JP3429503B2 - Magnetic adsorption sheet - Google Patents

Magnetic adsorption sheet

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Publication number
JP3429503B2
JP3429503B2 JP2001240620A JP2001240620A JP3429503B2 JP 3429503 B2 JP3429503 B2 JP 3429503B2 JP 2001240620 A JP2001240620 A JP 2001240620A JP 2001240620 A JP2001240620 A JP 2001240620A JP 3429503 B2 JP3429503 B2 JP 3429503B2
Authority
JP
Japan
Prior art keywords
magnetic
weight
resin
ferromagnetic powder
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP2001240620A
Other languages
Japanese (ja)
Other versions
JP2003059714A (en
Inventor
伸一 松村
美貴 須藤
和人 川又
栄治 太田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sony Corp
Original Assignee
Sony Corp
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Filing date
Publication date
Application filed by Sony Corp filed Critical Sony Corp
Priority to JP2001240620A priority Critical patent/JP3429503B2/en
Publication of JP2003059714A publication Critical patent/JP2003059714A/en
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Publication of JP3429503B2 publication Critical patent/JP3429503B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【発明の属する技術分野】本発明は、磁気吸着シートに
関し、特に、磁性層と被吸着面との粘着が抑制された磁
気吸着シートに関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic attraction sheet, and more particularly to a magnetic attraction sheet in which adhesion between a magnetic layer and a surface to be attracted is suppressed.

【0002】[0002]

【従来の技術】現在、永久磁石の磁気吸着を利用した磁
気吸着シートは各種表示具として幅広く使われており、
特に事務用品としての用途が拡大しつつある。近年、パ
ーソナルコンピュータの急速な普及に伴い、プリンター
等の周辺機器の性能が著しく向上している。例えば、一
般用プリンターによる印刷の品質は、業務用印刷の品質
に匹敵しつつある。同時に、それらの印刷物を自在に利
用したいという欲求も高まっている。
2. Description of the Related Art At present, magnetic attraction sheets utilizing the magnetic attraction of permanent magnets are widely used as various display tools.
In particular, its use as office supplies is expanding. In recent years, along with the rapid spread of personal computers, the performance of peripheral devices such as printers has been remarkably improved. For example, the quality of printing by general-purpose printers is becoming comparable to the quality of commercial printing. At the same time, there is a growing desire to freely use those printed materials.

【0003】印刷物の第一の使用目的は、表示すること
である。提示場所に表示物を固定するために、各種接着
剤、接着テープ、画鋲、キャップマグネット等の固定材
が使用されている。磁気吸着シートは表示物自体が磁気
吸着性を有する固定材であるため、提示場所が強磁性体
である場合は、別の固定材を必要とせず、単独で表示す
ることが可能である。また、掲示場所からの脱着が自在
である。
The primary purpose of use of printed matter is to display it. Fixing materials such as various kinds of adhesives, adhesive tapes, pushpins, and cap magnets are used to fix the display object at the presentation place. Since the magnetic attraction sheet itself is a fixing material having a magnetic attraction property, when the presentation place is a ferromagnetic material, it is possible to display independently without the need for another fixing material. Also, it can be freely attached and detached from the display place.

【0004】磁気吸着シートは、シート状のボンド磁石
であり、用途が拡大するに従って、加工を容易に行える
ようにするための薄膜化が進んでいる。近年、押出成形
によって製造される磁性層厚0.1mm程度、全厚0.
2mm程度の磁気吸着シートが実用化されている。
The magnetic attraction sheet is a sheet-shaped bond magnet, and as the use thereof expands, the thickness of the magnetic attraction sheet is being reduced so that it can be easily processed. In recent years, the magnetic layer manufactured by extrusion molding has a thickness of about 0.1 mm and a total thickness of 0.
A magnetic adsorption sheet of about 2 mm has been put to practical use.

【0005】また、特開2001−76920号公報に
は、磁性塗料の塗布により磁性層が形成され、磁性層の
面内方向に磁化容易軸が配向し、面内方向に着磁された
可撓性磁石シートが提案されている。このシートによれ
ば、磁性層が押出成形等でなく、磁性塗料の塗布により
形成されるため、シートを均一に薄膜化することが可能
となる。また、磁化容易軸の方向に沿ってN極とS極が
交互に並ぶように着磁されることから、膜厚が同等であ
る垂直配向・垂直着磁の磁気吸着シートに比較して、強
い磁気吸着力が得られる。
Further, in Japanese Unexamined Patent Publication No. 2001-76920, a magnetic layer is formed by applying a magnetic coating, the easy axis of magnetization is oriented in the in-plane direction of the magnetic layer, and the flexible layer is magnetized in the in-plane direction. Magnetic magnet sheets have been proposed. According to this sheet, the magnetic layer is formed not by extrusion molding or the like but by applying a magnetic coating material, so that the sheet can be uniformly thinned. Further, since the N poles and the S poles are magnetized so as to be alternately arranged along the direction of the easy axis of magnetization, the magnetic attraction sheet is stronger than the vertically oriented and vertically magnetized magnetic attraction sheet having the same film thickness. A magnetic attraction force is obtained.

【0006】[0006]

【発明が解決しようとする課題】上記の特開2001−
76920号公報には、磁性層を形成するための磁性塗
料に用いることができる結合剤として、各種の樹脂が挙
げられている。しかしながら、好適な結合剤や、結合剤
を選択する際の基準等については記載がない。特に、結
合剤のガラス転移点Tg が磁気吸着シートの粘着性に与
える影響については、検討されていない。
DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Japanese Patent No. 76920 discloses various resins as a binder that can be used in a magnetic coating material for forming a magnetic layer. However, there is no description about a suitable binder and criteria for selecting the binder. In particular, the influence of the glass transition point T g of the binder on the tackiness of the magnetic adsorption sheet has not been examined.

【0007】従来の磁気吸着シートは、一般に磁性層の
粘着性が高い。したがって、磁性層を長期間、強磁性面
に磁気吸着させたり、あるいは、熱湯の入ったポットの
表面等、加温されている強磁性体に磁性層を磁気吸着さ
せたりした後、磁気吸着シートを強磁性体から剥離する
と、磁性層の少なくとも一部が強磁性体の表面に付着す
ることがある。この場合、磁気吸着シートの磁性層が破
壊されるだけでなく、強磁性体の表面も汚れる。
In the conventional magnetic adsorption sheet, the magnetic layer generally has high adhesiveness. Therefore, after magnetically adsorbing the magnetic layer on the ferromagnetic surface for a long period of time, or magnetically adsorbing the magnetic layer on a heated ferromagnetic material such as the surface of a pot containing hot water, the magnetic adsorption sheet When is removed from the ferromagnetic material, at least part of the magnetic layer may adhere to the surface of the ferromagnetic material. In this case, not only the magnetic layer of the magnetic adsorption sheet is destroyed, but also the surface of the ferromagnetic material is soiled.

【0008】特に、磁性塗料にTg の低い結合剤を用い
た場合には、このような問題が顕著となりやすい。本発
明は上記の問題点に鑑みてなされたものであり、したが
って本発明は、磁性層の粘着性が適切に制御され、磁気
吸着シートを被吸着面から剥離する際に、磁性層が被吸
着面に残りにくい磁気吸着シートを提供することを目的
とする。
In particular, when a binder having a low T g is used in the magnetic paint, such a problem tends to be remarkable. The present invention has been made in view of the above problems. Therefore, the present invention has an advantage that the adhesiveness of the magnetic layer is appropriately controlled, and when the magnetic attraction sheet is peeled from the attracted surface, the magnetic layer is attracted. It is an object of the present invention to provide a magnetic adsorption sheet that does not easily remain on the surface.

【0009】[0009]

【課題を解決するための手段】上記の目的を達成するた
め、本発明の磁気吸着シートは、非磁性支持体上に、強
磁性粉末と結合剤を主成分とする磁性塗料を塗布し、乾
燥させて磁性層が形成され、前記磁性層は面内方向に磁
化容易軸を有し、かつ磁化容易軸に沿って面内で磁化が
交互に反転するように多極着磁されている磁気吸着シー
トであって、前記磁性塗料は、結合剤としてガラス転移
点Tg≧80(℃)の樹脂を、全結合剤のうちの5〜6
重量%含有し、前記磁性塗料は、前記ガラス転移点T
g≧80(℃)の樹脂を含む全結合剤を、前記強磁性粉
末100重量部に対し8〜18重量部含有し、前記強磁
性粉末の保磁力は700〜4000エルステッド(O
e)であり、前記磁性層の膜厚は0.03〜0.10m
mであり、全厚は0.08〜0.25mmであり、前記
強磁性粉末の平均粒径は0.5〜5μmであることを特
徴とする。
In order to achieve the above-mentioned object, the magnetic adsorption sheet of the present invention comprises a non-magnetic support coated with a magnetic coating containing a ferromagnetic powder and a binder as main components and dried. To form a magnetic layer, the magnetic layer has an easy axis of magnetization in the in-plane direction, and is multi-pole magnetized so that the magnetization is alternately inverted in the plane along the easy axis of magnetization. In the sheet, the magnetic coating material comprises a resin having a glass transition point Tg ≧ 80 (° C.) as a binder, and 5 to 6 of all binders.
0% by weight , and the magnetic paint has the glass transition point T
Total binding agent comprising g ≧ 80 (℃) resin, the ferromagnetic powder against the 100 weight parts contain from 8 to 18 parts by weight, the strong magnetic
The coercive force of the powder is 700-4000 oersted (O
e), and the film thickness of the magnetic layer is 0.03 to 0.10 m.
m, the total thickness is 0.08 to 0.25 mm, and the average particle size of the ferromagnetic powder is 0.5 to 5 μm.

【0010】好適には、前記Tg≧80(℃)の樹脂
は、セルロースアセテート系樹脂を含む。好適には、前
記磁性塗料は、前記Tg≧80(℃)の樹脂を含む全結
合剤を、前記強磁性粉末100重量部に対し15.4
18重量部含有する。
Preferably, the resin having Tg ≧ 80 (° C.) contains a cellulose acetate resin. Preferably, the magnetic coating, the Tg ≧ 80 (℃) of the total binder containing a resin, wherein 100 parts by weight of the ferromagnetic powder in pairs to 15.4 ~
Contains 18 parts by weight.

