JPS63298811A - Magnetic recording medium - Google Patents
Magnetic recording mediumInfo
- Publication number
- JPS63298811A JPS63298811A JP62131272A JP13127287A JPS63298811A JP S63298811 A JPS63298811 A JP S63298811A JP 62131272 A JP62131272 A JP 62131272A JP 13127287 A JP13127287 A JP 13127287A JP S63298811 A JPS63298811 A JP S63298811A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- parts
- carbon black
- group
- reactivity
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- 239000006229 carbon black Substances 0.000 claims abstract description 40
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 30
- 230000009257 reactivity Effects 0.000 claims abstract description 11
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 claims description 6
- 125000004069 aziridinyl group Chemical group 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000011247 coating layer Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XEZCCHVCBAZAQD-UHFFFAOYSA-N 2-(aziridin-1-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CC1 XEZCCHVCBAZAQD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241000167857 Bourreria Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZBBHBTPTTSWHBA-UHFFFAOYSA-N Nicardipine Chemical compound COC(=O)C1=C(C)NC(C)=C(C(=O)OCCN(C)CC=2C=CC=CC=2)C1C1=CC=CC([N+]([O-])=O)=C1 ZBBHBTPTTSWHBA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940097611 cardene Drugs 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- BSCJIBOZTKGXQP-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCO BSCJIBOZTKGXQP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は磁気テープなどの磁気記録媒体に関し、更に詳
しくは基材の磁気記録面とは反対の面（以下背面という
）に帯電防止性及び耐擦傷性に優れ九バックコート層を
有する磁気記録層に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a magnetic recording medium such as a magnetic tape, and more specifically, the present invention relates to a magnetic recording medium such as a magnetic tape, and more specifically, the present invention relates to a magnetic recording medium such as a magnetic tape. The present invention relates to a magnetic recording layer having excellent scratch resistance and having nine back coat layers.
（従来の技術）
近年オーディオテープやビデオテープ等の磁気記録媒体
の普及が著しく、それらの性能に対する要求も増々高度
なものになってきている。特にビデオテープのような高
性能テープに於ては磁気記録層の性能向上のみならず、
磁気記録層への悪影響を排除するために背面の特性にも
着目されている。即ち、チリやゴミの付着を防止するた
めに帯電防止性が要求され、又、背面の磨耗による微粉
の発生を防ぐために耐磨耗性が要求されている。(Prior Art) In recent years, magnetic recording media such as audio tapes and video tapes have become widespread, and demands on their performance have become increasingly sophisticated. In particular, in high-performance tapes such as video tapes, not only the performance of the magnetic recording layer is improved, but also
Attention is also paid to the characteristics of the back surface in order to eliminate adverse effects on the magnetic recording layer. That is, antistatic properties are required to prevent the adhesion of dirt and dust, and wear resistance is required to prevent the generation of fine powder due to abrasion of the back surface.
これらの要求に応える為に、背面にカーボンブラック（
以下ＣＢと記す）を含むバックコート層が設けられてい
るが、従来公知のＣＢを使用したバックコート層は、Ｃ
Ｂがバックコートのバインダー成分との親和性や接着性
に欠けるためにＣＢのバインダー成分への均一分散が困
難であったり、コーティング層からＣＢの脱落が認めら
れたりコーティングｊ−の耐磨耗性が不充分であったり
する欠点がある。In order to meet these demands, carbon black (
A back coat layer containing CB (hereinafter referred to as CB) is provided, but a back coat layer using conventionally known CB is
Because B lacks affinity or adhesion with the binder component of the back coat, it may be difficult to uniformly disperse CB into the binder component, or CB may fall off from the coating layer, or the abrasion resistance of coating J- may be affected. There is a drawback that it may be insufficient.
この欠点を補なう為にＣＢの表面に重合体をグラフト化
することによって表面処理したものを使うことも試みら
れているが、ＣＢへの重合体のグラフト化率が低く、表
面処理効率が極めて悪いものであったためにバックコー
トのバインダー成分との親和性や接着性が不充分なもの
であった。In order to compensate for this drawback, attempts have been made to use surface treated CB by grafting a polymer onto the surface, but the grafting rate of the polymer to CB is low and the surface treatment efficiency is low. It was extremely poor, resulting in insufficient affinity and adhesion with the binder component of the back coat.
（本発明が改良しようとする問題点）
本発明の目的は前記の欠点のない・々ツクコート層を有
する磁気記録媒体を開発することにある。(Problems to be improved by the present invention) An object of the present invention is to develop a magnetic recording medium having a thin coat layer that does not have the above-mentioned drawbacks.
