JPH0310649B2 - - Google Patents
Info
- Publication number
- JPH0310649B2 JPH0310649B2 JP57173968A JP17396882A JPH0310649B2 JP H0310649 B2 JPH0310649 B2 JP H0310649B2 JP 57173968 A JP57173968 A JP 57173968A JP 17396882 A JP17396882 A JP 17396882A JP H0310649 B2 JPH0310649 B2 JP H0310649B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- group
- copolymer
- formula
- acrylate resin
- 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.)
- Expired - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 claims description 41
- 239000004925 Acrylic resin Substances 0.000 claims description 31
- 239000003566 sealing material Substances 0.000 claims description 27
- -1 hydroxyethoxy group Chemical group 0.000 claims description 25
- 125000000524 functional group Chemical group 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 20
- 239000003505 polymerization initiator Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 10
- 125000005113 hydroxyalkoxy group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000012948 isocyanate Substances 0.000 description 15
- 239000000565 sealant Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229940035024 thioglycerol Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- DYSJMQABFPKAQM-UHFFFAOYSA-N 1-benzothiophene-2-carboxylic acid Chemical compound C1=CC=C2SC(C(=O)O)=CC2=C1 DYSJMQABFPKAQM-UHFFFAOYSA-N 0.000 description 1
- WNYHOOQHJMHHQW-UHFFFAOYSA-N 1-chloropyrene Chemical compound C1=C2C(Cl)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WNYHOOQHJMHHQW-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SASYRHXVHLPMQD-UHFFFAOYSA-N 2-(1,2-dicarboxyethylsulfanyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)SC(C(O)=O)CC(O)=O SASYRHXVHLPMQD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NGCJVMZXRCLPRQ-UHFFFAOYSA-N 2-methylidenepentanedinitrile Chemical compound N#CC(=C)CCC#N NGCJVMZXRCLPRQ-UHFFFAOYSA-N 0.000 description 1
- XBGNYAOLZNHWDC-UHFFFAOYSA-N 2-sulfanylnaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C(S)C=CC2=C1 XBGNYAOLZNHWDC-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- DOFIAZGYBIBEGI-UHFFFAOYSA-N 3-sulfanylphenol Chemical compound OC1=CC=CC(S)=C1 DOFIAZGYBIBEGI-UHFFFAOYSA-N 0.000 description 1
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QPHPUQJVKQXISS-UHFFFAOYSA-N 4-oxo-4-sulfanylbutanoic acid Chemical compound OC(=O)CCC(S)=O QPHPUQJVKQXISS-UHFFFAOYSA-N 0.000 description 1
- NEJMTSWXTZREOC-UHFFFAOYSA-N 4-sulfanylbutan-1-ol Chemical compound OCCCCS NEJMTSWXTZREOC-UHFFFAOYSA-N 0.000 description 1
- XNQWGXXYMVCZKR-UHFFFAOYSA-N 5-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(O)CCCCOC(=O)C(C)=C XNQWGXXYMVCZKR-UHFFFAOYSA-N 0.000 description 1
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- VHJLVAABSRFDPM-ZXZARUISSA-N dithioerythritol Chemical compound SC[C@H](O)[C@H](O)CS VHJLVAABSRFDPM-ZXZARUISSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 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 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はシーリング材用（メタ）アクリレート
系樹脂及びその製法に関する。
構造物等の目地を充填するシーリング剤は、建
材等の構造物の気候の変化に応じた目地の動きに
追従できる高度の弾性を有することが要求され、
またこれ等の構造物に対する接着性に優れている
ことも同時に要求される。このようなシーリング
材は、上記のような諸特性を有すると共にタツク
フリー性が良好であり、高温時スランプが生じ難
く且つ耐候性に優れていることも重要である。
従来、この様なシーリング材としては、（メタ）
アクリレート系樹脂と多官能性イソシアナートよ
りなる二成分系のシーリング材が広く使用されて
いる。このようなシーリング材用（メタ）アクリ
レート系樹脂については従来いろいろな改良の試
みがなされており、例えば特開昭53−92868号で
はポリマー末端に１ケのOH基及び／又はCOOH
基、ポリマーの任意位置に１ケのOH基及び／又
はCOOH基を有する（メタ）アクリレート系樹
脂を用いることが提案されている。また特開昭55
−18456号では、ポリマー中に1.7〜10ケのOH基
及び／又はCOOH基を有する（メタ）アクリレ
ート系樹脂を用いることが提案されている。之等
の、（メタ）アクリレート系樹脂を用いたシーリ
ング材は確かに良好な弾力性及び接着性を示す
が、反面高温でスランプ（施工時の垂れ下り）を
生じやすく耐候性にも劣るなどの欠点を有するこ
とが判つた。本発明者等は、これ等の欠点を改良
すべく鋭意研究を重ねた結果、物性面でセメント
モルタルやアルミサツシへの接着性に優れ、しか
も高弾性で良好な耐候性を有し、高温時スランプ
が無く、揮発成分がない、シーリング材用（メ
タ）アクリレート系樹脂を完成するに至つた。以
下に本発明のシーリング材用の（メタ）アクリル
系樹脂及びその製法の詳細について説明する。
本発明のシーリング材用の（メタ）アクリル系
樹脂は、式
こゝでR1はＨを表わし、R2は炭素原子数４〜
８のアルキル基を表わす、
の構成単位及び式
ここでR3はＨ又はCH3を表わし、R4はOH又は
ヒドロキシアルコキシ基を表わす、
の構成単位を主要な構成単位とする共重合体であ
つて、官能基を共重合体の末端位置に0.5〜0.9
個／分子、末端以外の任意位置に1.4〜4.5個／分
子、合計2.3〜5.0個／分子有することを特徴とす
るシーリング材用の（メタ）アクリレート系樹脂
である。
本発明のシーリング材用の（メタ）アクリル系
