piperidinium bis(fluorosulfonyl)imide, 1-{(chlorodimethylsilyl)methyl}-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-{(chlorodimethylsilyl) Tylsilyl)methyl}pyridinium chloride, 1-{(chlorodimethylsilyl)methyl}pyridinium bis(fluorosulfonyl)imide, 1-{(chlorodimethylsilyl)methyl}pyridinium bis(trifluoromethanesulfonyl)imide, 1-{(chlorodimethyl silyl)methyl}-2-methylpyridinium chloride, 1-{(chlorodimethylsilyl)methyl}-2-methylpyridinium bis(fluorosulfonyl)imide, 1-{(chlorodimethylsilyl)methyl}-2-methylpyridinium bis( trifluoromethanesulfonyl)imide, 1-{(chlorodimethylsilyl)methyl}-3-methylpyridinium chloride, 1-{(chlorodimethylsilyl)methyl}-3-methylpyridinium bis(fluorosulfonyl)imide, 1-{(chloro dimethylsilyl)methyl}-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-{(chlorodimethylsilyl)methyl}-4-methylpyridinium chloride, 1-{(chlorodimethylsilyl)methyl}-4-methylpyridinium Bis(fluorosulfonyl)imide, 1-{(chlorodimethylsilyl)methyl}-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, tributyl{(chlorodimethylsilyl)methyl}phosphonium chloride, tributyl{(chlorodimethylsilyl)methyl }phosphonium bis(fluorosulfonyl)imide, tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, trihexyl{(chlorodimethylsilyl)methyl}phosphonium chloride, trihexyl{(chlorodimethylsilyl)methyl}phosphonium bis (fluorosulfonyl)imide, trihexyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}phosphonium chloride, trioctyl{(chlorodimethylsilyl)methyl}phosphonium bis(fluorosulfonyl) ) imide, trioctyl {(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, 3-{(chlorodimethylsilyl)methyl}-1-methylimidazolium chloride, 3-{(chlorodi methylsilyl)methyl}-1-methylimidazolium bis(fluorosulfonyl)imide, 3-{(chlorodimethylsilyl)methyl}-1-methylimidazolium bis(trifluoromethanesulfonyl)imide, 3-{(chlorodimethylsilyl)methyl }-1-ethylimidazolium chloride, 3-{(chlorodimethylsilyl)methyl}-1-ethylimidazolium bis(fluorosulfonyl)imide, 3-{(chlorodimethylsilyl)methyl}-1-ethylimidazolium bis( trifluoromethanesulfonyl)imide, 3-{(chlorodimethylsilyl)methyl}-1-octylimidazolium chloride, 3-{(chlorodimethylsilyl)methyl}-1-octylimidazolium bis(fluorosulfonyl)imide, 3-{ (Chlorodimethylsilyl)methyl}-1-octylimidazolium bis(trifluoromethanesulfonyl)imide, 3-{(chlorodimethylsilyl)methyl}-1,2-dimethylimidazolium chloride, 3-{(chlorodimethylsilyl)methyl }-1,2-dimethylimidazolium bis(fluorosulfonyl)imide, 3-{(chlorodimethylsilyl)methyl}-1,2-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, tributyl{3-(chlorodimethylsilyl ) propyl}phosphonium chloride, tributyl{3-(chlorodimethylsilyl)propyl}phosphonium bis(fluorosulfonyl)imide, tributyl{3-(chlorodimethylsilyl)propyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{3-( Chlorodimethylsilyl)propyl}phosphonium chloride, trioctyl{3-(chlorodimethylsilyl)propyl}phosphonium bis(fluorosulfonyl)imide, trioctyl{3-(chlorodimethylsilyl)propyl}phosphonium bis(trifluoromethanesulfonyl)imide, tributyl{ 8-(chlorodimethylsilyl)octyl}phosphonium chloride, tributyl{8-(chlorodimethylsilyl)octyl}phosphonium bis(fluorosulfonyl)imide, tributyl{8-(chlorodimethylsilyl)octyl}phosphonium bis(trifluoromethanesulfonyl)imide , trioctyl {8-(chlorodimethylsilyl a) octyl}phosphonium chloride, trioctyl{8-(chlorodimethylsilyl)octyl}phosphonium bis(fluorosulfonyl)imide, trioctyl{8-(chlorodimethylsilyl)octyl}phosphonium bis(trifluoromethanesulfonyl)imide, tributyl {(methoxy dimethylsilyl)methyl}phosphonium chloride, tributyl{(methoxydimethylsilyl)methyl}phosphonium bis(fluorosulfonyl)imide, tributyl{(methoxydimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{(methoxydimethylsilyl) methyl}phosphonium chloride, trioctyl{(methoxydimethylsilyl)methyl}phosphonium bis(fluorosulfonyl)imide, trioctyl{(methoxydimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, tributyl{(ethoxydimethylsilyl)methyl}phosphonium chloride, tributyl {(ethoxydimethylsilyl)methyl}phosphonium bis(fluorosulfonyl)imide, tributyl{(ethoxydimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl {(ethoxydimethylsilyl)methyl}phosphonium chloride, trioctyl {(ethoxydimethylsilyl)methyl}phosphonium bis(fluorosulfonyl)imide, trioctyl {(ethoxydimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, tributyl {(dimethylsilanol)methyl}phosphonium chloride, tributyl {(dimethylsilanol) )methyl}phosphonium bis(fluorosulfonyl)imide, tributyl{(dimethylsilanol)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{(dimethylsilanol)methyl}phosphonium chloride, trioctyl{(dimethylsilanol)methyl}phosphonium bis( fluorosulfonyl)imide, trioctyl{(dimethylsilanol)methyl}phosphonium bis(trifluoromethanesulfonyl)imide and the like, but are not limited thereto.
これらの中でも、上記シラノール性水酸基含有オルガノポリシロキサン化合物（６）との反応性と、得られるオルガノポリシロキサン化合物の撥水性、滑水性およびその耐久性の観点から、トリブチル｛（クロロジメチルシリル）メチル｝アンモニウム クロリド、トリブチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝アンモニウム クロリド、トリオクチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム クロリド、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム クロリド、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム クロリド、トリブチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム クロリド、トリオクチル｛３－（クロロジメチルシリル）プロピル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム クロリド、トリブチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム クロリド、トリオクチル｛８－（クロロジメチルシリル）オクチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドが好ましく、トリブチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝アンモニウム ビス（トリフルオロメタンスルホニル）イミド、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドがより好ましく、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミド、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドがより一層好ましい。 Among these, tributyl {(chlorodimethylsilyl)methyl }ammonium chloride, tributyl{(chlorodimethylsilyl)methyl}ammonium bis(trifluoromethanesulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}ammonium chloride, trioctyl{(chlorodimethylsilyl)methyl}ammonium bis(trifluoromethanesulfonyl) imide, tributyl{(chlorodimethylsilyl)methyl}phosphonium chloride, tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}phosphonium chloride, trioctyl{(chlorodimethylsilyl) ) methyl}phosphonium bis(trifluoromethanesulfonyl)imide, tributyl{3-(chlorodimethylsilyl)propyl}phosphonium chloride, tributyl{3-(chlorodimethylsilyl)propyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{3- (Chlorodimethylsilyl)propyl}phosphonium chloride, trioctyl{3-(chlorodimethylsilyl)propyl}phosphonium bis(trifluoromethanesulfonyl)imide, tributyl{8-(chlorodimethylsilyl)octyl}phosphonium chloride, tributyl{8-(chloro dimethylsilyl)octyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{8-(chlorodimethylsilyl)octyl}phosphonium chloride, trioctyl{8-(chlorodimethylsilyl)octyl}phosphonium bis(trifluoromethanesulfonyl)imide are preferred, tributyl{(chlorodimethylsilyl)methyl}ammonium bis(trifluoromethanesulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}ammonium bis(trifluoromethanesulfonyl)imide, tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethane) sulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}phos Phonium bis(trifluoromethanesulfonyl)imide is more preferred, tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide being even more preferred. preferable.
