JPH0363123B2 - - Google Patents
Info
- Publication number
- JPH0363123B2 JPH0363123B2 JP15355684A JP15355684A JPH0363123B2 JP H0363123 B2 JPH0363123 B2 JP H0363123B2 JP 15355684 A JP15355684 A JP 15355684A JP 15355684 A JP15355684 A JP 15355684A JP H0363123 B2 JPH0363123 B2 JP H0363123B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- magnetic
- copolymer
- vinyl
- 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
Links
- 230000005291 magnetic effect Effects 0.000 claims description 34
- 229920001577 copolymer Polymers 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 13
- 230000005294 ferromagnetic effect Effects 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 150000003460 sulfonic acids Chemical class 0.000 claims description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- 239000011230 binding agent Substances 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 22
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000006247 magnetic powder Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000005415 magnetization Effects 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- 229910006069 SO3H Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 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
- 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 1
- FXKMTSIKHBYZSZ-UHFFFAOYSA-N 2-chloroethanesulfonic acid Chemical compound OS(=O)(=O)CCCl FXKMTSIKHBYZSZ-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 CoâNi Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- VZBZCLRLPBEOBO-UHFFFAOYSA-N carboxyoxy octan-3-yl carbonate Chemical compound CCCCCC(CC)OC(=O)OOC(O)=O VZBZCLRLPBEOBO-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- MPOGZNTVZCEKSW-UHFFFAOYSA-N ethenyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC=C MPOGZNTVZCEKSW-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000003449 preventive effect Effects 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
- 238000005185 salting out Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Magnetic Record Carriers (AREA)
Description
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(Industrial Application Field) The present invention relates to a magnetic recording medium, and in particular an improvement using a special ternary copolymer mainly composed of vinyl chloride, which exhibits excellent performance as a binder for ferromagnetic powder. The present invention relates to magnetic recording media. (Prior Art) Magnetic recording media are generally made by applying magnetic powder to the surface of a support such as polyester using a binder such as synthetic resin. Examples of magnetic powders include γ-Fe 2 O 3 , Fe 3 O 4 and those obtained by adsorbing or doping cobalt ions, or Cr 2 O, as well as Fe, Co, Fe, etc.
-Acicular fine particles containing Co or Ni in some cases are used, but in recent years household use
With the spread of VTRs and the improved performance of audio cassette tapes, high signal density and high playback output for short wavelength recording are required. In order to cope with these trends, magnetic powder has become finer than ever before, and has an extremely large magnetic moment, which causes the particles to coagulate with each other, making it possible to disperse them more uniformly in the binder resin than before. It's becoming difficult. To solve this technical problem, from the viewpoint of improving the affinity of the binder resin for magnetic powder, it is necessary to impart to the binder resin the hydrophilic properties of the particle surface of metal oxide and alloy fine particles, which are magnetic fine particles. It is being widely studied. For example, hydrophilic functional groups such as carboxyl groups and hydroxyl groups have been introduced into the vinyl chloride-vinyl acetate copolymer, which has been used practically as a binder. , No. 4 (1981), pp. 155-162, "Magnetic Tape and Polymers," contains a research report on introducing various hydrophilic functional groups into polymeric materials used as binders for magnetic paints. According to this document, the types of anchor segments in the binder and the order of functional group effects are described as follows. JP-A No. 58-108032 also describes the introduction of sulfonic acid groups into binder resins. , vinylsulfonic acid, vinylbenzenesulfonic acid, 2-acrylamide-2-