樹脂における式（）及び式（）で示される主
要な構成単位の夫々の構成割合は、式（）の構
成単位が式（）の構成単位と式（）の構成単
位の合計に対して80〜98重量％、式（）の構成
単位が式（）の構成単位と式（）の構成単位
の合計に対して20〜２重量％、好ましくは式
（）の構成単位が85〜97重量％、式（）の構
成単位が15〜３重量％である。式（）の構成単
位が98重量％を超えるとタツクフリー性及び耐汚
染性が低下する傾向があり、また80重量％未満で
は伸びが小さくなり、押し出し性も悪くなる傾向
を示す。
本明細書において本発明の（メタ）アクリル系
樹脂の主要な構成単位の「主要な」という言葉
は、式（）及び式（）の構成単位の合計重量
が、（メタ）アクリル系樹脂共重合体当り80重量
％以上、好ましくは90重量％以上を占めているこ
とを表わす意味で用いるものである。
本発明のシーリング材用（メタ）アクリル系樹
脂の主要な構成単位の一つである式（）
の構成単位では、R1はＨを表わし、R2は炭素数
４〜８のアルキル基、例えばｎ−ブチル、sec−
ブチル、ter−ブチル、ｎ−ペンチル、iso−ペン
チル、ｎ−ヘキシル、iso−ヘキシル、ｎ−ヘプ
チル、iso−ヘプチル、ｎ−オクチル、２−エチ
ル−ヘキシル基等を表わすが、中でもｎ−ブチル
基が特に好ましい。また、式（）の構成単位は
必要に応じ２種以上併用されることである。
一方、主要な構成単位の一つである式（）
の構成単位では、R3はＨ又はCH3を表わすが、
好ましくはＨを表わし、R4はOH又はヒドロキシ
アルコキシ基、最も好ましくはヒドロキシアルコ
キシ基を表わす。このようなヒドロキシアルコキ
シ基の例としては、２−ヒドロキシエトキシ、２
−ヒドロキシ−ｎプロポキシ、２−ヒドロキシ
isoプロポキシ、２−ヒドロキシ−ｎブトオキシ、
５−ヒドロキシヘキシオキシ、８−ヒドロキシｎ
オクトキシ基等があるが、中でもアルキル部分の
炭素数が２〜３のヒドロキシアルコキシ基、例え
ば２−ヒドロキシエトキシ、２−ヒドロキシ−ｎ
プロポキシ、２−ヒドロキシ−isoプロポキシ基
が好適であり、特に２−ヒドロキシ−エトキシ基
が好ましい。また、式（）の構成単位は必要に
応じ２種以上併用されることもある。
本発明のシーリング材用の（メタ）アクリレー
ト系樹脂は、上記式（）の構成単位及び式
（）の構成単位の外に、重合開始剤や連鎖移動
剤に由来する構成単位を含むことは勿論、共重合
可能なコーモノマーに由来する式（）及び式
（）以外の第三の構成単位を随意含むものであ
る。このような第三の構成単位としては、式
（）以外の（メタ）アクリレート類、ビニルエ
ステル類、ビニルエーテル類、ビニルピリジン、
アクリロニトリル、メタアクリロニトリル、メチ
レングルタルニトリル、Ｎ，Ｎ−ジメチルアミノ
エチルアクリレート、ブタジエン、スチレン、ク
ロロピレン等のコモノマーの共重合に由来する構
成単位があり、シーリング材の使用目的に応じて
適宜配合量が決定される。
本発明のシーリング材用（メタ）アクリレート
系樹脂は、前記式（）及び式（）の単量体を
主要成分とする共重合体であつて、数平均分子量
（Ｍ）が1000〜10000であることが好ましい。共
重合体の数平均分子量が1000未満と小さ過ぎでは
タツク性が出てゴミが付着し汚れ易くなり、また
コンクリート等基地への移行が起るので好ましく
ない。一方10000を超えて大きすぎると樹脂の柔
軟性が低下し弾性も小さく、流動性が失われ作業
性が悪くなるので好ましくない。好ましくは1000
〜8000、より好ましくは1500〜6000の数平均分子
量の共重合体が用いられる。
一方、本願発明のシーリング材用（メタ）アク
リレート系樹脂は、官能基を共重合体の末端位置
に0.5〜0.9個／分子、好ましくは0.6〜0.9個／分
子、最も好ましくは0.7〜0.8個／分子を有し、末
端以外の任意位置に1.4〜4.5個／分子、好ましく
は1.4〜3.5個／分子、最も好ましくは1.6〜2.5
個／分子を有し、官能基の合計数が共重合体当り
2.3〜5.0個／分子、好ましくは2.3〜4.0個／分子、
最も好ましくは2.4〜3.0個／分子を有するもので
ある。
本発明で「官能基」とは、本発明のシーリング
材用（メタ）アクリレート系樹脂を多官能性イソ
シアナート化合物と配合してシーリング材を調製
する際、多官能性イソシアナート化合物のイソシ
アナート基NCOと反応する基を表わす意味で用
いられるものである。この様な官能基の例として
は、OH基、COOH基、NH2基、等があるが、
OH基及びCOOH基が好ましく、OH基が最も好
ましい。一方、本発明のシーリング材用（メタ）
アクリレート系樹脂に配合される多官能性イソシ
アナート化合物とは、１分子中に２又は２以上の
イソシアネート基を有する化合物をいうもので、
そのような多官能性イソシアネート化合物として
は、たとえばトリレン２，４−ジイソシアネー
ト、トリレン２，６−ジイソシアネート、ジフエ
ニルメタン−４，４−ジイソシアネート、ナフチ
レン１，５−ジイソシアネート、ヘキサメチレン
ジイソシアネート、イソホロンジイソシアネー
ト、トリレンジイソシアネート、メタキシレンジ
イソシアネート、１モルのトリメチロールプロパ
ンと３モルのトリレンジイソシアネートの反応生
成物もしくは１モルのポリエチレングリコール、
１モルのポリプロピレングリコールや１モルのポ
リオキシテトラメチレングリコールと２モルのト
リレンジイソシアネートの反応生成物の如きポリ
オールと各種イソシアネートとの反応生成物、三
量化もしくは多量化イソシアネート、高温でイソ
シアネート基を遊離するたとえばポリイソシアネ
ートとフエノールの反応生成物などが挙げられ
る。
好適な多官能性イソシアナート化合物として
は、ポリトリレンジイソシアネート、ポリヘキサ
メチレンジイソシアネート、ポリキシレンジイソ
シアネート、ポリジフエニルメタンジイソシアネ
ート、ポリオールと各種イソシアネートよりなる
イソシアネートプレポリマー等を挙げることがで
きる。
本発明のシーリング材組成物における（メタ）
アクリレート系樹脂と多官能性イソシアネート化
合物の配合比は、樹脂の官能基１当量当り多官能
性イソシアネート化合物のNCO基が0.7〜1.5当
量、好ましくは0.8〜1.2当量である。0.7当量未満
であるとタツクフリー性が得られず接着力、高弾
性が低下し、耐薬品性も低下するので好ましくな
い。一方1.5当量を超えると高弾性が失なわれ、
耐候性も低下し脆くなるので好ましくない。
本発明のシーリング材用（メタ）アクリレート
系樹脂共重合体の末端位置の官能基が0.9個／分
子を超えて多すぎては、ゴム状の弾性が失われた
柔軟性のない、かたいシーリング材になるので好
ましくなく、また0.5個／分子未満と少なすぎて
は、ベタ付きがあり、ゴム状の弾性がえられない
ので好ましくない。一方、末端位置の官能基及び
末端位置以外の任意位置の官能基の合計が5.0
個／分子を超えて多すぎては、高弾性が失われ、
脆くなり、目地の動きに追従できないので好まし
くなく、また2.3個／分子未満と少なすぎては、
接着力が劣り、且つ、タツクフリーとならないの
で好ましくない。
本発明の（メタ）アクリル系重合体のガラス転
移点（以下「Tg」という）は、好ましくは−10
℃以下、より好ましくは−20℃以下、更に好まし
くは−40℃以下であり、Tgが−10℃を超えて高
すぎては、高ゴム弾性が失なわれるので好ましく
ない。本明細書でいうTgは以下の方法によつて
決定されるものをいう。
又、本発明のガラス転移点（以下、「Tg」と略
することあり）とは、L.E.ニールセル著、小野木
宜治訳「高分子の力学的性質」11頁〜35頁に記載
されているような一般の高分子で測定されるTg
であり、共重合体の場合は同書26〜27頁に記載さ
れている計算Tgである。
即ち共重合体のTgは次式によつて計算された
ものである。
１／Tg＝W1／Tg1＋W2／Tg2＋…＋Wn／Tgn
（但しW1＋W2＋…＋Wn＝１）
ここでTgとは共重合体ガラス転移温度であり
絶対温度に換算し計算する。Tg1、Tg2…および
Tgnは成分１、成分２…、および成分ｎのそれぞ
れ純粋な単独重合体１、２…およびｎのガラス転
移温度であり絶対温度に換算し計算する。W1、
W2…およびWnはそれぞれの成分の重量分率で
ある。
本発明のシーリング材用（メタ）アクリレート
系樹脂共重合体の製法は以下の通りである。
主たる原料単量体は、前記式（）及び式
（）の構成単位に対応する不飽和単量体であり、
The present invention relates to a (meth)acrylate resin for sealing materials and a method for producing the same. Sealants that fill the joints of structures, etc. are required to have a high degree of elasticity that can follow the movement of the joints in response to changes in the climate of the building materials and other structures.