（問題点を解決するための手段及び作用）本発明者らは
、バックコートのバインダー成分や溶剤との親和性及び
バインダー成分との接着性の優れたＣＢを使用すれば前
記の欠点のないバックコート層を形成することができ長
期間の使用に耐えうる磁気記録媒体を得ることができる
との観点から鋭意検討を行った結果、ＣＢにＣＢとの反
応性を有する重合体を特定条件下で反応させて得られる
カーがンブラックグラフトポリマー（以下、ＣＢグラフ
トプリマーと記す）を使用することによシ目標を達成し
うろことを見出し本発明に到達したものである。(Means and effects for solving the problem) The present inventors have discovered that if CB is used which has excellent affinity with the binder component and solvent of the back coat and has excellent adhesion to the binder component, the back coating will not have the above-mentioned drawbacks. As a result of intensive studies from the viewpoint of obtaining a magnetic recording medium that can form a coat layer and withstand long-term use, we found that under specific conditions, we added a polymer that is reactive with CB to CB. The present invention was achieved by discovering that the objective could be achieved by using a carbon black graft polymer (hereinafter referred to as CB graft polymer) obtained by the reaction.
即ち１本発明はＣＢとＣＢとの反応性を有する重合体（
以下、重合体（４）という。）とを常温〜３５０℃の条
件下に反応して得られるＣＢグラフトポリマーを含有す
る・ぐツクコート層を有す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, 1 the present invention is a polymer having reactivity with CB and CB (
Hereinafter, it will be referred to as polymer (4). This invention relates to a magnetic recording medium characterized in that it has a thick coat layer containing a CB graft polymer obtained by reacting CB graft polymers with CB graft polymers under conditions of room temperature to 350°C.
本発明において、カーボンブラックグラフトポリマーを
得るために、０８表面の官能基（−ＯＨ。In the present invention, in order to obtain a carbon black graft polymer, functional groups (-OH) on the 08 surface.
−ＣＯＯＨ，Ｃ−０等）を利用する。本発明における重
合体（Ａ）としては、０８表面に存在する官能基と容易
に反応しうる反応性基を有する重合体であれば特に制限
なく用いることが出来る。０８表面に存在する官能基と
容易に反応しうる反応性基としては、例えばアジリシン
基、オキサゾリン基、Ｎ−ヒドロキシアルキルアミド基
、エポキシ基、チオエポキシ基、イソシアネート基、ビ
ニル基、珪素系加水分解性基、アミノ基等を挙げること
ができ、重合体（４）としては前記反応性基を分子内に
１個以上有するビニル系重合体、ポリエステル、？リウ
レタン、ポリエーテル等を挙げる事が出来る。この様な
重合体（４）を得るには、例えば前記の反応性基を分子
内に有する重合性単量体を必要によりその他の重合性単
量体と公知の手順に従って重合する方法や前記反応性基
を分子内に有する化合物と該化合物と反応しうる基を有
する重合体とを反応する方法等を適宜採用することがで
きる。本発明においては、特にＣＢの表面に存在する官
能基との反応性の面で、アジリジン基、オキサゾリン基
、Ｎ−ヒドロキシアルキルアミド基、エポキシ基、チオ
エポキシ基、イソシアネート基から選ばれる１種又は２
種以上を反応性基として有する重合体を用いるのが好ま
しく、よシ好ましくはアジリジン基、オキサゾリン基、
Ｎ−ヒドロキシアルキルアミド基モから選ばれる１種又
は２種以上を反応性基として有する重合体（蜀である。-COOH, C-0, etc.). As the polymer (A) in the present invention, any polymer can be used without particular limitation as long as it has a reactive group that can easily react with the functional group present on the surface of 08. Examples of reactive groups that can easily react with functional groups present on the surface of 08 include azilysine groups, oxazoline groups, N-hydroxyalkylamide groups, epoxy groups, thioepoxy groups, isocyanate groups, vinyl groups, and silicon-based hydrolyzable groups. Examples of the polymer (4) include vinyl polymers, polyesters, and polyesters having one or more of the above-mentioned reactive groups in the molecule. Examples include urethane and polyether. In order to obtain such a polymer (4), for example, the above-mentioned polymerizable monomer having a reactive group in the molecule may be polymerized with other polymerizable monomers according to a known procedure or the above-mentioned reaction. A method of reacting a compound having a functional group in the molecule with a polymer having a group capable of reacting with the compound can be appropriately employed. In the present invention, one or two selected from aziridine groups, oxazoline groups, N-hydroxyalkylamide groups, epoxy groups, thioepoxy groups, and isocyanate groups are used, especially in terms of reactivity with functional groups present on the surface of CB.
It is preferable to use a polymer having at least one reactive group, more preferably an aziridine group, an oxazoline group,
A polymer having one or more types selected from N-hydroxyalkylamide groups as a reactive group (Shu).
本発明に於て、重合体（４）の種類はＣＢグラフトポリ
マーに付与すべき特性、即ち、バックコートのバインダ
ー成分との接着性、バインダー成分や溶媒との親和性に
応じて適宜選択する。In the present invention, the type of polymer (4) is appropriately selected depending on the properties to be imparted to the CB graft polymer, that is, the adhesiveness with the binder component of the back coat and the affinity with the binder component and the solvent.
