JPH02209972A - Magnetic coating compound and magnetic recording medium - Google Patents
Magnetic coating compound and magnetic recording mediumInfo
- Publication number
- JPH02209972A JPH02209972A JP1255384A JP25538489A JPH02209972A JP H02209972 A JPH02209972 A JP H02209972A JP 1255384 A JP1255384 A JP 1255384A JP 25538489 A JP25538489 A JP 25538489A JP H02209972 A JPH02209972 A JP H02209972A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- resin
- magnetic
- vinyl chloride
- acid
- 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.)
- Granted
Links
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 60
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 238000000576 coating method Methods 0.000 title abstract description 18
- 239000011248 coating agent Substances 0.000 title abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 76
- 239000011347 resin Substances 0.000 claims description 76
- 239000003973 paint Substances 0.000 claims description 31
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000006247 magnetic powder Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- PGPVHMZVZVOUBA-UHFFFAOYSA-N OC([S])=O Chemical compound OC([S])=O PGPVHMZVZVOUBA-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 238000006116 polymerization reaction Methods 0.000 description 28
- 238000011156 evaluation Methods 0.000 description 25
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 238000010998 test method Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- -1 alkylene glycols Chemical class 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229920001228 polyisocyanate Polymers 0.000 description 11
- 239000005056 polyisocyanate Substances 0.000 description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 10
- 238000007872 degassing Methods 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000006249 magnetic particle Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 5
- CJNXVNXBZXMHKG-UHFFFAOYSA-N 1-prop-2-enoxypropan-2-ol Chemical compound CC(O)COCC=C CJNXVNXBZXMHKG-UHFFFAOYSA-N 0.000 description 5
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 235000010981 methylcellulose Nutrition 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- TURGQPDWYFJEDY-UHFFFAOYSA-N 1-hydroperoxypropane Chemical compound CCCOO TURGQPDWYFJEDY-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- VJFPVACZAZLCCM-UAIGNFCESA-N (z)-but-2-enedioic acid;chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C.OC(=O)\C=C/C(O)=O VJFPVACZAZLCCM-UAIGNFCESA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 description 1
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 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
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VSKHJJMTIPNCOH-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)OCCO.C(=C)Cl Chemical compound C(C=C)(=O)O.C(C=C)(=O)OCCO.C(=C)Cl VSKHJJMTIPNCOH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DNCQWNWCEBTKGC-UHFFFAOYSA-N azane;phosphorous acid Chemical compound N.N.OP(O)O DNCQWNWCEBTKGC-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- KEYZMFWOMWWJGZ-UHFFFAOYSA-N methylphosphonic acid;prop-2-enamide Chemical compound CP(O)(O)=O.NC(=O)C=C KEYZMFWOMWWJGZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- BIRVVRGTJRWSKV-UHFFFAOYSA-N phosphoric acid;propan-2-ol Chemical compound CC(C)O.OP(O)(O)=O BIRVVRGTJRWSKV-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- LDZHTQSBXDDUFB-UHFFFAOYSA-M potassium;4-aminobenzenesulfonate Chemical compound [K+].NC1=CC=C(S([O-])(=O)=O)C=C1 LDZHTQSBXDDUFB-UHFFFAOYSA-M 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- BVIXLMYIFZGRBH-UHFFFAOYSA-M sodium;2-chloroethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCl BVIXLMYIFZGRBH-UHFFFAOYSA-M 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、塩化ビニル系樹脂を磁性粉末のバインダーと
する磁性塗料及びそれを使用する磁気記録媒体に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a magnetic coating material using a vinyl chloride resin as a binder for magnetic powder, and a magnetic recording medium using the same.
（従来の技術〕
一般に、磁気テープやフロッピーディスク等の磁気記録
媒体は、有機高分子をバインダーとして強磁性粉末を有
機溶媒中に分散させた磁性塗料を、高分子フィルムやシ
ート上に塗布することにより製造されている。(Prior Art) Generally, magnetic recording media such as magnetic tapes and floppy disks are produced by coating a polymer film or sheet with a magnetic paint in which ferromagnetic powder is dispersed in an organic solvent using an organic polymer as a binder. Manufactured by.
この磁性塗料中の有機高分子としては、通常ＰＶＣ，ポ
リビニルブチラール、ニトロセルロース、アセチルセル
ロース等の、比較的硬い樹脂と、ポリエステル、ポリウ
レタン、アクリロニトリル−ブタジェン共重合体等の軟
質材料とが組み合わされて使用されることが多（、また
、塗膜の耐久性を向上する目的で通常熱硬化成分として
、ポリイソシアネート化合物を使用する例が多い。従っ
てバインダーとして使用される樹脂の特性として、他の
高分子との相溶性やポリイソシアネートとの反応性が適
当であることはもちろんのこと、磁粉によくなじみ、こ
れを均一に塗料中に分散させる働きが要求される。The organic polymer in this magnetic paint is usually a combination of a relatively hard resin such as PVC, polyvinyl butyral, nitrocellulose, or acetylcellulose, and a soft material such as polyester, polyurethane, or acrylonitrile-butadiene copolymer. In addition, polyisocyanate compounds are often used as thermosetting components to improve the durability of paint films. It is required not only to have appropriate compatibility with molecules and reactivity with polyisocyanates, but also to be compatible with magnetic particles and to disperse them uniformly into the paint.
近年磁気記録媒体の記録密度の向上やＳ／Ｎ比の改良要
求に伴って、磁粉は、−より微細化、高抗磁力化してき
ているので、磁粉を均一に塗料中に分散させ、平滑で充
てん度の高い磁性層を形成させて、前記の媒体としての
性能の向上を達成するためには、バインダーの分散性能
が決定的に重要な要因となる。In recent years, with the increase in the recording density of magnetic recording media and the demand for improved S/N ratio, magnetic particles have become finer and have higher coercive force. In order to form a magnetic layer with a high degree of filling and to achieve the above-mentioned improvement in performance as a medium, the dispersion performance of the binder is a decisively important factor.
これまで、磁粉の分散を改良するためには分散剤として
低分子量の界面活性剤を使うのが通例とされているが、
分散剤の多量使用は、磁気記録媒体の耐久性、ヘッド汚
れなどの点からその使用量におのずと限度があり、さら
に、磁気記録媒体の信転性の向上の観点からも、バイン
ダー自身に高度の分散能を有することが要求されている
。一方、媒体の耐久性、信転性を高めるために、ポリイ
ソシアネート化合物を代表とする硬化性化合物を塗料中
に含ませ磁性層を架橋塗膜化することが特に録画用磁気
テープでは常用されており、バインダーとしてポリイソ
シアネートと適当な反応性を有することが要求される。Until now, it has been customary to use a low molecular weight surfactant as a dispersant to improve the dispersion of magnetic particles.
There is a natural limit to the amount of dispersant used in terms of durability of the magnetic recording medium, head contamination, etc. Furthermore, from the perspective of improving the reliability of the magnetic recording medium, the binder itself must have a high degree of It is required to have dispersion ability. On the other hand, in order to improve the durability and reliability of the media, it is commonly used, especially in recording magnetic tapes, to crosslink the magnetic layer by incorporating a curable compound, typically a polyisocyanate compound, into the paint. Therefore, it is required to have appropriate reactivity with polyisocyanate as a binder.
この場合、反応性が良すぎると、塗料のポットライフが
短く不経済であり、遅すぎると期待する耐久性や走行性
の向上がみられない。In this case, if the reactivity is too good, the pot life of the paint will be short and uneconomical, and if the reactivity is too slow, the expected improvements in durability and runnability will not be seen.
本発明者は、こうした磁気記録媒体の高性能化に応える
バインダーの改良検討をＰｖＣについて行うにあたり、
これまで知られるＰｖＣバインダーについて評価を得た
ところ、塩化ビニル−ビニルアルコール−酢酸ビニル共
重合体は、ビニルアルコールの比率増加につれて磁粉の
分散性能は向上するが、その程度は低く、分散剤の助け
を必要トスるうえ、ビニルアルコール量増大に伴いポッ
トライフが短くなって塗膜の耐湿性が低下し、また熱分
解の速度も早くなる。一方塩化ビニルーマレイン酸−酢
酸ビニル共重合体は、磁粉に強く吸着し、優れた分散能
力を発揮するが、塗料が増粘ゲル化しやすく、またポリ
イソシアネートとの反応が局部的に起き勝ちである。The present inventor conducted an investigation on improving binders for PvC to meet the demands for higher performance of magnetic recording media.
An evaluation of the known PvC binders revealed that the dispersion performance of magnetic particles of vinyl chloride-vinyl alcohol-vinyl acetate copolymer improves as the ratio of vinyl alcohol increases, but the degree of dispersion is low; In addition, as the amount of vinyl alcohol increases, the pot life becomes shorter, the moisture resistance of the coating film decreases, and the rate of thermal decomposition increases. On the other hand, vinyl chloride-maleic acid-vinyl acetate copolymer strongly adsorbs to magnetic particles and exhibits excellent dispersion ability, but the paint tends to thicken and gel, and reactions with polyisocyanate tend to occur locally. be.
これらの代表的なＰＶＣバインダーの問題点を解決する
試みとして、塩化ビニル−ビニルアルコール−酢酸ビニ
ル−マレイン酸共重合体が提案されているが、これは、
塩化ビニル−ビニルアルコール−酢酸ビニル共重合体の
反応性と塩化ビニル−マレイン酸−酢酸ビニル共重合体
の分散性の良さを兼ね備えてするもののそのレベルは不
充分である。また、この共重合体は通常塩化ビニル−マ
レイン酸−酢酸ビニル共重合体をケン化して得られるが
、ケン化時に重合体が劣化するため、化学的な熱安定性
に乏しい。In an attempt to solve the problems of these typical PVC binders, a vinyl chloride-vinyl alcohol-vinyl acetate-maleic acid copolymer has been proposed;
Although it has the reactivity of vinyl chloride-vinyl alcohol-vinyl acetate copolymer and the good dispersibility of vinyl chloride-maleic acid-vinyl acetate copolymer, its level is insufficient. Further, this copolymer is usually obtained by saponifying a vinyl chloride-maleic acid-vinyl acetate copolymer, but the polymer deteriorates during saponification and thus has poor chemical thermal stability.