It has been disclosed that a polymer obtained by copolymerizing a polymerizable unsaturated sulfonic acid such as methylpropanesulfonic acid is used as a binder for magnetic powder. However, although the introduction of sulfonic acid groups does have an excellent effect on improving the dispersibility of magnetic powder when examined, for example, in the case of vinyl chloride-vinyl fatty acid copolymers, the introduction of sulfonic acid groups is still effective in improving the dispersibility of magnetic powders. It appears to be insufficient, and also has the disadvantage that the amount of saturation magnetization decreases significantly over time. Note that the introduction of carboxyl groups or hydroxyl groups has a small effect on improving dispersibility, and the purpose is not achieved. On the other hand, for copolymers into which vinyl alcohol units have been introduced, such as vinyl chloride-vinyl acetate-vinyl alcohol copolymers, -SO 3 M, -COOM, -OSO 3 M, etc. are added for the purpose of improving the dispersibility of the OH groups. It has been proposed to use a polymer formed by introducing a hydrophilic group containing a group (M is a metal atom) as a binder resin for magnetic powder. However, this binder resin is manufactured through a complicated three-step reaction process: copolymerization of vinyl chloride and vinyl acetate, saponification of the copolymer, and sulfonation of the saponified product, so it is not suitable for industrial use. Not only is the cost high, but because each molecule contains an OH group, a Cl atom, and a metal base such as an SO 3 M group, a de-HCl reaction occurs, which deteriorates the magnetic properties over time and reduces the saturation magnetization. There is a drawback that it decreases significantly. (Structure of the Invention) The present inventors have solved the above-mentioned drawbacks, and have created a bond that has better dispersibility for various magnetic powders and has excellent durability without causing deterioration of magnetic properties over time. The present invention was achieved as a result of extensive research aimed at developing a magnetic recording medium and using it to obtain a magnetic recording medium with high performance and reliability. That is, the present invention provides a copolymer obtained by copolymerizing vinyl chloride, a fatty acid vinyl ester having 8 to 16 carbon atoms, and a polymerizable unsaturated sulfonic acid on a support, and then neutralizing it with a basic substance. The present invention relates to a magnetic recording medium in which a magnetic layer in which fine ferromagnetic powder is dispersed is formed. The binder resin used in the present invention has excellent dispersibility and filling properties of the ferromagnetic fine powder, has sufficient compatibility with the polyurethane resin etc. used in combination, and also has vinyl acetate in the molecule. Since it does not contain units such as vinyl propionate, it has various performance advantages such as thermal decomposition reactions and dehydrochlorination reactions are extremely difficult to occur, so by using it, high performance magnetic recording with improved long-term durability can be achieved. medium can be obtained. The present invention will be explained in detail below. The binder resin used in the present invention is a copolymer of each of the monomers described above neutralized with a basic substance, and this copolymer is particularly suitable for vinyl chloride units.
65 to 90% by weight, 8 to 25% by weight of fatty acid vinyl ester units having 8 to 16 carbon atoms, and 0.1 to 10% by weight of polymerizable unsaturated sulfonic acid units, and having an average degree of polymerization of 200 to 800. It is desirable to do so. If the vinyl chloride unit is too small, the physical strength will be reduced, and if it is too large, the solubility will be reduced, which is disadvantageous in use. Regarding fatty acid vinyl ester units, those with a small number of carbon atoms, such as vinyl acetate, vinyl propionate, vinyl lactate, etc., will not only have poor dispersibility, but also cause thermal decomposition of these units, resulting in the elimination of vinyl chloride. Hydrochloric acid is accelerated and the durability of magnetic recording media (magnetic tape, etc.) decreases. On the other hand, if this fatty acid vinyl ester is a polymer with a total number of carbon atoms of 17 or more in the molecule, such as vinyl stearate, the dispersibility will decrease, so if the total number of carbon atoms in the molecule is in the range of 8 to 16, the dispersibility will decrease. It is desirable to use certain fatty acid vinyl esters. This fatty acid moiety can be both linear and branched, but for the purposes of the present invention, branched fatty acids are preferred, specifically birtissuccinic acid (trade name manufactured by Ciel Chemical Co., Ltd., carbon number 9, 10 or 11 tertiary monocarboxylic acids) is preferred. In addition, if the amount of fatty acid vinyl ester units in the copolymer is too small, the solubility will decrease, and if it is too large, the dispersibility of the ferromagnetic powder will decrease, and the thermal stability will also decrease, causing magnetic deterioration over time. The content is preferably in the range of 8 to 25% by weight. As polymerizable unsaturated sulfonic acids, CH 2 = CH-SO 3 H, CH 2 = CH-C 6 H 4 -
SO3H , CH2 =CH-CO-NH-C( CH3 ) 2