重合体（４）の分子量については特に制限されないが、
ＣＢに対する顕著な処理効果やＣＢとの反応時の作業性
の面で平均分子量が２００〜１，０００，０００の範囲
とするのが好ましく、より好ましくは３００〜Ｉ Ｏ（
ｉ’６００の範囲である。The molecular weight of the polymer (4) is not particularly limited, but
In terms of remarkable treatment effects on CB and workability during reaction with CB, the average molecular weight is preferably in the range of 200 to 1,000,000, more preferably 300 to IO(
i'600 range.
また、重合体囚は反応性基を平均して１分子中に１個以
上有していなければならないが、ＣＢとの反応性や得ら
れるＣＢグラフトポリマーの性質を良好な範囲とするた
めには、平均して１分子中に１〜５個とするのが好まし
く、よシ好ましくは１〜２個である。In addition, the polymer matrix must have one or more reactive groups per molecule on average, but in order to keep the reactivity with CB and the properties of the resulting CB graft polymer within a good range, On average, it is preferable that the number is 1 to 5, and more preferably 1 to 2 in one molecule.
本発明の製造方法において、ＣＢグラフトポリ拌混合し
て反応することにより得られるものである。反応時の温
度条件が３５０℃を越える場合はポリマー成分が変質す
るので好ましくない。In the production method of the present invention, the CB graft polyester is obtained by stirring and mixing and reacting. If the temperature condition during the reaction exceeds 350°C, the quality of the polymer component will change, which is not preferable.
本発明で使用するＣＢの種類は特に制限されないが、重
合体（４）の反応性基がエポキシ基やチオエポキシ基の
如き比較的反応性の低いものの場合は声が７以下のＣＢ
、特にその表面のカルポキシル基の量が０．０５ ミリ
グラム当量／ｙ以上のＣＢをイソシアネート基などの如
き反応性の比較的高いものの場合はＣＢの種類を制限す
る必要がなく各４のＣＢを好適に使用することができる
。The type of CB used in the present invention is not particularly limited, but if the reactive group of the polymer (4) is one with relatively low reactivity such as an epoxy group or a thioepoxy group, a CB with a voice of 7 or less may be used.
In particular, when the CB having a surface carpoxyl group amount of 0.05 milligram equivalent/y or more is relatively highly reactive such as an isocyanate group, there is no need to limit the type of CB, and 4 CBs are preferred. It can be used for.
ＣＢと重合体（４）の使用比率に特に制限はないが、好
ましくはＣＢ１００重量部に対し、重合体（４）１番会
擦〜１”０００重量部、特に好ましくは５台＃〜５００
重債部である。There is no particular restriction on the ratio of CB to polymer (4), but preferably 100 parts by weight of CB to 1"000 parts by weight of polymer (4), particularly preferably 5 parts to 500 parts by weight.
This is the heavy debt section.
ＣＢと重合体（４）との反応は、これら二成分だけを反
応する方法であってもよく、又重合体（４）に該当しな
いポリマー成分、重合性単量体は、有機溶剤、水等他の
物質の混在下での反応であってもよいＯ
このようにして得られたＣＢグラフトポリマーはバック
コート剤に極めて容易に溶解、分散するのでＣＢが均一
にミクロ分散したバックコート剤を得ることができる。The reaction between CB and polymer (4) may be a method in which only these two components are reacted, and polymer components and polymerizable monomers that do not correspond to polymer (4) may be reacted with organic solvents, water, etc. The reaction may be carried out in the presence of other substances. Since the CB graft polymer obtained in this way is extremely easily dissolved and dispersed in the back coating agent, a back coating agent in which CB is uniformly microdispersed can be obtained. be able to.
バックコート剤のバインダー成分は公知の塩化ビニル系
樹脂、塩化ビニル−酢酸ビニル共重合系樹脂、アクリル
系樹脂、スチレン系樹脂、ポリウレタン系樹脂、ポリエ
ステル系樹脂などを使用することができ、又、バインダ
ー成分を使用せず、本発明のＣＢグラフトカーデンを溶
剤に分散してバックコート剤として用いることもできる
。これらのバインダー成分及び／又は溶剤へのＣＢグラ
フトポリマーの溶解・分散は通常、ＣＢグラフトポリマ
ーとバインダー成分及び／又は溶剤を室温で数分〜数十
分攪拌混合するだけでよいが必要であればロールミル、
サンドミル、ゾールミー、超音波分散機、デ、ス、ｚ
％モパＸ、
ジナイザー等を用いて混線・分散を行ってもよい。As the binder component of the back coating agent, known vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, acrylic resins, styrene resins, polyurethane resins, polyester resins, etc. can be used. The CB graft cardene of the present invention can also be dispersed in a solvent and used as a back coating agent without using any other components. Dissolving and dispersing the CB graft polymer in these binder components and/or solvents usually requires stirring and mixing the CB graft polymer and the binder component and/or solvent at room temperature for several minutes to several tens of minutes, but if necessary, roll mill,
sand mill, zolmy, ultrasonic dispersion machine, de, s, z
Crosstalk and dispersion may be performed using %MOPAX, Genizer, etc.