【0011】これにより、磁性表面の粘着性が抑制され
る。したがって、磁気吸着シートを被吸着面から剥離し
た際に、被吸着面に磁性層の一部が付着して残留するの
を防止できる。
As a result, the adhesion of the magnetic surface is suppressed. Therefore, when the magnetic attraction sheet is peeled from the attracted surface, it is possible to prevent a part of the magnetic layer from adhering and remaining on the attracted surface.

【0012】[0012]

【発明の実施の形態】以下に、本発明の磁気吸着シート
の実施の形態について、図面を参照して説明する。図1
は、本実施形態の磁気吸着シートの断面図である。図1
に示すように、磁気吸着シート1は一方の面に磁性層2
を有する。
BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the magnetic attraction sheet of the present invention will be described below with reference to the drawings. Figure 1
FIG. 3 is a cross-sectional view of the magnetic attraction sheet of this embodiment. Figure 1
As shown in FIG. 1, the magnetic adsorption sheet 1 has a magnetic layer 2 on one surface.
Have.

【0013】磁性層2は、強磁性粉末と結合剤樹脂を主
成分とする磁性塗料を非磁性支持体3上に塗布し、乾燥
させて形成される。本実施形態の磁気吸着シートによれ
ば、磁性塗料には結合剤樹脂として、Tg が80℃以上
である樹脂またはセルロースアセテート系樹脂が添加さ
れる。これにより、磁性層2の粘着性が適切に制御され
る。磁性層2は面内方向に磁化容易軸を有し、面内方向
に磁化容易軸に沿って、磁化が交互に反転するように一
定のピッチで多極着磁されている。
The magnetic layer 2 is formed by applying a magnetic coating material containing a ferromagnetic powder and a binder resin as a main component on the non-magnetic support 3 and drying it. According to the magnetic adsorption sheet of this embodiment, a resin having a T g of 80 ° C. or higher or a cellulose acetate-based resin is added to the magnetic paint as a binder resin. Thereby, the adhesiveness of the magnetic layer 2 is appropriately controlled. The magnetic layer 2 has an easy axis of magnetization in the in-plane direction, and is multi-pole magnetized at a constant pitch so that the magnetization alternates in the in-plane direction along the easy axis of magnetization.

【0014】非磁性支持体3としては、一方の面に塗布
される磁性塗料、特に磁性塗料中の溶剤が他方の面に向
かって浸透しないように、表面に樹脂コートが施された
コート紙、合成紙、または合成フィルムを用いることが
好ましい。合成フィルムとしては例えば、表面に易接着
処理が施された白色ポリエステルフィルム等が挙げられ
る。また、白色以外に着色された非磁性支持体3を用い
ることもできる。
The non-magnetic support 3 is coated with a resin coating on the surface so that the magnetic coating applied to one surface, especially the solvent in the magnetic coating, does not penetrate to the other surface. It is preferable to use synthetic paper or synthetic film. Examples of the synthetic film include a white polyester film whose surface is subjected to an easy-adhesion treatment. Further, the non-magnetic support 3 colored other than white can be used.

【0015】非磁性支持体3の一方の面には磁性層2が
形成され、他方の面には必要に応じて、各種の印刷が可
能な印刷受容層4が設けられる。印刷受容層4として
は、例えば感熱層、熱転写インク受容層、インクジェッ
ト受容層、バブルインクジェット受容層、ドットインパ
クト受容層、レーザープリンタートナー受容層等が挙げ
られる。印刷受容層4の種類は、印刷方法や印刷物の表
示目的に応じて適宜選択する。また、非磁性支持体3の
材質や表面状態によっては、必ずしも印刷受容層4を設
けなくてもよい。
A magnetic layer 2 is formed on one surface of the non-magnetic support 3, and a print receiving layer 4 capable of various types of printing is provided on the other surface of the non-magnetic support 3, if necessary. Examples of the print receiving layer 4 include a heat sensitive layer, a thermal transfer ink receiving layer, an inkjet receiving layer, a bubble inkjet receiving layer, a dot impact receiving layer, and a laser printer toner receiving layer. The type of the print receiving layer 4 is appropriately selected according to the printing method and the display purpose of the printed matter. The print receiving layer 4 may not be necessarily provided depending on the material and surface state of the non-magnetic support 3.

【0016】磁性層2を形成するための磁性塗料には、
強磁性粉末として、例えばSrフェライト粉末やBaフ
ェライト粉末等の強磁性酸化鉄を分散させることが好ま
しい。磁性塗料に、例えばSm−Co粉末、Sm−Fe
−N粉末、Nd−Fe−B粉末のような保磁力Hcの高
い希土類強磁性粉末を用いた場合、着磁が難しくなる。
The magnetic paint for forming the magnetic layer 2 includes
As the ferromagnetic powder, it is preferable to disperse a ferromagnetic iron oxide such as Sr ferrite powder or Ba ferrite powder. For magnetic paint, for example, Sm-Co powder, Sm-Fe
When a rare earth ferromagnetic powder having a high coercive force Hc such as -N powder or Nd-Fe-B powder is used, it becomes difficult to magnetize.

【0017】強磁性粉末の保磁力は700〜4000O
e程度が好ましい。保磁力が4000Oeを超えると、
保磁力が高すぎて着磁が難しくなる。一方、保磁力が7
00Oeより低い場合には、十分な磁気吸着力が得られ
ない。磁気吸着力には、強磁性粉末をシート状にしたと
きの残留磁束密度も影響する。残留磁束密度が1500
G以上であれば、高い磁気吸着力を得やすい。
The coercive force of the ferromagnetic powder is 700 to 4000 O.
About e is preferable. When the coercive force exceeds 4000 Oe,
The coercive force is too high, making it difficult to magnetize. On the other hand, the coercive force is 7
If it is lower than 00 Oe, a sufficient magnetic attraction force cannot be obtained. The magnetic attraction force is also affected by the residual magnetic flux density when the ferromagnetic powder is formed into a sheet. Residual magnetic flux density is 1500
If it is G or more, it is easy to obtain a high magnetic attraction force.

【0018】Srフェライト粉末およびBaフェライト
粉末の平均粒径は、0.5〜5μm程度が好ましい。平
均粒径が0.5μmより小さいと、磁性塗膜における磁
性粉末の密度が大きくなり過ぎて磁性塗膜にカールが発
生し、最終的にはクラックが発生する。また、平均粒径
が5μmより大きいと、磁性塗膜の密度が粗くなり、塗
膜強度が低下する。
The average particle size of the Sr ferrite powder and the Ba ferrite powder is preferably about 0.5 to 5 μm. If the average particle size is smaller than 0.5 μm, the density of the magnetic powder in the magnetic coating film becomes too large, curling occurs in the magnetic coating film, and finally cracks occur. On the other hand, if the average particle diameter is larger than 5 μm, the density of the magnetic coating film becomes coarse and the coating film strength decreases.

【0019】上記のような強磁性粉末を分散させる高分
子結合剤としては、熱可塑性および熱硬化性樹脂を好適
に用いることができる。例えば、エポキシ樹脂、エチレ
ン酢酸ビニル共重合体、エチレン酢酸ビニルブロック共
重合体、エチレン−(メタ)アクリレートとの共重合
体、もしくはブロック共重合体ポリエチレン、アクリル
樹脂、ポリエステル樹脂、ポリウレタン樹脂等の有機高
分子材料が挙げられる。これらは単独で、あるいは数種
類の樹脂を組み合わせて使用できる。
As the polymer binder for dispersing the ferromagnetic powder as described above, thermoplastic and thermosetting resins can be preferably used. For example, epoxy resin, ethylene vinyl acetate copolymer, ethylene vinyl acetate block copolymer, copolymer with ethylene- (meth) acrylate, or block copolymer polyethylene, acrylic resin, polyester resin, organic resin such as polyurethane resin Polymer materials can be mentioned. These can be used alone or in combination of several kinds of resins.

【0020】磁性塗料中の結合剤の割合は、通常の磁気
吸着シートを作製する場合、強磁性粉末100重量部に
対して、8〜18重量部であることが好ましい。結合剤
の割合がこれより小さいと、磁気吸着力を大きく出来る
反面、塗膜が脆弱になる。したがって、磁気吸着シート
の着脱時の変形により、粉落ちやクラック等の塗膜破壊
が起こりやすくなる。一方、結合剤の割合が大き過ぎる
と、磁束密度が不足して、十分な磁気吸着力が得られな
い。
The ratio of the binder in the magnetic paint is preferably 8 to 18 parts by weight with respect to 100 parts by weight of the ferromagnetic powder when a usual magnetic adsorption sheet is produced. If the proportion of the binder is smaller than this, the magnetic adsorption force can be increased, but the coating film becomes brittle. Therefore, the deformation of the magnetic attraction sheet during attachment / detachment easily causes the coating film to break such as powder drop and cracks. On the other hand, if the proportion of the binder is too large, the magnetic flux density becomes insufficient, and a sufficient magnetic attraction force cannot be obtained.

【0021】また、強磁性粉末に対する結合剤の割合が
8〜18重量部の範囲内であっても、約15.4重量部
より小さくなると、磁性塗料中で強磁性粉末の沈殿が起
こりやすくなる。磁気吸着シートに用いられる強磁性粉
末の平均粒径は例えば1.5μm程度であり、塗布型の
磁気テープ等に用いられる強磁性粉末の粒径に比較する
と大きい。したがって、強磁性粉末に対する結合剤の割
合が低くなると、強磁性粉末の沈殿が特に起こりやすく
なる。
Further, even if the ratio of the binder to the ferromagnetic powder is in the range of 8 to 18 parts by weight, if it is less than about 15.4 parts by weight, precipitation of the ferromagnetic powder in the magnetic coating is likely to occur. . The average particle size of the ferromagnetic powder used in the magnetic attraction sheet is, for example, about 1.5 μm, which is larger than the particle size of the ferromagnetic powder used in the coating type magnetic tape or the like. Therefore, when the ratio of the binder to the ferromagnetic powder is low, precipitation of the ferromagnetic powder is particularly likely to occur.