また、本発明では、上記シラノール性水酸基含有オルガノポリシロキサン化合物（６）について、Ｚは、得られるオルガノポリシロキサン化合物の撥水性、滑水性およびその耐久性の観点から、Ｄ単位単独のオルガノポリシロキサン構造がより好ましい。 Further, in the present invention, in the silanol hydroxyl group-containing organopolysiloxane compound (6), Z is an organopolysiloxane having a single D unit, from the viewpoint of the water repellency, water slippage, and durability of the resulting organopolysiloxane compound. Structure is more preferred.
したがって、上記シラノール性水酸基含有オルガノポリシロキサン化合物（６）としては、平均構造式が下記式（８）で表されるもの（以下、シラノール性水酸基含有オルガノポリシロキサン化合物（８）という）が好ましく、このような化合物を用いることで、得られるオルガノポリシロキサン化合物はさらに良好な撥水性、滑水性およびその耐久性が発揮される。 Therefore, as the silanol hydroxyl group-containing organopolysiloxane compound (6), a compound having an average structural formula represented by the following formula (8) (hereinafter referred to as a silanol hydroxyl group-containing organopolysiloxane compound (8)) is preferable. By using such a compound, the resulting organopolysiloxane compound exhibits even better water repellency, water sliding property and durability.
上記シラノール性水酸基含有オルガノポリシロキサン化合物（６）または（８）のシラノール性水酸基と、上記イオン性化合物（７）の脱離基とのシロキサン結合形成反応は、従来公知の一般的な方法で行うことができる。
より具体的には、塩基性化合物の存在下、シラノール性水酸基含有オルガノポリシロキサン化合物（６）または（８）と、イオン性化合物（７）とを脱アルコール反応、脱ハロゲン化水素反応および脱水反応のいずれかの反応形態によりシロキサン結合を形成する反応を行う。
The siloxane bond forming reaction between the silanol hydroxyl group of the silanol hydroxyl group-containing organopolysiloxane compound (6) or (8) and the leaving group of the ionic compound (7) is carried out by a conventionally known general method. be able to.
More specifically, a dealcoholization reaction, a dehydrohalogenation reaction and a dehydration reaction of the silanol hydroxyl group-containing organopolysiloxane compound (6) or (8) and the ionic compound (7) in the presence of a basic compound. Perform a reaction to form a siloxane bond by any one of the reaction modes.
上記塩基性化合物としては、通常、上記のシロキサン結合形成反応に用いられている各種の塩基性化合物を使用できる。
具体的には、水素化ナトリウム、水素化リチウム、水素化カリウム、水素化セシウム等のアルカリ金属水素化物；水素化カルシウム等のアルカリ土類金属水素化物；水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム等のアルカリ金属水酸化物およびその水溶液、水酸化バリウム、水酸化カルシウム等のアルカリ土類金属水酸化物およびその水溶液；カリウムｔ－ブトキシド、ナトリウムｔ－ブトキシド等のアルカリ金属およびアルカリ土類アルコキシド；炭酸カリウム、炭酸ナトリウム、炭酸カルシウム等のアルカリ金属およびアルカリ土類金属炭酸塩；炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属およびアルカリ土類炭酸水素塩；トリエチルアミン、トリブチルアミン、Ｎ，Ｎ－ジイソプロピルエチルアミン、テトラメチルエチレンジアミン、ピリジン、Ｎ，Ｎ－ジメチル－４－アミノピリジン等の３級アミンなどが挙げられる。
これらの中でも、反応効率の観点から、トリエチルアミン、トリブチルアミン、Ｎ，Ｎ－ジイソプロピルエチルアミン、テトラメチルエチレンジアミン、ピリジン、Ｎ，Ｎ－ジメチル－４－アミノピリジン等の３級アミンが好ましく、トリエチルアミン、トリブチルアミンがより好ましい。
As the basic compound, various basic compounds that are usually used in the siloxane bond-forming reaction can be used.
Specifically, sodium hydride, lithium hydride, potassium hydride, alkali metal hydride such as cesium hydride; alkaline earth metal hydride such as calcium hydride; lithium hydroxide, sodium hydroxide, potassium hydroxide , alkali metal hydroxides such as cesium hydroxide and their aqueous solutions, alkaline earth metal hydroxides such as barium hydroxide and calcium hydroxide and their aqueous solutions; potassium t-butoxide, sodium t-butoxide and other alkali metals and alkalis earth alkoxides; alkali metal and alkaline earth metal carbonates such as potassium carbonate, sodium carbonate, calcium carbonate; alkali metal and alkaline earth metal carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate; triethylamine, tributylamine, N, Tertiary amines such as N-diisopropylethylamine, tetramethylethylenediamine, pyridine and N,N-dimethyl-4-aminopyridine.
Among these, from the viewpoint of reaction efficiency, tertiary amines such as triethylamine, tributylamine, N,N-diisopropylethylamine, tetramethylethylenediamine, pyridine, N,N-dimethyl-4-aminopyridine are preferred, and triethylamine and tributylamine. is more preferred.
塩基性化合物の使用量は特に限定されるものではないが、シロキサン結合形成反応を十分進行させて原料の残存を防止するとともに、塩基性化合物の過剰な残存を防止して得られるオルガノポリシロキサン化合物の保存安定性や諸特性を高めることを考慮すると、式（６）で表される化合物のシラノール性水酸基１ｍｏｌに対し、塩基性化合物０．５～１０ｍｏｌが好ましく、０．８～５ｍｏｌがより好ましく、０．９～２ｍｏｌがより一層好ましい。 The amount of the basic compound to be used is not particularly limited, but the organopolysiloxane compound is obtained by allowing the siloxane bond-forming reaction to proceed sufficiently to prevent the raw material from remaining and preventing the basic compound from remaining excessively. Considering improving the storage stability and various properties of the compound represented by formula (6), 0.5 to 10 mol of a basic compound is preferable, and 0.8 to 5 mol is more preferable, per 1 mol of the silanol hydroxyl group of the compound represented by formula (6). , 0.9 to 2 mol is even more preferred.
上記シロキサン結合形成反応では、用いる原料を溶解し、かつ用いる原料と反応しない溶媒を用いることができる。
その具体例としては、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、シクロヘキサン等の炭化水素系溶媒；ベンゼン、トルエン、キシレン等の芳香族系溶媒；ホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、ピロリドン、Ｎ－メチルピロリドン等のアミド系溶媒；ジエチルエーテル、ジブチルエーテル、シクロペンチルメチルエーテル、テトラヒドロフラン、１，４－ジオキサン等のエーテル系溶媒；アセトニトリル等のニトリル系溶媒などが挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。
これらの中でも、反応効率の観点から、トルエン、キシレン、ジメチルホルムアミド、シクロペンチルメチルエーテル、テトラヒドロフラン、アセトニトリルが好ましく、アセトニトリルがより好ましい。
In the siloxane bond-forming reaction, a solvent that dissolves the starting material to be used and that does not react with the starting material to be used can be used.
Specific examples include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, and cyclohexane; aromatic solvents such as benzene, toluene, and xylene; formamide, N,N-dimethylformamide, pyrrolidone, N-methyl amide solvents such as pyrrolidone; ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; nitrile solvents such as acetonitrile; More than one species may be used in combination.
Among these, from the viewpoint of reaction efficiency, toluene, xylene, dimethylformamide, cyclopentylmethyl ether, tetrahydrofuran, and acetonitrile are preferred, and acetonitrile is more preferred.