こうして得られるバックコート剤はロールコータ−、エ
アーナイフコーター、エアードクターコーター、スプレ
ーコーター等公知の手段を用いて基材Ｋｍ布し、その背
面にバックコート層を形成させることができる。The back coat agent thus obtained can be coated on a substrate using a known means such as a roll coater, air knife coater, air doctor coater, spray coater, etc., and a back coat layer can be formed on the back surface thereof.
本発明の磁気記録媒体に用いる基材としては、公知のポ
リエステル、酢酸セルロース、ポリ塩化ビニルなどのフ
ィルム、シート、チー７’を使用Ｌ、磁気記鍮層は公知
の磁性粉末を含有するコート剤を塗布する方法あるいは
磁性体を蒸着する方法等によって形成することができる
。The base material used in the magnetic recording medium of the present invention is a film, sheet, or Q7' made of known polyester, cellulose acetate, or polyvinyl chloride.The magnetic recording layer is a coating agent containing known magnetic powder. It can be formed by a method of coating a magnetic material, a method of vapor depositing a magnetic material, or the like.
（発明の効果）
本発明の磁気記録媒体は、ＣＢの表面にＣＢとの反応性
を有する重合体（４）をグラフト化したＣＢグラフトポ
リマーを含有するバックコート層を有する。該重合体（
４）は従来公知のグラフト化方法にくらべてＣＢへのグ
ラフト化率が極めて良く、０８表面に重合体が強固に結
合しており又、重合体の骨格として各稽のものが選択で
きるのでＣＢの表面性質を、使用するバックコート剤に
適合するように自在にしかも効果的、経済的に改質する
ことができる。従って、本発明のＣＢグラフトポリマー
はバックコート層に均一にミクロ分散し、ＣＢとバイン
ダー成分が緊密に接着し、そのために該バックコート層
は極めて堅牢であり、ＣＢが脱落することがなく、耐磨
耗性に優れているものである。即ち本発明の磁気記録媒
体は堅牢なバックコート層を有している丸めに、長時間
くり返し使用しても品質の劣化が極めて少ないものであ
る。(Effects of the Invention) The magnetic recording medium of the present invention has a back coat layer containing a CB graft polymer in which a polymer (4) having reactivity with CB is grafted onto the surface of CB. The polymer (
4) has an extremely high grafting rate to CB compared to conventionally known grafting methods, the polymer is strongly bonded to the 08 surface, and various types of polymer skeletons can be selected, so CB The surface properties of the coating can be freely, effectively and economically modified to match the back coating used. Therefore, the CB graft polymer of the present invention is uniformly micro-dispersed in the backcoat layer, and the CB and binder components are tightly adhered, so that the backcoat layer is extremely robust, CB does not fall off, and it is resistant to It has excellent abrasion resistance. That is, the magnetic recording medium of the present invention has a strong back coat layer, so even if it is used repeatedly for a long time, there is very little deterioration in quality.
（実施例）
以下、実施例によシ本発明の詳細な説明するが、本発明
は以下の実施例によって限定されるものではない。尚、
例中の部は重量部を、チは重量％をそれぞれ示す。(Examples) Hereinafter, the present invention will be explained in detail using Examples, but the present invention is not limited to the following Examples. still,
In the examples, parts indicate parts by weight, and % by weight.
参考例１
攪拌機、不活性ガス導入管、還流冷却管及び温度針を備
えたフラスコにポリビニルアルコール０．２部を溶解し
た脱イオン水４００部を仕込んだ。Reference Example 1 A flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser, and a temperature needle was charged with 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved.
そこへ予め調整しておいたスチレン１９６部およびイン
グロペニルオキサゾリ７４部からなる重合性単量体にベ
ンゾイルパーオキサイド１６部を溶解した混合物を仕込
み、高速で攪拌して均一な懸濁液とした。次いで窒素ガ
スを吹き込みながら８０℃に加熱し、この温度で５時間
攪拌を続けて重合反応を行った後冷却して重合体懸濁液
を得た。A mixture of 16 parts of benzoyl peroxide dissolved in a polymerizable monomer consisting of 196 parts of styrene and 74 parts of ingropenyl oxazole, prepared in advance, was added thereto, and stirred at high speed to form a uniform suspension. did. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer suspension.
この重合体懸濁液を口過、洗浄した後乾燥して反応性基
としてオキサゾリン基を有する重合体を得た。この重合
体の分子量はＧＰＣ測定によｌ） Ｍｎ ＝５．８００
であった。This polymer suspension was passed through the mouth, washed, and then dried to obtain a polymer having an oxazoline group as a reactive group. The molecular weight of this polymer was determined by GPC measurement l) Mn = 5.800
Met.