At the same time, it is also required to have excellent adhesion to these structures. It is important that such a sealing material has the above-mentioned properties, has good tack-free properties, is resistant to slump at high temperatures, and has excellent weather resistance. Conventionally, such sealing materials include (meta)
Two-component sealants consisting of an acrylate resin and a polyfunctional isocyanate are widely used. Various attempts have been made to improve such (meth)acrylate resins for sealing materials. For example, in Japanese Patent Application Laid-open No. 53-92868, one OH group and/or COOH group was added to the polymer end.
It has been proposed to use a (meth)acrylate resin having one OH group and/or COOH group at any position of the polymer. Also, JP-A-55
No.-18456 proposes the use of (meth)acrylate resins having 1.7 to 10 OH groups and/or COOH groups in the polymer. Sealants using (meth)acrylate resins such as these do show good elasticity and adhesion, but on the other hand, they tend to slump (sag during construction) at high temperatures and have poor weather resistance. It was found that it had some drawbacks. As a result of intensive research aimed at improving these drawbacks, the inventors of the present invention have found that in terms of physical properties, it has excellent adhesion to cement mortar and aluminum sash, has high elasticity and good weather resistance, and has slump at high temperatures. We have completed a (meth)acrylate resin for sealing materials that is free of volatile components. The details of the (meth)acrylic resin for the sealing material of the present invention and the manufacturing method thereof will be explained below. The (meth)acrylic resin for the sealant of the present invention has the formula Here, R 1 represents H, and R 2 has 4 to 4 carbon atoms.
The structural unit and formula representing the alkyl group of 8 Here, R 3 represents H or CH 3 and R 4 represents OH or a hydroxyalkoxy group. It is a copolymer having the following structural units as main structural units, and the functional group is placed at the terminal position of the copolymer. 0.5~0.9
This is a (meth)acrylate resin for sealing materials, characterized by having 1.4 to 4.5 molecules/molecule at arbitrary positions other than the ends, and a total of 2.3 to 5.0 molecules/molecule. In the (meth)acrylic resin for the sealing material of the present invention, the constituent units of the formula () and the formula () are the constituent units of the formula () and the constituent units of the formula (). 80 to 98% by weight based on the total of the structural units of formula (), 20 to 2% by weight of the total of the structural units of formula () and the structural units of formula (), preferably formula The structural unit of formula () is 85 to 97% by weight, and the structural unit of formula () is 15 to 3% by weight. When the structural unit of formula () exceeds 98% by weight, tack-free properties and stain resistance tend to decrease, and when it is less than 80% by weight, elongation tends to decrease and extrudability tends to deteriorate. In this specification, the word "main" in the main constituent units of the (meth)acrylic resin of the present invention means that the total weight of the formula () and the constituent units of the formula () is the (meth)acrylic resin copolymer. This term is used to mean that the amount is 80% or more, preferably 90% or more by weight per body weight. Formula () is one of the main constituent units of the (meth)acrylic resin for sealing materials of the present invention. In the structural unit, R 1 represents H and R 2 represents an alkyl group having 4 to 8 carbon atoms, such as n-butyl, sec-
It represents butyl, ter-butyl, n-pentyl, iso-pentyl, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethyl-hexyl group, among others, n-butyl group. is particularly preferred. Moreover, two or more types of structural units of formula () may be used in combination as necessary. On the other hand, one of the main structural units is the formula () In the structural unit, R 3 represents H or CH 3 ,
Preferably it represents H and R 4 represents OH or a hydroxyalkoxy group, most preferably a hydroxyalkoxy group. Examples of such hydroxyalkoxy groups include 2-hydroxyethoxy, 2
-Hydroxy-n-propoxy, 2-hydroxy
isopropoxy, 2-hydroxy-n-butoxy,
5-hydroxyhexoxy, 8-hydroxyn
There are octoxy groups, among others, hydroxyalkoxy groups whose alkyl moiety has 2 to 3 carbon atoms, such as 2-hydroxyethoxy, 2-hydroxy-n
Propoxy, 2-hydroxy-isopropoxy groups are preferred, especially 2-hydroxy-ethoxy groups. Moreover, two or more types of structural units of formula () may be used in combination as necessary. The (meth)acrylate resin for the sealing material of the present invention naturally contains structural units derived from a polymerization initiator and a chain transfer agent in addition to the structural units of the above formula () and the structural units of the formula (). , which optionally contains formula () derived from a copolymerizable comonomer and a third structural unit other than formula (). Such third structural units include (meth)acrylates other than formula (), vinyl esters, vinyl ethers, vinylpyridine,
There are structural units derived from copolymerization of comonomers such as acrylonitrile, methacrylonitrile, methylene glutaronitrile, N,N-dimethylaminoethyl acrylate, butadiene, styrene, and chloropyrene, and the blending amount is determined appropriately depending on the intended use of the sealant. be done. The (meth)acrylate resin for sealing materials of the present invention is a copolymer containing the monomers of the above formulas () and () as main components, and has a number average molecular weight (M) of 1000 to 10000. It is preferable. If the number average molecular weight of the copolymer is too small, such as less than 1000, it is undesirable because it becomes tough and easily attracts dirt and stains, and also causes migration to a base such as concrete. On the other hand, if it is too large, exceeding 10,000, the flexibility of the resin decreases, the elasticity decreases, fluidity is lost, and workability deteriorates, which is not preferable. preferably 1000
A copolymer having a number average molecular weight of 8000 to 8000, more preferably 1500 to 6000 is used. On the other hand, the (meth)acrylate resin for sealing materials of the present invention has functional groups at the end positions of the copolymer at 0.5 to 0.9/molecule, preferably 0.6 to 0.9/molecule, and most preferably 0.7 to 0.8/molecule. 1.4 to 4.5 molecules/molecule, preferably 1.4 to 3.5 molecules/molecule, most preferably 1.6 to 2.5 molecules at any position other than the terminal.
per molecule, and the total number of functional groups per copolymer.
2.3 to 5.0 pieces/molecule, preferably 2.3 to 4.0 pieces/molecule,
Most preferably it has 2.4 to 3.0 molecules/molecule. In the present invention, "functional group" refers to the isocyanate group of the polyfunctional isocyanate compound when preparing the sealant by blending the (meth)acrylate resin for sealing material of the present invention with a polyfunctional isocyanate compound. It is used to represent a group that reacts with NCO. Examples of such functional groups include OH group, COOH group, NH2 group, etc.
OH and COOH groups are preferred, and OH group is most preferred. On the other hand, for the sealing material of the present invention (meta)
The polyfunctional isocyanate compound blended into the acrylate resin refers to a compound having two or more isocyanate groups in one molecule.
Examples of such polyfunctional isocyanate compounds include tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane-4,4-diisocyanate, naphthylene 1,5-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate. Isocyanate, metaxylene diisocyanate, reaction product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate or 1 mol of polyethylene glycol,
Reaction products of polyols and various isocyanates, such as reaction products of 1 mol of polypropylene glycol or 1 mol of polyoxytetramethylene glycol and 2 mol of tolylene diisocyanate, trimerized or multimerized isocyanates, liberating isocyanate groups at high temperatures. Examples include reaction products of polyisocyanates and phenols. Suitable polyfunctional isocyanate compounds include polytolylene diisocyanate, polyhexamethylene diisocyanate, polyxylene diisocyanate, polydiphenylmethane diisocyanate, and isocyanate prepolymers made of polyol and various isocyanates. (Meta) in the sealant composition of the present invention
The blending ratio of the acrylate resin and the polyfunctional isocyanate compound is such that the NCO group of the polyfunctional isocyanate compound is 0.7 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, per equivalent of the functional group of the resin. If it is less than 0.7 equivalent, tack-free properties will not be obtained, adhesive strength and high elasticity will decrease, and chemical resistance will also decrease, which is not preferable. On the other hand, if the amount exceeds 1.5 equivalents, high elasticity will be lost,
It is not preferable because it also reduces weather resistance and becomes brittle. If the number of functional groups at the terminal positions of the (meth)acrylate resin copolymer for sealing materials of the present invention is too large, exceeding 0.9 per molecule, rubber-like elasticity is lost, resulting in a hard seal with no flexibility. If the number is too small (less than 0.5 pieces/molecule), it becomes sticky and rubber-like elasticity is not obtained, which is not preferable. On the other hand, the sum of the functional groups at the terminal positions and the functional groups at arbitrary positions other than the terminal positions is 5.0.