シロキサン結合形成時の反応温度は、特に限定されるものではないが、反応速度を適切にすることを考慮すると、０～１００℃が好ましく、２５～８０℃が好ましく、４０～７０℃がより一層好ましい。
反応時間は特に制限されないが、通常１０分～２４時間である。
The reaction temperature at the time of siloxane bond formation is not particularly limited, but in consideration of making the reaction rate appropriate, it is preferably 0 to 100 ° C., preferably 25 to 80 ° C., and more preferably 40 to 70 ° C. preferable.
Although the reaction time is not particularly limited, it is usually 10 minutes to 24 hours.
シラノール性水酸基含有オルガノポリシロキサン化合物（６）または（８）のシラノール性水酸基と、イオン性化合物（７）の脱離基との反応割合は、シロキサン結合形成反応時の副生物を抑制するとともに、得られるオルガノポリシロキサン化合物の保存安定性や特性を高めることを考慮すると、上記シラノール性水酸基１ｍｏｌに対し、上記脱離基０．８～１．２ｍｏｌとなる割合が好ましく、０．９～１．１ｍｏｌとなる割合がより好ましい。 The reaction ratio between the silanol hydroxyl group of the silanol hydroxyl group-containing organopolysiloxane compound (6) or (8) and the leaving group of the ionic compound (7) suppresses by-products during the siloxane bond formation reaction, In consideration of enhancing the storage stability and properties of the resulting organopolysiloxane compound, the ratio of 0.8 to 1.2 mol of the leaving group per 1 mol of the silanol hydroxyl group is preferable, and the ratio is 0.9 to 1.0 mol. A ratio of 1 mol is more preferable.
本発明の撥水剤組成物および撥水性コーティング剤は、上述した本発明のオルガノポリシロキサン化合物（１）を少なくとも１種含有するものである。
上述したオルガノポリシロキサン化合物（１）は、それ単独で撥水剤組成物として使用することもできるが、主剤となる有機樹脂、硬化触媒、溶媒等のその他の成分を混合した形態として使用することもできる。
上記のその他の成分を配合する場合、撥水剤組成物および撥水性コーティング剤中のオルガノポリシロキサン化合物（１）の含有量は特に限定されず、例えば、９０質量％以上、７０質量％以上、５０質量％以上、３０質量％以上、１０質量％以上、５質量％以上、１質量％以上、０．５質量％以上、０．１質量％以上等から適宜設定できる。
中でも、０．１～１０質量％程度が好ましく、０．５～５質量％がより好ましい。なお、オルガノポリシロキサン化合物が溶剤を含む場合、上記含有量は、溶剤を除いた不揮発分を意味する。
The water repellent composition and water repellent coating agent of the present invention contain at least one of the organopolysiloxane compounds (1) of the present invention described above.
Although the organopolysiloxane compound (1) described above can be used alone as a water repellent composition, it can be used in the form of a mixture of other components such as an organic resin as a main ingredient, a curing catalyst, and a solvent. can also
When the above other components are blended, the content of the organopolysiloxane compound (1) in the water repellent composition and water repellent coating agent is not particularly limited. It can be set appropriately from 50% by mass or more, 30% by mass or more, 10% by mass or more, 5% by mass or more, 1% by mass or more, 0.5% by mass or more, 0.1% by mass or more, and the like.
Among them, about 0.1 to 10% by mass is preferable, and 0.5 to 5% by mass is more preferable. In addition, when an organopolysiloxane compound contains a solvent, the said content means the non-volatile matter except a solvent.
溶媒としては、撥水剤組成物に含まれるオルガノポリシロキサン化合物（１）および上記のその他の成分と反応せず、かつオルガノポリシロキサン化合物（１）および上記のその他の成分の溶解能を有していれば特に限定されるものではないが、オルガノポリシロキサン化合物（１）および上記のその他の成分との非反応性、溶解性および揮発性等の観点から、ベンゼン、トルエン、キシレン等の芳香族系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル等のエステル系溶剤；ジエチルエーテル、ジブチルエーテル、シクロペンチルメチルエーテル、テトラヒドロフラン、１，４－ジオキサン等のエーテル系溶剤；アセトニトリル等が挙げられる。中でも、トルエン、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル、ジブチルエーテル、シクロペンチルメチルエーテル、テトラヒドロフラン、アセトニトリルが好ましく、メチルエチルケトン、メチルイソブチルケトン、アセトニトリルがより好ましい。 The solvent does not react with the organopolysiloxane compound (1) and the above other components contained in the water repellent composition, and has the ability to dissolve the organopolysiloxane compound (1) and the above other components. However, aromatic compounds such as benzene, toluene, and xylene are used from the viewpoint of non-reactivity, solubility, and volatility with the organopolysiloxane compound (1) and the above-mentioned other components. ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane ether-based solvents such as; acetonitrile and the like. Among them, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran and acetonitrile are preferred, and methyl ethyl ketone, methyl isobutyl ketone and acetonitrile are more preferred.
本発明の撥水剤組成物に含まれる主剤となる有機樹脂は特に限定されるものではないが、主剤となる有機樹脂としては活性エネルギー線硬化型樹脂が好ましく、特に重合性モノマーとしてエチレン性不飽和二重結合を有する化合物を含むものが好ましい。
上記エチレン性不飽和二重結合を有する化合物としては、特に限定されるものではなく、その具体例としては、Ｎ－ビニルピロリドン；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、グリシジル（メタ）アクリレート、アクリロイルモルフォリンテトラヒドロフルフリールアクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、リン酸（メタ）アクリレート、エチレンオキサイド変性リン酸（メタ）アクリレート、フェノキシ（メタ）アクリレート、エチレンオキサイド変性フェノキシ（メタ）アクリレート、プロピレンオキサイド変性フェノキシ（メタ）アクリレート、ノニルフェノール（メタ）アクリレート、エチレンオキサイド変性ノニルフェノール（メタ）アクリレート、プロピレンオキサイド変性ノニルフェノール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシプロピレングリコール（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピルフタレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルハイドロゲンフタレート、２－（メタ）アクリロイルオキシプロピルハイドロゲンフタレート、２－（メタ）アクリロイルオキシプロピルヘキサヒドロハイドロゲンフタレート、２－（メタ）アクリロイルオキシプロピルテトラヒドロハイドロゲンフタレート、ジメチルアミノエチル（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、ヘキサフルオロプロピル（メタ）アクリレート、オクタフルオロプロピル（メタ）アクリレート、オクタフルオロプロピル（メタ）アクリレート、アダマンチルモノ（メタ）アクリレート等のモノ（メタ）アクリレート；ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、エトキシ化ヘキサンジオールジ（メタ）アクリレート、プロポキシ化ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エトキシ化ネオペンチルグリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、１，３－ビス［（メタ）アクリロキシメチル］－１，１，３，３－テトラメチルジシロキサン等のジ（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、トリス２―ヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート等のトリ（メタ）アクリレート；ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の４官能以上の（メタ）アクリレート、ウレタンアクリレート、エポキシアクリレート、エステルアクリレートなどが挙げられる。
The organic resin that is the main ingredient contained in the water repellent composition of the present invention is not particularly limited, but the organic resin that is the main ingredient is preferably an active energy ray-curable resin. Those containing compounds with saturated double bonds are preferred.