反応性基としてオキサゾリン基を有する重合体２０部と
カーがンブラックＭＡ−６００（三菱化成工業（株）製
）２０部とをラボプラストミル（東洋精機（株）製）を
用いて１６０℃、１００ ｒｐｍの条件下に混練して反
応した後冷却、粉砕してカーボンブラックグラフトポリ
マー（１）を得た。20 parts of a polymer having an oxazoline group as a reactive group and 20 parts of Cargan Black MA-600 (manufactured by Mitsubishi Chemical Industries, Ltd.) were heated at 160°C using a Laboplastomill (manufactured by Toyo Seiki Co., Ltd.). After kneading and reacting at 100 rpm, the mixture was cooled and pulverized to obtain carbon black graft polymer (1).
参考例２
参考例１で用いたのと同じフラスコにトルエン２００部
及びメチルイソブチルケトン２００部を仕込み、窒素ガ
スを吹き込みながら８０℃に加熱した。そこへ予め用意
しておいたスチレン１００部、アクリル酸ブチル９０部
及び２−（１−アジリジニル）エチルメタクリレート１
０部からなる重合性単量体にペンゾイルノや一オキサイ
ド４部を溶解した混合物を２時間に亘って滴下ロートよ
シ滴下し、更に５時間攪拌を続けて重合反応を行った後
冷却して重合体溶液を得た。この重合体の分子量はＧＰ
Ｃ測定によｌ） Ｍｎ ＝ ３，０００であった。Reference Example 2 The same flask as used in Reference Example 1 was charged with 200 parts of toluene and 200 parts of methyl isobutyl ketone, and heated to 80° C. while blowing nitrogen gas. 100 parts of styrene, 90 parts of butyl acrylate and 1 part of 2-(1-aziridinyl)ethyl methacrylate prepared in advance therein.
A mixture of 0 parts of polymerizable monomer and 4 parts of penzoylno or monooxide was added dropwise through the dropping funnel over 2 hours, and stirring was continued for another 5 hours to carry out the polymerization reaction, after which it was cooled and polymerized. A combined solution was obtained. The molecular weight of this polymer is GP
According to C measurement, Mn = 3,000.
反応゛性基としてアジリジン基を有する重合体の溶液２
０部とカーボンブラックＭＡ−６００を２０部とを加圧
ニーダーを用いて１６０℃にて反応してカーボンブラッ
クグラフトポリマー（２）の分散液を得た。Solution 2 of a polymer having an aziridine group as a reactive group
0 parts of carbon black MA-600 were reacted with 20 parts of carbon black MA-600 at 160° C. using a pressure kneader to obtain a dispersion of carbon black graft polymer (2).
参考例３
参考例１における重合性単量体の代わシにスチレン１２
０部、アクリル酸エチル７６部及びＮ−ヒドロキシエチ
ルメタクリルアミド４部を使用する他は参考例１と同じ
操作をくシ返してＭｎ ＝５”５００の反応性基として
、Ｎ−ヒドロキシアルキルアミド基を有する重合体を得
、該重合体１０部、バックコート剤のバインダー成分で
あるポリタレ２フ１０部及びカーがンブラックＭＡ−６
００２０部をラボプラストミルを用いて参考例１と同様
の操作をくシ返してカーがンブラックグラフトポリマー
（３）を得た。Reference Example 3 Styrene 12 was used instead of the polymerizable monomer in Reference Example 1.
The same operation as in Reference Example 1 was repeated except that 0 parts of ethyl acrylate, 76 parts of ethyl acrylate, and 4 parts of N-hydroxyethylmethacrylamide were used to prepare an N-hydroxyalkylamide group as a reactive group with Mn = 5''500. 10 parts of the polymer, 10 parts of Polytale 2F, which is a binder component of the back coating agent, and Cargan Black MA-6 were obtained.
Cargan black graft polymer (3) was obtained by repeating the same operation as in Reference Example 1 using Labo Plastomill.
参考例４
参考例１で用いたのと同じフラスコにトルエン２１７部
を仕込み、窒素ガスを吹き込みながら９０℃に加熱した
。そこへ予め用意しておいたメタクリル酸メチル４８０
部及びアクリル酸ｎ−ブチル２０部からなる重合性単量
体にチオグリコール酸５．４４部、アゾビスインブチロ
ニトリル１．３２部とを溶解した混合物を２時間にわた
って滴下ロートよシ滴下し、更に５時間攪拌を続けて重
合反応を行った。この重合体の分子量はＧＰＣ測定によ
ｐ Ｍｎ ＝９，５００であった。Reference Example 4 217 parts of toluene was charged into the same flask as used in Reference Example 1, and heated to 90° C. while blowing nitrogen gas. Methyl methacrylate 480 prepared in advance
A mixture of 5.44 parts of thioglycolic acid and 1.32 parts of azobisinbutyronitrile dissolved in a polymerizable monomer consisting of 20 parts of n-butyl acrylate was added dropwise through a dropping funnel over 2 hours. Then, stirring was continued for an additional 5 hours to carry out the polymerization reaction. The molecular weight of this polymer was p Mn =9,500 by GPC measurement.