【0022】沈殿が微量である場合は、磁性塗料の再攪
拌により強磁性粉末を分散させることができる。しかし
ながら、磁性塗料中で沈殿した強磁性粉末は、自重で圧
縮固化してしまうため、磁性塗料の調製から塗布までの
時間が長い場合等には、再攪拌による強磁性粉末の分散
が非常に困難となる。
When the amount of precipitation is very small, the ferromagnetic powder can be dispersed by re-stirring the magnetic paint. However, the ferromagnetic powder precipitated in the magnetic paint is compressed and solidified by its own weight, so it is very difficult to disperse the ferromagnetic powder by re-stirring when the time from preparation of the magnetic paint to application is long. Becomes

【0023】したがって、塗布前に磁性塗料を長時間放
置する場合には、磁性塗料中の結合剤の割合を、強磁性
粉末100重量部に対して15.4〜18重量部程度に
することが好ましい。結合剤の割合を15.4〜18重
量部にした場合、強磁性粉末の沈降が遅く、磁性塗料の
再攪拌が容易である。また、磁性塗料の塗布中に強磁性
粉末が沈降せず、一定の組成の磁性塗料を塗布できる。
Therefore, when leaving the magnetic coating for a long time before coating, the proportion of the binder in the magnetic coating should be about 15.4 to 18 parts by weight based on 100 parts by weight of the ferromagnetic powder. preferable. When the ratio of the binder is 15.4 to 18 parts by weight, the sedimentation of the ferromagnetic powder is slow and the magnetic paint can be easily re-stirred. Further, the ferromagnetic powder does not settle during the application of the magnetic paint, and the magnetic paint having a constant composition can be applied.

【0024】磁性層の粘着を防止する目的で、結合剤に
添加されるTg≧80(℃)の樹脂としては、ポリエス
テルポリウレタン系樹脂(例えば、東洋紡製 UR1400
Tg=83(℃))、アクリル系樹脂(例えば、呉羽化
学社製 バイヨンTg=80(℃))、アセタール系樹
脂(例えば、積水化学社製 KS-10 Tg=106
(℃)、KS-5 Tg=110(℃)、KX-5 Tg=86
(℃))、ポリイミドアミド(例えば、東洋紡製 T100
NR Tg=175(℃))、ニトロセルロース(例え
ば、旭化成製 NC-H301 、HIG-1 、SL-1、HI-1000 全て
Tg≧150(℃))等が挙げられる。
The resin having Tg ≧ 80 (° C.) added to the binder for the purpose of preventing adhesion of the magnetic layer is a polyester polyurethane resin (for example, UR1400 manufactured by Toyobo Co., Ltd.).
Tg = 83 (° C.)), acrylic resin (for example, Bayon Tg = 80 (° C.) manufactured by Kureha Chemical Co., Ltd.), acetal resin (for example, KS-10 Tg = 106 manufactured by Sekisui Chemical Co., Ltd.).
(℃), KS-5 Tg = 110 (℃), KX- 5 Tg = 86
(° C)), polyimide amide (eg Toyobo T100
NR Tg = 175 (° C.)), nitrocellulose (for example, NC-H301, HIG-1, SL-1, HI-1000 manufactured by Asahi Kasei, Tg ≧ 150 (° C.)).

【0025】また、Tg ≧80(℃)の樹脂として、特
願平11−308153号の磁気記録媒体に用いられる
ものと同様のポリウレタン樹脂を用いることもできる。
このポリウレタン樹脂によれば、鎖延長剤の選択に応じ
て、Tgの上限を通常のポリウレタン樹脂の70〜90
℃から、110〜120℃程度まで上昇させることがで
きる。
As the resin having T g ≧ 80 (° C.), the same polyurethane resin as that used in the magnetic recording medium of Japanese Patent Application No. 11-308153 can be used.
According to this polyurethane resin, the upper limit of T g is 70 to 90 of that of a normal polyurethane resin depending on the selection of the chain extender.
The temperature can be raised from 0 ° C to about 110 to 120 ° C.

【0026】特に、セルロースアセテートブチラート
(例えば、イーストマンケミカル社製CAB-381-0.1 Tg
=123(℃)、CAB-381-0.5 Tg =130(℃)、CA
B-551-0.2 Tg =101(℃))やセルロースアセテー
トプロピオネート(例えば、イーストマンケミカル社製
CAP-482-0.5 Tg =142(℃)、CAP-482-20 T g
=147(℃))等のセルロースアセテート系樹脂を結
合剤として用いた場合には、磁性層の粘着が効果的に防
止される。
In particular, cellulose acetate butyrate
(For example, Eastman Chemical Co. CAB-381-0.1 Tg 
= 123 (℃), CAB-381-0.5 Tg = 130 (℃), CA
B-551-0.2 Tg = 101 (℃)) and cellulose acetate
Topropionate (for example, Eastman Chemical Co.
  CAP-482-0.5 Tg = 142 (℃), CAP-482-20 T g 
= 147 (℃)) etc.
When used as a mixture, it effectively prevents the adhesion of the magnetic layer.
Be stopped.

【0027】これらの樹脂のTg が80℃より低い場合
は、十分な粘着防止効果が得られない。本実施形態にお
いて、ガラス転移点Tg は熱分析のJIS規格(JISK71
21)または熱分析のISO規格(ISO11357-1/-2)に規
定されるものとした。
If the T g of these resins is lower than 80 ° C., a sufficient anti-adhesion effect cannot be obtained. In the present embodiment, the glass transition point T g is the JIS standard (JISK71) for thermal analysis.
21) or the ISO standard for thermal analysis (ISO11357-1 / -2).

【0028】上記のTg ≧80(℃)の樹脂またはセル
ロースアセテート系樹脂が結合剤中に占める割合は、全
結合剤を100%とした場合に5〜60%が好ましい。
この割合が5%より小さいと、磁性層の粘着を防止する
効果が十分に得られない。一方、この割合が60%より
大きいと、塗膜強度が極端に低下してしまう。
The ratio of the resin having the above T g ≧ 80 (° C.) or the cellulose acetate resin in the binder is preferably 5 to 60% when the total binder is 100%.
If this ratio is less than 5%, the effect of preventing sticking of the magnetic layer cannot be sufficiently obtained. On the other hand, if this ratio is larger than 60%, the coating film strength will be extremely lowered.

【0029】非磁性支持体の膜厚は0.05〜0.15
mmの範囲が好ましい。本実施形態の磁気吸着シートが
印刷受容層を有する場合には、印刷受容層を含む非磁性
支持体の膜厚が0.05〜0.15mmであることが好
ましい。非磁性支持体の膜厚が0.05mm未満の場
合、印刷受容層または非磁性支持体の表面に印刷を施し
て表示する際に、磁性層の色が非磁性支持体の表面に透
けてしまい、表示外観が悪くなることがある。
The film thickness of the non-magnetic support is 0.05 to 0.15.
The range of mm is preferred. When the magnetic adsorption sheet of the present embodiment has a print receiving layer, the thickness of the non-magnetic support including the print receiving layer is preferably 0.05 to 0.15 mm. When the thickness of the non-magnetic support is less than 0.05 mm, the color of the magnetic layer is transparent to the surface of the non-magnetic support when the print-receiving layer or the surface of the non-magnetic support is printed and displayed. , The display appearance may deteriorate.

【0030】磁性層の膜厚は0.03〜0.1mmの範
囲が好ましい。磁石の磁気的エネルギーは磁石の体積に
比例するため、磁性層の膜厚が0.03mm未満の場
合、十分な磁気吸着力を得られないことがある。例え
ば、磁気吸着シートを壁面のような地面に垂直な被吸着
面に固定したいとき、磁性層の膜厚が薄すぎると、磁性
層と非磁性支持体を合わせた磁気吸着シートの重量を、
磁性層の磁気吸着力で支持できず、磁気吸着シートが落
下することがある。
The thickness of the magnetic layer is preferably in the range of 0.03 to 0.1 mm. Since the magnetic energy of the magnet is proportional to the volume of the magnet, when the film thickness of the magnetic layer is less than 0.03 mm, a sufficient magnetic attraction force may not be obtained. For example, when the magnetic attraction sheet is to be fixed to a surface such as a wall surface that is perpendicular to the ground, and the thickness of the magnetic layer is too thin, the weight of the magnetic attraction sheet including the magnetic layer and the non-magnetic support is
The magnetic attraction force of the magnetic layer may not be supported, and the magnetic attraction sheet may fall.

【0031】一方、磁性層の膜厚が0.1mmを超える
場合、磁気吸着力は十分に得られるが、長期間使用時
に、着脱時のシートの繰り返し変形で、機械的疲労によ
る塗膜破壊が起こりやすくなる。また、磁性層の膜厚が
厚くなり過ぎると、磁気吸着力が過剰となる。したがっ
て、磁気吸着シートを積層したときにシートが互いに吸
着し、プリンター等により印刷を行うのが困難となる。
また、磁気吸着シートの全厚は0.08〜0.25mm
の範囲が好ましい。磁性層を含む磁気吸着シートの全厚
が0.25mmを超えた場合、一般家庭用印刷機で対応
可能な範疇を逸脱してしまう。
On the other hand, when the thickness of the magnetic layer exceeds 0.1 mm, a sufficient magnetic adsorption force is obtained, but during long-term use, repeated deformation of the sheet at the time of attachment and detachment causes damage to the coating film due to mechanical fatigue. It is easy to happen. Further, when the film thickness of the magnetic layer becomes too thick, the magnetic attraction force becomes excessive. Therefore, when the magnetic attraction sheets are laminated, the sheets are attracted to each other, and it becomes difficult to print with a printer or the like.
Moreover, the total thickness of the magnetic adsorption sheet is 0.08 to 0.25 mm.
Is preferred. If the total thickness of the magnetic attraction sheet including the magnetic layer exceeds 0.25 mm, it falls outside the range that can be supported by general household printing machines.

【0032】本実施形態の磁気吸着シートは、磁性層の
面内方向に磁化容易軸が配向され、磁化容易軸に沿って
面内方向に着磁されるため、磁極間距離は磁性層の膜厚
に依存しない。したがって、磁性層の膜厚を薄くして
も、磁極間距離を十分に確保でき、反磁界が増大せずに
減磁し難い。これにより、前述したような普通印刷用紙
と同等の薄さを実現できる。
In the magnetic attraction sheet of this embodiment, the easy axis of magnetization is oriented in the in-plane direction of the magnetic layer and magnetized in the in-plane direction along the easy axis of magnetization. Does not depend on thickness. Therefore, even if the thickness of the magnetic layer is reduced, the distance between the magnetic poles can be sufficiently secured, the demagnetizing field does not increase, and demagnetization is difficult. As a result, it is possible to realize the same thinness as that of the plain printing paper as described above.