また別の試みとして、塩化ビニル−ヒドロキシエチルア
クリレート−アクリル酸共重合体を使う方法が提案され
ているが、溶剤への溶解性を満足するために比較的多量
のヒドロキシエチルアクリ１ノートを使用すると、ポリ
イソシアネート化合物添加時のポットライフが短くなっ
てしまう。一方、ポットライフが適当な程度までヒドロ
キシエチルアクリレートの共重合量を減すると溶剤への
溶解性が低下し、溶液がゲル化増粘しやすくなってしま
う。As another attempt, a method using vinyl chloride-hydroxyethyl acrylate-acrylic acid copolymer has been proposed, but in order to satisfy the solubility in the solvent, a relatively large amount of hydroxyethyl acrylic 1 note is used. , the pot life becomes short when a polyisocyanate compound is added. On the other hand, if the amount of copolymerized hydroxyethyl acrylate is reduced to a level where the pot life is appropriate, the solubility in the solvent decreases, and the solution tends to gel and thicken.
こうした従来のアルコール性水酸基を含有するｐｖｃＯ
問題点の解決方法について鋭意検討した結果、本発明者
らは特定の塩化ビニル共重合体を用いることにより優れ
た磁粉の分散性及び分散の経時安定性を示し、しかも極
めて少量の水酸基含量にもかかわらず良好なポリイソシ
アネートとの反応性を与え、かつ、化学的熱安定性に優
れること、さらには、この樹脂をバインダーとして、ポ
リイソシアネートを硬化剤として使用し、磁粉を分散さ
せた塗料をポリエステルフィルム上に塗布して得た磁気
記録媒体は、優れた磁気特性、電磁変換特性、耐久性を
示すことを確認したのである。These conventional pvcO containing alcoholic hydroxyl groups
As a result of intensive studies on how to solve the problem, the present inventors have shown that by using a specific vinyl chloride copolymer, excellent dispersibility and stability of dispersion over time can be achieved even with extremely small amounts of hydroxyl group content. Furthermore, this resin can be used as a binder and polyisocyanate as a curing agent, and a paint with magnetic particles dispersed can be made into polyester. It was confirmed that the magnetic recording medium obtained by coating the film has excellent magnetic properties, electromagnetic conversion properties, and durability.
即ち、本発明では水酸基を与える単量体として、ポリヒ
ドロキシ化合物のモノアリルエーテルを使用することに
より、他の水酸基を与える単量体に比して、さらに小量
の水酸基量で充分な反応性が得られること、さらに化学
的熱安定性がよくなること、加えて本発明の樹脂をバイ
ンダーとして使用した磁性塗料は、良好な分散安定性を
示すことが可能であること、そしてその塗料を用いて得
られる磁気記録媒体は塗膜の表面平滑性及び耐久性が良
好であり、かつ走行性、磁気特性、電磁変換特性が優れ
ることを見出し、本発明を完成するに到った。That is, in the present invention, by using monoallyl ether of a polyhydroxy compound as a monomer that provides a hydroxyl group, sufficient reactivity can be achieved with a smaller amount of hydroxyl group than with other monomers that provide a hydroxyl group. In addition, the magnetic paint using the resin of the present invention as a binder can exhibit good dispersion stability, and the paint can be used to improve chemical and thermal stability. It was discovered that the resulting magnetic recording medium has a coating film with good surface smoothness and durability, as well as excellent running properties, magnetic properties, and electromagnetic conversion properties, leading to the completion of the present invention.
すなわち本発明における第１の発明は磁性粉のバインダ
ーの少なくとも一成分が水酸基、及びカルボン酸基また
は硫黄もしくはリンを含む強酸根を含有する塩化ビニル
の共重合体で、該水酸基を供給する単量体がポリヒドロ
キシ化合物のモノアリルエーテルであることを特徴とす
る磁性塗料に関するものであり、また第２の発明は磁性
粉のバインダーの少なくとも一成分が水酸基及びカルボ
ン酸基または硫黄もしくはリンを含む強酸根を含有する
塩化ビニルの共重合体で、該水酸基を供給する単量体が
ポリヒドロキシ化合物のモノアリルエーテルの樹脂であ
る磁性塗料を用いることを特徴とする磁気記録媒体に関
するものである。That is, the first aspect of the present invention is that at least one component of the binder of the magnetic powder is a copolymer of vinyl chloride containing a hydroxyl group and a carboxylic acid group or a strong acid group containing sulfur or phosphorus, and a monomer supplying the hydroxyl group. The second invention relates to a magnetic paint characterized in that the body is a monoallyl ether of a polyhydroxy compound, and the second invention relates to a magnetic paint in which at least one component of the binder of the magnetic powder is a strong acid containing a hydroxyl group and a carboxylic acid group, or sulfur or phosphorus. The present invention relates to a magnetic recording medium characterized in that a magnetic paint is used, which is a copolymer of vinyl chloride containing hydroxyl groups, and the monomer supplying the hydroxyl groups is a resin of monoallyl ether of a polyhydroxy compound.
これらのポリヒドロキシ化合物のモノ了りルエーテルの
使用量は、水酸基が共重合体中Ｏ，ＯＳ〜３．０重量％
好ましくは０．１〜２．０重量％となるような範囲で使
用される。０．０５重貴重未満では、ポリイソシアネー
トとの架橋効果が発揮されず、３．０重量％を越えると
、ポットライフが短かすぎる。The amount of monotriether used in these polyhydroxy compounds is such that the hydroxyl group in the copolymer is O,OS ~ 3.0% by weight.
It is preferably used in an amount of 0.1 to 2.0% by weight. If it is less than 0.05% by weight, the crosslinking effect with the polyisocyanate will not be exhibited, and if it exceeds 3.0% by weight, the pot life will be too short.
本発明に係る共重合体中水酸基を与える、ポリヒドロキ
シ化合物のモノアリルエーテルの例としては、アリル−
２−ヒドロキシエチルエーテル、アリル−２−ヒドロキ
シプロピルエーテル、アリル−３−ヒドロキシプロピル
エーテル、アリル−２−ヒドロキシブチルエーテル、ア
リル−３−ヒドロキシブチルエーテル、アリル−４−ヒ
ドロキシブチルエーテル、アリル−６−ヒドロキシエチ
ルエーテルなどのアルキレングリコールのモノアリルエ
ーテル類、ジエチレングリコールモノアリルエーテル、
ジプロピレングリコールモノアリルエーテルなどのポリ
オキシアルキレングリコールモノアリルエーテル類、グ
リセリンモノアリルエーテル、アリル−２−クロロ−３
−ヒドロキシプロピルエーテル、アリル−２−ヒドロキ
シ−３＝クロロプロピルエーテルなどの、（ポリ）アル
キレングリコールのハロゲン置換体、ヒドロキシ置換体
のモノアリルエーテル類、オイゲノール、イソオイゲノ
ールなどの多価フェノールのモノアリルエーテル類およ
びそのハロゲン置換体などが挙げられる０以上に例示し
たアリルアルコールとポリヒドロキシ化合物のエーテル
の他、アリルアルコールにかえてアリルチオールを使っ
たチオエーテルも、本発明に係る水酸基を与える単量体
として使用可能であり、その例としては、アリル−２−
ヒドロキシエチルチオエーテル、アリル−２−ヒドロキ
シプロピルチオエーテルなどが挙げられる。Examples of monoallyl ethers of polyhydroxy compounds that provide hydroxyl groups in the copolymer according to the present invention include allyl-
2-hydroxyethyl ether, allyl-2-hydroxypropyl ether, allyl-3-hydroxypropyl ether, allyl-2-hydroxybutyl ether, allyl-3-hydroxybutyl ether, allyl-4-hydroxybutyl ether, allyl-6-hydroxyethyl ether Alkylene glycol monoallyl ethers such as diethylene glycol monoallyl ether,
Polyoxyalkylene glycol monoallyl ethers such as dipropylene glycol monoallyl ether, glycerin monoallyl ether, allyl-2-chloro-3
-Halogen-substituted (poly)alkylene glycols such as hydroxypropyl ether, allyl-2-hydroxy-3=chloropropyl ether, monoallyl ethers of hydroxy-substituted products, and monoallyls of polyhydric phenols such as eugenol and isoeugenol. In addition to the ethers of allyl alcohol and polyhydroxy compounds listed above, which include ethers and their halogen-substituted products, thioethers using allyl thiol instead of allyl alcohol are also monomers that provide hydroxyl groups according to the present invention. Examples include allyl-2-
Examples include hydroxyethyl thioether and allyl-2-hydroxypropyl thioether.
本発明に係る共重合体にカルボン酸基を与える方法とし
てはカルボン酸基含有単量体を使用する。A carboxylic acid group-containing monomer is used as a method for imparting a carboxylic acid group to the copolymer according to the present invention.