次いで、この反応生成物（末端にカルゲキシル基を有す
るブレポリマーを含む溶液）１８５．１部に２−ｐ−フ
ェニレン−ビス−２−オキサゾリン２．９５部を加え８
０℃で２時間反応して、末端に反応性基としてオキサゾ
リン基を有する重合体の溶液（不揮発分７０チ）を得た
。Next, 2.95 parts of 2-p-phenylene-bis-2-oxazoline was added to 185.1 parts of this reaction product (a solution containing a brepolymer having a calgexyl group at the end).
The reaction was carried out at 0° C. for 2 hours to obtain a solution of a polymer having an oxazoline group as a reactive group at the end (non-volatile content: 70%).
末端にオキサゾリン基を有する重合体の溶液（不揮発分
７０チ）４０部とカーがンプラック風−１０ＯＲ２０部
を加圧ニーダ−を用いて１６０℃の条件下に混練し拷キ
反応してカーボンブラックグラフトポリマー（４）の分
散液を得た。40 parts of a solution of a polymer having an oxazoline group at the end (non-volatile content: 70%) and 20 parts of Kerr-Plac-10OR were kneaded at 160°C using a pressure kneader and subjected to a torture reaction to form a carbon black graft. A dispersion of polymer (4) was obtained.
参考例５
参考例１で用いたのと同じフラスコに末端カル１Ｎ−＃
シル基含有線状飽和ポリエステルアロプラツツ０Ｂ−６
３（日本触媒化学工業（株）Ｍ、分子量Ｍｎ ＝ ｊ’
ｏ ＯＯ、不揮発分５０％）２００部、２−ｐ−フェニ
レン−ビス−２−オキサゾリン３．６０部を加え、１０
０℃で２時間反応して、末端に反応性基としてオキサゾ
リン基を有する重合体のｉＩ液（不揮発分５０．９ ％
）を得た。末端にオキサゾリン基を有する重合体の溶
液（不揮発分５０．９％）４０部とカーゲンブラックＭ
Ａ−１０ＯＲ２０部とを参考例４と同様の条件下で混線
反応し、カー？ンブラックグラフト４リマ−（５）の分
散液を得た。Reference Example 5 Into the same flask as used in Reference Example 1, add terminal cal 1N-#.
Syl group-containing linear saturated polyester Alloprats 0B-6
3 (Nippon Shokubai Kagaku Kogyo Co., Ltd.) M, molecular weight Mn = j'
o OO, nonvolatile content 50%), 3.60 parts of 2-p-phenylene-bis-2-oxazoline were added, and 10
After reacting at 0°C for 2 hours, a solution iI (non-volatile content: 50.9%) of a polymer having an oxazoline group as a terminal reactive group was obtained.
) was obtained. 40 parts of a solution of a polymer having an oxazoline group at the end (non-volatile content 50.9%) and Cargen Black M
20 parts of A-10OR was subjected to a crosstalk reaction under the same conditions as in Reference Example 4, and a car? A dispersion of Black Graft 4 Limer (5) was obtained.
参考例６
参考例１で用いたのと同じフラスコに平均分子ｉ １”
ＯＯＯのポリプロピレングリコール８２部、トルイレン
ジイソシアネート１８部、ジプチル錫ジラウレート０．
２部及びトルエン１００部を仕込み撹拌しながら８０℃
で５時間反応を行ない、末端イソシアネート基含有ポリ
ウレタンの５０チ溶液を得た。このものの分子量をＧＰ
Ｃで測定するとφ
Ｍｎ ＝ ４９００であった。Reference Example 6 In the same flask as used in Reference Example 1, the average molecule i 1”
OOO polypropylene glycol 82 parts, toluylene diisocyanate 18 parts, diptyltin dilaurate 0.
Add 2 parts and 100 parts of toluene and heat to 80°C while stirring.
The reaction was carried out for 5 hours to obtain a 50% solution of polyurethane containing terminal isocyanate groups. The molecular weight of this substance is GP
When measured at C, φ Mn = 4900.
末端にイソシアネート基を有する重合体の溶液３０部と
カーメンブラックＭＡ−６００２０部とを参考例４と同
様の条件下で混線反応し、カーボンブラックグラフトポ
リマー（６）を得た。30 parts of a solution of a polymer having isocyanate groups at the terminals and 20 parts of Carmen Black MA-600 were subjected to crosstalk reaction under the same conditions as in Reference Example 4 to obtain a carbon black graft polymer (6).
参考例７
参考例６で得たポリウレタン溶液２００部に２中
−（２−オキサシリル）ｆ口ｉ４ノール−１５，３部を
加え８０℃で２時間反応して、末端に反応性基としてオ
キサゾリン基を有する重合体の溶液（不揮発分５１％）
を得た。Reference Example 7 To 200 parts of the polyurethane solution obtained in Reference Example 6, 15.3 parts of -(2-oxacylyl)f-i4nol-2 was added and reacted at 80°C for 2 hours to form an oxazoline group as a reactive group at the end. (non-volatile content 51%)
I got it.