【0033】図2は、多極着磁された磁性層を模式的に
示す斜視図である。磁性層2は面内方向に磁化容易軸を
有し、磁性層2には磁化容易軸に沿って(N−S)(S
−N)(N−S)・・・のような多極着磁が一定のピッ
チPで施される。磁性層2からは磁力線5で示すような
磁界が発生する。
FIG. 2 is a perspective view schematically showing a multi-pole magnetized magnetic layer. The magnetic layer 2 has an easy axis of magnetization in the in-plane direction, and the magnetic layer 2 has (NS) (S) along the easy axis of magnetization.
Multi-pole magnetization such as −N) (NS) is performed at a constant pitch P. A magnetic field as indicated by magnetic force lines 5 is generated from the magnetic layer 2.

【0034】S極とS極、またはN極とN極が対向する
磁極面からは、磁性層面に対して垂直方向に極大となる
ような漏れ磁束が発生する。これにより、磁性層2と被
吸着体6である鋼板等との間に、効果的に磁気吸着力が
作用する。磁気吸着時には被吸着体6がヨークとなり、
ほぼ完全に磁気回路が閉じ、漏れ磁束は極小である。
From the magnetic pole surfaces where the S poles and the S poles or the N poles and the N poles face each other, a leakage magnetic flux that maximizes in the direction perpendicular to the magnetic layer surface is generated. Thereby, the magnetic attraction force effectively acts between the magnetic layer 2 and the steel plate or the like that is the attracted body 6. When magnetically attracting, the attracted body 6 becomes a yoke,
The magnetic circuit is almost completely closed and the leakage flux is minimal.

【0035】本実施形態の磁気吸着シートの磁性層は、
強磁性粉末を高分子結合剤および溶剤に十分に分散させ
て得られた磁性塗料を、非磁性支持体上に塗布して形成
される。磁性塗料の塗布には、例えばグラビアコータ
ー、ダイコーター、ナイフコーター等を用いることがで
きる。
The magnetic layer of the magnetic attraction sheet of this embodiment is
It is formed by coating a non-magnetic support with a magnetic paint obtained by sufficiently dispersing ferromagnetic powder in a polymer binder and a solvent. A gravure coater, a die coater, a knife coater or the like can be used to apply the magnetic paint.

【0036】磁性塗料が塗布された非磁性支持体は、配
向磁場中を通過する。これにより、強磁性粉末の磁化容
易軸が磁性塗膜の面内方向へ配向される。さらに、非磁
性支持体が熱風乾燥機を通過することにより、磁性塗料
中の溶剤が蒸発して磁性塗膜が乾燥固化する。これによ
り、押出成形のような高温高圧設備を使用せずに、薄膜
の磁性層が連続的に形成される。
The non-magnetic support coated with the magnetic coating passes through the orientation magnetic field. As a result, the easy axis of magnetization of the ferromagnetic powder is oriented in the in-plane direction of the magnetic coating film. Further, when the non-magnetic support passes through the hot air dryer, the solvent in the magnetic paint evaporates and the magnetic coating film is dried and solidified. As a result, a thin magnetic layer is continuously formed without using high temperature and high pressure equipment such as extrusion molding.

【0037】磁性塗膜中の強磁性粉末の磁化容易軸を磁
性塗膜の面内方向に連続的に配向させるには、磁性塗料
を塗布した直後の非磁性支持体に、非磁性支持体の進行
方向と平行な磁束の磁界を印加すればよい。例えば、図
3に示すように、1対の永久磁石7a、7bを同極が対
向するように配置して、磁力線8で示すような磁界を発
生させる。永久磁石7a、7b間の磁気的反発により、
非磁性支持体3の進行方向に磁束が発生する。この空間
を非磁性支持体3が通過することにより、磁性塗膜9中
の強磁性粉末が配向する。
In order to continuously orient the easy axis of magnetization of the ferromagnetic powder in the magnetic coating in the in-plane direction of the magnetic coating, the non-magnetic support immediately after the magnetic coating is applied to the non-magnetic support. A magnetic field having a magnetic flux parallel to the traveling direction may be applied. For example, as shown in FIG. 3, a pair of permanent magnets 7a and 7b are arranged so that the same poles face each other, and a magnetic field as indicated by magnetic force lines 8 is generated. Due to the magnetic repulsion between the permanent magnets 7a and 7b,
A magnetic flux is generated in the traveling direction of the nonmagnetic support 3. The ferromagnetic powder in the magnetic coating film 9 is oriented by the non-magnetic support 3 passing through this space.

【0038】あるいは、図示しないが、1対のソレノイ
ドコイルを対向するように配置して磁界を発生させても
よい。この場合も、磁性塗料を塗布された非磁性支持体
が、ソレノイドコイル間を通過することにより、磁性塗
膜中の強磁性粉末が配向する。磁気吸着シートにおい
て、高い磁気吸着力を安定に得るためには、磁場中で強
磁性粉末の磁化容易軸を配向させながら、同時に磁性塗
膜を乾燥(磁場中乾燥)させてもよい。
Alternatively, although not shown, a pair of solenoid coils may be arranged so as to face each other to generate a magnetic field. Also in this case, the non-magnetic support coated with the magnetic paint passes between the solenoid coils, so that the ferromagnetic powder in the magnetic coating film is oriented. In the magnetic adsorption sheet, in order to stably obtain a high magnetic adsorption force, the magnetic coating film may be dried (dried in the magnetic field) at the same time while orienting the easy axis of magnetization of the ferromagnetic powder in the magnetic field.

【0039】上記のように強磁性粉末の磁化容易軸を配
向させた後、磁性層の面内方向に多極着磁が施される。
図4は、本実施形態の磁気吸着シート1に着磁を行う方
法の一例を示す概略図である。図4に示すように、長尺
方向に交互に多極着磁を施した1対の角柱状の磁石バー
11a、11bを同極対向するように平行に配置する。
これらの磁石バー11a、11bの間隙に、磁気吸着シ
ート1を通過させて着磁を行う。
After orienting the easy axis of magnetization of the ferromagnetic powder as described above, multipole magnetization is performed in the in-plane direction of the magnetic layer.
FIG. 4 is a schematic view showing an example of a method of magnetizing the magnetic attraction sheet 1 of this embodiment. As shown in FIG. 4, a pair of prismatic magnet bars 11a and 11b, which are alternately magnetized in the longitudinal direction and have multiple poles, are arranged in parallel so as to face each other.
The magnetic attraction sheet 1 is passed through the gap between the magnet bars 11a and 11b for magnetization.

【0040】このとき、磁性層2の磁化容易軸と磁石バ
ー11a、11bの長尺方向とが平行となり、かつ磁化
容易軸と磁気吸着シート1の進行方向とが直交するよう
に、磁気吸着シート1を移動させる。磁石バー11a、
11bとしては例えば希土類の永久磁石を用いる。希土
類の永久磁石として、例えばSm−Co磁石、Sm−F
e−N磁石あるいはNd−Fe−B磁石等を用いること
により、例えば6000Oe以上の磁界が発生する。し
たがって、着磁対象であるSrフェライト粉末等の強磁
性酸化鉄に十分着磁を行うことができる。
At this time, the easy axis of magnetization of the magnetic layer 2 and the longitudinal directions of the magnet bars 11a and 11b are parallel to each other, and the easy axis of magnetization and the traveling direction of the magnetic attraction sheet 1 are orthogonal to each other. Move 1 Magnet bar 11a,
As 11b, for example, a rare earth permanent magnet is used. Examples of rare earth permanent magnets include Sm-Co magnets and Sm-F.
By using an e-N magnet or an Nd-Fe-B magnet, a magnetic field of, for example, 6000 Oe or more is generated. Therefore, it is possible to sufficiently magnetize the ferromagnetic iron oxide such as Sr ferrite powder which is the object of magnetization.

【0041】以上の構成を有する本実施形態の磁気吸着
シートにおいて、磁気特性の一つである磁気吸着力は、
ほぼ0.4gf/cm2 以上が好ましい。磁気吸着力が
0.4gf/cm2 未満の場合は、磁気吸着シートを壁
面のような地面に垂直な被吸着面に固定しても、磁気吸
着シートの自重で落下したり、振動、衝撃あるいは室内
空調の風圧等の外乱によって磁気吸着シートが容易に剥
離したりする。また、磁気吸着シートの表面磁束密度
は、ほぼ40G以上が好ましい。表面磁束密度がほぼ4
0G未満の場合、十分な磁気吸着力を得るのが難しい。
In the magnetic attraction sheet of the present embodiment having the above structure, the magnetic attraction force, which is one of the magnetic characteristics, is
It is preferably about 0.4 gf / cm 2 or more. When the magnetic attraction force is less than 0.4 gf / cm 2 , even if the magnetic attraction sheet is fixed to a surface such as a wall surface that is perpendicular to the ground, the magnetic attraction sheet may drop due to its own weight, or may be subject to vibration, shock, or The magnetic adsorption sheet is easily peeled off due to disturbance such as wind pressure of indoor air conditioning. The surface magnetic flux density of the magnetic adsorption sheet is preferably about 40 G or more. Surface magnetic flux density is almost 4
If it is less than 0 G, it is difficult to obtain a sufficient magnetic attraction force.

【0042】上記の本実施形態の磁気吸着シートは、磁
性層がTg ≧80(℃)の樹脂またはセルロースアセテ
ート系樹脂を所定の割合で含有するため、長期間にわた
って磁気吸着シートを磁気吸着させた場合や、被吸着面
が加温される場合等にも、磁気吸着シートを被吸着面か
ら剥離する際の塗膜破壊が防止される。
In the magnetic adsorption sheet of this embodiment described above, the magnetic layer contains a resin having a T g ≧ 80 (° C.) or a cellulose acetate resin in a predetermined ratio, so that the magnetic adsorption sheet is magnetically adsorbed for a long period of time. When the magnetic attraction sheet is peeled from the attracted surface, the coating film is prevented from being broken even when the attracted surface is heated.

【0043】本実施形態の磁気吸着シートには、汎用さ
れている複写機や、インクジェットプリンター、熱転写
プリンター、昇華型プリンターおよびレーザープリンタ
ー等の各種プリンターを用いて印刷を行うことが可能で
ある。したがって、例えばデジタルカメラ等で撮影した
画像や、スキャナーで取り込んだ画像等を印刷して掲示
したり、ユーザーが独自に編集したカレンダーや料理の
レシピ、スケジュール表等を印刷して、例えば冷蔵庫等
の被吸着面に固定したりできる。また、磁気吸着シート
の固定には、各種接着剤、接着テープ、画鋲、キャップ
マグネット等の固定材が不要である。したがって、例え
ば店舗内のポスター等としても好適に用いることができ
る。
The magnetic attraction sheet of this embodiment can be printed using a general-purpose copying machine, various printers such as an ink jet printer, a thermal transfer printer, a sublimation type printer and a laser printer. Therefore, for example, an image taken by a digital camera or the like, an image captured by a scanner, or the like is printed and displayed, or a calendar, a cooking recipe, a schedule table, or the like edited by the user is printed, and the image is displayed on a refrigerator or the like. It can be fixed to the attracted surface. In addition, fixing materials such as various adhesives, adhesive tapes, thumbtacks, and cap magnets are not required for fixing the magnetic attraction sheet. Therefore, it can be suitably used, for example, as a poster in a store.