カルボン酸基含有単量体としては、アクリル酸、メタク
リル酸、マレイン酸、イタコン酸、クロトン酸などの不
飽和モノ又はジ°カルボン酸、マレイン酸、イタコン酸
などの不飽和ジカルボン酸のモノアルキルエステルなど
が使用できる。この単量体は、共重合体中のカルボン酸
基が０．３〜５．０重量％となる範囲で使用されること
が好ましい、これより少ないと磁性粉の分散性が不良で
あり、これより多いと、塗料がゲル化増粘しやすい。Examples of carboxylic acid group-containing monomers include unsaturated mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and crotonic acid, and monoalkyl esters of unsaturated dicarboxylic acids such as maleic acid and itaconic acid. etc. can be used. This monomer is preferably used in a range where the carboxylic acid group in the copolymer is 0.3 to 5.0% by weight; if it is less than this, the dispersibility of the magnetic powder will be poor; If the amount is higher, the paint tends to gel and thicken.
また、水酸基とカルボン酸基との当量比は０．１〜３．
０、好ましくは０．２〜２．０であることが必要であっ
て、この比が３．０を越えると磁性粉の分散性が著しく
低下し、０．１未満では、ポリヒドロキシ化合物のモノ
アリルエーテルを加えた効果がない。Further, the equivalent ratio of hydroxyl group to carboxylic acid group is 0.1 to 3.
0, preferably 0.2 to 2.0; if this ratio exceeds 3.0, the dispersibility of the magnetic powder will decrease significantly, and if it is less than 0.1, the monomerization of the polyhydroxy compound will decrease. There is no effect of adding allyl ether.
本発明に係る重合体に硫黄またはリンを含む強酸根を導
入するための単量体としては、スルホン酸、硫酸、リン
酸、ホスホン酸などの硫黄またはリンを含む強酸、およ
びそのアルカリ金属塩またはアンモニウム塩を有するラ
ジカル重合性単量体が挙げられる。該強酸のうちでは、
スルホン酸およびその塩が入手しやす（、その種類も多
い０例えばビニルスルホン酸、メチルビニルスルホン酸
、（メタ）アリルスルホン酸、スチレンスルホン酸、（
メタ）アクリル酸−２−スルホン酸エチル、２−アクリ
ルアミド−２−メチルプロパンスルホン酸、３−アリロ
キシ−２−ヒドロキシプロパンスルホン酸などの酸およ
びそのアルカリ金属塩やアンモニウム塩などがあげられ
る。また硫酸およびその塩を有する単量体の例としては
、（メタ）アクリルＭ−２−硫酸エチル、３−アリロキ
シ−２−ヒドロキシプロパン硫酸などの酸およびそのア
ルカリ金属塩あるいはアンモニウム塩などがある。Monomers for introducing strong acid groups containing sulfur or phosphorus into the polymer according to the present invention include strong acids containing sulfur or phosphorus, such as sulfonic acid, sulfuric acid, phosphoric acid, and phosphonic acid, and alkali metal salts thereof, or Examples include radically polymerizable monomers having ammonium salts. Among the strong acids,
Sulfonic acids and their salts are readily available (and there are many types, such as vinyl sulfonic acid, methylvinyl sulfonic acid, (meth)allylsulfonic acid, styrene sulfonic acid,
Examples include acids such as ethyl meth)acrylate-2-sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxypropanesulfonic acid, and their alkali metal salts and ammonium salts. Examples of monomers containing sulfuric acid and its salts include acids such as (meth)acrylic M-2-ethyl sulfate and 3-allyloxy-2-hydroxypropane sulfate, and their alkali metal salts or ammonium salts.
さらにリン酸の塩を有する単量体の例としては、（メタ
）アクリル酸−３−クロロ−２−リン酸プロピル、（メ
タ）アクリル酸−２−リン酸エチル、３−アリロキシ−
２−ヒドロキシプロパンリン酸などの酸およびそのアル
カリ金属塩あるいはアンモニウム塩が、ホスホン酸の塩
を有する単量体の例としては、ビニルホスホン酸、アク
リルアミドメタンホスホン酸、２−ホスホン酸エチル−
（メタ）アクリレート、３−アリロキシ−２−ヒドロキ
シプロパンホスホン酸などの酸およびそのアルカリ金属
塩あるいはアンモニウム塩があげられる。Examples of monomers containing phosphoric acid salts include propyl (meth)acrylate-3-chloro-2-phosphate, ethyl (meth)acrylate-2-phosphate, and 3-allyloxy-
Examples of monomers in which acids such as 2-hydroxypropane phosphoric acid and their alkali metal salts or ammonium salts have phosphonic acid salts include vinylphosphonic acid, acrylamide methanephosphonic acid, and ethyl 2-phosphonate.
Examples include acids such as (meth)acrylate and 3-allyloxy-2-hydroxypropanephosphonic acid, and their alkali metal salts or ammonium salts.
共重合体中の硫黄またはリンを含む強酸根の含量は該樹
脂を酸素燃焼フラスコ法で燃焼して該樹脂中の硫黄また
はリンの量を硫酸またはリン酸として測定した場合の５
Ｏ４−またはｐｏ、−−一の量として０．１〜４．０重
量％好ましくは０．３〜２．０重量％の範囲で使用され
る。０．１重量％未満では磁性粉の分散性が不充分とな
り、４．０重量％を越えると強酸根の親水性が強くなり
、溶剤への溶解性が不充分になるばかりか、塗膜の耐湿
性が低下し、更には磁性粉の凝集が起きて返って分散性
が悪くなる。The content of strong acid groups containing sulfur or phosphorus in the copolymer is determined by burning the resin using an oxygen combustion flask method and measuring the amount of sulfur or phosphorus in the resin as sulfuric acid or phosphoric acid.
O4- or po-- is used in an amount of 0.1 to 4.0% by weight, preferably 0.3 to 2.0% by weight. If it is less than 0.1% by weight, the dispersibility of the magnetic powder will be insufficient, and if it exceeds 4.0% by weight, the hydrophilicity of the strong acid group will become strong, which will not only result in insufficient solubility in solvents, but also cause the coating film to deteriorate. Moisture resistance decreases, and furthermore, magnetic powder agglomerates, resulting in poor dispersibility.
また、必要に応じて共重合可能な他の単量体を併用する
ことも可能である。他の共単量体の例としては酢酸ビニ
ル、プロピオン酸ビニル等のカルボン酸ビニルエステル
；メチルビニルエーテル、イソブチルビニルエーテル、
セチルビニルエーテル等のビニルエーテル；塩化ビニリ
デン、弗化ビニリデン等のビニリデン；アクリル酸、メ
タアクリル酸、マレイン酸、イタコン酸のごとき不飽和
カルボン酸；無水マレイン酸のごとき不飽和カルボン酸
無水物；マレイン酸ジエチル、マレイン酸ジブチル、イ
タコン酸ジエチル、（メタ）アクリル酸メチル、（メタ
）アクリル酸エチル等の不飽和カルボン酸アルキルエス
テル；エチレン、プロピ慕ン等のオレフィン； （メタ
）アクリロニトリルなどの不飽和ニトリル；スチレン、
α−メチルスチレン、ｐ−メチルスチレン等の芳香族ビ
ニル；アリルグリシジルエーテル、グリシジルメタクリ
レート、ビニルシクロヘキセンモノオキサイド等の含エ
ポキシ車量体などが挙げられる。Moreover, it is also possible to use other copolymerizable monomers in combination, if necessary. Examples of other comonomers include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; methyl vinyl ether, isobutyl vinyl ether,
Vinyl ethers such as cetyl vinyl ether; vinylidenes such as vinylidene chloride and vinylidene fluoride; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride; diethyl maleate , unsaturated carboxylic acid alkyl esters such as dibutyl maleate, diethyl itaconate, methyl (meth)acrylate, and ethyl (meth)acrylate; olefins such as ethylene and propylene; unsaturated nitriles such as (meth)acrylonitrile; styrene,
Examples include aromatic vinyls such as α-methylstyrene and p-methylstyrene; epoxy-containing carmers such as allyl glycidyl ether, glycidyl methacrylate, and vinyl cyclohexene monoxide.
これらの共単量体は共重合体と他の樹脂とを混合したと
きの両者の相溶性及び軟化点を調節しつつ１．共重合体
の溶解性を向上する目的で使用される。These comonomers adjust the compatibility and softening point of the copolymer and other resin when they are mixed together. Used to improve the solubility of copolymers.
また、特に含エポキシ単量体を水酸基含有単量体及び塩
化ビニルと共重合する場合に、その共重合反応の過程で
または反応の前または後に水系または非水系でエポキシ
基部位に硫黄またはリンを含む強酸のアルカリ金属塩ま
たはアンモニウム塩を付加させる方法を採ることもでき
る。その場合における硫黄またはリンを含む強酸のアリ
カリ金属塩、またはアンモニウム塩の例としては、亜硫
酸カリウム、チオ硫酸ナトリウム、硫酸水素アンモニウ
ム、リン酸水素二ナトリウム、亜リン酸水素アンモニウ
ム、スルファニル酸カリウム、過硫酸カリウム、過リン
酸ナトリウムなどが挙げられる。このエポキシ基含有モ
ノマーと塩化ビニルとの共重合における硫黄またはリン
を含む強酸塩付加の方法は特開昭６０−２３８３０６
、特開昭６０−２３８３７１及び特開昭６１−５３３６
７により詳しく記載されている。In particular, when copolymerizing an epoxy-containing monomer with a hydroxyl-containing monomer and vinyl chloride, sulfur or phosphorus may be added to the epoxy group site in an aqueous or non-aqueous system during the copolymerization reaction, or before or after the reaction. It is also possible to adopt a method of adding an alkali metal salt or ammonium salt of a strong acid. Examples of alkali metal salts or ammonium salts of strong acids containing sulfur or phosphorus in that case include potassium sulfite, sodium thiosulfate, ammonium hydrogen sulfate, disodium hydrogen phosphate, ammonium hydrogen phosphite, potassium sulfanilate, Examples include potassium sulfate and sodium superphosphate. The method of adding a strong acid salt containing sulfur or phosphorus in the copolymerization of this epoxy group-containing monomer and vinyl chloride is disclosed in Japanese Patent Application Laid-Open No. 60-238306.