末端にオキサゾリン基を有する重合体の溶液４０部、バ
ックコート剤の・々インダー成分であるポリウレタン２
０部とカーゲンブラックＭＡ−１０ＯＲ２０部とを参考
例４と同様の条件下で混練反応し、カーボンブラックグ
ラフトポリマー（７）を得た。40 parts of a solution of a polymer having an oxazoline group at the end, polyurethane 2 which is an inder component of the back coating agent
Carbon black graft polymer (7) was obtained by kneading and reacting 0 parts of Cargen Black MA-10OR and 20 parts of Cargen Black MA-10OR under the same conditions as in Reference Example 4.
参考例８
参考例１において、用いた重合性単量体をスチレン１０
０部、メタクリル酸メチル９５部およびメタクリル酸グ
リシジル５部とする以外は参考例１と同じ方法をく）返
して反応性基としてエポキシ基を有する重合体を得た。Reference Example 8 In Reference Example 1, the polymerizable monomer used was styrene 10
A polymer having an epoxy group as a reactive group was obtained by repeating the same method as in Reference Example 1 except that 0 parts, 95 parts of methyl methacrylate, and 5 parts of glycidyl methacrylate were used.
反応性基としてエポキシ基を有する重合体２０部とカー
ボンブラックＭＡ−１０ＯＲ（三菱化成工業（ａ製）２
０部とをう♂プラストミルを用いて２２０℃、１００
ｒｐｍの条件下に混練して反応した後冷却、粉砕してカ
ーボンブラックグラフトポリマー（８）を得た。20 parts of a polymer having an epoxy group as a reactive group and carbon black MA-10OR (manufactured by Mitsubishi Chemical Corporation (a) 2
Using a plastomill with 0 parts, 220℃, 100
After kneading and reacting under rpm conditions, the mixture was cooled and pulverized to obtain a carbon black graft polymer (8).
参考例９
参考例１において、用いた重合性単量体を、メタクリル
酸メチル１００部、ブチルアクリレート９５部及び２，
３−エビチオプロピルメタクリレート５部とする以外は
参考例１と同じ方法をくり返して反応性基としてチオエ
ポキシ基を有する重合体を得た。Reference Example 9 In Reference Example 1, the polymerizable monomers used were 100 parts of methyl methacrylate, 95 parts of butyl acrylate, and 2,
The same method as in Reference Example 1 was repeated except that 5 parts of 3-evithiopropyl methacrylate was used to obtain a polymer having a thioepoxy group as a reactive group.
反応性基としてチオエポキシ基を有する重合体１６部と
カーボンブラックＭＡ−１０ＯＲ（三菱化成工業（株）
製）２４部とをラボプラストミルを用いて２２０℃、１
１００ｒｐの条件下に混練して反応した後冷却、粉砕し
てカーがンブラックグラフトポリマー（９）を得た。16 parts of a polymer having a thioepoxy group as a reactive group and carbon black MA-10OR (Mitsubishi Chemical Industries, Ltd.)
24 parts of
After kneading and reacting at 100 rpm, the mixture was cooled and pulverized to obtain a carbon black graft polymer (9).
比較参考例１
反応性基を有しないポリスチレンであるスタイ仝
ロン−６６６（旭化成工業（株）製、Ｍｎ＝４００００
）２０部とカーボンブラックＭＡ−６００２０部とを参
考例１と同様に反応した後、冷却、粉砕して比較用カー
ボンブラックグラ７）／リマー（１）を得た。Comparative Reference Example 1 Stylon-666 (manufactured by Asahi Kasei Corporation, Mn = 40000), which is polystyrene without reactive groups
) and 20 parts of carbon black MA-600 were reacted in the same manner as in Reference Example 1, and then cooled and pulverized to obtain comparative carbon black Gura 7)/Rimer (1).
比較参考例２
参考例１で用いたものと同様のフラスコにキシレン２０
０部、メタクリル酸ブチル２５部、アゾビスイソブチ≠
ロニトリル０．２部及びカーボンブラックＭＡ−６００
を１００部仕込み窒素ガスを吹き込みながら、８０℃に
加熱し、この温度で１０時間攪拌を続けて重合反応を行
った後冷却した。反応中
後、生成物をメタノール７０００部に再沈し、比較用カ
ーボンブラックグラフトポリマー（２）を得た。Comparative Reference Example 2 In a flask similar to that used in Reference Example 1, xylene 20
0 parts, butyl methacrylate 25 parts, azobisisobuty≠
Ronitrile 0.2 parts and carbon black MA-600
100 parts of the mixture were charged and heated to 80° C. while blowing nitrogen gas. Stirring was continued at this temperature for 10 hours to carry out a polymerization reaction, and then the mixture was cooled. After the reaction was completed, the product was reprecipitated in 7000 parts of methanol to obtain a comparative carbon black graft polymer (2).