【0044】以下、本実施形態の磁気吸着シートを、実
際に作製した実験例に基づいて説明する。但し、本発明
の実施形態は下記の実験例に限定されない。 (実験例1)下記の組成に従って強磁性粉末、結合剤お
よび溶剤をボールミルで混合し、強磁性粉末を均一に分
散させ、磁性塗料を調製した。磁性層の粘着を防止する
目的で、結合剤にはセルロースアセテート系樹脂を添加
した。
Hereinafter, the magnetic adsorption sheet of this embodiment will be described based on an experimental example actually produced. However, the embodiment of the present invention is not limited to the following experimental examples. (Experimental Example 1) According to the following composition, a ferromagnetic powder, a binder and a solvent were mixed by a ball mill to uniformly disperse the ferromagnetic powder to prepare a magnetic paint. A cellulose acetate resin was added to the binder in order to prevent the magnetic layer from sticking.

【0045】磁性塗料材料 磁性粉末 Srフェライト粉末 100重量部 結合剤 ポリエステルポリウレタン樹脂 10.8重量部 セルロースアセテートブチラート 4.6重量部 溶剤 メチルエチルケトン 66重量部 Magnetic coating material Magnetic powder Sr ferrite powder 100 parts by weight Binder Polyester polyurethane resin 10.8 parts by weight Cellulose acetate butyrate 4.6 parts by weight Solvent Methyl ethyl ketone 66 parts by weight

【0046】Srフェライト粉末としては平均粒径1.
2μm、飽和磁化量σs=59(emu/g)、Hc=2
800(Oe)の等方性粒子(戸田工業(株)製)を用
いた。ポリエステルポリウレタン樹脂としては、数平均
分子量Mn=30000、Tg=10(℃)のものを用
いた。セルロースアセテートブチラート(以下、必要に
応じてCABまたは樹脂Aとする。)としては、Tg=
101(℃)のもの(イーストマンケミカル社製、CAB-
551-0.2 )を用いた。
The Sr ferrite powder has an average particle size of 1.
2 μm, saturation magnetization σs = 59 (emu / g), Hc = 2
800 (Oe) isotropic particles (manufactured by Toda Kogyo Co., Ltd.) were used. As the polyester polyurethane resin, one having a number average molecular weight Mn = 30000 and Tg = 10 (° C.) was used. Cellulose acetate butyrate (hereinafter referred to as CAB or resin A as necessary) has Tg =
101 (℃) (Eastman Chemical Co., CAB-
551-0.2) was used.

【0047】この塗料に硬化剤(日本ポリウレタン社製
コロネートHL)を0.3重量部添加した後、グラビ
アコーターを用いて、非磁性支持体であるインクジェッ
ト対応受容層付き白色合成紙(膜厚0.08mm)の印
刷面の裏面に塗布した。続いて、図3に示すように、永
久磁石の同極対向による面内配向磁場2kG中を通過さ
せて、磁化容易軸の面内配向を行った。
After 0.3 part by weight of a curing agent (Coronate HL manufactured by Nippon Polyurethane Co., Ltd.) was added to this coating material, a white synthetic paper with an ink jet-compatible receiving layer which is a non-magnetic support (thickness 0 It was applied to the back side of the printed surface (0.08 mm). Subsequently, as shown in FIG. 3, an in-plane orientation of the easy axis of magnetization was performed by passing through an in-plane orientation magnetic field of 2 kG due to homopolar facing of a permanent magnet.

【0048】次に、塗膜を乾燥させて磁性層厚0.05
mm、全厚0.13mmの原反を得た。得られた原反
を、50℃環境中に20時間以上保存して硬化処理し
た。その後、図4に示すような着磁機を用いて、面内方
向に磁化が交互に反転するように、ピッチ幅2.0mm
で多極着磁を施し、磁気吸着シートを得た。
Next, the coating film is dried to a magnetic layer thickness of 0.05.
mm, and a total thickness of 0.13 mm was obtained. The obtained raw fabric was stored in a 50 ° C. environment for 20 hours or more and cured. Then, using a magnetizing machine as shown in FIG. 4, a pitch width of 2.0 mm so that the magnetization is alternately inverted in the in-plane direction.
Multi-polarization was performed to obtain a magnetic adsorption sheet.

【0049】(実験例2) 結合剤のCABをセルロースアセテートプロピオネート
(以下、必要に応じてCAPまたは樹脂Bとする。)に
変更した以外は実験例1と同様にして、磁気吸着シート
を得た。CAPとしては、Tg=14(℃)のもの
(イーストマンケミカル社製 CAP-482-0.5)を用い
た。
(Experimental Example 2) A magnetic adsorption sheet was prepared in the same manner as in Experimental Example 1, except that the binder CAB was changed to cellulose acetate propionate (hereinafter, referred to as CAP or resin B as necessary). Obtained. The CAP, was used Tg = 14 0 (℃) those of (Eastman Chemical Co. CAP-482-0.5).

【0050】(実験例3) 結合剤のCABをポリエステルポリウレタン系樹脂に変
更した以外は実験例1と同様にして、磁気吸着シートを
得た。ポリエステルポリウレタン系樹脂としては、Tg
=8(℃)のもの(東洋紡(株)製 UR1400、以下、
必要に応じて樹脂Cとする。)を用いた。
(Experimental Example 3) A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1, except that the binder CAB was changed to a polyester polyurethane resin. As polyester polyurethane resin, Tg
= 8 0 (° C.) of those (Toyobo Co., Ltd. UR1400, below,
Resin C is used if necessary. ) Was used.

【0051】(実験例4) 結合剤のCABをアセタール系樹脂に変更した以外は実
験例1と同様にして、磁気吸着シートを得た。アセター
ル系樹脂としては、Tg=8(℃)のもの(積水化学
(株)製 BX-5、以下、必要に応じて樹脂Dとする。)
を用いた。
Experimental Example 4 A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the binder CAB was changed to an acetal resin. The acetal resin, Tg = 8 5 C.) of those (Sekisui Chemical Co., Ltd. BX-5, hereinafter referred to as resin D as necessary.)
Was used.

【0052】(実験例5)実験例1におけるポリエステ
ルポリウレタン樹脂(Tg =10(℃))の添加量を1
4.6重量部に変更し、CABの添加量を0.8重量部
に変更した。これにより、強磁性粉末100重量部に対
する全結合剤の添加量を15.4重量部としたまま、全
結合剤中のCABの割合を30%から5%に変更した。
これ以外は実験例1と同様にして、磁気吸着シートを得
た。
(Experimental Example 5) The amount of polyester polyurethane resin (T g = 10 (° C.)) added in Experimental Example 1 was adjusted to 1
The amount of CAB added was changed to 4.6 parts by weight, and the amount of CAB added was changed to 0.8 parts by weight. As a result, the proportion of CAB in the total binder was changed from 30% to 5% while the total amount of the binder added was 15.4 parts by weight with respect to 100 parts by weight of the ferromagnetic powder.
A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0053】(実験例6)実験例1におけるポリエステ
ルポリウレタン樹脂(Tg =10(℃))の添加量を
6.2重量部に変更し、CABの添加量を9.2重量部
に変更した。これにより、強磁性粉末100重量部に対
する全結合剤の添加量を15.4重量部としたまま、全
結合剤中のCABの割合を30%から60%に変更し
た。これ以外は実験例1と同様にして、磁気吸着シート
を得た。
(Experimental Example 6) The amount of polyester polyurethane resin (T g = 10 (° C)) added in Experimental Example 1 was changed to 6.2 parts by weight, and the amount of CAB added was changed to 9.2 parts by weight. . As a result, the proportion of CAB in the total binder was changed from 30% to 60% while the addition amount of the total binder was 15.4 parts by weight with respect to 100 parts by weight of the ferromagnetic powder. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0054】(実験例7)実験例1におけるポリエステ
ルポリウレタン樹脂(Tg =10(℃))の添加量を
5.6重量部に変更し、CABの添加量を2.4重量部
に変更した。これにより、全結合剤中のCABの割合を
30%としたまま、強磁性粉末100重量部に対する全
結合剤の添加量を15.4重量部から8重量部に変更し
た。これ以外は実験例1と同様にして、磁気吸着シート
を得た。
(Experimental Example 7) The amount of polyester polyurethane resin (T g = 10 (° C)) in Experimental Example 1 was changed to 5.6 parts by weight, and the amount of CAB was changed to 2.4 parts by weight. . As a result, the addition amount of the total binder with respect to 100 parts by weight of the ferromagnetic powder was changed from 15.4 parts by weight to 8 parts by weight while keeping the ratio of CAB in the total binder at 30%. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0055】(実験例8)実験例1におけるポリエステ
ルポリウレタン樹脂(Tg =10(℃))の添加量を1
2.6重量部に変更し、CABの添加量を5.4重量部
に変更した。これにより、全結合剤中のCABの割合を
30%としたまま、強磁性粉末100重量部に対する全
結合剤の添加量を15.4重量部から18重量部に変更
した。これ以外は実験例1と同様にして、磁気吸着シー
トを得た。
(Experimental Example 8) The addition amount of the polyester polyurethane resin (T g = 10 (° C.)) in Experimental Example 1 was 1
It was changed to 2.6 parts by weight and the amount of CAB added was changed to 5.4 parts by weight. As a result, the addition amount of the total binder with respect to 100 parts by weight of the ferromagnetic powder was changed from 15.4 parts by weight to 18 parts by weight while keeping the ratio of CAB in the total binder at 30%. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0056】(実験例9)強磁性粉末をHc =700
(Oe)のBaフェライト粉末に変更した以外は実験例
1と同様にして、磁気吸着シートを得た。 (実験例10)Srフェライト粉末のHc を4000O
eに変更した以外は実験例1と同様にして、磁気吸着シ
ートを得た。
(Experimental Example 9) Ferromagnetic powder was prepared with H c = 700.
A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the Ba ferrite powder of (Oe) was used. 4000O an H c of (Experimental Example 10) Sr ferrite powder
A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the magnetic adsorption sheet was changed to e.