, JP-A-60-238371 and JP-A-61-5336
7 is described in more detail.
共重合体の重合度は２００〜９００、好ましくは２５０
〜５００である。２００未満では磁性層の耐摩耗性が不
充分であり、９００を越えると塗料の粘度が高く磁粉の
分散が不充分になりやすい。The degree of polymerization of the copolymer is 200 to 900, preferably 250
~500. If it is less than 200, the abrasion resistance of the magnetic layer will be insufficient, and if it exceeds 900, the viscosity of the paint will be high and the dispersion of magnetic particles will tend to be insufficient.
本発明に係る磁気塗料用樹脂は、公知のいずれの重合方
法を用いても製造し得る１重合体の溶解性の点からは溶
液重合や重合媒体としてメタノール、エタノールなどの
低級アルコール単独あるいは、これと脱イオン水との組
合せを使用した懸濁重合方法によって製造するのが好ま
しいし、また硫黄またはリンを含む強酸根を有する水溶
性塩を反応に使用する場合は乳化重合が好都合である。The resin for magnetic coatings according to the present invention can be produced by any known polymerization method.From the viewpoint of solubility of a single polymer, the resin can be produced by solution polymerization or by using a lower alcohol such as methanol or ethanol alone as a polymerization medium, or a lower alcohol such as methanol or ethanol. Preferably, they are prepared by a suspension polymerization method using a combination of 1 and 2 and deionized water, and emulsion polymerization is advantageous when water-soluble salts with strongly acidic radicals containing sulfur or phosphorus are used in the reaction.
樹脂の製造に使用される重合開始剤としては、例えば過
酸化ラウロイル、ジイソプロピルパーオキシジカーボネ
ート、ジー２−エチルヘキシルパーオキシジカーボネー
ト、ｔ−ブチルパーオキシピバレート、３．５．５−ト
リメプルヘキサノイルパーオキシドのごとき有機過酸化
物、α、α′アゾビスイソブチロニトリルのごときアブ
化合物、または過硫酸アンモニウム、過硫酸カリウムな
どがあげられる。懸濁剤としては、例えば、ポリビニル
アルコール、ポリ酢酸ビニルの部分ケン化物、メチルセ
ルロースなどのセルロース誘導体、ポリビニルピロリド
ン、無水マレイン酸−酢酸ビニル共重合体、ポリアクリ
ルアミドのごとき合成高分子物質、及びデンプン、ゼラ
チンなどの天然高分酸ソーダなどのアニオン性乳化剤や
ポリオキシエチレンアルキルエーテル、ポリオキシエチ
レンソルビタン脂肪酸部分エステルなどの非イオン性乳
化剤などがあげられる。また必要に応じてトリクロルエ
チレン、チオグリコールなどの分子ｉｔ調整剤を用いる
こともできる。前記した重合開始剤、塩化ビニルおよび
その他の単量体、懸濁剤、乳化剤、分子量調整剤などは
重合開始時に一括して重合系に添加してもよいし、重合
中に分割して添加することもできる０重合は通常３５〜
８０℃の温度で撹拌下にて行われる。Examples of polymerization initiators used in the production of resins include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, and 3.5.5-trimeprhexa. Examples include organic peroxides such as noyl peroxide, ab compounds such as α,α′ azobisisobutyronitrile, ammonium persulfate, potassium persulfate, and the like. Suspending agents include, for example, polyvinyl alcohol, partially saponified polyvinyl acetate, cellulose derivatives such as methylcellulose, polyvinylpyrrolidone, maleic anhydride-vinyl acetate copolymer, synthetic polymeric substances such as polyacrylamide, and starch. Examples include anionic emulsifiers such as natural high acid sodium chloride such as gelatin, and nonionic emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid partial ester. Further, molecular IT regulators such as trichlorethylene and thioglycol can also be used if necessary. The above-described polymerization initiator, vinyl chloride and other monomers, suspending agents, emulsifiers, molecular weight regulators, etc. may be added to the polymerization system all at once at the start of polymerization, or they may be added in portions during polymerization. 0 polymerization is usually 35~
It is carried out under stirring at a temperature of 80°C.
このようにして得られた塩化ビニル共重合体は、通常の
磁性塗料用塩化ビニル系樹脂バインダーと同様、一般に
はポリウレタン樹脂、ポリイソシアネート系に代表され
る硬化剤及び磁性粉末などと共に任意の溶剤溶液として
調製され、使用に供される。The vinyl chloride copolymer obtained in this way is generally used as a vinyl chloride resin binder for magnetic paints, and is generally used in an arbitrary solvent solution together with a polyurethane resin, a curing agent typified by polyisocyanate, and magnetic powder. It is prepared and ready for use.
ポリウレタン樹脂としてはポリエステルポリオール類又
はポリエーテルポリオール類とイソシアネート類との反
応によって得られたものが代表例として挙げられるが、
特に水酸基を残存するものが好ましい。また、所望に応
じて塩化ビニル−酢酸ビニル共重合体樹脂、繊維素系樹
脂、フェノキシ樹脂、エポキシ樹脂、ブチラール樹脂、
アクリル系樹脂及びアクリロニトリル−ブタジェンゴム
などの通常の磁気塗料用樹脂バインダーを本発明の目的
が達成される範囲で併用することも可能である。Typical examples of polyurethane resins include those obtained by reacting polyester polyols or polyether polyols with isocyanates.
Particularly preferred are those in which hydroxyl groups remain. In addition, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, phenoxy resin, epoxy resin, butyral resin,
It is also possible to use common resin binders for magnetic coatings, such as acrylic resins and acrylonitrile-butadiene rubber, as long as the object of the present invention is achieved.
また、磁性粉末としては、ｒ−Ｆｅ４０ｘ＋ Ｐｅ３０
＊、Ｃ。In addition, as magnetic powder, r-Fe40x+ Pe30
*,C.
含有γ−ＰｅｚＯ，，，Ｃｏ含有Ｆｅユ０４などの酸化
鉄の粉末及びＣｒｙ、粉末の他にＦｅ粉末、Ｆｅ−Ｃｏ
粉末などの金属磁性粉末も使用される。。In addition to powders of iron oxides such as γ-PezO,, Co-containing Fe-04, and Cry powders, Fe powders, Fe-Co
Metallic magnetic powders such as powders are also used. .
本発明に係る樹脂においては、水酸基含有成分として、
酢酸ビニル部分をケン化させた水酸基の代りに前記の水
酸基にかえることにより、イソシアネートとの反応性を
大幅に向上せしめうるので、これによって、反応に必要
な水酸基を大幅に減少させることができる。この理由に
ついては明らかではないが、反応にあずかる水酸基が共
重合体主鎖より離れていて自由度が増加していること、
及び水酸基の分布が均一であることによると思われる。In the resin according to the present invention, as a hydroxyl group-containing component,
By replacing the saponified hydroxyl group in the vinyl acetate portion with the above-mentioned hydroxyl group, the reactivity with isocyanate can be greatly improved, thereby making it possible to significantly reduce the number of hydroxyl groups required for the reaction. The reason for this is not clear, but the hydroxyl groups that participate in the reaction are separated from the main chain of the copolymer, increasing the degree of freedom.
This is probably due to the uniform distribution of hydroxyl groups.
なお、磁粉分散性の飛躍的向上の機構は、より小量の水
酸基により反応性が達成されることから、カルボキシル
基と水酸基との相互作用が減少することによると思われ
、磁性塗料の分散安定性の高さも、滑剤として常用され
る脂肪酸との相互作用の少なさに起因するものと考えら
れる。The mechanism of the dramatic improvement in magnetic powder dispersibility is thought to be due to the fact that reactivity is achieved with a smaller amount of hydroxyl groups, which reduces the interaction between carboxyl groups and hydroxyl groups, resulting in stable dispersion of the magnetic paint. The high properties are also thought to be due to the low interaction with fatty acids commonly used as lubricants.
以下に本発明を実施例によって具体的に説明する。なお
、各側における部数および％数は重量基準である。The present invention will be specifically explained below using examples. Note that parts and percentages on each side are based on weight.
実施例１
塩化イニル１００部、グリセリンモノアリルエーテル３
部、アセトン１８０部、過酸化ベンゾイル２部をオート
クレーブに仕込み、脱気後温度５０℃で重合を開始した
後、直ちに無水マレイン酸３部と塩化ビニリデン１０部
とメタノール４０部とを予め充分混合したものを、連続
的にオートクレーブ中に注入した後、反応圧力が１ ｋ
ｇ／ｃｄになったところで未反応塩化ビニルを回収し、
水２５０部を加えて７０℃に加温して溶媒と共重合体を
分離後乾燥して、樹脂Ａを得た。この樹脂を後述の樹脂
特性の評価（１）の試験法により磁気記録媒体用に適す
るかを評価した。Example 1 100 parts of inyl chloride, 3 parts of glycerin monoallyl ether
180 parts of acetone, and 2 parts of benzoyl peroxide were charged into an autoclave, and after degassing, polymerization was started at a temperature of 50°C. Immediately after, 3 parts of maleic anhydride, 10 parts of vinylidene chloride, and 40 parts of methanol were thoroughly mixed in advance. After continuously injecting the material into the autoclave, the reaction pressure is 1 k.
g/cd, unreacted vinyl chloride is collected,
Resin A was obtained by adding 250 parts of water and heating to 70°C to separate the solvent and copolymer, followed by drying. The suitability of this resin for use in magnetic recording media was evaluated by the test method (1) for evaluation of resin properties described below.