The compound having an ethylenically unsaturated double bond is not particularly limited, and specific examples thereof include N-vinylpyrrolidone; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate ) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate ) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, phenoxy (meth) Acrylate, ethylene oxide-modified phenoxy (meth)acrylate, propylene oxide-modified phenoxy (meth)acrylate, nonylphenol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, propylene oxide-modified nonylphenol (meth)acrylate, methoxydiethylene glycol (meth)acrylate , methoxypolyethylene glycol (meth)acrylate, methoxypropyleneglycol (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth) acryloyloxyethyl hydrogen phthalate, 2-(meth) acryloyloxypropyl hydrogen phthalate, 2-(meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2-(meth) acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, Trifluoroethyl (meth)acrylate, Tetrafluoropropyl (meth)acrylate, Hexafluoropropyl (meth)acrylate, Octafluoropropyl (meth)acrylate , octafluoropropyl (meth)acrylate, adamantyl mono(meth)acrylate, etc.; butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxy Hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth) Di(meth)acrylates such as acrylates, neopentylglycol hydroxypivalate di(meth)acrylate, 1,3-bis[(meth)acryloxymethyl]-1,1,3,3-tetramethyldisiloxane; trimethylol Propane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tris-2-hydroxyethyl isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, penta Tri(meth)acrylates such as erythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, di Tetra- or higher-functional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, urethane acrylates, epoxy acrylates, ester acrylates, and the like can be mentioned.
本発明の撥水剤組成物に含まれる硬化触媒は特に限定されるものではないが、硬化触媒としては光重合開始剤、熱重合開始剤が好ましく、特に光重合開始剤が好ましい。
光重合開始剤としては、活性エネルギー線によりラジカル種を発生する開始剤であれば特に限定されるものではなく、アセトフェノン系、ベンゾフェノン系、ベンゾイン系、アシルフォスフィンオキサイド系、チオキサントン系等の公知の光重合開始剤から適宜選択して用いることができる。
光重合開始剤の具体例としては、ベンゾフェノン、ベンジル、ミヒラーズケトン、チオキサントン誘導体、ベンゾインエチルエーテル、ジエトキシアセトフェノン、ベンジルジメチルケタール、２－ヒドロキシ－２－メチルプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、アシルフォスフィンオキサイド誘導体、２－メチル－１－｛４－（メチルチオ）フェニル｝－２－モルフォリノプロパン－１－オン、４－ベンゾイル－４’－メチルジフェニルスルファイド、２，４，６－トリメチルベンゾイルジフェニルフォスフィン等が挙げられ、これらは単独で用いても、２種以上を組み合わせて用いてもよい。
The curing catalyst contained in the water repellent composition of the present invention is not particularly limited, but the curing catalyst is preferably a photopolymerization initiator or a thermal polymerization initiator, and particularly preferably a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it is an initiator that generates radical species by active energy rays. It can be appropriately selected from photopolymerization initiators and used.
Specific examples of photopolymerization initiators include benzophenone, benzyl, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, acyl Phosphine oxide derivatives, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyl diphenylphosphine and the like, and these may be used alone or in combination of two or more.
光重合開始剤は市販品として入手することができ、市販品としては、例えば、ダロキュア１１７３、ダロキュアＭＢＦ、イルガキュア１２７、イルガキュア１８４、イルガキュア３６９、イルガキュア３７９、イルガキュア３７９ＥＧ、イルガキュア６５１、イルガキュア７５４、イルガキュア７８４、イルガキュア８１９、イルガキュア８１９ＤＷ、イルガキュア９０７、イルガキュア１８００、イルガキュア２９５９、ルシリンＴＰＯ（いずれもＢＡＳＦジャパン社製）等が挙げられる。 Photopolymerization initiators can be obtained as commercial products such as Darocure 1173, Darocure MBF, Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 379EG, Irgacure 651, Irgacure 754 and Irgacure 784. , Irgacure 819, Irgacure 819DW, Irgacure 907, Irgacure 1800, Irgacure 2959, Lucilin TPO (all manufactured by BASF Japan), and the like.
本発明の撥水剤組成物および撥水性コーティング剤には、さらに、使用目的に応じて、硬化剤、接着性改良剤、無機および有機の紫外線吸収剤、光安定化剤、保存安定性改良剤、可塑剤、充填剤、顔料等の各種添加剤を添加してもよい。 The water repellent composition and water repellent coating agent of the present invention may further contain a curing agent, an adhesion improver, an inorganic and organic UV absorber, a light stabilizer, and a storage stability improver, depending on the purpose of use. , plasticizers, fillers, pigments, and other additives may be added.
以上説明した本発明の撥水剤組成物および撥水性コーティング剤を、固体基材の表面に塗布し、硬化させて被覆層を形成することで、撥水性硬化物品である被覆固体基材が得られる。
塗布方法としては特に限定されず、その具体例としては、スプレーコート、スピンコート、ディップコート、ローラーコート、刷毛塗り、バーコート、フローコート等の公知の方法から適宜選択して用いることができる。
固体基材としても特に限定されず、その具体例としては、エポキシ樹脂、フェノール樹脂、ポリカーボネート類およびポリカーボネートブレンド、ポリ（メタクリル酸メチル）等のアクリル系樹脂、ポリ（エチレンテレフタレート），ポリ（ブチレンテレフタレート），不飽和ポリエステル樹脂等のポリエステル樹脂、ポリアミド樹脂、ポリイミド樹脂、アクリロニトリル－スチレン共重合体、スチレン－アクリロニトリル－ブタジエン共重合体、ポリ塩化ビニル樹脂、ポリスチレン樹脂、ポリスチレンとポリフェニレンエーテルとのブレンド、セルロースアセテートブチレート、ポリエチレン樹脂などの有機ポリマー基材、鋼板等の金属基材、塗料塗布面、ガラス、セラミック、コンクリート、スレート板、テキスタイル、木材、石材、瓦、（中空）シリカ，チタニア，ジルコニア，アルミナ等の無機フィラー、ガラス繊維をはじめとしたガラスクロス，ガラステープ，ガラスマット，ガラスペーパー等のガラス繊維製品などが挙げられ、基材の材質および形状については特に限定されるものではない。
A coated solid substrate, which is a water-repellent cured article, is obtained by applying the water repellent composition and the water-repellent coating agent of the present invention described above to the surface of a solid substrate and curing them to form a coating layer. be done.
The coating method is not particularly limited, and specific examples thereof include spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, flow coating, and other known methods.
The solid substrate is not particularly limited, and specific examples thereof include epoxy resins, phenolic resins, polycarbonates and polycarbonate blends, acrylic resins such as poly(methyl methacrylate), poly(ethylene terephthalate), and poly(butylene terephthalate). ), polyester resins such as unsaturated polyester resins, polyamide resins, polyimide resins, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride resins, polystyrene resins, blends of polystyrene and polyphenylene ether, cellulose Acetate butyrate, organic polymer substrates such as polyethylene resin, metal substrates such as steel plates, coated surfaces, glass, ceramics, concrete, slate plates, textiles, wood, stone materials, roof tiles, (hollow) silica, titania, zirconia, Examples include inorganic fillers such as alumina, glass cloth such as glass fiber, glass tape, glass mat, glass fiber products such as glass paper, and the like, and the material and shape of the substrate are not particularly limited.
以下、合成例、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、下記において、各生成物の粘度は、オストワルド粘度計による２５℃における測定値であり、各生成物中に含まれるシラノール性水酸基の含有量（質量％）は、各生成物にグリニャール試薬（メチルマグネシウムヨージド）を作用させた際のメタンガス発生量より定量した。また、各生成物のシリコーン平均組成は、日本電子（株）製３００ＭＨｚ－ＮＭＲ測定装置を用いて、1Ｈ－ＮＭＲおよび29Ｓｉ－ＮＭＲにおける検出スペクトルの積分値から算出した。
また、下記におけるシリコーン平均組成中のＴＦＳＩ-はビス（トリフルオロメタンスルホニル）イミドアニオンを表す。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the following, the viscosity of each product is a value measured by an Ostwald viscometer at 25° C., and the content (% by mass) of silanol hydroxyl groups contained in each product is calculated using a Grignard reagent ( Methylmagnesium iodide) was quantified from the amount of methane gas generated when acting. The average silicone composition of each product was calculated from the integrated values of the detected spectra in 1 H-NMR and 29 Si-NMR using a JEOL 300 MHz-NMR spectrometer.