【0057】(実験例11)Srフェライト粉末の平均
粒径を0.5μmに変更した以外は実験例1と同様にし
て、磁気吸着シートを得た。 (実験例12)Srフェライト粉末の平均粒径を5μm
に変更した以外は実験例1と同様にして、磁気吸着シー
トを得た。
Experimental Example 11 A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the average particle size of Sr ferrite powder was changed to 0.5 μm. (Experimental example 12) The average particle diameter of Sr ferrite powder is 5 μm.
A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the above was changed.

【0058】(実験例13)結合剤のCABをポリエス
テル樹脂に変更した以外は実験例1と同様にして、磁気
吸着シートを得た。ポリエステル樹脂としては、Tg
50(℃)のもの(東洋紡(株)製 バイロン600 、以
下、必要に応じて樹脂Eとする。)を用いた。
(Experimental Example 13) A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the binder CAB was changed to a polyester resin. For polyester resin, T g =
The one having a temperature of 50 (° C.) (Vylon 600 manufactured by Toyobo Co., Ltd., hereinafter referred to as Resin E if necessary) was used.

【0059】(実験例14)結合剤のCABをポリエス
テルポリウレタン樹脂に変更した以外は実験例1と同様
にして、磁気吸着シートを得た。ポリエステルポリウレ
タン樹脂としては、Tg =30(℃)のもの(日本ポリ
ウレタン(株)製 ニッポラン2301、以下、必要に応じ
て樹脂Fとする。)を用いた。
Experimental Example 14 A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the binder CAB was changed to polyester polyurethane resin. As the polyester polyurethane resin, one having T g = 30 (° C.) (Nipporan 2301, manufactured by Nippon Polyurethane Industry Co., Ltd., hereinafter referred to as Resin F if necessary) was used.

【0060】(実験例15)実験例1におけるポリエス
テルポリウレタン樹脂(Tg =10(℃))の添加量を
4.2重量部に変更し、CABの添加量を1.8重量部
に変更した。これにより、全結合剤中のCABの割合を
30%としたまま、強磁性粉末100重量部に対する全
結合剤の添加量を15.4重量部から6重量部に変更し
た。これ以外は実験例1と同様にして、磁気吸着シート
を得た。
(Experimental Example 15) The amount of polyester polyurethane resin (T g = 10 (° C)) in Experimental Example 1 was changed to 4.2 parts by weight, and the amount of CAB was changed to 1.8 parts by weight. . As a result, the addition amount of the total binder with respect to 100 parts by weight of the ferromagnetic powder was changed from 15.4 parts by weight to 6 parts by weight while keeping the ratio of CAB in the total binder at 30%. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0061】(実験例16)実験例1におけるポリエス
テルポリウレタン樹脂(Tg =10(℃))の添加量を
14.0重量部に変更し、CABの添加量を6.0重量
部に変更した。これにより、全結合剤中のCABの割合
を30%としたまま、強磁性粉末100重量部に対する
全結合剤の添加量を15.4重量部から20重量部に変
更した。これ以外は実験例1と同様にして、磁気吸着シ
ートを得た。
(Experimental Example 16) The amount of polyester polyurethane resin (T g = 10 (° C)) added in Experimental Example 1 was changed to 14.0 parts by weight, and the amount of CAB added was changed to 6.0 parts by weight. . As a result, the amount of all binders added to 100 parts by weight of the ferromagnetic powder was changed from 15.4 parts by weight to 20 parts by weight while keeping the proportion of CAB in the total binder at 30%. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0062】(実験例17)実験例1におけるポリエス
テルポリウレタン樹脂(Tg =10(℃))の添加量を
15.4重量部に変更し、CABを添加しなかった。こ
れにより、強磁性粉末100重量部に対する全結合剤の
添加量を15.4重量部としたまま、全結合剤中のCA
Bの割合を30%から0%に変更した。これ以外は実験
例1と同様にして、磁気吸着シートを得た。
Experimental Example 17 The amount of polyester polyurethane resin (T g = 10 (° C.)) in Experimental Example 1 was changed to 15.4 parts by weight, and CAB was not added. As a result, the CA content in the total binder was kept at 15.4 parts by weight with respect to 100 parts by weight of the ferromagnetic powder.
The proportion of B was changed from 30% to 0%. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0063】(実験例18)実験例1におけるポリエス
テルポリウレタン樹脂(Tg =10(℃))の添加量を
15.09重量部に変更し、CABの添加量を0.31
重量部に変更した。これにより、強磁性粉末100重量
部に対する全結合剤の添加量を15.4重量部としたま
ま、全結合剤中のCABの割合を30%から2%に変更
した。これ以外は実験例1と同様にして、磁気吸着シー
トを得た。
Experimental Example 18 The amount of polyester polyurethane resin (T g = 10 (° C.)) added in Experimental Example 1 was changed to 15.09 parts by weight, and the amount of CAB added was 0.31.
Changed to parts by weight. As a result, the proportion of CAB in the total binder was changed from 30% to 2% while the addition amount of the total binder was 15.4 parts by weight with respect to 100 parts by weight of the ferromagnetic powder. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0064】(実験例19)実験例1におけるポリエス
テルポリウレタン樹脂(Tg =10(℃))の添加量を
4.6重量部に変更し、CABの添加量を10.8重量
部に変更した。これにより、強磁性粉末100重量部に
対する全結合剤の添加量を15.4重量部としたまま、
全結合剤中のCABの割合を30%から70%に変更し
た。これ以外は実験例1と同様にして、磁気吸着シート
を得た。
(Experimental Example 19) The amount of polyester polyurethane resin (T g = 10 (° C)) in Experimental Example 1 was changed to 4.6 parts by weight, and the amount of CAB was changed to 10.8 parts by weight. . As a result, the total amount of binders added to 100 parts by weight of the ferromagnetic powder remains 15.4 parts by weight,
The proportion of CAB in the total binder was changed from 30% to 70%. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0065】(実験例20)実験例1においてポリエス
テルポリウレタン樹脂(Tg =10(℃))を添加せ
ず、CABの添加量を15.4重量部に変更した。これ
により、強磁性粉末100重量部に対する全結合剤の添
加量を15.4重量部としたまま、全結合剤中のCAB
の割合を30%から100%に変更した。これ以外は実
験例1と同様にして、磁気吸着シートを得た。
Experimental Example 20 The polyester polyurethane resin (T g = 10 (° C.)) in Experimental Example 1 was not added, and the amount of CAB added was changed to 15.4 parts by weight. As a result, the CAB content in the total binder was kept at 15.4 parts by weight with respect to 100 parts by weight of the ferromagnetic powder.
Was changed from 30% to 100%. A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except for this.

【0066】(実験例21)強磁性粉末をHc =300
(Oe)のBaフェライト粉末に変更した以外は実験例
1と同様にして、磁気吸着シートを得た。 (実験例22)強磁性粉末をHc =5000(Oe)の
希土類粉末に変更した以外は実験例1と同様にして、磁
気吸着シートを得た。希土類としてはSm−Co粉末を
用いた。
(Experimental Example 21) A ferromagnetic powder was prepared with H c = 300.
A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the Ba ferrite powder of (Oe) was used. (Experimental Example 22) except that the ferromagnetic powder was changed to rare earth powder H c = 5000 (Oe) in the same manner as in Experimental Example 1 to obtain a magnetic adsorption sheet. Sm-Co powder was used as the rare earth.

【0067】(実験例23)Srフェライト粉末の平均
粒径を0.1μmに変更した以外は実験例1と同様にし
て、磁気吸着シートを得た。 (実験例24)Srフェライト粉末の平均粒径を8μm
に変更した以外は実験例1と同様にして、磁気吸着シー
トを得た。
(Experimental Example 23) A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the average particle size of Sr ferrite powder was changed to 0.1 μm. (Experimental Example 24) The average particle diameter of Sr ferrite powder was 8 μm.
A magnetic adsorption sheet was obtained in the same manner as in Experimental Example 1 except that the above was changed.

【0068】上記の実験例1〜24において、ポリエス
テルポリウレタン樹脂(Tg =10(℃))とともに結
合剤として用いられる樹脂の種類(樹脂A〜Fのいずれ
か)およびそのTg 、強磁性粉末100重量部に対する
全結合剤の添加量、樹脂A〜Eのいずれかの全結合剤中
での割合(全結合剤の添加量を100%としたときの割
合であり、表1の※樹脂添加量に対応する)、強磁性粉
末の種類、保磁力および平均粒径を表1にまとめた。
In Experimental Examples 1 to 24, the type of resin (any of resins A to F) used as a binder together with the polyester polyurethane resin (T g = 10 (° C.)), its T g , and ferromagnetic powder. Addition amount of total binder to 100 parts by weight, ratio in the total binder of any one of Resins A to E (The ratio when the added amount of all binders is 100%, * Resin addition in Table 1 (Corresponding to the amount), the type of ferromagnetic powder, the coercive force and the average particle size are summarized in Table 1.

【0069】[0069]

【表1】 [Table 1]

【0070】上記の実験例1〜24の磁気吸着シートに
ついて、ブロッキング(耐粘着性)、磁気吸着力、表面
磁束密度および接着強度を評価した。ブロッキングの評
価は、以下のように行った。各磁気吸着シートを8cm
×8cmに切り出して金属に対して磁気吸着させた。そ
の上に同形に切り出した磁気吸着シートを磁気吸着さ
せ、45℃、湿度75%に維持された恒温槽の中に7日
間放置した。その後、重ねられた磁気吸着シートを剥離
し、シート間の粘着の有無を確認した。シート間の粘着
が見られなかった場合を○、シート間の粘着が見られた
場合を×と判定した。
Blocking (adhesion resistance), magnetic adsorption force, surface magnetic flux density and adhesive strength were evaluated for the magnetic adsorption sheets of Experimental Examples 1 to 24 described above. The evaluation of blocking was performed as follows. 8cm for each magnetic adsorption sheet
It was cut to a size of 8 cm and magnetically adsorbed to the metal. A magnetic adsorption sheet cut out in the same shape was magnetically adsorbed thereon and left in a constant temperature bath maintained at 45 ° C. and a humidity of 75% for 7 days. Then, the stacked magnetic adsorption sheets were peeled off, and the presence or absence of adhesion between the sheets was confirmed. The case where the adhesion between the sheets was not observed was evaluated as ◯, and the case where the adhesion between the sheets was observed was evaluated as x.