実施例２
塩化ビニル１００部、酢酸ビニル８部、アリル−２−ヒ
ドロキシエチルエーテル５部、イタコン酸３部、メタノ
ール１２０部、脱イオン水１２０部、メチルセルロース
０．６部、ラウリル硫酸ソーダ０．２部、過酸化ラウロ
イル１．２部をオートクレーブに仕込み、脱気後６０℃
で重合を開始させ３ｋｇ／−になったとき、未反応塩化
ビニルを回収し、脱液して共重合体を回収し、冷水で洗
浄して乾燥し樹脂Ｂを得た。この樹脂を樹脂特性の評価
（１１の試験法により評価した。Example 2 100 parts of vinyl chloride, 8 parts of vinyl acetate, 5 parts of allyl-2-hydroxyethyl ether, 3 parts of itaconic acid, 120 parts of methanol, 120 parts of deionized water, 0.6 parts of methyl cellulose, 0.2 parts of sodium lauryl sulfate. 1.2 parts of lauroyl peroxide were placed in an autoclave and heated to 60°C after degassing.
Polymerization was started, and when the weight reached 3 kg/-, unreacted vinyl chloride was collected, and the copolymer was collected by dehydration, washed with cold water, and dried to obtain resin B. This resin was evaluated for resin properties (evaluated by 11 test methods).
実施例３
アリル−２−ヒドロキシエチルエーテルにかえて、アリ
ル−２−ヒドロキシ−３−クロロプロピルエーテルを使
った以外は実施例２と同様に操作して、樹脂Ｃを得た。Example 3 Resin C was obtained in the same manner as in Example 2 except that allyl-2-hydroxy-3-chloropropyl ether was used instead of allyl-2-hydroxyethyl ether.
この樹脂を樹脂特性の評価（１）の試験法により評価し
た。This resin was evaluated by the test method of evaluation of resin properties (1).
実施例４
塩化ビニル６０部、アリル−２−ヒドロキシプロピルエ
ーテル５部、マレイン酸モノメチル２部、酢酸ビニル８
部、脱イオン水１５０部、アゾビスイソブチロニトリル
１部、ポリオキシエチレンステアリルエーテル１部、メ
チルセルロース０．１部をオートクレーブに仕込み、脱
気後６０℃で重合を開始させるとともに、塩化ビニル４
０部を重合開始後３時間目より、７時間目にわたって連
続的にオートクレーブ中に注入し、オートクレーブの圧
力が３ ｋｇ／ｃｄになったとき、未反応塩化ビニルを
回収し、脱水後脱イオン水で洗浄して乾燥し、樹脂りを
得た。この樹脂を樹脂特性の評価（１）の試験法により
評価した。Example 4 60 parts of vinyl chloride, 5 parts of allyl-2-hydroxypropyl ether, 2 parts of monomethyl maleate, 8 parts of vinyl acetate
1 part, deionized water 150 parts, azobisisobutyronitrile 1 part, polyoxyethylene stearyl ether 1 part, and methyl cellulose 0.1 part were charged into an autoclave, and after degassing, polymerization was started at 60°C, and vinyl chloride 4
0 part was continuously injected into an autoclave from 3 hours after the start of polymerization to 7 hours, and when the pressure of the autoclave reached 3 kg/cd, unreacted vinyl chloride was recovered, and after dehydration, deionized water was added. The resin was washed with water and dried to obtain a resin. This resin was evaluated by the test method of evaluation of resin properties (1).
実施例５
？ １Ｊルー２−ヒドロキシプロピルエーテルにかえて
、アリル−６−ヒドロキシエチルエーテルを使用した以
外は、実施例５と同様に操作して樹脂Ｅを得た。この樹
脂を樹脂特性の評価（１）の試験法により評価した。Example 5? Resin E was obtained in the same manner as in Example 5, except that allyl-6-hydroxyethyl ether was used instead of 1J-2-hydroxypropyl ether. This resin was evaluated by the test method of evaluation of resin properties (1).
比較例１
グリセリンモノアリルエーテルにかえて、２−ヒドロキ
シエチルメタクリレートを用いた以外は実施例１と同様
に操作して、樹脂Ｆを得た。この樹脂を樹脂特性の評価
（１）の試験法により評価した。Comparative Example 1 Resin F was obtained in the same manner as in Example 1 except that 2-hydroxyethyl methacrylate was used instead of glycerin monoallyl ether. This resin was evaluated by the test method of evaluation of resin properties (1).
比較例２
塩化ビニル１００部、イソブチルビニルエーテル１０部
、アセトン１８０部、過酸化ベンゾイル２部をオートク
レーブに仕込み、脱気後５５℃で重合を開始した後、直
ちにアクリル酸４．５部、水１、５部、メタノール４４
部の混合液と、２−ヒドロキシエチルメタクリレート５
部、メタノール４５部の混合液とを各々別の注入口より
連続的に、オートクレーブの圧力が２．０ｋｇ／−にな
るまでに全量注入し、さらに圧力が１．０ｋｇ／−にな
ったとき、未反応塩化ビニルを回収し、脱イオン水２５
０部を加え加温して、溶媒と共重合体を分離後、乾燥し
て樹脂Ｇを得た。この樹脂を樹脂特性（１）の試験法に
より評価した。Comparative Example 2 100 parts of vinyl chloride, 10 parts of isobutyl vinyl ether, 180 parts of acetone, and 2 parts of benzoyl peroxide were charged into an autoclave, and after degassing, polymerization was started at 55°C. Immediately after that, 4.5 parts of acrylic acid, 1 part of water, 5 parts, methanol 44
A mixture of 5 parts of 2-hydroxyethyl methacrylate and 5 parts of 2-hydroxyethyl methacrylate
Continuously inject a mixture of 1 part and 45 parts of methanol from separate injection ports until the pressure of the autoclave reaches 2.0 kg/-, and when the pressure reaches 1.0 kg/-, Collect unreacted vinyl chloride and add 25 ml of deionized water.
After adding 0 parts and heating, the solvent and copolymer were separated and dried to obtain Resin G. This resin was evaluated by the test method of resin characteristics (1).
比較例３
アリル−２−ヒドロキシプロピルエーテルにかえてヒド
ロキシプロピルメタクリレートを用いた以外は実施例４
と同様に操作して樹脂Ｈを得た。Comparative Example 3 Example 4 except that hydroxypropyl methacrylate was used instead of allyl-2-hydroxypropyl ether
Resin H was obtained in the same manner as above.
この樹脂を樹脂特性（１）の試験法により評価した。This resin was evaluated by the test method of resin characteristics (1).
比較例４
２−ヒドロキシエチルメタクリレートを２０部とし、イ
ソブチルビニルエーテルを使わない以外は比較例２と同
様にして樹脂Ｉを得た。この樹脂を樹脂特性［１）の試
験法により評価した。Comparative Example 4 Resin I was obtained in the same manner as Comparative Example 2, except that 2-hydroxyethyl methacrylate was used as 20 parts and that isobutyl vinyl ether was not used. This resin was evaluated by the test method of resin properties [1].
比較例５〜７
塩化ビニル５０部、酢酸ビニル２０部、アセトン１８０
部、過酸化ベンゾイル２部をオートクレーブに仕込み、
脱気後、５５℃で重合を開始し、オートクレーブの圧力
が０．５ｋｇ／ｄ低下する毎に塩化ビニルを１０部づつ
５回に分けて合計５０部注入した。一方、重合開始直後
より無水マレイン酸５部とメタノール４５部を連続的に
オートクレーブ内に注入し、オートクレーブの圧力が１
ｋｇ／−になったところで未反応の塩化ビニルを回収し
た０次に、メタノール１０００部、６５％硝酸６部の混
合液に反応液を加えて、７０℃で１２時間加温撹拌混合
した後、さらに１０００部の脱イオン水を加えて、共重
合体を媒体から分離回収した。Comparative Examples 5 to 7 50 parts of vinyl chloride, 20 parts of vinyl acetate, 180 parts of acetone
1 part and 2 parts of benzoyl peroxide into an autoclave.
After degassing, polymerization was started at 55° C., and 50 parts of vinyl chloride was injected into the autoclave in 5 parts each time the pressure of the autoclave decreased by 0.5 kg/d. On the other hand, immediately after the start of polymerization, 5 parts of maleic anhydride and 45 parts of methanol were continuously injected into the autoclave until the pressure of the autoclave was 1.
kg/-, unreacted vinyl chloride was collected.Next, the reaction solution was added to a mixture of 1000 parts of methanol and 6 parts of 65% nitric acid, and the mixture was stirred and heated at 70°C for 12 hours. An additional 1000 parts of deionized water was added to separate and recover the copolymer from the medium.
その後、アセトン５００部と共重合体を６０℃で撹拌混
合後メタノール１０００部を加えて、共重合体を分離回
収し、さらに、水洗し乾燥して樹脂Ｊを得た。この樹脂
を樹脂特性の評価（１）の試験法により評価した。Thereafter, 500 parts of acetone and the copolymer were stirred and mixed at 60° C., then 1000 parts of methanol was added, the copolymer was separated and recovered, and further washed with water and dried to obtain Resin J. This resin was evaluated by the test method of evaluation of resin properties (1).
これらの共重合体の組成を、市販の塩化ビニル−酢酸ビ
ニル−マレイン酸三元共重合体（Ｋ）、及び塩化ビニル
−酢酸ビニル−ビニルアルコール（Ｌ）とともに表１に
示した。なお、共重合体中のカルボキシ基の％は滴定に
より、また、水酸基の％は赤外吸光分析により求めた。The compositions of these copolymers are shown in Table 1 along with commercially available vinyl chloride-vinyl acetate-maleic acid terpolymer (K) and vinyl chloride-vinyl acetate-vinyl alcohol (L). The percentage of carboxy groups in the copolymer was determined by titration, and the percentage of hydroxyl groups in the copolymer was determined by infrared absorption analysis.