実施例１
参考例１〜９で得られたカーがンブラックグラフトポリ
マー（１）〜（９）及び比較参考例１〜２で得られた比
較用カーがンブラックグラフトボリマ−（１）〜（２）
更に未処理のカーボンブラックＭＡ−１００Ｒを第１表
に示したバインダー成分及び溶剤と混合してバックコー
ト剤を調製しビデオテープの背面に塗布して性能試験を
行った。試験方法を下に記し試験結果を第１表にまとめ
て記す。Example 1 Car black graft polymers (1) to (9) obtained in Reference Examples 1 to 9 and comparative car black graft polymers (1) to (1) obtained in Comparative Reference Examples 1 to 2 (2)
Further, untreated carbon black MA-100R was mixed with the binder components and solvents shown in Table 1 to prepare a back coating agent, which was coated on the back side of a videotape for performance testing. The test method is described below, and the test results are summarized in Table 1.
く試験方法〉 １、試験試料の調製 ■カーがンブラックグラフトポリマーの分散。Test method> 1. Preparation of test sample ■Dispersion of cargan black graft polymer.
カーボンブラックグラフトポリマー、バインダー成分、
溶剤の所定量を容器に仕込み、プロ（う羽根攪拌機を用
い室温で１５分間攪拌した。Carbon black graft polymer, binder component,
A predetermined amount of the solvent was charged into a container, and the mixture was stirred at room temperature for 15 minutes using a professional ferrule stirrer.
■バックコート層の厚さ。■Thickness of back coat layer.
乾燥膜厚約５１ｓｒＬとした。The dry film thickness was about 51 srL.
２、性能試験 ■カーボンブラックの分散度。2. Performance test ■Dispersion degree of carbon black.
バックコート剤に分散されたカーボンブラックの粒径（
単位μｍ）を遠心沈降法によって測定した。Particle size of carbon black dispersed in back coating agent (
(unit: μm) was measured by centrifugal sedimentation method.
■バックコート層の耐磨耗性。■Abrasion resistance of back coat layer.
白色の綿布を３５０９／１ｙｎ２の力でバックコ−ト層
に押付けながら一定時間ピデオテープを送行させ、綿布
の汚染の程度によシ◎〜×の評価を行った。A white cotton cloth was pressed against the back coat layer with a force of 3509/1yn2 while the videotape was fed for a certain period of time, and the degree of contamination of the cotton cloth was evaluated from ◎ to ×.
◎ 綿布の汚染なしくＣＢの脱落なし）Ｏわずかあシ◎ No contamination of cotton cloth and no falling off of CB)
Claims (1)
有する重合体とを常温〜３５０℃の条件下に反応して得
られるカーボンブラックグラフトポリマーを含有するバ
ックコート層を有することを特徴とする磁気記録媒体。 ２、カーボンブラックとの反応性を有する重合体が、分
子内にアジリジン基、オキサゾリン基、Ｎ−ヒドロキシ
アルキルアミド基、エポキシ基、チオエポキシ基、イソ
シアネート基から選ばれる１種又は２種以上の反応性基
を有する重合体である特許請求の範囲第１項記載の磁気
記録媒体。[Claims] 1. A back coat layer containing a carbon black graft polymer obtained by reacting carbon black and a polymer having reactivity with carbon black at room temperature to 350°C. Features of magnetic recording media. 2. The polymer having reactivity with carbon black has one or more reactivity selected from aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group, thioepoxy group, and isocyanate group in the molecule. The magnetic recording medium according to claim 1, which is a polymer having a group.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62131272A JPS63298811A (en) | 1987-05-29 | 1987-05-29 | Magnetic recording medium |
| US07/134,319 US4880857A (en) | 1986-12-17 | 1987-12-16 | Carbon black-graft polymer, method for production thereof, and use thereof |
| EP87311145A EP0272127A3 (en) | 1986-12-17 | 1987-12-17 | Carbon black-graft polymer, its production and use |
| KR1019870014435A KR940007357B1 (en) | 1986-12-17 | 1987-12-17 | Carbon black-graft polymer, its production and use |
| US07/373,234 US4940749A (en) | 1986-12-17 | 1989-06-29 | Carbon black-graft polymer, method for production thereof, and use thereof |
| US07/533,780 US4994520A (en) | 1986-12-17 | 1990-06-06 | Carbon black-graft polymer, method for production thereof, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62131272A JPS63298811A (en) | 1987-05-29 | 1987-05-29 | Magnetic recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63298811A true JPS63298811A (en) | 1988-12-06 |
Family
ID=15054052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62131272A Pending JPS63298811A (en) | 1986-12-17 | 1987-05-29 | Magnetic recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63298811A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08337737A (en) * | 1995-06-14 | 1996-12-24 | Nippon Shokubai Co Ltd | Surface modification of solid fine particle |
-
1987
- 1987-05-29 JP JP62131272A patent/JPS63298811A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08337737A (en) * | 1995-06-14 | 1996-12-24 | Nippon Shokubai Co Ltd | Surface modification of solid fine particle |
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