【0071】磁気吸着力の評価は、以下のように行っ
た。各磁気吸着シートを5cm×5cmに切り出し、磁
気吸着面の裏側にシートと同形の樹脂板を粘着剤で貼り
付けた。それを水平に固定した0.5mm厚鋼板上に磁
気吸着させて、鋼板から垂直上方に剥離する際の最小剥
離力をばね秤により測定した。ここで、{最小剥離力−
(シート重量+粘着剤重量+樹脂板重量)}/シート面
積=磁気吸着力とした。
The magnetic attraction force was evaluated as follows. Each magnetic adsorption sheet was cut into a size of 5 cm × 5 cm, and a resin plate having the same shape as the sheet was attached to the back side of the magnetic adsorption surface with an adhesive. It was magnetically adsorbed on a horizontally fixed 0.5 mm thick steel plate, and the minimum peeling force when peeling vertically upward from the steel plate was measured by a spring balance. Here, {minimum peeling force-
(Sheet weight + pressure-sensitive adhesive weight + resin plate weight)} / sheet area = magnetic attraction force.

【0072】表面磁束密度の評価は、以下のように行っ
た。ベル社製ガウスメーター(4048型)およびトラ
ンスバース型プローブ(T−4048−001)を使用
し、磁性層面に対して垂直方向の磁束密度の極大値を、
磁性層の表面の任意の5点で測定した。これらの測定値
を平均して、表面磁束密度とした。
The surface magnetic flux density was evaluated as follows. The maximum value of the magnetic flux density in the direction perpendicular to the magnetic layer surface was measured using a Gauss meter (4048 type) and a transverse probe (T-4048-001) manufactured by Bell Co.
The measurement was performed at arbitrary 5 points on the surface of the magnetic layer. These measured values were averaged to obtain the surface magnetic flux density.

【0073】接着強度の評価は、以下のように行った。
各磁気吸着シートの磁性面上にシリコンテープを貼り付
けた。30分後、シリコンテープを剥離して、磁性層の
剥離の有無を確認した。磁性層の剥離がなく、シリコン
テープ上で磁性層片が見られなかった場合を○、磁性層
の少なくとも一部が剥離し、シリコンテープ上に磁性層
片が見られた場合を×と判定した。なお、シリコンテー
プ貼付直後にシリコンテープを剥離した場合の磁性層の
剥離についても試験したが、貼付直後と30分後で結果
に違いは見られなかった。上記の各項目の評価結果を表
2にまとめた。
The adhesive strength was evaluated as follows.
A silicon tape was attached on the magnetic surface of each magnetic adsorption sheet. After 30 minutes, the silicon tape was peeled off to confirm whether or not the magnetic layer was peeled off. When there was no peeling of the magnetic layer and no magnetic layer pieces were found on the silicon tape, it was judged as ○, and when at least a part of the magnetic layer was peeled and magnetic layer pieces were found on the silicon tape, it was judged as ×. . The peeling of the magnetic layer was also tested when the silicon tape was peeled immediately after the silicone tape was attached, but no difference was found in the results immediately after attachment and 30 minutes later. The evaluation results of the above items are summarized in Table 2.

【0074】[0074]

【表2】 [Table 2]

【0075】表2に示すように、実験例1〜12では、
ブロッキング特性と接着強度が○と判定され、磁気吸着
力も0.4gf/cm2 以上となった。それに対し、実
験例13〜20および実験例24はブロッキング特性と
接着強度の一方が×と判定された。また、実験例21〜
23はブロッキング特性と接着強度は○と判定された
が、磁気吸着力が不足した。
As shown in Table 2, in Experimental Examples 1 to 12,
The blocking property and the adhesive strength were judged to be good, and the magnetic adsorption force was 0.4 gf / cm 2 or more. On the other hand, in Experimental Examples 13 to 20 and Experimental Example 24, one of the blocking property and the adhesive strength was judged as x. In addition, Experimental Examples 21 to
No. 23 was judged to have a blocking property and an adhesive strength of O, but the magnetic adsorption force was insufficient.

【0076】表1に示すように、実験例1〜12は保磁
力700〜4000Oe、平均粒径0.5〜1.5μm
の強磁性粉末を用い、Tg ≧80(℃)の樹脂またはセ
ルロースアセテート系樹脂を全結合剤の5〜60%添加
した場合に対応する。この場合、磁性層表面の粘着が抑
制された。
As shown in Table 1, in Experimental Examples 1 to 12, coercive force was 700 to 4000 Oe and average particle diameter was 0.5 to 1.5 μm.
This corresponds to the case where the ferromagnetic powder of No. 1 is used and a resin having a T g ≧ 80 (° C.) or a cellulose acetate resin is added in an amount of 5 to 60% of the total binder. In this case, adhesion on the surface of the magnetic layer was suppressed.

【0077】実験例13および14では、強磁性粉末は
実験例1〜11と同様のものを用い、結合剤樹脂として
g ≧80(℃)の樹脂またはセルロースアセテート系
樹脂のかわりに、Tg =50(℃)のポリエステル樹脂
またはTg =30(℃)のポリウレタン樹脂を添加し
た。この場合、磁気吸着シートを長期間にわたって磁気
吸着させた場合や、例えばポット等の加温される被吸着
体に磁気吸着シートを磁気吸着させた場合、粘着が起こ
る。
In Experimental Examples 13 and 14, the same ferromagnetic powder as in Experimental Examples 1 to 11 was used, and T g ≧ 80 (° C.) resin or cellulose acetate resin was used as a binder resin instead of T g. = 50 (° C.) polyester resin or T g = 30 (° C.) polyurethane resin was added. In this case, adhesion occurs when the magnetic adsorption sheet is magnetically adsorbed for a long period of time, or when the magnetic adsorption sheet is magnetically adsorbed on a heated object such as a pot.

【0078】また、実験例15に示すように、強磁性粉
末に対する全結合剤の添加量の割合を減らした場合、強
磁性粉末を分散させることができず、塗膜の形成が困難
である。塗膜が形成された場合にも、強磁性粉末の粉落
ちが起こりやすい。一方、実験例16に示すように、全
結合剤が過剰に添加されている場合、磁気吸着シートを
長期間にわたって磁気吸着させた場合や、加温される被
吸着体に磁気吸着シートを磁気吸着させた場合、粘着が
起こった。また、表面磁束密度も低かった。以上から、
全結合剤の割合は強磁性粉末100重量部に対して、8
〜18重量部の範囲が好ましいことがわかる。
Further, as shown in Experimental Example 15, when the ratio of the total amount of the binder added to the ferromagnetic powder was reduced, the ferromagnetic powder could not be dispersed and it was difficult to form a coating film. Even when a coating film is formed, the powder of the ferromagnetic powder easily falls off. On the other hand, as shown in Experimental Example 16, when the total binder was excessively added, when the magnetic adsorption sheet was magnetically adsorbed for a long period of time, or when the magnetic adsorption sheet was magnetically adsorbed on an object to be heated. When allowed, sticking occurred. The surface magnetic flux density was also low. From the above,
The ratio of the total binder is 8 with respect to 100 parts by weight of the ferromagnetic powder.
It can be seen that the range of -18 parts by weight is preferable.

【0079】実験例17および18では、Tg ≧80℃
の樹脂またはセルロースアセテート系樹脂を添加してい
ないか、添加量が極めて少ない。したがって、全結合剤
中でTg の低い樹脂が占める割合が多く、それらの樹脂
によって粘着が起こりやすい。例えば、磁気吸着シート
を長期間にわたって磁気吸着させた場合や、加温される
被吸着体に磁気吸着シートを磁気吸着シートを磁気吸着
させた場合、粘着が起こる。
In Experimental Examples 17 and 18, T g ≧ 80 ° C.
No resin or cellulose acetate resin is added, or the addition amount is extremely small. Therefore, the resin having a low T g occupies a large proportion of the total binder, and these resins tend to cause sticking. For example, when the magnetic attraction sheet is magnetically attracted for a long period of time, or when the magnetic attraction sheet and the magnetic attraction sheet are magnetically attracted to an object to be heated, adhesion occurs.

【0080】一方、実験例19および20では、Tg
80(℃)の樹脂またはセルロースアセテート系樹脂が
全結合剤に対して占める割合が60%を超えている。こ
の場合、磁性層表面の粘着は抑制されたが、磁性塗膜が
脆くなり、接着強度が低下して印刷時に粉落ちが起き
た。以上のように、全結合剤に対するTg ≧80(℃)
およびセルロースアセテート系樹脂の割合を5〜60%
にすることにより、適切な塗膜強度を保ちつつ、磁性層
面の粘着を防止することができる。
On the other hand, in Experimental Examples 19 and 20, T g
The ratio of the resin of 80 (° C.) or the cellulose acetate resin to the total binder exceeds 60%. In this case, the adhesion on the surface of the magnetic layer was suppressed, but the magnetic coating film became brittle, the adhesive strength was lowered, and powder was dropped during printing. As described above, T g ≧ 80 (° C.) for all binders
And the proportion of cellulose acetate resin is 5 to 60%
By this, adhesion of the magnetic layer surface can be prevented while maintaining an appropriate coating film strength.

【0081】実験例21では保磁力300Oeの強磁性
粉末を用いた。保磁力700Oe未満の強磁性粉末を用
いた場合、表面磁束密度が低く、磁気吸着シートに要求
される磁気吸着力が得られなかった。一方、実験例22
では保磁力5000Oeの希土類強磁性粉末を用いた。
保磁力が4000Oeを超える強磁性粉末を用いた場
合、十分に着磁することができなかった。したがって、
表面磁束密度が低く、磁気吸着シートに要求される磁気
吸着力が得られなかった。以上のように、強磁性粉末と
しては保磁力がほぼ700〜4000Oeの範囲にある
Srフェライト粉末やBaフェライト粉末が好ましいと
いえる。
In Experimental Example 21, a ferromagnetic powder having a coercive force of 300 Oe was used. When a ferromagnetic powder having a coercive force of less than 700 Oe was used, the surface magnetic flux density was low and the magnetic attraction force required for the magnetic attraction sheet could not be obtained. On the other hand, Experimental Example 22
Then, a rare earth ferromagnetic powder having a coercive force of 5000 Oe was used.
When a ferromagnetic powder having a coercive force of more than 4000 Oe was used, it could not be sufficiently magnetized. Therefore,
The surface magnetic flux density was low, and the magnetic attraction force required for the magnetic attraction sheet was not obtained. As described above, it can be said that Sr ferrite powder or Ba ferrite powder having a coercive force in the range of approximately 700 to 4000 Oe is preferable as the ferromagnetic powder.