If the amount exceeds 100%/molecule, high elasticity will be lost,
It is undesirable because it becomes brittle and cannot follow the movement of the joint, and if it is too small (less than 2.3 pieces/molecule),
This is not preferable because it has poor adhesive strength and is not tack-free. The glass transition point (hereinafter referred to as "Tg") of the (meth)acrylic polymer of the present invention is preferably −10
C or lower, more preferably -20 C or lower, still more preferably -40 C or lower; if Tg is too high, exceeding -10 C, high rubber elasticity is lost, which is not preferred. Tg as used herein refers to one determined by the following method. In addition, the glass transition point (hereinafter sometimes abbreviated as "Tg") of the present invention is defined as the glass transition point (hereinafter sometimes abbreviated as "Tg") as described in "Mechanical Properties of Polymers" by LE Niersel, translated by Yoshiharu Onogi, pages 11 to 35. Tg measured with general polymers
In the case of a copolymer, it is the calculated Tg described on pages 26-27 of the same book. That is, the Tg of the copolymer was calculated using the following formula. 1/Tg=W1/Tg1+W2/Tg2+...+Wn/Tgn (however, W1+W2+...+Wn=1) Here, Tg is the copolymer glass transition temperature, and is calculated by converting it into an absolute temperature. Tg1, Tg2…and
Tgn is the glass transition temperature of pure homopolymers 1, 2... and n of component 1, component 2... and component n, respectively, and is calculated by converting it into an absolute temperature. W1,
W2... and Wn are the weight fractions of the respective components. The method for producing the (meth)acrylate resin copolymer for sealing materials of the present invention is as follows. The main raw material monomer is an unsaturated monomer corresponding to the structural unit of the formula () and formula (),
【式】としては、例えばｎ−ブチル
（メタ）アクリレート、sec−ブチル（メタ）アク
リレート、ter−ブチル（メタ）アクリレート等
のブチル（メタ）アクリレート、ペンチル（メ
タ）アクリレート、ヘキシル（メタ）アクリレー
ト、ヘプチル（メタ）アクリレート、２−エチル
ヘキシル（メタ）アクリレート、ｎ−オクチル
（メタ）アクリレート等のオクチル（メタ）アク
リレートがあり、また[Formula] is, for example, butyl (meth)acrylate such as n-butyl (meth)acrylate, sec-butyl (meth)acrylate, ter-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, There are octyl (meth)acrylates such as heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, and
【式】として
は、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−ヒドロキシブチルアクリレート、５−ヒ
ドロキシヘキシルメタアクリレート、８−ヒドロ
キシオクチルアクリレート、アクリル酸、メタア
クリル酸、メタアクリル酸アミド、アクリル酸ア
ミド等がある。また前記式（）及び式（）の
構成単位以外の構成単位に対応する不飽和単量体
の例は、既に（メタ）アクリレート系樹脂の第三
の構成単位についての説明の所で例示した通りで
ある。
本発明の（メタ）アクリル系重合体の重合に使
用される重合開始剤としては、一般に用いられて
いる重合開始剤がいずれも使用でき、たとえばベ
ンゾイルパーオキシド、ラウロイルパーオキシ
ド、メチルエチルケトンパーオキシド、クメンハ
イドロパーオキシド、アゾビスイソブチロニトリ
ル、ジ−ｎ−プロピルパオキシジカーボネート、
ｔ−ブチルハイドロパオキサイド、iso−ブチル
パオキサイド、１−ブチル−２−エチルヘキサノ
エート、などが挙げられ、通常は不飽和単量体
100重量部に対して0.05〜10重量部の割合で使用
すればよいが、この重合開始剤によつて共重合体
の分子量を低い値に調節したいときにはこれ以上
の量を使用することができる。
しかし、本発明の（メタ）アクリル系共重合体
の重合に用いられる重合開始剤としては、OH基
を有するメルカプタン誘導体やCOOH基を有す
るメルカプト誘導体が特に好適に用いられる。
この様なメルカプタン誘導体としては、例えば
ｏ−メルカプトフエノール、ｍ−メルカプトフエ
ノール、チオグリセロール、１−チオグリセリ
ン、１，２−チオグリセリン、２−メルカプトエ
タノール、３−メルカプトプロパノール、４−メ
ルカプトブタノール、チオジエチレングリコー
ル、ジチオエリトリトール、２，３−ジメルカプ
ト−１−プロパノール、メルカプトナフトール等
のOH基を有するものや、またチオグリコール
酸、チオコハク酸、チオサリチル酸、チオフマル
酸、チオオキサル酸、ジメルカプトコハク酸、チ
オジグリコール酸、ジチオジグリコール酸、メル
カプトプロピオン酸、３−メチルカプトプロピオ
ン酸、チオフエンジカルボン酸、チオナフテン−
２−カルボン酸、チオフエンテトラカルボン酸、
チオジプロピオン酸等のCOOH基を有するもの
があるが、OH基を有するものが特に好ましく、
その中でも２−メルカプトエタノール、メルカプ
トフエノール、メルカプトブタノール、メルカプ
トプロパノール、１，２ジチオグリセリン、チオ
グリセロールなどが特に好ましい。之等メルカプ
タン誘導体を重合開始剤として用いる場合は、不
飽和単量体100重量部に対して1.0〜15重量部の割
合で使用される。
また、重合開始剤としては、一般にラジカル重
合反応において用いられる重合開始剤をメルカプ
タン誘導体とともに適宜併用することができる。
このような重合開始剤としては、例えばベンゾイ
ルパーオキシド、ラウロイルパーオキシド、メチ
ルエチルケトンパーオキシド、クメンハイドロパ
ーオキシド、アゾビス−ｉ−ブチロニトリル、ジ
−ｎ−プロピルパーオキシジカーボネート、ｔ−
ブチルハイドロパーオキシド、ｉ−ブチルパーオ
キシド、１−ブチル−２−エチルヘキサノエート
等が挙げられ、通常は不飽和単量体100重量部に
対して0.05〜10重量部程度の割合で使用される
が、要すればこれ以上の量を使用することもでき
る。
メルカプタン誘導体を重合開始剤として好適に
用いられる理由は、使用するメルカプタンが開始
および付加反応で
を経てポリマー鎖の末端の一部になり、また停止
反応で[Formula] is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl acrylate, 5-hydroxyhexyl methacrylate, 8-hydroxyoctyl acrylate, acrylic acid, methacrylic acid, Examples include methacrylic acid amide and acrylamide. In addition, examples of unsaturated monomers corresponding to structural units other than the structural units of formula () and formula () are as already exemplified in the explanation of the third structural unit of the (meth)acrylate resin. It is. As the polymerization initiator used in the polymerization of the (meth)acrylic polymer of the present invention, any commonly used polymerization initiators can be used, such as benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, and cumene. Hydroperoxide, azobisisobutyronitrile, di-n-propylpaoxydicarbonate,
Examples include t-butyl hydroperoxide, iso-butyl peroxide, 1-butyl-2-ethylhexanoate, and are usually unsaturated monomers.