（樹脂特性の評価（１））
次に実施例１〜５及び比較例１〜７で得た試料の磁性塗
料及び磁気記録媒体としての評価を次に記す方法で行っ
た。その結果を表１に示す。(Evaluation of resin properties (1)) Next, the samples obtained in Examples 1 to 5 and Comparative Examples 1 to 7 were evaluated as magnetic paints and magnetic recording media by the following method. The results are shown in Table 1.
■）ポットライフ
塩化ビニル共重合体１００部を、メチルエチルケトン２
００部、メチルイソブチルケトン１００部及びトルエン
１００部よりなる混合溶剤に６５℃で１時間撹拌溶解さ
せて得た溶液にポリイソシアネート（日本ポリウレタン
工業■製、コロネートＬ）を塩化ビニル共重合体１００
部当り、２０部添加して２３℃で保存し、容器を逆さに
しても溶液が流動しなくなるまでの日数をポットライフ
とした。■) Add 100 parts of pot-life vinyl chloride copolymer to 2 parts of methyl ethyl ketone.
00 parts of vinyl chloride copolymer, 100 parts of methyl isobutyl ketone, and 100 parts of toluene with stirring at 65°C for 1 hour.
20 parts per part was added and stored at 23°C, and the pot life was defined as the number of days until the solution stopped flowing even when the container was turned upside down.
２）反応性
ポットライフ試験に用いた溶液をガラス板上にキャスト
して得たシートを６０℃で２４時間処理する。このシー
ト０．５ｇを精秤し５０ｇｒのテトラヒドロフランとと
もに２４時間混合したのち、不溶解分をろ過洗浄し、乾
燥して、精秤する。2) A sheet obtained by casting the solution used in the reactivity pot life test on a glass plate is treated at 60° C. for 24 hours. After accurately weighing 0.5 g of this sheet and mixing it with 50 g of tetrahydrofuran for 24 hours, insoluble matter is filtered and washed, dried, and accurately weighed.
ゲル分率＝不溶解分の重量／試料重量（％）３）熱安定
性
ポットライフ試験に用いた溶液を、水準器で水平に保っ
たガラス板上にキャストして、厚さ０．２鶴のシートと
し、これをＪＩＳ−に−６７２３に準じ８０℃のオイル
バス中で加熱し、コンゴレッド紙が変色するまでの時間
を測定する。Gel fraction = weight of undissolved content / weight of sample (%) 3) The solution used for the thermal stability pot life test was cast onto a glass plate kept horizontal with a spirit level, and a 0.2 mm thick sample was cast. This sheet is heated in an oil bath at 80° C. according to JIS-6723, and the time until the Congo red paper changes color is measured.
４）光沢性
コバルト被着磁性酸化鉄粉末４００部（比表面積３０ｍ
／ｇ）、塩化ビニル共重合体５０部、ポリウレタン樹脂
（水酸基量０．３％、１．４−ブタンジオールアジペー
ト−ＭＤＩ系 分子量７０．０００）４０部、メチルエ
チルケトン５００部、メチルイソブチルケトン３００部
、トルエン３００部、カーボンブランク２部、アルミナ
４部、ミリスチン酸２部、ブチルステアレート１部より
なる混合物を９０分間高速剪断分散した後、１５部のポ
リイソシアネート（日本ポリウレタン工業■製コロネー
トＬ）を加え、更に１５分間分散させ磁性塗料とした。4) 400 parts of glossy cobalt-coated magnetic iron oxide powder (specific surface area: 30 m
/g), 50 parts of vinyl chloride copolymer, 40 parts of polyurethane resin (hydroxyl group content 0.3%, 1.4-butanediol adipate-MDI system molecular weight 70.000), 500 parts methyl ethyl ketone, 300 parts methyl isobutyl ketone, After dispersing a mixture consisting of 300 parts of toluene, 2 parts of carbon blank, 4 parts of alumina, 2 parts of myristic acid, and 1 part of butyl stearate under high-speed shearing for 90 minutes, 15 parts of polyisocyanate (Coronate L manufactured by Nippon Polyurethane Industries, Ltd.) was added. In addition, the mixture was further dispersed for 15 minutes to obtain a magnetic paint.
得られた磁性塗料をポリエステルフィルム上に塗膜厚５
μｍとなるように塗布し磁場配向処理した後乾燥した。The obtained magnetic paint was applied to a polyester film with a film thickness of 5
It was coated to a thickness of μm, subjected to magnetic field orientation treatment, and then dried.
その磁性塗膜を光沢計を用いて６０部反射角の反射率を
測定した。The reflectance of the magnetic coating film at a reflection angle of 60 parts was measured using a glossmeter.
５）分散安定性
光沢性の評価に使用した塗料を１時間静置した後、ポリ
エステルフィルム上に塗膜厚５μｍとなる様に塗布し、
磁場配向処理した後乾燥し、その磁性塗膜を光沢計を用
いて６０部反射角の反射率を測定した。5) Dispersion stability After allowing the paint used to evaluate glossiness to stand for 1 hour, it was applied onto a polyester film to a film thickness of 5 μm.
After being subjected to magnetic field orientation treatment, it was dried, and the reflectance of the magnetic coating film at a 60 parts reflection angle was measured using a gloss meter.
６）角型比（ｆｉｒ／ａｍ）
光沢性の評価に使用した磁性塗膜を１２．５ ｎ＋ ｘ
５０ｍｍに切出して、磁気特性測定機により測定した。6) Squareness ratio (fir/am) The magnetic coating used for gloss evaluation was 12.5 n+ x
It was cut into 50 mm pieces and measured using a magnetic property measuring machine.
７）耐久性
光沢性評価に用いた磁性塗膜をカレンダーロールで平滑
化処理してから６５℃で６５時間加熱処理した後、荷重
１００ｇをかけ、研摩紙を張付けた回転ドラムに接触さ
せて、１５０ｒｐｍで回転させ、磁性塗料が研摩紙に付
着した程度を目視してＡ、Ｂ、Ｃの三段階で測定した。7) The magnetic coating used for durability and gloss evaluation was smoothed with a calendar roll and then heat-treated at 65°C for 65 hours, and then brought into contact with a rotating drum covered with abrasive paper under a load of 100 g. It was rotated at 150 rpm, and the extent to which the magnetic paint adhered to the abrasive paper was visually observed and measured in three stages A, B, and C.
Ａ：汚れなし、Ｂ：汚れ少しあり、Ｃ：汚れが多い
実施例６
重合器にメタノール１１７部、メチルセルロース０．６
部、ポリオキシエチレンソルビタン脂肪酸部分エステル
０．２部を仕込んで封缶し、減圧脱気後、塩化ビニル１
００部、酢酸ビニル１０部、アリル−２−ヒドロキシプ
ロピルエーテル６部を仕込み５０℃で撹拌した。その後
３，５．５−トリメチルヘキサノイルパーオキシド０．
６部を仕込んで重合を開始すると同時に、メタノール８
０部に溶解させた２−アクリルアミド−２−メチルプロ
パンスルホン酸３部を８時間で全量消費される様に一定
速度で連続的に仕込んだ０反応１０時間後、重合器の圧
力が２ｋｇ／ｃ＋Ｊになった時点で冷却し、未反応塩化
ビニルを回収した後、脱液、洗滌、乾燥して樹脂（Ｎ）
を得た。この樹脂を後述の樹脂特性の評価（２）の試験
法により磁気記録媒体用に適するかを評価した。A: No stain, B: Slight stain, C: Much stain Example 6 117 parts of methanol and 0.6 parts of methylcellulose were added to the polymerization vessel.
1 part, 0.2 part of polyoxyethylene sorbitan fatty acid partial ester was charged, the can was sealed, and after degassing under reduced pressure, 1 part of vinyl chloride was charged.
00 parts of vinyl acetate, 10 parts of vinyl acetate, and 6 parts of allyl-2-hydroxypropyl ether were charged and stirred at 50°C. Then 3,5,5-trimethylhexanoyl peroxide 0.
At the same time, 8 parts of methanol was added to start polymerization.
After 10 hours of 0 reaction, 3 parts of 2-acrylamido-2-methylpropanesulfonic acid dissolved in 0 parts was continuously charged at a constant rate so that the entire amount was consumed in 8 hours, and the pressure in the polymerization vessel was 2 kg/c+J. At the point when
I got it. The suitability of this resin for use in magnetic recording media was evaluated by the test method (2) for evaluation of resin properties described below.
実施例７
２−アクリルアミド−２−メチルプロパンスルホン酸に
かえてメタクリル酸−２−リン酸エチルを使用した以外
は実施例６と同様に操作して樹脂（０）を得た。この樹
脂を樹脂特性の評価（２）の試験法により評価した。Example 7 Resin (0) was obtained in the same manner as in Example 6 except that ethyl methacrylate-2-phosphate was used instead of 2-acrylamido-2-methylpropanesulfonic acid. This resin was evaluated by the test method of evaluation of resin properties (2).
実施例８
２−アクリルアミド−２−メチルプロパンスルホン酸に
かえてスチレンスルホン酸ナトリウムを使用した以外は
実施例６と同様に操作して樹脂ＣＰ）を得た。この樹脂
を樹脂特性の評価（２）の試験法により評価した。Example 8 Resin CP) was obtained in the same manner as in Example 6, except that sodium styrene sulfonate was used instead of 2-acrylamido-2-methylpropanesulfonic acid. This resin was evaluated by the test method of evaluation of resin properties (2).
実施例９
アリル−２−ヒドロキシエチルエーテルにかえでオイゲ
ノールを使用した以外は、実施例子と同様に操作して樹
脂（Ｑ）を得た。この樹脂を樹脂特性の評価（２）の試
験法により評価した。Example 9 Resin (Q) was obtained in the same manner as in Example except that eugenol was used instead of allyl-2-hydroxyethyl ether. This resin was evaluated by the test method of evaluation of resin properties (2).