Also, TFSI- in the silicone average composition below represents a bis(trifluoromethanesulfonyl)imide anion.
［１］オルガノポリシロキサン化合物の合成
［合成例１］オルガノポリシロキサン化合物１の合成
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２００ｍＬセパラブルフラスコに、下記式（９）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物４．８ｇ、トルエン４５ｇ、３，５－ジｔ－ブチル－４－ヒドロキシトルエン０．０３ｇおよびトリエチルアミン３．２ｇを仕込み、４０℃に加熱した。その中に、イオン性化合物としてトリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液３５．２ｇを滴下投入し、５０℃にて２時間加熱撹拌した。シラノール性水酸基の含有量測定により、原料のシラノール性水酸基含有オルガノポリシロキサン化合物由来のシラノール性水酸基が完全に消費され０質量％となったことを確認し、反応終了とした。反応終了後の混合物を、１０質量％芒硝水３０ｇを用いて２回水洗および分液操作を行った後、減圧留去（８０℃、５ｍｍＨｇ）を１時間実施し、濾過することで、対応するオルガノポリシロキサン化合物１を１７ｇ得た。
得られたオルガノポリシロキサン化合物１は、無色透明液体であり、粘度９０ｍｍ2／ｓ、下記式（１０）で表されるシリコーン平均組成であった。
[1] Synthesis of organopolysiloxane compound [Synthesis Example 1] Synthesis of organopolysiloxane compound 1
A 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 4.8 g of a silanol hydroxyl group-containing organopolysiloxane compound represented by the following formula (9), 45 g of toluene, 3,5-di 0.03 g of t-butyl-4-hydroxytoluene and 3.2 g of triethylamine were charged and heated to 40°C. 35.2 g of a 50% by weight toluene solution of tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide as an ionic compound was added dropwise thereto, and the mixture was heated and stirred at 50° C. for 2 hours. By measuring the content of silanol hydroxyl groups, it was confirmed that the silanol hydroxyl groups derived from the starting silanol hydroxyl group-containing organopolysiloxane compound were completely consumed to 0% by mass, and the reaction was terminated. After the reaction was completed, the mixture was washed twice with 30 g of 10% by mass sodium sulfate solution and subjected to liquid separation, followed by distillation under reduced pressure (80° C., 5 mmHg) for 1 hour, followed by filtration. 17 g of organopolysiloxane compound 1 was obtained.
The resulting organopolysiloxane compound 1 was a colorless transparent liquid with a viscosity of 90 mm 2 /s and an average silicone composition represented by the following formula (10).
［合成例２］オルガノポリシロキサン化合物２の合成
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２００ｍＬセパラブルフラスコに、下記式（１１）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物２１ｇ、トルエン１０ｇ、アセトニトリル４０ｇ、３，５－ジｔ－ブチル－４－ヒドロキシトルエン０．０３ｇおよびトリエチルアミン５．８ｇを仕込み、４０℃に加熱した。その中に、イオン性化合物としてトリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液６４．８ｇを滴下投入し、５０℃にて２時間加熱撹拌した。シラノール性水酸基の含有量測定により、原料のシラノール性水酸基含有オルガノポリシロキサン化合物由来のシラノール性水酸基が完全に消費され０質量％となったことを確認し、反応終了とした。反応終了後の混合物を、１０質量％芒硝水１００ｇを用いて２回水洗および分液操作を行った後、減圧留去（８０℃、５ｍｍＨｇ）を１時間実施し、濾過することで、対応するオルガノポリシロキサン化合物２を４９ｇ得た。
得られたオルガノポリシロキサン化合物２は、無色透明液体であり、粘度８８ｍｍ2／ｓ、下記式（１２）で表されるシリコーン平均組成であった。
[Synthesis Example 2] Synthesis of organopolysiloxane compound 2
A 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 21 g of a silanol hydroxyl group-containing organopolysiloxane compound represented by the following formula (11), 10 g of toluene, 40 g of acetonitrile, 3,5- 0.03 g of di-t-butyl-4-hydroxytoluene and 5.8 g of triethylamine were charged and heated to 40°C. 64.8 g of a 50% by weight toluene solution of tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide as an ionic compound was added dropwise thereto, and the mixture was heated and stirred at 50° C. for 2 hours. By measuring the content of silanol hydroxyl groups, it was confirmed that the silanol hydroxyl groups derived from the starting silanol hydroxyl group-containing organopolysiloxane compound were completely consumed to 0% by mass, and the reaction was terminated. After the reaction was completed, the mixture was washed twice with 100 g of 10% by mass sodium sulfate solution and subjected to liquid separation, followed by distillation under reduced pressure (80° C., 5 mmHg) for 1 hour, followed by filtration. 49 g of organopolysiloxane compound 2 was obtained.
The resulting organopolysiloxane compound 2 was a colorless and transparent liquid with a viscosity of 88 mm 2 /s and an average silicone composition represented by the following formula (12).
［合成例３］オルガノポリシロキサン化合物３の合成
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２００ｍＬセパラブルフラスコに、下記式（１３）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物３３．２ｇ、トルエン１０ｇ、アセトニトリル４０ｇ、３，５－ジｔ－ブチル－４－ヒドロキシトルエン０．０４ｇおよびトリエチルアミン５．８ｇを仕込み、４０℃に加熱した。その中に、イオン性化合物としてトリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液６４．８ｇを滴下投入し、５０℃にて２時間加熱撹拌した。シラノール性水酸基の含有量測定により、原料のシラノール性水酸基含有オルガノポリシロキサン化合物由来のシラノール性水酸基が完全に消費され０質量％となったことを確認し、反応終了とした。反応終了後の混合物を、１０質量％芒硝水１００ｇを用いて２回水洗および分液操作を行った後、減圧留去（８０℃、５ｍｍＨｇ）を１時間実施し、濾過することで、対応するオルガノポリシロキサン化合物３を６０ｇ得た。
得られたオルガノポリシロキサン化合物３は、無色透明液体であり、粘度７１ｍｍ2／ｓ、下記式（１４）で表されるシリコーン平均組成であった。
[Synthesis Example 3] Synthesis of organopolysiloxane compound 3
A 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 33.2 g of a silanol hydroxyl group-containing organopolysiloxane compound represented by the following formula (13), 10 g of toluene, 40 g of acetonitrile, 3, 0.04 g of 5-di-t-butyl-4-hydroxytoluene and 5.8 g of triethylamine were charged and heated to 40°C. 64.8 g of a 50% by weight toluene solution of tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide as an ionic compound was added dropwise thereto, and the mixture was heated and stirred at 50° C. for 2 hours. By measuring the content of silanol hydroxyl groups, it was confirmed that the silanol hydroxyl groups derived from the starting silanol hydroxyl group-containing organopolysiloxane compound were completely consumed to 0% by mass, and the reaction was terminated. After the reaction was completed, the mixture was washed twice with 100 g of 10% by mass sodium sulfate solution and subjected to liquid separation, followed by distillation under reduced pressure (80° C., 5 mmHg) for 1 hour, followed by filtration. 60 g of organopolysiloxane compound 3 was obtained.
The resulting organopolysiloxane compound 3 was a colorless transparent liquid with a viscosity of 71 mm 2 /s and an average silicone composition represented by the following formula (14).