It may be used in an amount of 0.05 to 10 parts by weight per 100 parts by weight, but if it is desired to control the molecular weight of the copolymer to a low value with this polymerization initiator, a larger amount can be used. However, as the polymerization initiator used in the polymerization of the (meth)acrylic copolymer of the present invention, mercaptan derivatives having an OH group and mercapto derivatives having a COOH group are particularly preferably used. Examples of such mercaptan derivatives include o-mercaptophenol, m-mercaptophenol, thioglycerol, 1-thioglycerin, 1,2-thioglycerin, 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, and thioglycerol. Those with an OH group such as diethylene glycol, dithioerythritol, 2,3-dimercapto-1-propanol, and mercaptonaphthol, as well as thioglycolic acid, thiosuccinic acid, thiosalicylic acid, thiofumaric acid, thioxalic acid, dimercaptosuccinic acid, and thiodisuccinic acid. Glycolic acid, dithiodiglycolic acid, mercaptopropionic acid, 3-methylcaptopropionic acid, thiophenedicarboxylic acid, thionaphthene-
2-carboxylic acid, thiophenetetracarboxylic acid,
Some have a COOH group such as thiodipropionic acid, but those having an OH group are particularly preferred.
Among these, 2-mercaptoethanol, mercaptophenol, mercaptobutanol, mercaptopropanol, 1,2 dithioglycerin, thioglycerol and the like are particularly preferred. When such mercaptan derivatives are used as polymerization initiators, they are used in an amount of 1.0 to 15 parts by weight per 100 parts by weight of the unsaturated monomer. Furthermore, as the polymerization initiator, a polymerization initiator generally used in radical polymerization reactions can be used in combination with the mercaptan derivative as appropriate.
Examples of such polymerization initiators include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azobis-i-butyronitrile, di-n-propyl peroxydicarbonate, t-
Examples include butyl hydroperoxide, i-butyl peroxide, 1-butyl-2-ethylhexanoate, etc., and are usually used in a proportion of about 0.05 to 10 parts by weight per 100 parts by weight of the unsaturated monomer. However, larger amounts can be used if necessary. The reason why mercaptan derivatives are preferably used as polymerization initiators is that the mercaptans used are capable of initiation and addition reactions. It becomes part of the end of the polymer chain through a termination reaction.
【式】を
経て、ポリマー鎖の末端の一部になる。それゆえ
にOH基含有メルカプタン、例えば２−メルカプ
トエタノール、COOH基含有メルカプタン、例
えばチオグリコール酸を用いることによりこれら
の官能基をポリマー鎖の末端に導入できる。この
ようにしてメルカプタン誘導体を重合開始剤とし
て用いて製造された（メタ）アクリレート系樹脂
と多官能性イソシアナートを含有してなるシーリ
ング材は、理由はよく判らないが、耐候性（ゴム
弾性、耐亀裂性）及び変色性（黄変）の点等にお
いて極めて優れていることが判つた。
一方、連鎖移動剤としては、重合の途中で重合
連鎖を移動しうる能力の大きな化合物であれば、
例えば四塩化炭素、四臭化炭素、三塩化酢酸等も
用いられ、また上記重合開始剤として用いられる
メルカプタン誘導体が連鎖移動剤としても働く。
連鎖移動剤は、不飽和単量体100重量部当り通常
0.1〜15重量部の割合で用いられる。
本発明の（メタ）アクリレート系樹脂共重合体
を製造するため前記単量体を共重合させるには一
般に知られている任意の重合方法、例えば高圧
下、加圧下で塊状重合、懸濁重合、乳化重合、溶
液重合法等、当該分野で行われている通常のラジ
カル重合法より重合するが、分子量が比較的小さ
いものが得られやすい点から溶液重合、塊状重合
が好ましい。
重合に際し単量体混合物の仕込み方法は重合当
初から全量を一括して仕込んでもよいし、はじめ
に一部だけを仕込み残りの混合物を重合反応の進
行とともに滴下法で徐々に仕込んでもよい。後者
の方法はとくに重合発熱が問題になりやすいもの
に対して有利であり、温度、時間などの重合条件
はゲル状共重合体が生じないように或いは未反応
の単量体ができるだけ残存しないように調節す
る。未反応の単量体の残存は共重合体の溶剤の如
き作用を行なうからシーラントとして施工時の臭
気、施工後の目やせなどを起こし好ましくない。
重合開始剤は、前記単量体と連鎖移動剤との混
合物が仕込まれた内浴が所定の重合温度になり、
しかも重合槽内の空気を窒素などの不活性気体で
充分に置換してから添加するとよい。
溶剤を使用するならば、たとえばｎ−ヘプタ
ン、ｎ−ヘキサン、トルエン、キシレン、エチル
セロソルブ、ブチルセロソルブ、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、イ
ソプロパノールなどの溶剤を使用すればよい。
重合温度は、単量体および重合開始剤の種類に
より異なるが、一般に約20〜120℃の範囲が好適
である。もし重合温度が高くなりすぎて発熱が激
しすぎるときは水冷などの手段により適当に調節
する。重合時間は主として上記重合温度および単
量体の種類に依存する。
本発明の（メタ）アクリレート系樹脂を用いた
シーリング材組成物は、（メタ）アクリレート系
樹脂及び多官能性イソシアネート化合物の外、必
要に応じて触媒、充填剤が添加される。このよう
な触媒としては、たとえばジブチルチンジラウレ
ート、モノブチルチンオキシド、ジオクチルチン
ジラウレート、スタナスオクトエートの如き金属
化合物もしくはトリエチレンジアミン、トリエチ
レンテトラミン、ジメチルベンジルアミンなどの
アミン類などが使用できる。添加量は低分子量共
重合体100重量部に対し通常0.01〜５重量部でよ
い。
充填剤は、弾性シーリング材の強度を向上させ
るとともにシーリング材の粘度を適度なものとし
て作業性を向上させるためのものであつて、たと
えば炭酸カルシウム、シリカ粉、タルク、ガラス
粉、マグネシア、粘土粉、酸化チタンなどが好ま
しく用いられる。その添加割合は（メタ）アクリ
レート系共重合体100重量部に対して30〜200重量
部とするのがよく、これよりも少ない量では所望
の強度を有するものが得にくく、またあまり多す
ぎては硬化物の伸び率が低くなつて好ましい弾性
特性を得ることが難しい。
弾性シーリング材は上述した成分以外に一般の
シーリング材に使用されるような可塑剤、顔料、
老化防止剤、防カビ剤、酸化防止剤、紫外線吸収
剤、オゾン劣化防止剤、粘着付与剤、チキソトロ
ープ剤などを添加することもできる。
以下に実施例により、本発明の詳細を更に具体
的に説明する。なお、本明細書で部又は％等の数
量表示は、特にことわらない限り重量による表示
である。
なお、共重合体の特性値は下記の方法によつて
測定した。
(1) 数平均分子量（Ｍ）測定
GPC（Gel.permeation Chromatography）
で測定した標準分子量ポリスチレン相当値での
数平均分子量。
(2) 官能基数の算出法
イ 官能基の合計数（個／分子）の算出
JIS・Ｋ−0070−1966に準じて水酸基価及
び酸価を測定し、官能基の合計数（個／分
子）を算出した。
ロ 共重合体の末端位置の官能基数（個／分
子）の算出
共重合体中の硫黄含量（％）を実験化学溝
座15巻分析化学下p417〜418「硫黄元素の測
定法」によつて測定した。重合開始剤として
の前記メルカプタン誘導体は１分子中に１個
のＳ原子を有し、且つメルカプタン誘導体に
由来する共重合体の末端位置の構成単位が１
ケのOH基又はCOOH基を有するものとし
て、硫黄含量（％）より共重合体の末端位置
の官能基数を算出した。
ハ 共重合の末端位置以外の任意位置の官能基
数（個／分子）の算出
上記官能基の合計数より上記末端位置の官
能基数を差し引いて求めた。
以下、用いた単量体は下記略号で示した。
BA ：アクリル酸ブチル
2EHA ：アクリル酸２−エチルヘキシル
AN ：アクリロニトリル
2HEA ：アクリル酸２ヒドロキシエチル
2HEMA
：メタクリル酸２−ヒドロキシエチル
2MEt ：２−メルカプトエタノール
TGA ：チオグリコール酸
実施例 １
（シーリング材用樹脂Ａ−１）
滴下装置、撹拌機、還流冷却、温度計を備えた
加圧反応装置にBA190部、2HEA10部、を加え撹
拌しながら90℃に昇温した。昇温したところで
4.0部の２−メルカプトエタノールを逐次添加し
た。約1/3添加したところで急に発熱し120〜135
℃まで上昇したが、そのまゝ滴下を続け約60分間
で滴下を終了した。そのまま反応を続け２時間後
に85〜90℃に制御されたところで、パーブチル
PV（日本油脂製）0.3部を30分毎1/5ずつ５回に分
割添加し、５回目添加後２時間反応を続行した。
不揮発分99.3％の共重合体を得た。
これの水洗を数回くり返した後、減圧下で乾燥
し不揮発分99.7％の低分子共重体「Ａ−１」を得
た。この低分子量共重合体の粘度は22000cps、Ｍ
ｎ＝4850で、共重合体の官能基は末端の位置に
OH基0.74個、任意の位置にOH基2.0個合計2.74
個であつた。
実施例 ２
（シーリング材用樹脂Ａ−２）
滴下装置、撹拌機、還流冷却器、温度計を備え
た反応装置に乾燥されトルエン60部、チオグリコ
ール酸８部を入れ、撹拌しながら100℃に昇温し
た。昇温した後、BA146部、2EHA30部、
2HMEA24部、パーブチルPV2部、（日本油脂製）