実施例１０
重合器に、アセトン１８０℃、脱イオン水７０部、過酸
化ラウロイル２部、アリル−２−ヒドロキシ−３−クロ
ロプロピルエーテル６部、３−アリロキシ−２−ヒドロ
キシプロパン硫酸アンモニウーム１０部、イソブチルビ
ニルエーテル１０部を仕込んで脱気後場化ビニル１００
部を仕込み、５５℃に昇温した６重合圧力が３ｋｇ／−
になったら、未反応塩化ビニルを減圧回収して、反応液
を脱イオン水１０００部と混合し、樹脂を分離し、乾燥
して樹脂（Ｒ）を得た。Example 10 Acetone at 180°C, 70 parts of deionized water, 2 parts of lauroyl peroxide, 6 parts of allyl-2-hydroxy-3-chloropropyl ether, and 10 parts of 3-allyloxy-2-hydroxypropane ammonium sulfate were placed in a polymerization vessel. After adding 10 parts of isobutyl vinyl ether and degassing, 100 parts of vinyl ether was added.
The polymerization pressure was 3 kg/- when the temperature was raised to 55℃.
When the temperature reached 1, unreacted vinyl chloride was recovered under reduced pressure, the reaction solution was mixed with 1000 parts of deionized water, and the resin was separated and dried to obtain resin (R).
実施例１１
重合器に、脱イオン水１５０部、ラウリル硫酸ナトリウ
ム１部、過硫酸カリウム１部を仕込み、脱気後、塩化ビ
ニル６０部、酢酸ビニル３部、イソブチルビニルエーテ
ル３部、アリル−２−ヒドロキシプロピルエーテル６部
を仕込んで６０℃に昇温しで重合を開始した０重合開始
後、スチレンスルホン酸ナトリウム２部と水５０部の混
合液を連続的に１０時間にわたって注入する一方４０部
の塩化ビニルを４分割して仕込み１０時間反応させた後
、未反応塩化ビニルを回収して重合液を得た。この重合
液１００部にメチルエチルケトン５部を混合して、凍結
、融解して重合物を回収洗浄し乾燥して、樹脂（Ｓ）を
得た。この樹脂を樹脂特性の評価法（２）の試験法によ
り評価した。Example 11 A polymerization vessel was charged with 150 parts of deionized water, 1 part of sodium lauryl sulfate, and 1 part of potassium persulfate, and after degassing, 60 parts of vinyl chloride, 3 parts of vinyl acetate, 3 parts of isobutyl vinyl ether, and allyl-2- 6 parts of hydroxypropyl ether was charged and the temperature was raised to 60°C to start polymerization. After the start of polymerization, a mixture of 2 parts of sodium styrene sulfonate and 50 parts of water was continuously injected over 10 hours, while 40 parts of Vinyl chloride was divided into four parts and reacted for 10 hours, and unreacted vinyl chloride was collected to obtain a polymerization solution. 100 parts of this polymerization solution was mixed with 5 parts of methyl ethyl ketone, frozen and thawed, and the polymer was collected, washed and dried to obtain a resin (S). This resin was evaluated by the test method of resin property evaluation method (2).
比較例８
アリル−２−ヒドロキシプロピルエーテルを使わず、２
−ヒドロキシプロピルメタクリレート８部を２−アクリ
ルアミド−２−メチルプロパンスルホン酸３部とともに
、反応中に仕込んだ以外は実施例６と同様に操作して樹
脂（Ｔ）を得た。この樹脂を樹脂特性の評価法（２）の
試験法により評価した。Comparative Example 8 Without using allyl-2-hydroxypropyl ether, 2
Resin (T) was obtained in the same manner as in Example 6, except that 8 parts of -hydroxypropyl methacrylate and 3 parts of 2-acrylamido-2-methylpropanesulfonic acid were charged during the reaction. This resin was evaluated by the test method of resin property evaluation method (2).
比較例９
２−ヒドロキシプロピルメタクリレートにかえてプロピ
ルメタクリレートを使用した以外は比較例８と同様に操
作して樹脂（Ｕ）を得た。この樹脂を樹脂特性の評価法
（２）の試験法により評価した。Comparative Example 9 Resin (U) was obtained in the same manner as Comparative Example 8 except that propyl methacrylate was used instead of 2-hydroxypropyl methacrylate. This resin was evaluated by the test method of resin property evaluation method (2).
比較例１０
２−アクリルアミド−２−メチルプロパンスルホン酸を
使用しなかった以外は実施例６と同様に操作して樹脂（
Ｖ）を得た。この樹脂を樹脂特性の評価法（２）の試験
法により評価した。Comparative Example 10 Resin (
V) was obtained. This resin was evaluated by the test method of resin property evaluation method (2).
比較例１１
市販の塩化ビニル−酢酸ビニル−ビニルアルコール共重
合体（Ｍｉ成：塩化ビニル９１重量％、酢酸ビニル３重
量％、ビニルアルコール６重量％）１００部、２−クロ
ロエチルスルホン酸ナトリウム１０部及びジメチルホル
ムアミド５００部を２０℃にて撹拌混合し、この混合液
中に、ピリジン５部を少量ずつ滴下し、３時間撹拌部合
を続けた。得られた反応液を脱イオン水５０００部と混
合して樹脂を回収し、テトラヒドロフランに溶解させた
後、メタノールにより再沈操作を行い、乾燥して樹脂（
Ｗ＞を得た。この樹脂を樹脂特性の評価法（２）の試験
法により評価した。Comparative Example 11 100 parts of commercially available vinyl chloride-vinyl acetate-vinyl alcohol copolymer (Mi composition: 91% by weight of vinyl chloride, 3% by weight of vinyl acetate, 6% by weight of vinyl alcohol), 10 parts of sodium 2-chloroethylsulfonate and 500 parts of dimethylformamide were stirred and mixed at 20° C., 5 parts of pyridine was added dropwise little by little into this mixed solution, and stirring was continued for 3 hours. The resulting reaction solution was mixed with 5000 parts of deionized water to recover the resin, dissolved in tetrahydrofuran, reprecipitated with methanol, dried, and the resin (
W> was obtained. This resin was evaluated by the test method of resin property evaluation method (2).
比較例１２〜１４
アセトン１８０部、過酸化ベンゾイル２部、酢酸ビニル
２５部を重合器に仕込み、脱気後、塩化ビニル５０部を
仕込んで５５℃で重合を開始した後、スチレンスルホン
酸ナトリウム３部と脱イオン水１７部との混合液を連続
的に一定速度で８時間にわたって注入する一方、５０部
の塩化ビニルを４分割して仕込み、１０時間反応させた
後、未反応塩化ビニルを回収して重合液を得た。この重
合液にメタノール３００部、６５％硝酸６部を加えて８
０℃で１２時間加温撹拌混合した後、１０００部の脱イ
オン水を加えて樹脂を分離した。さらにアセトン４００
部とプロピオンオキサイド５部を加えて、６０℃で２時
間混合したあとメタノール１０００部と混合して、脱液
乾燥して樹脂（Ｘ）を得た。この樹脂を樹脂特性の評価
法（２）の試験法により評価した。Comparative Examples 12 to 14 180 parts of acetone, 2 parts of benzoyl peroxide, and 25 parts of vinyl acetate were charged into a polymerization vessel, and after degassing, 50 parts of vinyl chloride was charged and polymerization was started at 55°C, followed by 3 parts of sodium styrene sulfonate. A mixture of 50 parts of vinyl chloride and 17 parts of deionized water was continuously injected at a constant rate for 8 hours, while 50 parts of vinyl chloride was charged in 4 parts and reacted for 10 hours, after which unreacted vinyl chloride was recovered. A polymerization solution was obtained. To this polymerization solution, 300 parts of methanol and 6 parts of 65% nitric acid were added.
After heating and stirring at 0°C for 12 hours, 1000 parts of deionized water was added to separate the resin. Furthermore, acetone 400
1 part and 5 parts of propion oxide were added thereto, mixed at 60° C. for 2 hours, mixed with 1000 parts of methanol, and dried to obtain resin (X). This resin was evaluated by the test method of resin property evaluation method (2).
これらの樹脂の性状を市販の塩化ビニル−酢酸ビニル−
マレイン酸三元共重合体（Ｙ）及び塩化ビニル−酢酸ビ
ニル−ビニルアルコール三元共重合体（Ｚ）とともに表
２に示した。なお樹脂中の水酸基量は赤外吸光分析によ
り、塩化ビニル量は燃焼による塩素の定量により、強酸
根は元素分析と赤外吸光分析の併用によりそれぞれ求め
た。The properties of these resins are as follows: commercially available vinyl chloride-vinyl acetate-
It is shown in Table 2 together with the maleic acid terpolymer (Y) and the vinyl chloride-vinyl acetate-vinyl alcohol terpolymer (Z). The amount of hydroxyl groups in the resin was determined by infrared absorption analysis, the amount of vinyl chloride was determined by quantifying chlorine by combustion, and the amount of strong acid groups was determined by a combination of elemental analysis and infrared absorption analysis.
（樹脂特性の評価（２））
次に実施例６〜１１及び比較例８〜１４で得た各樹脂を
磁性塗料及び磁気記録媒体としての評価に供した。その
結果を表２に示す。なお、評価方法は下記に依った。(Evaluation of resin properties (2)) Next, the resins obtained in Examples 6 to 11 and Comparative Examples 8 to 14 were evaluated as magnetic paints and magnetic recording media. The results are shown in Table 2. The evaluation method was as follows.