［合成例４］オルガノポリシロキサン化合物４の合成
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２００ｍＬセパラブルフラスコに、下記式（１５）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物４５．４ｇ、トルエン６．５ｇ、アセトニトリル５０ｇ、３，５－ジｔ－ブチル－４－ヒドロキシトルエン０．０５ｇおよびトリエチルアミン３．８ｇを仕込み、４０℃に加熱した。その中に、イオン性化合物としてトリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液４２．１ｇを滴下投入し、５０℃にて２時間加熱撹拌した。シラノール性水酸基の含有量測定により、原料のシラノール性水酸基含有オルガノポリシロキサン化合物由来のシラノール性水酸基が完全に消費され０質量％となったことを確認し、反応終了とした。反応終了後の混合物を、１０質量％芒硝水１００ｇを用いて２回水洗および分液操作を行った後、減圧留去（８０℃、５ｍｍＨｇ）を１時間実施し、濾過することで、対応するオルガノポリシロキサン化合物４を５８ｇ得た。
得られたオルガノポリシロキサン化合物４は、無色透明液体であり、粘度８１ｍｍ2／ｓ、下記式（１６）で表されるシリコーン平均組成であった。
[Synthesis Example 4] Synthesis of organopolysiloxane compound 4
A 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 45.4 g of a silanol hydroxyl group-containing organopolysiloxane compound represented by the following formula (15), 6.5 g of toluene, 50 g of acetonitrile, 0.05 g of 3,5-di-t-butyl-4-hydroxytoluene and 3.8 g of triethylamine were charged and heated to 40°C. 42.1 g of a 50% by weight toluene solution of tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide as an ionic compound was added dropwise thereto, and the mixture was heated and stirred at 50° C. for 2 hours. By measuring the content of silanol hydroxyl groups, it was confirmed that the silanol hydroxyl groups derived from the starting silanol hydroxyl group-containing organopolysiloxane compound were completely consumed to 0% by mass, and the reaction was terminated. After the reaction was completed, the mixture was washed twice with 100 g of 10% by mass sodium sulfate solution and subjected to liquid separation, followed by distillation under reduced pressure (80° C., 5 mmHg) for 1 hour, followed by filtration. 58 g of organopolysiloxane compound 4 was obtained.
The resulting organopolysiloxane compound 4 was a colorless transparent liquid with a viscosity of 81 mm 2 /s and an average silicone composition represented by the following formula (16).
［合成例５］オルガノポリシロキサン化合物５の合成
イオン性化合物であるトリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液を、トリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム クロリドの７２質量％アセトニトリル溶液２６．４ｇに変更した以外は、実施例１－３と同様の手順で合成し、対応するオルガノポリシロキサン化合物５を４５ｇ得た。
得られたオルガノポリシロキサン化合物５は、無色透明液体であり、粘度５２ｍｍ2／ｓ、下記式（１７）で表されるシリコーン平均組成であった。
[Synthesis Example 5] Synthesis of organopolysiloxane compound 5
A 50 mass% toluene solution of tributyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, which is an ionic compound, was mixed with 26.4 g of a 72 mass% acetonitrile solution of tributyl{(chlorodimethylsilyl)methyl}phosphonium chloride. 45 g of the corresponding organopolysiloxane compound 5 was obtained by synthesizing in the same procedure as in Example 1-3 except that
The resulting organopolysiloxane compound 5 was a colorless and transparent liquid with a viscosity of 52 mm 2 /s and an average silicone composition represented by the following formula (17).
［合成例６］オルガノポリシロキサン化合物６の合成
イオン性化合物であるトリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液を、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液８３．３ｇに変更した以外は、実施例１－３と同様の手順で合成し、対応するオルガノポリシロキサン化合物６を７０ｇ得た。
得られたオルガノポリシロキサン化合物６は、無色透明液体であり、粘度６８ｍｍ2／ｓ、下記式（１８）で表されるシリコーン平均組成であった。
[Synthesis Example 6] Synthesis of organopolysiloxane compound 6
A 50 mass% toluene solution of tributyl {(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, which is an ionic compound, was added to 50 mass of trioctyl {(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide. % toluene solution was changed to 83.3 g, synthesis was performed in the same manner as in Example 1-3 to obtain 70 g of the corresponding organopolysiloxane compound 6.
The resulting organopolysiloxane compound 6 was a colorless transparent liquid with a viscosity of 68 mm 2 /s and an average silicone composition represented by the following formula (18).
［合成例７］オルガノポリシロキサン化合物７の合成
イオン性化合物であるトリブチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液を、トリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム クロリドの８０質量％アセトニトリル溶液３５．３ｇに変更した以外は、実施例１－３と同様の手順で合成し、対応するオルガノポリシロキサン化合物７を５５ｇ得た。
得られたオルガノポリシロキサン化合物７は、無色透明液体であり、粘度１７０ｍｍ2／ｓ、下記式（１９）で表されるシリコーン平均組成であった。
[Synthesis Example 7] Synthesis of organopolysiloxane compound 7
A 50 mass% toluene solution of tributyl {(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide, which is an ionic compound, was added to 35.3 g of an 80 mass% acetonitrile solution of trioctyl {(chlorodimethylsilyl)methyl}phosphonium chloride. 55 g of the corresponding organopolysiloxane compound 7 was obtained by synthesizing in the same manner as in Example 1-3 except that
The resulting organopolysiloxane compound 7 was a colorless and transparent liquid with a viscosity of 170 mm 2 /s and an average silicone composition represented by the following formula (19).
［合成例８］オルガノポリシロキサン化合物８の合成
式（１３）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物を、下記式（２０）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物６０．３ｇに変更した以外は、実施例１－３と同様の手順で合成し、対応するオルガノポリシロキサン化合物８を７９ｇ得た。
得られたオルガノポリシロキサン化合物８は、無色微濁液体であり、粘度６５ｍｍ2／ｓ、下記式（２１）で表されるシリコーン平均組成であった。
[Synthesis Example 8] Synthesis of organopolysiloxane compound 8
Example 1-3, except that the silanol hydroxyl-containing organopolysiloxane compound represented by formula (13) was changed to 60.3 g of a silanol hydroxyl-containing organopolysiloxane compound represented by formula (20) below. By synthesizing in the same procedure, 79 g of the corresponding organopolysiloxane compound 8 was obtained.
The resulting organopolysiloxane compound 8 was a colorless, slightly turbid liquid with a viscosity of 65 mm 2 /s and an average silicone composition represented by the following formula (21).
［合成例９］オルガノポリシロキサン化合物９の合成
式（１３）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物を、下記式（２２）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物４６．７ｇに変更した以外は、実施例１－３と同様の手順で合成し、対応するオルガノポリシロキサン化合物９を６９ｇ得た。
得られたオルガノポリシロキサン化合物９は、無色微濁液体であり、粘度７２ｍｍ2／ｓ、下記式（２３）で表されるシリコーン平均組成であった。
[Synthesis Example 9] Synthesis of organopolysiloxane compound 9
Example 1-3, except that the silanol hydroxyl-containing organopolysiloxane compound represented by formula (13) was changed to 46.7 g of a silanol hydroxyl-containing organopolysiloxane compound represented by formula (22) below. By synthesizing in the same procedure, 69 g of the corresponding organopolysiloxane compound 9 was obtained.
The resulting organopolysiloxane compound 9 was a slightly turbid colorless liquid with a viscosity of 72 mm 2 /s and an average silicone composition represented by the following formula (23).