の混合物を約３時間で連続的に滴下し、添加終了
したのち１時間反応を続け、さらにパーブチル
PV0.5部加え２時間反応を続行した。得られた反
応液を減圧下で濃縮し、さらに水洗を数回くり返
した後、減圧下で乾燥し不揮発分99.5％の低分子
量共重合体「Ａ−２」を得た。この低分子量共重
合体は粘度9600cps、Ｍ＝2400で、共重合体の
官能基は末端の位置にCOO基0.85個、任意の位置
にOH基2.1個、合計2.95個であつた。
実施例 ３
BA91部、2HEA9部、2MEt2部、を用い、
2MEtを一括添加した以外は実施例１と同様に重
合、後処理を行つて低分子量共重合体「Ａ−３」
を得た。結果を表−１に示す。
実施例 ４
BA79部、AN3部、2HEMA18部、2MEt6部、
を用い反応温度100℃、にした以外は実施例１と
同様に重合、後処理を行つて低分子量共重合体
「Ａ−４」を得た。結果を表−１に示す。
実施例 ５
BA78部、2EHA20部、2HEA2部、2MEt1.5部
を用い、反応温度75℃で、2MEtを60分間で逐次
添加した以外は実施例１と同様に重合、後処理を
行つて低分子量共重合体「Ａ−５」を得た。結果
を表−１に示す。
比較例 １
BA89部、2HEA11部、2MEt2部、を用いた以
外は実施例１と同様に行つて低分子量共重合体
「Ａ−６」を得た結果を表−１に示す。
比較例 ２
BA97部、2EHA3部、2MEt2部、を用い反応
温度75℃で2MEtを60分間で逐次添加した以外は
実施例１と同様に重合、後処理を行つて低分子量
共重合体「Ａ−７」を得た結果を表−１に示す。
比較例 ３
BA70部、2HEMA30部、2MEt6部、トリクロ
ロプロメタン１部、を用いた以外は、実施例３と
同様に行つて、低分子量共重合体「Ａ−８」を得
た。結果を表−１に示す。
比較例 ４
BA96.5部、2HEMA3.5部、2MEt2部、を用い
た以外は実施例１と同様に行つて低分子量共重合
体「Ａ−９」を得た。結果を表−１に示す。Through [formula], it becomes part of the end of the polymer chain. Therefore, by using mercaptans containing OH groups, such as 2-mercaptoethanol, and mercaptans containing COOH groups, such as thioglycolic acid, these functional groups can be introduced at the ends of the polymer chains. The sealing material containing (meth)acrylate resin and polyfunctional isocyanate produced using a mercaptan derivative as a polymerization initiator has good weather resistance (rubber elasticity, It was found to be extremely excellent in terms of crack resistance) and discoloration (yellowing). On the other hand, as a chain transfer agent, if it is a compound with a large ability to transfer polymer chains during polymerization,
For example, carbon tetrachloride, carbon tetrabromide, acetic acid trichloride, etc. are also used, and the mercaptan derivatives used as the polymerization initiators also function as chain transfer agents.
The chain transfer agent is usually used per 100 parts by weight of unsaturated monomer.
It is used in a proportion of 0.1 to 15 parts by weight. To copolymerize the monomers to produce the (meth)acrylate resin copolymer of the present invention, any generally known polymerization method may be used, such as bulk polymerization under high pressure, suspension polymerization, Polymerization is performed by conventional radical polymerization methods used in the field, such as emulsion polymerization and solution polymerization, but solution polymerization and bulk polymerization are preferred because they tend to yield products with relatively small molecular weights. During the polymerization, the monomer mixture may be charged in its entirety at once from the beginning of the polymerization, or only a portion may be initially charged and the remaining mixture may be added dropwise as the polymerization reaction progresses. The latter method is particularly advantageous for products where polymerization heat generation is a problem, and the polymerization conditions such as temperature and time should be adjusted so that no gel-like copolymer is formed or unreacted monomer remains as much as possible. Adjust to Remaining unreacted monomer acts like a solvent for the copolymer, which is undesirable as it causes odor during application as a sealant and causes eye discoloration after application. The polymerization initiator is used so that the inner bath containing the mixture of the monomer and the chain transfer agent reaches a predetermined polymerization temperature,
Moreover, it is preferable to sufficiently replace the air in the polymerization tank with an inert gas such as nitrogen before adding. If a solvent is used, for example, n-heptane, n-hexane, toluene, xylene, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isopropanol, and the like may be used. The polymerization temperature varies depending on the type of monomer and polymerization initiator, but is generally preferably in the range of about 20 to 120°C. If the polymerization temperature becomes too high and generates too much heat, adjust it appropriately by cooling with water or the like. The polymerization time mainly depends on the polymerization temperature and the type of monomer. In the sealing material composition using the (meth)acrylate resin of the present invention, in addition to the (meth)acrylate resin and the polyfunctional isocyanate compound, a catalyst and a filler are added as necessary. As such a catalyst, for example, metal compounds such as dibutyltin dilaurate, monobutyltin oxide, dioctyltin dilaurate, stannath octoate, or amines such as triethylenediamine, triethylenetetramine, dimethylbenzylamine, etc. can be used. The amount added may generally be 0.01 to 5 parts by weight per 100 parts by weight of the low molecular weight copolymer. The filler is used to improve the strength of the elastic sealant and to adjust the viscosity of the sealant to improve workability.For example, fillers include calcium carbonate, silica powder, talc, glass powder, magnesia, and clay powder. , titanium oxide, etc. are preferably used. The addition ratio is preferably 30 to 200 parts by weight per 100 parts by weight of the (meth)acrylate copolymer; if the amount is smaller than this, it will be difficult to obtain a product with the desired strength, and if there is too much In this case, the elongation rate of the cured product becomes low, making it difficult to obtain desirable elastic properties. In addition to the above-mentioned ingredients, elastic sealants contain plasticizers, pigments, and other ingredients used in general sealants.