( CH2SO3H ), (However, R' in the formula is an alkyl group having 12 to 14 carbon atoms) CH2 =CH( CH3 )-CO-O- C4O8 - SO3H , CH2 =CH( CH3 )-CO- Examples include O - C2H4 - SO3H . If the amount of polymerizable unsaturated sulfonic acid is too large, the solubility will be poor and gelation will easily occur, while if the amount is too small, the dispersibility of the magnetic powder will be poor. Therefore, it is desirable that the amount of this polymerizable unsaturated sulfonic acid be within the range described above, particularly within the range of 0.5 to 7% by weight. Regarding the degree of polymerization of the copolymer, if it is too low, its strength as a binder will be reduced and powder will easily fall off, reducing durability. If it is too high, the viscosity will become high, resulting in poor workability and reduced dispersibility. Therefore, it is desirable that the average degree of polymerization is in the range of 200 to 800 (particularly 250 to 500). In addition, if a polymerizable unsaturated sulfonic acid salt is used in the copolymerization instead of the above polymerizable unsaturated sulfonic acid,
This sulfonate has poor solubility in other monomers such as vinyl chloride, fatty acid vinyl ester, and organic solvents, so it is difficult to uniformly copolymerize, and the resulting copolymer is difficult to dissolve in organic solvents. Therefore, the objects and effects of the present invention cannot be achieved. Polymerization methods for obtaining copolymers include bulk polymerization, solution polymerization, and
Emulsion polymerization, suspension polymerization, etc. may be used, and the polymerization method itself is not limited. In the present invention, the copolymer obtained by copolymerization must not be used as it is, but must be neutralized with a basic substance. This neutralization is carried out by adding a basic substance after the copolymerization reaction is completed. Specifically, it may be carried out in a manner desired by each polymerization method. For example, in the solution polymerization method, after the polymerization reaction is completed, neutralization is performed by adding an alcoholic solution of sodium hydroxide, and then alcohol, which is a non-solvent for the copolymer, is added to neutralize the polymerization reaction. The desired copolymer can be obtained by reprecipitating with a solvent or a hydrocarbon solvent such as n-hexane, washing with the same solvent, and removing liquid and drying. In addition, in the suspension polymerization method, the polymer slurry after the polymerization reaction is neutralized by adding an aqueous solution of alkali metal hydroxide, aqueous ammonia, etc., and the copolymer is obtained by washing, removing liquid, and drying. In the emulsion polymerization method, a copolymer is obtained by neutralizing in substantially the same manner, followed by salting out, washing, excessive dehydration, and drying in accordance with conventional methods. When using the above-mentioned copolymer as a binder resin, other resins may be used in equal or less amounts as necessary, and resins that can be used in combination include polyurethane resins, nitrocellulose, epoxy resins,
Polyamide resin, phenolic resin, acrylic ester, methacrylic ester, styrene, acrylonitrile, butadiene, ethylene,
Examples include various polymers such as propylene, vinylidene chloride, acrylamide, vinyl ethers, and copolymers. Among these, polyurethane resins and nitrocellulose are particularly preferred. In addition, it is desirable to use a polyisocyanate-based curing agent in combination, and examples of this curing agent include bifunctional isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and hexane diisocyanate, and Coronate L (trade name, manufactured by Nippon Polyurethane Industries). , Days module L
Examples include trifunctional isocyanates such as (trade name, manufactured by Bayer AG), and urethane polymers containing isocyanate groups at both ends. The amount of these curing agents used is 40% per 100 parts by weight of binder resin.
It should be less than parts by weight. The ferromagnetic fine powder used in the present invention includes γ
- Fe 2 O 3 , Fe 3 O 4 and these adsorbed or doped with cobalt ions, CrO 3 etc., and acicular fine particle materials containing Fe, Co, Fe-Co or in some cases Ni etc. , and various other conventionally known magnetic powders. The mixing ratio of ferromagnetic fine powder and binder resin is
Preferably, the amount of binder resin is 8 to 30 parts by weight per 100 parts by weight. In addition, in order to uniformly disperse the ferromagnetic powder and the binder resin, it is necessary to add commonly used lubricants, abrasives, antistatic agents, dispersion aids, rust preventives, etc., as well as coating media. Various other organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, and toluene may be used as in the past, and there are no particular restrictions on these points. As the support, synthetic resins such as polyester, polyolefin, cellulose acetate, and polycarbonate, other nonmagnetic metals, and ceramics are used, and the support is in the form of a film, tape, sheet, plate, etc. The coating means for forming the magnetic layer on the support may be any conventionally known method, and by appropriately performing a smoothing treatment such as calendaring treatment,