［合成例１０］オルガノポリシロキサン化合物１０の合成
撹拌機、還流冷却器、滴下ロートおよび温度計を備えた２００ｍＬセパラブルフラスコに、下記式（２４）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物３４．０ｇ、トルエン１０ｇ、アセトニトリル４０ｇ、３，５－ジｔ－ブチル－４－ヒドロキシトルエン０．０４ｇおよびトリエチルアミン５．８ｇを仕込み、４０℃に加熱した。その中に、イオン性化合物としてトリオクチル｛（クロロジメチルシリル）メチル｝ホスホニウム ビス（トリフルオロメタンスルホニル）イミドの５０質量％トルエン溶液８３．３ｇを滴下投入し、５０℃にて２時間加熱撹拌した。シラノール性水酸基の含有量測定により、原料のシラノール性水酸基含有オルガノポリシロキサン化合物由来のシラノール性水酸基が完全に消費され０質量％となったことを確認し、反応終了とした。反応終了後の混合物を、１０質量％芒硝水１００ｇを用いて２回水洗および分液操作を行った後、減圧留去（８０℃、５ｍｍＨｇ）を１時間実施し、濾過することで、対応するオルガノポリシロキサン化合物１０を７２ｇ得た。
得られたオルガノポリシロキサン化合物１０は、無色透明液体であり、粘度７０ｍｍ2／ｓ、下記式（２５）で表されるシリコーン平均組成であった。
[Synthesis Example 10] Synthesis of organopolysiloxane compound 10
A 200 mL separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 34.0 g of a silanol hydroxyl group-containing organopolysiloxane compound represented by the following formula (24), 10 g of toluene, 40 g of acetonitrile, 3, 0.04 g of 5-di-t-butyl-4-hydroxytoluene and 5.8 g of triethylamine were charged and heated to 40°C. 83.3 g of a 50% by weight toluene solution of trioctyl{(chlorodimethylsilyl)methyl}phosphonium bis(trifluoromethanesulfonyl)imide as an ionic compound was added dropwise thereto, and the mixture was heated and stirred at 50° C. for 2 hours. By measuring the content of silanol hydroxyl groups, it was confirmed that the silanol hydroxyl groups derived from the starting silanol hydroxyl group-containing organopolysiloxane compound were completely consumed to 0% by mass, and the reaction was terminated. After the reaction was completed, the mixture was washed twice with 100 g of 10% by mass sodium sulfate solution and subjected to liquid separation, followed by distillation under reduced pressure (80° C., 5 mmHg) for 1 hour, followed by filtration. 72 g of organopolysiloxane compound 10 was obtained.
The resulting organopolysiloxane compound 10 was a colorless transparent liquid with a viscosity of 70 mm 2 /s and an average silicone composition represented by the following formula (25).
［合成例１１］オルガノポリシロキサン化合物１１の合成
式（２４）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物を、下記式（２６）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物３３．２ｇに変更した以外は、実施例１－１０と同様の手順で合成し、対応するオルガノポリシロキサン化合物１１を６８ｇ得た。
得られたオルガノポリシロキサン化合物１１は、無色透明液体であり、粘度８８ｍｍ2／ｓ、下記式（２７）で表されるシリコーン平均組成であった。
[Synthesis Example 11] Synthesis of organopolysiloxane compound 11
Example 1-10, except that the silanol hydroxyl-containing organopolysiloxane compound represented by formula (24) was changed to 33.2 g of a silanol hydroxyl-containing organopolysiloxane compound represented by formula (26) below. Synthesis was carried out in the same manner to obtain 68 g of the corresponding organopolysiloxane compound 11.
The resulting organopolysiloxane compound 11 was a colorless and transparent liquid with a viscosity of 88 mm 2 /s and an average silicone composition represented by the following formula (27).
［合成例１２］オルガノポリシロキサン化合物１２の合成
式（２４）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物を、下記式（２８）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物３３．９ｇに変更した以外は、実施例１－１０と同様の手順で合成し、対応するオルガノポリシロキサン化合物１２を７１ｇ得た。
得られたオルガノポリシロキサン化合物１２は、無色透明液体であり、粘度８５ｍｍ2／ｓ、下記式（２９）で表されるシリコーン平均組成であった。
[Synthesis Example 12] Synthesis of organopolysiloxane compound 12
Example 1-10, except that the silanol hydroxyl-containing organopolysiloxane compound represented by formula (24) was changed to 33.9 g of a silanol hydroxyl-containing organopolysiloxane compound represented by formula (28) below. Synthesis was carried out in the same manner to obtain 71 g of the corresponding organopolysiloxane compound 12.
The resulting organopolysiloxane compound 12 was a colorless transparent liquid with a viscosity of 85 mm 2 /s and an average silicone composition represented by the following formula (29).
［合成例１３］オルガノポリシロキサン化合物１３の合成
式（２４）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物を、下記式（３０）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物６９．６ｇに変更した以外は、実施例１－１０と同様の手順で合成し、対応するオルガノポリシロキサン化合物１３を９５ｇ得た。
得られたオルガノポリシロキサン化合物１３は、無色透明液体であり、粘度４３５ｍｍ2／ｓ、下記式（３１）で表されるシリコーン平均組成であった。
[Synthesis Example 13] Synthesis of organopolysiloxane compound 13
Example 1-10, except that the silanol hydroxyl-containing organopolysiloxane compound represented by formula (24) was changed to 69.6 g of a silanol hydroxyl-containing organopolysiloxane compound represented by formula (30) below. By synthesizing in the same procedure, 95 g of the corresponding organopolysiloxane compound 13 was obtained.
The resulting organopolysiloxane compound 13 was a colorless and transparent liquid with a viscosity of 435 mm 2 /s and an average silicone composition represented by the following formula (31).
［合成例１４］オルガノポリシロキサン化合物１４の合成
式（２４）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物を、下記式（３２）で表されるシラノール性水酸基含有オルガノポリシロキサン化合物６５．３ｇに変更した以外は、実施例１－１０と同様の手順で合成し、対応するオルガノポリシロキサン化合物１４を９０ｇ得た。
得られたオルガノポリシロキサン化合物１４は、無色透明液体であり、粘度７１０ｍｍ2／ｓ、下記式（３３）で表されるシリコーン平均組成であった。
[Synthesis Example 14] Synthesis of organopolysiloxane compound 14
Example 1-10, except that the silanol hydroxyl group-containing organopolysiloxane compound represented by formula (24) was changed to 65.3 g of a silanol hydroxyl group-containing organopolysiloxane compound represented by the following formula (32). By synthesizing in the same procedure, 90 g of the corresponding organopolysiloxane compound 14 was obtained.
The resulting organopolysiloxane compound 14 was a colorless and transparent liquid with a viscosity of 710 mm 2 /s and an average silicone composition represented by the following formula (33).
［２］撥水剤組成物およびその硬化物品の調製
撥水剤組成物およびその硬化物品を調製する際に用いる各成分について説明する。
［エチレン性不飽和二重結合を有する化合物］
・ジペンタエリスリトールヘキサアクリレート
［硬化触媒（光重合開始剤）］
・２－ヒドロキシ－２－メチルプロピオフェノン
［溶剤］
・メチルエチルケトン
［オルガノポリシロキサン化合物］
・合成例１～１４で得られた各オルガノポリシロキサン化合物１～１４
[2] Preparation of water repellent composition and its cured product Each component used in preparing the water repellent composition and its cured product will be described.
[Compound having an ethylenically unsaturated double bond]
・Dipentaerythritol hexaacrylate [curing catalyst (photoinitiator)]
・2-hydroxy-2-methylpropiophenone [solvent]
・Methyl ethyl ketone [organopolysiloxane compound]
- Organopolysiloxane compounds 1 to 14 obtained in Synthesis Examples 1 to 14
［実施例１－１］
ジペンタエリスリトールヘキサアクリレート５．０ｇ、メチルエチルケトン５．０ｇ、２－ヒドロキシ－２－メチルプロピオフェノン０．２５ｇおよびオルガノポリシロキサン化合物１ ０．１０ｇを混合して均一溶解させ、撥水剤組成物を得た。
続いて、得られた撥水剤組成物を、厚さ１００μｍのポリエチレンテレフタラートフィルムの片面に、バーコーターを用いて乾燥膜厚が約５μｍとなるよう塗布した後、窒素雰囲気下、塗膜側に高圧水銀ＵＶランプ（１２０Ｗ／ｃｍ2）の紫外線を積算光量約６００ｍＪ／ｃｍ2の条件で照射して塗膜を硬化させ、撥水性硬化物品として活性エネルギー線硬化型樹脂でコーティングされた被覆層を有する試験片を作製した。
[Example 1-1]
5.0 g of dipentaerythritol hexaacrylate, 5.0 g of methyl ethyl ketone, 0.25 g of 2-hydroxy-2-methylpropiophenone and 0.10 g of organopolysiloxane compound were mixed and uniformly dissolved to form a water repellent composition. Obtained.