Antiaging agents, antifungal agents, antioxidants, ultraviolet absorbers, ozone deterioration inhibitors, tackifiers, thixotropic agents, and the like can also be added. The details of the present invention will be explained below in more detail with reference to Examples. In this specification, numerical expressions such as parts or percentages are expressed by weight unless otherwise specified. In addition, the characteristic values of the copolymer were measured by the following method. (1) Number average molecular weight (M) measurement GPC (Gel permeation chromatography)
Number-average molecular weight measured using standard molecular weight polystyrene equivalent values. (2) Calculation method for the number of functional groups a. Calculation of the total number of functional groups (pieces/molecule) Measure the hydroxyl value and acid value according to JIS K-0070-1966, and measure the total number of functional groups (pieces/molecule) was calculated. (b) Calculation of the number of functional groups (pieces/molecule) at the terminal position of the copolymer. Calculate the sulfur content (%) in the copolymer using Jikken Kagaku Mizoza Vol. 15, Analytical Chemistry, p. 417-418, "Method for measuring elemental sulfur." It was measured. The mercaptan derivative used as a polymerization initiator has one S atom in one molecule, and the terminal position of the copolymer derived from the mercaptan derivative has one structural unit.
The number of functional groups at the terminal positions of the copolymer was calculated from the sulfur content (%), assuming that the copolymer has OH or COOH groups. C. Calculation of the number of functional groups (units/molecule) at arbitrary positions other than the terminal positions of copolymerization. Calculation was performed by subtracting the number of functional groups at the terminal positions from the total number of functional groups. Hereinafter, the monomers used are indicated by the following abbreviations. BA: Butyl acrylate 2EHA: 2-ethylhexyl acrylate AN: Acrylonitrile 2HEA: 2-hydroxyethyl acrylate 2HEMA
: 2-hydroxyethyl methacrylate 2MEt : 2-mercaptoethanol TGA : Thioglycolic acid Example 1 (Resin A-1 for sealing material) BA190 was placed in a pressurized reaction apparatus equipped with a dropping device, a stirrer, reflux cooling, and a thermometer. 2 parts and 10 parts of HEA were added, and the temperature was raised to 90°C while stirring. When the temperature rises
4.0 parts of 2-mercaptoethanol were added sequentially. When about 1/3 was added, it suddenly generated heat and reached 120-135
Although the temperature rose to ℃, the dropwise addition continued and was completed in about 60 minutes. The reaction continued as it was, and after 2 hours, when the temperature was controlled to 85-90℃, the perbutyl
0.3 part of PV (manufactured by NOF Corporation) was added in 5 portions of 1/5 every 30 minutes, and the reaction was continued for 2 hours after the fifth addition.
A copolymer with a nonvolatile content of 99.3% was obtained. This was washed with water several times and then dried under reduced pressure to obtain a low molecular weight copolymer "A-1" with a non-volatile content of 99.7%. The viscosity of this low molecular weight copolymer is 22000 cps, M
When n=4850, the functional group of the copolymer is at the terminal position.
0.74 OH groups, 2.0 OH groups at any position, total 2.74
It was individual. Example 2 (Resin A-2 for sealing material) 60 parts of dried toluene and 8 parts of thioglycolic acid were placed in a reaction apparatus equipped with a dropping device, a stirrer, a reflux condenser, and a thermometer, and the mixture was heated to 100°C while stirring. The temperature rose. After heating up, 146 parts of BA, 30 parts of 2EHA,
24 parts of 2HMEA, 2 parts of Perbutyl PV, (manufactured by NOF)
A mixture of
0.5 part of PV was added and the reaction was continued for 2 hours. The resulting reaction solution was concentrated under reduced pressure, washed with water several times, and then dried under reduced pressure to obtain a low molecular weight copolymer "A-2" with a non-volatile content of 99.5%. This low molecular weight copolymer had a viscosity of 9600 cps and M=2400, and the copolymer had a total of 2.95 functional groups, including 0.85 COO groups at the terminal positions and 2.1 OH groups at arbitrary positions. Example 3 Using 91 parts of BA, 9 parts of 2HEA, and 2 parts of 2MEt,
Polymerization and post-treatment were carried out in the same manner as in Example 1, except that 2MEt was added all at once, and a low molecular weight copolymer "A-3" was obtained.
I got it. The results are shown in Table-1. Example 4 79 parts of BA, 3 parts of AN, 18 parts of 2HEMA, 6 parts of 2MEt,
A low molecular weight copolymer "A-4" was obtained by performing polymerization and post-treatment in the same manner as in Example 1, except that the reaction temperature was 100°C. The results are shown in Table-1. Example 5 Polymerization and post-treatment were carried out in the same manner as in Example 1, except that 78 parts of BA, 20 parts of 2EHA, 2 parts of 2HEA, and 1.5 parts of 2MEt were used at a reaction temperature of 75°C, and 2MEt was added sequentially over 60 minutes. A copolymer "A-5" was obtained. The results are shown in Table-1. Comparative Example 1 A low molecular weight copolymer "A-6" was obtained in the same manner as in Example 1 except that 89 parts of BA, 11 parts of 2HEA, and 2 parts of 2MEt were used. The results are shown in Table 1. Comparative Example 2 A low molecular weight copolymer "A- 7'' is shown in Table 1. Comparative Example 3 A low molecular weight copolymer "A-8" was obtained in the same manner as in Example 3, except that 70 parts of BA, 30 parts of 2HEMA, 6 parts of 2MEt, and 1 part of trichloropromethane were used. The results are shown in Table-1. Comparative Example 4 A low molecular weight copolymer "A-9" was obtained in the same manner as in Example 1 except that 96.5 parts of BA, 3.5 parts of 2HEMA, and 2 parts of 2MEt were used. The results are shown in Table-1.
【表】
以下に上記実施例及び比較例の樹脂を用いてシ
ーリング材を製造し、その特性を比較した試験を
示す。シーリング材の特性の測定方法は下記のと
おりである。
Γ引張特性
離型紙張りの上にシーリング材を厚み約３〜
3.5mmになる様、泡の入らぬよう平らにならし、
室温×７日間養生した後、50℃±３℃で７日間
養生、室温で24時間放置後、JIS・Ｋ−6301に
規定する１号形ダンペル状試験片に打抜きJIS
−Ａ−5757に準じ測定。
ｏタツク、スランプ、汚染性、ブリージン
グ、押出し性はJIS・Ａ−5757に準じ測定。
タツク及び汚染性の表示
〇：なし
△：わずかにあり
×：あり
××：強くあり
参考例 １
（シーリング材）
実施例１で合成した低分子量共重合体樹脂（Ａ
−１）100部に酸化チタン25部、炭酸カルシウム
105部、カーボンブラツク１部、ジブチルチンジ
ラウレート１部をニーダーであら練りしたのち、
３本ロールで充分混練りし、これにタケネートＬ
−1032、95部を加え脱泡しながら均一に混合し、
本発明のシーリング材とした。その特性を表−３
に示す。
参考例 ２〜13
（シーリング材）
表−２のシーリング材配合によつた以外は参考
例１と同一の条件でシーリング材を製造した。そ
の特性を表−３に示す。[Table] Below is a test in which sealing materials were manufactured using the resins of the above Examples and Comparative Examples and their properties were compared. The method for measuring the properties of the sealant is as follows. Γ Tensile properties Apply sealant to a thickness of about 3~ on the release paper
Flatten it so that it is 3.5mm without any bubbles,
After curing at room temperature for 7 days, curing at 50°C ± 3°C for 7 days, and leaving it at room temperature for 24 hours, punched into a No. 1 damper-shaped test piece specified in JIS K-6301.