A high-performance magnetic recording medium, which is the object of the present invention, can be obtained. Next, examples of synthesis of binder resins and specific examples using the binder resins will be given. Synthesis Example 1 (Synthesis of Polymer A) In an autoclave equipped with a stirring device, 400 parts by weight of methanol, 86 parts by weight of vinyl chloride, 20 parts by weight of Beoba #10 (trade name manufactured by Ciel Chemical Co., Ltd.), and 8 parts by weight of allyldodecyl sulfosuccinate. part, di(2-
6 parts by weight of (ethylhexyl) peroxydicarbonate and 2 parts by weight of partially saponified polyvinyl alcohol were charged, and the temperature was raised to 50°C while stirring in a nitrogen gas atmosphere to start the reaction, and then 86 parts by weight of vinyl chloride was added for 8 hours. In short, continuous pressure injection was carried out to cause a copolymerization reaction. Autoclave internal pressure reaches 0 after 12 hours
Kg/ cm2 . Cool the resulting slurry to 10%
The mixture was neutralized with an aqueous potassium hydroxide solution, washed three times with 1000 parts by weight of methanol, and filtered and dried to obtain 160 parts by weight of a copolymer powder. This is called Polymer A. Synthesis Example 2 (Synthesis of Polymer B) The following composition was charged into an autoclave equipped with a stirring device: Deionized water 400 parts by weight Vinyl chloride 79 Beopa #9 (vinyl versatility, trade name manufactured by Ciel Chemical Co., Ltd.) 24 ã 2-ethylhexyl acrylate 10 ã 2-acrylamido-2-methylpropanesulfonic acid 14 ã Ammonium persulfate 1 part by weight polyoxyethylene nonyl phenyl ether
4. The reaction was started by heating to 55°C while stirring. Further, 80 parts by weight of vinyl chloride was continuously added over a period of 8 hours to cause a copolymerization reaction, and a thermal reaction was further carried out for 1 hour to obtain an emulsion. This emulsion was neutralized with a 28% ammonia aqueous solution, 50 parts by weight of sodium chloride and 500 parts by weight of hot water were added, and the slurry was filtered to obtain a cake. This product was dispersed in 1200 parts by weight of water, washed five times, and then dried to obtain 125 parts by weight of copolymer powder. This will be referred to as Polymer B. Comparative Synthesis Example 1 (Synthesis of Polymer C) A copolymer was obtained in exactly the same manner as Synthesis Example 1 except that neutralization with a 10% aqueous potassium hydroxide solution was omitted. This will be referred to as Polymer C. Comparative Synthesis Example 2 (Synthesis of Polymer D) A copolymer was obtained in exactly the same manner as in Synthesis Example 1 except that 20 parts by weight of vinyl acetate was used instead of Beoba #10. This will be referred to as Polymer D. Comparative Synthesis Example 3 (Synthesis of Polymer E) In a reactor equipped with a cooling tube and a stirrer, 100 parts by weight of vinyl chloride-vinyl acetate-vinyl alcohol copolymer (vinyl alcohol 12% by weight), 400 parts by weight of dimethylformamide, 21.5 parts by weight of pyridine and 45 parts by weight of monochloroethylsulfonate Na salt (Cl-C 2 H 4 OSO 3 Na) were charged and heated at 80â.
The reaction was allowed to proceed for 10 hours, and after cooling, the solid matter was filtered and added to 1000 parts by weight of methanol to precipitate a polymer. Furthermore, the operation of dispersing and washing using 1000 parts by weight of methanol was repeated three times, followed by drying to obtain 88 parts by weight of copolymer powder. This is called Polymer E. Examples 1 and 2 Co-γ-Fe 2 O 3 as ferromagnetic powder (coercive force 640 oersted, saturation magnetization 74 emu/g, specific surface area 23
m 2 /g) 300 parts by weight, 30 parts by weight of polymer A or B, 20 parts by weight of polyurethane Nituporan N-5032 (trade name manufactured by Nippon Polyurethane Industries), 0.5 parts by weight of silicone oil KF-96 (trade name manufactured by Shin-Etsu Chemical Industries). A composition consisting of 300 parts by weight of methyl ethyl ketone, 300 parts by weight of methyl isobutyl ketone and 300 parts by weight of toluene was kneaded and dispersed in a ball mill for 10 hours, and then 25 parts by weight of Coronate L (trade name, manufactured by Nippon Polyurethane Industries, Ltd., a low molecular weight isocyanate compound) was added. of the mixture was added and kneaded and dispersed again in a ball mill for 1 hour. The magnetic paint thus obtained was applied onto a polyester film to a dry film thickness of 5 ÎŒm.