１）熔解性
塩化ビニル共重合体１００部、メチルエチルケトン２０
０部、トルエン２００部よりなる溶液をつくり、この溶
液の透明性の程度を目視してＡ。1) 100 parts of soluble vinyl chloride copolymer, 20 parts of methyl ethyl ketone
Prepare a solution consisting of 0 parts of toluene and 200 parts of toluene, and visually check the degree of transparency of this solution.
Ｂ、Ｃの三段階で判定した。Judgment was made in three stages: B and C.
Ａ：透明、Ｂ：不溶解物少、Ｃ：不溶解物多２）熱安定
性
塩化ビニル共重合体１．０グラムを１５ｃｃ試験管に採
り、その開口部をコンゴーレッド試験紙をはさんだ脱脂
綿で栓をして１５０℃のオイルバス中に置き、発生する
塩酸によってコンゴーレッド試験紙が変色するまでの時
間を測定した。A: Transparent, B: Few insolubles, C: Many insolubles 2) 1.0 g of heat-stable vinyl chloride copolymer was placed in a 15 cc test tube, and the opening was covered with absorbent cotton with Congo red test paper in between. The container was sealed with a stopper and placed in an oil bath at 150° C., and the time until Congo red test paper changed color due to the generated hydrochloric acid was measured.
３）分散安定性
金属鉄磁性粉４００部、塩化ビニル共重合体１００部、
メチルエチルケトン３００部、メチルイソブチルケトン
３００部、トルエン３００部からなる混合物を９０分間
高速剪断分散させた。この分散塗料をサンプル瓶に採取
して２５℃の恒温槽内に保存し、ゲルの発生状況を観察
した。ゲルが発生しているか否かは、分散塗料の一部を
ガラス板上に取出し、約５倍量のメチルエチルケトンで
希釈し、ガラス棒を用いて混合して目視する方法によっ
た。ゲル発生の少ない順にＡ、Ｂ、Ｃで示す。3) 400 parts of dispersion-stable metal iron magnetic powder, 100 parts of vinyl chloride copolymer,
A mixture consisting of 300 parts of methyl ethyl ketone, 300 parts of methyl isobutyl ketone, and 300 parts of toluene was subjected to high-speed shear dispersion for 90 minutes. This dispersed paint was collected in a sample bottle and stored in a constant temperature bath at 25° C., and the state of gel formation was observed. The generation of gel was determined by taking out a portion of the dispersed paint onto a glass plate, diluting it with about 5 times the amount of methyl ethyl ketone, mixing with a glass rod, and visually observing. They are shown as A, B, and C in descending order of gel formation.
４）光沢性
金属鉄磁性粉４００部、塩化ビニル共重合体７０部、ポ
リウレタン樹脂（日本ポリウレタンエ業■製ニッポラン
２３０４）３０部、メチルエチルケトン３００部、メチ
ルイソブチルケトン３００部、トルエン３００部、高級
脂肪酸４部、シリコンオイル２部よりなる混合物を９０
分間高速剪断分散させた後ポリイソシアネート（日本ポ
リウレタン工業側製コロネートし）１５部及びシクロへ
キサノン１００部を加え、更に９０分間分散させ磁性塗
料とした。得られた磁性塗料をポリエステルフィルム上
に塗膜厚５μｍとなるように塗布し磁場配向処理した後
乾燥した。その磁性塗膜の６０部反射角の反射率を光沢
針を用いて測定した。4) 400 parts of shiny metallic iron magnetic powder, 70 parts of vinyl chloride copolymer, 30 parts of polyurethane resin (Nipporan 2304 manufactured by Nippon Polyurethane Industry Co., Ltd.), 300 parts of methyl ethyl ketone, 300 parts of methyl isobutyl ketone, 300 parts of toluene, higher fatty acid 90 parts of a mixture of 4 parts and 2 parts of silicone oil.
After high-speed shear dispersion for a minute, 15 parts of polyisocyanate (Coronate, manufactured by Nippon Polyurethane Industries) and 100 parts of cyclohexanone were added, and the mixture was further dispersed for 90 minutes to obtain a magnetic paint. The obtained magnetic paint was applied onto a polyester film to a film thickness of 5 μm, subjected to magnetic field orientation treatment, and then dried. The reflectance of the magnetic coating film at a reflection angle of 60 parts was measured using a glossy needle.
５）角型比（Ｂｒ／Ｂａｄ）
光沢性の評価に使用した磁性塗膜を１２．５ｆｌＸ５０
龍に切出して、磁気特性測定機により測定した。5) Squareness ratio (Br/Bad) The magnetic coating used for gloss evaluation was 12.5 fl x 50
It was cut out into a dragon shape and measured using a magnetic property measuring machine.
６）耐久性
光沢性評価に用いた磁性塗膜をカレンダーロールで平滑
化処理してから６．５℃で６５時間加熱処理した後、荷
重１００ｇをかけ、研摩紙を張り付けた回転ドラムに接
触させて、１５０ｒｐｍで回転させ、磁性塗料が研摩紙
に付着した程度を目視してＡ、 Ｂ、 Ｃ，Ｄの四段
階で判定した。6) The magnetic coating used for durability and gloss evaluation was smoothed with a calendar roll, then heat treated at 6.5°C for 65 hours, and then brought into contact with a rotating drum covered with abrasive paper under a load of 100g. The paper was rotated at 150 rpm, and the degree of adhesion of the magnetic paint to the abrasive paper was visually observed and evaluated in four grades: A, B, C, and D.
Ａ：汚れなし、Ｂ：ごく僅かに汚れあり、Ｃ：汚れ少し
あり、Ｄ：汚れ多い
７）走行性
耐久性評価と同じ方法で塗膜と回転ドラム間に発生する
力を６５℃、相対湿度８０％の雰囲気でＵゲージにより
測定し、走行抵抗が少ない順にＡ。A: No stain, B: Slight stain, C: Slight stain, D: Lots of stain 7) The force generated between the paint film and the rotating drum was measured at 65°C and relative humidity using the same method as in running performance and durability evaluation. Measured using a U gauge in an 80% atmosphere, A is ranked in descending order of running resistance.
Ｂ、Ｃの三段階で判定した。Judgment was made in three stages: B and C.
Ａ：低い、Ｂ：中位い、Ｃ：高いA: Low, B: Medium, C: High
Claims (1)
びカルボン酸基または硫黄もしくはリンを含む強酸根を
含有する塩化ビニルの共重合体で、該水酸基を供給する
単量体がポリヒドロキシ化合物のモノアリルエーテルで
あることを特徴とする磁性塗料。 ２、磁性粉のバインダーの少なくとも一成分が水酸基及
びカルボン酸基または硫黄もしくはリンを含む強酸根を
含有する塩化ビニルの共重合体で、該水酸基を供給する
単量体がポリヒドロキシ化合物のモノアリルエーテルの
樹脂である磁性塗料を用いることを特徴とする磁気記録
媒体。[Claims] 1. At least one component of the binder of the magnetic powder is a vinyl chloride copolymer containing a hydroxyl group and a carboxylic acid group or a strong acid group containing sulfur or phosphorus, and the monomer supplying the hydroxyl group is A magnetic paint characterized by being a monoallyl ether of a polyhydroxy compound. 2. At least one component of the binder of the magnetic powder is a copolymer of vinyl chloride containing a hydroxyl group and a carboxylic acid group or a strong acid group containing sulfur or phosphorus, and the monomer that supplies the hydroxyl group is a monoallyl of a polyhydroxy compound. A magnetic recording medium characterized by using a magnetic paint made of ether resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1255384A JPH0681812B2 (en) | 1988-10-26 | 1989-09-30 | Magnetic paint and magnetic recording medium |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27057388 | 1988-10-26 | ||
| JP63-270573 | 1988-10-26 | ||
| JP1255384A JPH0681812B2 (en) | 1988-10-26 | 1989-09-30 | Magnetic paint and magnetic recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02209972A true JPH02209972A (en) | 1990-08-21 |
| JPH0681812B2 JPH0681812B2 (en) | 1994-10-19 |
Family
ID=26542184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1255384A Expired - Fee Related JPH0681812B2 (en) | 1988-10-26 | 1989-09-30 | Magnetic paint and magnetic recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0681812B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013640A (en) * | 2006-07-05 | 2008-01-24 | Fuji Xerox Co Ltd | Magnetic polymer particle, method for producing the same and aqueous dispersion |
| JP2011525034A (en) * | 2008-06-09 | 2011-09-08 | ビーエーエスエフ ソシエタス・ヨーロピア | Dispersion for applying metal layer |
| JP2012140598A (en) * | 2010-12-31 | 2012-07-26 | Rohm & Haas Co | New polymeric bead composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60206876A (en) * | 1984-03-30 | 1985-10-18 | Nippon Zeon Co Ltd | Magnetic paint resin |
| JPS60235814A (en) * | 1984-05-08 | 1985-11-22 | Nippon Zeon Co Ltd | Resin for magnetic paint |
-
1989
- 1989-09-30 JP JP1255384A patent/JPH0681812B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60206876A (en) * | 1984-03-30 | 1985-10-18 | Nippon Zeon Co Ltd | Magnetic paint resin |
| JPS60235814A (en) * | 1984-05-08 | 1985-11-22 | Nippon Zeon Co Ltd | Resin for magnetic paint |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013640A (en) * | 2006-07-05 | 2008-01-24 | Fuji Xerox Co Ltd | Magnetic polymer particle, method for producing the same and aqueous dispersion |
| JP2011525034A (en) * | 2008-06-09 | 2011-09-08 | ビーエーエスエフ ソシエタス・ヨーロピア | Dispersion for applying metal layer |
| JP2012140598A (en) * | 2010-12-31 | 2012-07-26 | Rohm & Haas Co | New polymeric bead composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0681812B2 (en) | 1994-10-19 |
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