Subsequently, the obtained water repellent composition was applied to one side of a polyethylene terephthalate film having a thickness of 100 μm using a bar coater so that the dry film thickness was about 5 μm. is irradiated with ultraviolet light from a high-pressure mercury UV lamp (120 W/cm 2 ) at an accumulated light amount of about 600 mJ/cm 2 to cure the coating film, and a coating layer coated with an active energy ray-curable resin as a water-repellent cured product. A test piece having
［実施例１－２～１－１４］
オルガノポリシロキサン化合物１を、オルガノポリシロキサン化合物２～１４にそれぞれ変更した以外は、実施例１－１と同様にして撥水剤組成物およびその撥水性硬化物品を作製した。
[Examples 1-2 to 1-14]
A water repellent composition and a water repellent cured article thereof were prepared in the same manner as in Example 1-1, except that organopolysiloxane compound 1 was changed to organopolysiloxane compounds 2 to 14, respectively.
［比較例１－１］
オルガノポリシロキサン化合物１を用いなかった以外は、実施例１－１と同様にして硬化性組成物およびその硬化物品を作製した。
[Comparative Example 1-1]
A curable composition and a cured article thereof were prepared in the same manner as in Example 1-1, except that organopolysiloxane compound 1 was not used.
［比較例１－２］
オルガノポリシロキサン化合物１を、信越化学工業（株）製シリコーン系撥水・滑水性付与剤ＫＰ－９８３ ０．１０ｇに変更した以外は、実施例１－１と同様にして硬化性組成物およびその硬化物品を作製した。
[Comparative Example 1-2]
A curable composition and its composition were prepared in the same manner as in Example 1-1, except that organopolysiloxane compound 1 was changed to 0.10 g of Shin-Etsu Chemical Co., Ltd.'s silicone-based water-repellent/water-sliding agent KP-983. A cured article was made.
［比較例１－３］
オルガノポリシロキサン化合物１を、アクリル酸３，３，４，４，５，５，６，６，７，７，８，８，８－トリデカフルオロオクチル（以下、Ｃ６ＦＡという。）０．１０ｇに変更した以外は、実施例１－１と同様にして硬化性組成物およびその硬化物品を作製した。
[Comparative Example 1-3]
Organopolysiloxane compound 1 was added to 0.10 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate (hereinafter referred to as C6FA). A curable composition and a cured article thereof were produced in the same manner as in Example 1-1, except for the changes.
上記の手順で作製した各硬化物品について、以下に示す方法により評価を行った。
［撥水性］
協和界面科学（株）製ＤＭ７０１を用いて、水滴量２μＬの条件下における試験片のコーティング面の水の接触角を測定した。結果を下記表１，２に示す。
［滑水性］
協和界面科学（株）製ＤＭ７０１を用いて、水滴量２０μＬの条件下における試験片のコーティング面の水の滑落角（転落角）を測定した。結果を下記表１，２に示す。
［耐久性］
作製した各硬化物品を、２５±３℃の条件下でイオン交換水に５時間浸漬した後、水滴を拭き取り、上記と同様の手順で水の接触角および滑落角を測定した。結果を下記表１，２に示す。
Each cured article produced by the above procedure was evaluated by the method shown below.
[Water repellency]
Using DM701 manufactured by Kyowa Interface Science Co., Ltd., the contact angle of water on the coated surface of the test piece was measured under the condition of a water droplet amount of 2 μL. The results are shown in Tables 1 and 2 below.
[Slippery]
A DM701 manufactured by Kyowa Interface Science Co., Ltd. was used to measure the sliding angle of water on the coating surface of the test piece under the condition of a water droplet amount of 20 μL. The results are shown in Tables 1 and 2 below.
[durability]
Each cured article thus prepared was immersed in ion-exchanged water at 25±3° C. for 5 hours, then water droplets were wiped off, and the contact angle and sliding angle of water were measured in the same manner as above. The results are shown in Tables 1 and 2 below.
表１，２に示されるように、上記各実施例で用いたオルガノポリシロキサン化合物１～１４は、比較例１－２のような従来のシリコーン系撥水・滑水性付与剤および比較例１－３のような従来のフッ素系撥水性付与剤に比べ、特に活性エネルギー線硬化型樹脂に対して高い撥水性、滑水性を付与でき、かつその撥水性、滑水性の耐久性に優れることがわかる。 As shown in Tables 1 and 2, the organopolysiloxane compounds 1 to 14 used in each of the above examples were the conventional silicone-based water repellent/water slippery imparting agents such as Comparative Example 1-2 and Comparative Example 1- Compared to conventional fluorine-based water repellency imparting agents such as No. 3, it can impart high water repellency and water slippage, especially to active energy ray-curable resins, and the durability of water repellency and water slippage is excellent. .
Claims (7)
Ｒ1は、それぞれ独立して、非置換もしくは置換の炭素原子数１～２０のアルキレン基を表し、
Ｒ2およびＲ3は、それぞれ独立して、非置換もしくは置換の炭素原子数１～１０のアルキル基、または炭素原子数６～１０のアリール基を表し、
Ｙは、（メタ）アクリロイルオキシ基および（メタ）アクリルアミド基から選ばれる１種であり,
ｐは、１～１０、ｑは、１～１０、かつ、ｐ＋ｑは、前記Ｚの価数に対応して２～２０を満たす数を表すが、前記Ｚが単結合の場合、ｐおよびｑはともに１であり、
Ａ-は、含フッ素アニオンまたはハロゲン化物イオンであり、
Ｑ+は、下記式（３）および（４）のいずれかで表される１価のカチオン性基を表す。
each R 1 independently represents an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms,
R 2 and R 3 each independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms;
Y is one selected from a (meth)acryloyloxy group and a (meth)acrylamide group,
p is 1 to 10, q is 1 to 10, and p+q is a number that satisfies 2 to 20 corresponding to the valence of Z, but when Z is a single bond, p and q are are both 1,
A - is a fluorine-containing anion or a halide ion,
Q + represents a monovalent cationic group represented by either formula (3) or (4) below.
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| JP2012177050A (en) | 2011-02-28 | 2012-09-13 | Nippon Kasei Chem Co Ltd | Antistatic resin composition, and film or molded product having antistatic layer |
| JP2017075237A (en) | 2015-10-15 | 2017-04-20 | 信越化学工業株式会社 | Radiation curable silicone composition and method for producing antistatic peeling film using the same |
| JP2020026510A (en) | 2018-08-17 | 2020-02-20 | 信越化学工業株式会社 | Organopolysiloxane compound and method for producing the same, and antistatic agent and curable composition containing the same |
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| JP2012177050A (en) | 2011-02-28 | 2012-09-13 | Nippon Kasei Chem Co Ltd | Antistatic resin composition, and film or molded product having antistatic layer |
| JP2017075237A (en) | 2015-10-15 | 2017-04-20 | 信越化学工業株式会社 | Radiation curable silicone composition and method for producing antistatic peeling film using the same |
| JP2020026510A (en) | 2018-08-17 | 2020-02-20 | 信越化学工業株式会社 | Organopolysiloxane compound and method for producing the same, and antistatic agent and curable composition containing the same |
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