It was subjected to magnetic field orientation treatment and dried. The surface gloss and magnetic properties of the magnetic recording medium thus obtained were measured. The surface gloss was measured by comparing the light reflectance at Gs60° with a standard glass plate using a gloss meter GM-3D (Murakami Color Giken). The magnetic properties were measured using a VSM-3 model (manufactured by Toei Kogyo) in an external magnetic field of 3000 oersteds. The result is the first
It was as shown in the table. Comparative Example 1 A magnetic recording medium was produced in the same manner as in Example 1 except that Polymer C was used instead of Polymer A or B, and the surface gloss and magnetic properties were measured. The results were as shown in Table 1.
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ÏSTïŒä¿é²ãã¹ãåŸé£œåç£åéïŒemuïŒïœïŒ[Table] Examples 3 and 4, Comparative Examples 2 to 4 Ferromagnetic powder Fe-Co-Ni 300 parts by weight Retention force 1500 Oersted saturation magnetization 135 emu/g Specific surface area 50/g Binder resin (Polymer A, B, C, D or E) 30 parts by weight Polyurethane Nitsuporan N-3022 (trade name manufactured by Nippon Polyurethane Industries) 20 parts by weight Silicone oil KF-96 3 parts by weight Methyl ethyl ketone 300 parts by weight Methyl isobutyl ketone 300 parts by weight Toluene 300 parts by weight The above composition Kneaded and dispersed in a ball mill for 10 hours,
Furthermore, 2 parts by weight of Coronate L (described above) was added and kneaded and dispersed again in a ball mill for 1 hour. The magnetic paint thus obtained was applied onto a polyester film to a dry film thickness of 5 ÎŒm, subjected to magnetic field orientation treatment, and after drying, calendering treatment was performed. For each tape thus obtained, the surface gloss and magnetic properties were measured in the same manner as in the previous example, and in order to evaluate the oxidation resistance of the ferromagnetic powder to the binder resin, each tape was heated in air at 60â and 90â. %
The rate of decrease in saturation magnetization was determined after being left at RH and accelerated over time. The results were as shown in Table 2. Decrease rate of saturation magnetization = Ï SO âÏ ST /Ï SO Ã100 Ï SO : Initial saturation magnetization (emu/g) Ï ST : Saturation magnetization after accelerated test (emu/g)
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žåæ§ã«ããããŠããã[Table] As can be seen from the above examples and comparative examples,
The magnetic recording medium according to the present invention has excellent dispersibility of ferromagnetic fine powder, small change in saturation magnetization over time, and excellent oxidation resistance.
Claims (1)
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æ°èšé²åªäœã[Claims] 1. A copolymer obtained by copolymerizing vinyl chloride, a fatty acid vinyl ester having 8 to 16 carbon atoms, and a polymerizable unsaturated sulfonic acid on a support, and then neutralizing it with a basic substance. A magnetic recording medium formed by forming a magnetic layer in which fine ferromagnetic powder is dispersed during coalescence. 2 The copolymer contains 65 to 90% by weight of vinyl chloride,
8-25% by weight of fatty acid vinyl ester having 8-16 carbon atoms and 0.1-10% by weight of polymerizable unsaturated sulfonic acid
2. The magnetic recording medium according to claim 1, which has an average degree of polymerization of 200 to 800 obtained by copolymerizing at a ratio of .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15355684A JPS6132216A (en) | 1984-07-24 | 1984-07-24 | Magnetic recording medium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15355684A JPS6132216A (en) | 1984-07-24 | 1984-07-24 | Magnetic recording medium |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6132216A JPS6132216A (en) | 1986-02-14 |
JPH0363123B2 true JPH0363123B2 (en) | 1991-09-30 |
Family
ID=15565080
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP15355684A Granted JPS6132216A (en) | 1984-07-24 | 1984-07-24 | Magnetic recording medium |
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JP (1) | JPS6132216A (en) |
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JP5424796B2 (en) * | 2009-09-29 | 2014-02-26 | å¯å£«ãã€ã«ã æ ªåŒäŒç€Ÿ | Binder for magnetic recording medium, composition for magnetic recording medium, and magnetic recording medium |
-
1984
- 1984-07-24 JP JP15355684A patent/JPS6132216A/en active Granted
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JPS6132216A (en) | 1986-02-14 |
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