- Measured according to A-5757. Tack, slump, contamination, breathing, and extrudability are measured according to JIS A-5757. Indication of tack and contamination 〇: None △: Slightly present ×: Present ××: Strongly Reference example 1 (Sealing material) Low molecular weight copolymer resin synthesized in Example 1 (A
-1) 100 parts, 25 parts of titanium oxide, calcium carbonate
After kneading 105 parts, 1 part of carbon black, and 1 part of dibutyltin dilaurate in a kneader,
Thoroughly knead with 3 rolls and add Takenate L to this.
Add 95 parts of −1032 and mix uniformly while defoaming.
It was made into the sealing material of this invention. Table 3 shows its characteristics.
Shown below. Reference Examples 2 to 13 (Sealing Materials) Sealing materials were manufactured under the same conditions as in Reference Example 1 except that the sealant formulations shown in Table 2 were used. Its characteristics are shown in Table 3.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
８のアルキル基を表わす、 の構成単位及び式 ここでR3はＨ又CH3を表わし、R4はOH又はヒ
ドロキシアルコキシ基を表わす、 の構成単位の合計が全体の80重量％以上を占め、
数平均分子量が1500〜10000である共重合体であ
つて、官能基を共重合体の末端位置に0.5〜0.9
個／分子、末端以外の任意位置に1.4〜4.5個／分
子、合計2.3〜5.0個／分子有することを特徴とす
るシーリング材用の（メタ）アクリレート系樹
脂。 ２ 末端位置の構成単位が単位内に硫黄原子を有
する構成単位である特許請求の範囲第１項記載の
（メタ）アクリレート系樹脂。 ３ 官能基がOH基である特許請求の範囲第１項
又は第２項記載の（メタ）アクリレート系樹脂。 ４ R1がＨ、R2がｎ−ブチル基である特許請求
の範囲第１〜３項の何れかに記載の（メタ）アク
リレート系樹脂。 ５ R3がＨ、R4がヒドロキシエトキシ基である
特許請求の範囲第１〜３項の何れかに記載の（メ
タ）アクリレート系樹脂。 ６ 式 ここでR1はＨを表わし、R2は炭素原子数４〜
８のアルキル基を表わす の単量体及び式 ここでR3はＨ又はCH3を表わし、R4はOH又は
ヒドロキシアルコキシ基を表わす、 の単量体を主要単量体として共重合を行う（メ
タ）アクリレート系樹脂（但し、上記式（）及
び式（）の単量体に基づく構成単位の合計が全
体の80重量％以上を占め、数平均分子量が1500〜
10000であつて、官能基を共重合体の末端位置に
0.5〜0.9個／分子、末端以外の位置に1.5〜4.5
個／分子、合計2.3〜5.0個／分子有する）の製法
において、OH基又はカルボキシル基を有するメ
ルカプタンを重合開始剤として共重合を行うこと
を特徴とする、シーリング材用の（メタ）アクリ
レート系樹脂の製法。[Claims] 1 formula Here, R 1 represents H, and R 2 has 4 to 4 carbon atoms.
The structural unit and formula representing the alkyl group of 8 where R 3 represents H or CH 3 , R 4 represents OH or a hydroxyalkoxy group, the total of the following structural units accounts for 80% by weight or more of the whole,
A copolymer with a number average molecular weight of 1,500 to 10,000, with a functional group at the terminal position of the copolymer of 0.5 to 0.9.
A (meth)acrylate resin for sealing materials, characterized by having 1.4 to 4.5 molecules/molecule at arbitrary positions other than the ends, and a total of 2.3 to 5.0 molecules/molecule. 2. The (meth)acrylate resin according to claim 1, wherein the structural unit at the terminal position is a structural unit having a sulfur atom within the unit. 3. The (meth)acrylate resin according to claim 1 or 2, wherein the functional group is an OH group. 4. The (meth)acrylate resin according to any one of claims 1 to 3, wherein R1 is H and R2 is an n-butyl group. 5. The (meth)acrylate resin according to any one of claims 1 to 3, wherein R3 is H and R4 is a hydroxyethoxy group. 6 formula Here, R 1 represents H, and R 2 has 4 to 4 carbon atoms.
Monomer and formula representing the alkyl group of 8 Here, R 3 represents H or CH 3 and R 4 represents OH or a hydroxyalkoxy group. A (meth)acrylate resin copolymerized using the following monomer as the main monomer (however, the above formula () and the total of the structural units based on the monomer of formula () accounts for 80% by weight or more of the whole, and the number average molecular weight is 1500 ~
10000, and the functional group is placed at the terminal position of the copolymer.
0.5-0.9 pieces/molecule, 1.5-4.5 at non-terminal positions
A (meth)acrylate resin for sealing materials, characterized in that copolymerization is carried out using a mercaptan having an OH group or a carboxyl group as a polymerization initiator, in a manufacturing method of 2.3 to 5.0 pieces/molecule in total. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17396882A JPS5964614A (en) | 1982-10-05 | 1982-10-05 | Sealant resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17396882A JPS5964614A (en) | 1982-10-05 | 1982-10-05 | Sealant resin and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5964614A JPS5964614A (en) | 1984-04-12 |
| JPH0310649B2 true JPH0310649B2 (en) | 1991-02-14 |
Family
ID=15970366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17396882A Granted JPS5964614A (en) | 1982-10-05 | 1982-10-05 | Sealant resin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5964614A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0819312B2 (en) * | 1987-03-25 | 1996-02-28 | 日本合成ゴム株式会社 | Acrylic resin emulsion |
| US5641829A (en) * | 1991-12-30 | 1997-06-24 | Ppg Industries, Inc. | Coating compositions prepared from base neutralized, stable aqueous dispersion of hydroxyl functional acrylic polymers |
| US5342878A (en) * | 1991-12-30 | 1994-08-30 | Ppg Industries, Inc. | Base neutralized, stable, aqueous dispersion of a hydroxyl functional acrylic polymer and coating compositions prepared therefrom |
| US5464897A (en) * | 1991-12-30 | 1995-11-07 | Ppg Industries, Inc. | Aqueous fluoropolymer dispersions |
| US5302629A (en) * | 1992-05-15 | 1994-04-12 | Berejka Anthony J | Hydrophilic acrylic pressure sensitive adhesives |
| JP4448919B2 (en) * | 1998-10-23 | 2010-04-14 | 綜研化学株式会社 | Bulk polymerization catalyst and bulk polymerization method using the catalyst |
| JP2000239308A (en) * | 1999-02-24 | 2000-09-05 | Soken Chem & Eng Co Ltd | Acrylic polymer, curing composition, cured product and their use |
| JP4247399B2 (en) * | 1999-03-31 | 2009-04-02 | 綜研化学株式会社 | Bulk polymerization catalyst and polymerization method using the catalyst |
| JP4048295B2 (en) * | 1999-07-21 | 2008-02-20 | 綜研化学株式会社 | Bulk polymerization of acrylic monomers |
| JP5048969B2 (en) * | 2006-05-16 | 2012-10-17 | 積水化学工業株式会社 | Method for producing acrylic polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55160009A (en) * | 1979-05-30 | 1980-12-12 | Asahi Chem Ind Co Ltd | Production of acrylic copolymer |
| JPS5742709A (en) * | 1980-08-26 | 1982-03-10 | Nitto Electric Ind Co Ltd | Heat-resistant photosensitive material |
-
1982
- 1982-10-05 JP JP17396882A patent/JPS5964614A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55160009A (en) * | 1979-05-30 | 1980-12-12 | Asahi Chem Ind Co Ltd | Production of acrylic copolymer |
| JPS5742709A (en) * | 1980-08-26 | 1982-03-10 | Nitto Electric Ind Co Ltd | Heat-resistant photosensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5964614A (en) | 1984-04-12 |
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