【0082】実験例23では平均粒径0.1μmの強磁
性粉末を用いた。平均粒径0.5μm未満の強磁性粉末
を用いた場合、磁性塗膜中の強磁性粉末の密度が高くな
り過ぎる。これにより、磁性塗膜にカールが発生し、最
終的にはクラックが発生する。これにより、表面磁束密
度が低くなり、磁気吸着シートに要求される磁気吸着力
が得られなかった。
In Experimental Example 23, a ferromagnetic powder having an average particle size of 0.1 μm was used. When a ferromagnetic powder having an average particle size of less than 0.5 μm is used, the density of the ferromagnetic powder in the magnetic coating film becomes too high. As a result, curling occurs in the magnetic coating film, and finally cracks occur. As a result, the surface magnetic flux density was lowered, and the magnetic attraction force required for the magnetic attraction sheet was not obtained.

【0083】一方、実験例24では平均粒径8μmの強
磁性粉末を用いた。平均粒径が5μmを超える強磁性粉
末を用いた場合、磁性塗膜中の強磁性粉末の密度が粗く
なり、塗膜強度が極端に低下する。以上のように、使用
する強磁性粉末の平均粒径は0.5〜5μmの範囲が好
ましい。
On the other hand, in Experimental Example 24, a ferromagnetic powder having an average particle size of 8 μm was used. When a ferromagnetic powder having an average particle size of more than 5 μm is used, the density of the ferromagnetic powder in the magnetic coating becomes coarse and the coating strength is extremely reduced. As described above, the average particle size of the ferromagnetic powder used is preferably in the range of 0.5 to 5 μm.

【0084】図5は、強磁性粉末の保磁力と磁気吸着力
の関係を示す図である。図5のデータは表1および表2
から実験例1、9、10、21および22のデータを抽
出したものである。これらの実験例において、全結合剤
中のCABの割合は30%で一定である。また、強磁性
粉末100重量部に対する全結合剤の添加量も15.4
重量部で一定である。強磁性粉末の平均粒径も1.5μ
mで一定であり、強磁性粉末の種類および保磁力のみ互
いに異なる。図5に示すように、強磁性粉末の保磁力が
700〜4000Oeのとき、磁気吸着力が0.4gf
/cm2 以上となり、磁気吸着シートに適した磁気吸着
力が得られる。
FIG. 5 is a diagram showing the relationship between the coercive force of the ferromagnetic powder and the magnetic attraction force. The data in FIG. 5 are shown in Table 1 and Table 2.
The data of Experimental Examples 1, 9, 10, 21 and 22 are extracted from. In these experimental examples, the proportion of CAB in the total binder is constant at 30%. Further, the addition amount of the total binder was 15.4 with respect to 100 parts by weight of the ferromagnetic powder.
It is constant in parts by weight. Average particle size of ferromagnetic powder is 1.5μ
m is constant, and only the type of ferromagnetic powder and the coercive force are different from each other. As shown in FIG. 5, when the coercive force of the ferromagnetic powder is 700 to 4000 Oe, the magnetic adsorption force is 0.4 gf.
/ Cm 2 or more, the magnetic attraction force suitable for the magnetic attraction sheet can be obtained.

【0085】図6は、磁気吸着シートの表面磁束密度と
磁気吸着力の関係を示す図である。図6のデータは実験
例1〜24のすべてについての表面磁束密度と磁気吸着
力の関係を示す。表1および表2に示すように、例えば
結合剤の添加量や強磁性粉末の粒径等が異なる場合であ
っても、表面磁束密度が同じであれば、磁気吸着力は同
じとなった。図6に示すように、磁気吸着シートの磁気
吸着力は表面磁束密度にほぼ比例した。
FIG. 6 is a diagram showing the relationship between the surface magnetic flux density of the magnetic attraction sheet and the magnetic attraction force. The data in FIG. 6 shows the relationship between the surface magnetic flux density and the magnetic attraction force for all of Experimental Examples 1 to 24. As shown in Tables 1 and 2, even when the addition amount of the binder and the particle size of the ferromagnetic powder are different, the magnetic attraction force is the same if the surface magnetic flux density is the same. As shown in FIG. 6, the magnetic attraction force of the magnetic attraction sheet was almost proportional to the surface magnetic flux density.

【0086】上記の本発明の実施形態の磁気吸着シート
によれば、結合剤中にTg ≧80(℃)またはセルロー
スアセテート系樹脂を所定量含有する磁性塗料を用いて
磁性層を形成することにより、磁性層の粘着を抑制する
ことが可能となる。したがって、強磁性体に磁気吸着し
た磁気吸着シートを剥離した際に、磁性層の一部が剥離
して、強磁性体に付着するのを防止できる。また、本実
施形態の磁気吸着シートは、磁性層面に対して面内方向
に磁化容易軸を有し、面内方向に着磁されるため、薄膜
化が可能であり、一般の複写機およびプリンターでの印
刷に適している。
According to the above magnetic adsorption sheet of the embodiment of the present invention, the magnetic layer is formed by using the magnetic coating material containing T g ≧ 80 (° C.) or a predetermined amount of cellulose acetate resin in the binder. Thereby, it becomes possible to suppress the adhesion of the magnetic layer. Therefore, when the magnetic attraction sheet magnetically attracted to the ferromagnetic substance is peeled off, it is possible to prevent a part of the magnetic layer from peeling off and adhering to the ferromagnetic substance. Further, the magnetic adsorption sheet of the present embodiment has an easy axis of magnetization in the in-plane direction with respect to the surface of the magnetic layer and is magnetized in the in-plane direction, so that it can be made into a thin film. Suitable for printing on.

【0087】一般家庭用のプリンター等を用いて、本実
施形態の磁気吸着シートに画像、写真または文字等を印
刷すれば、例えば自作のカレンダーやレシピ、スケジュ
ール表を作製することが可能であり、これらの印刷物は
例えば冷蔵庫の壁面等の強磁性体に任意に着脱可能であ
る。
By printing an image, a photograph, characters or the like on the magnetic adsorption sheet of this embodiment using a general household printer or the like, it is possible to prepare, for example, a self-made calendar, recipe, or schedule table. These printed materials can be arbitrarily attached to and removed from a ferromagnetic material such as a wall surface of a refrigerator.

【0088】磁気吸着シートの大きさは任意に変更でき
るため、例えばポスター等の大判の磁気吸着シートを提
供することも可能である。また、印刷インク等に耐水性
・耐光性の高いものを用いることにより、例えば車等の
外壁に表示を行うという応用も可能である。
Since the size of the magnetic attraction sheet can be arbitrarily changed, it is possible to provide a large-sized magnetic attraction sheet such as a poster. Further, by using a printing ink or the like having high water resistance and light resistance, it is possible to perform an application of displaying on the outer wall of a car or the like.

【0089】本発明の磁気吸着シートの実施形態は、上
記の説明に限定されない。例えば、上記の実験例以外の
g ≧80(℃)の樹脂を結合剤に添加してもよい。そ
の他、本発明の要旨を逸脱しない範囲で、種々の変更が
可能である。
The embodiment of the magnetic attraction sheet of the present invention is not limited to the above description. For example, a resin having T g ≧ 80 (° C.) other than the above experimental examples may be added to the binder. Besides, various modifications can be made without departing from the scope of the present invention.

【0090】[0090]

【発明の効果】本発明の磁気吸着シートによれば、磁性
層の粘着性が適切に制御されるため、磁気吸着シートを
被吸着面から剥離したとき、磁性層の一部が被吸着面に
付着して残るのを防止できる。
According to the magnetic attracting sheet of the present invention, since the adhesiveness of the magnetic layer is appropriately controlled, when the magnetic attracting sheet is peeled off from the attracted surface, a part of the magnetic layer is stuck to the attracted surface. It can be prevented from adhering and remaining.

【図面の簡単な説明】[Brief description of drawings]

【図1】図1は本発明の磁気吸着シートの断面図であ
る。
FIG. 1 is a cross-sectional view of a magnetic adsorption sheet of the present invention.

【図2】図2は本発明の磁気吸着シートの磁性層の多極
着磁および磁気吸着を示す模式図である。
FIG. 2 is a schematic diagram showing multi-pole magnetization and magnetic attraction of the magnetic layer of the magnetic attraction sheet of the present invention.

【図3】図3は本発明の磁気吸着シートの磁化容易軸を
磁性層の面内に配向させる方法の一例を示す概略図であ
る。
FIG. 3 is a schematic view showing an example of a method of orienting the easy axis of magnetization of the magnetic adsorption sheet of the present invention in the plane of the magnetic layer.

【図4】図4は本発明の磁気吸着シートに多極着磁を行
う方法の一例を示す概略図である。
FIG. 4 is a schematic view showing an example of a method for performing multipolar magnetization on the magnetic adsorption sheet of the present invention.

【図5】図5は本発明の磁気吸着シートの実施形態に係
り、保磁力と磁気吸着力の関係を示す。
FIG. 5 shows the relationship between the coercive force and the magnetic attraction force according to the embodiment of the magnetic attraction sheet of the present invention.

【図6】図6は本発明の磁気吸着シートの実施形態に係
り、表面磁束密度と磁気吸着力の関係を示す。
FIG. 6 relates to the embodiment of the magnetic attraction sheet of the present invention and shows the relationship between the surface magnetic flux density and the magnetic attraction force.

【符号の説明】[Explanation of symbols]

1…磁気吸着シート、2…磁性層、3…非磁性支持体、
4…印刷受容層、5…磁力線、6…被吸着体、7a、7
b…永久磁石、8…磁力線、9…磁性塗膜、11a、1
1b…磁石バー。
1 ... Magnetic adsorption sheet, 2 ... Magnetic layer, 3 ... Non-magnetic support,
4 ... Print receiving layer, 5 ... Magnetic field lines, 6 ... Adsorbed body, 7a, 7
b ... Permanent magnet, 8 ... Magnetic force line, 9 ... Magnetic coating film, 11a, 1
1b ... a magnet bar.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 川又 和人 東京都品川区北品川6丁目7番35号 ソ ニー株式会社内 (72)発明者 太田 栄治 東京都品川区北品川6丁目7番35号 ソ ニー株式会社内 (56)参考文献 特開2001−76920(JP,A) 特開2000−150226(JP,A) 特開 平9−115714(JP,A) 特開 平11−150012(JP,A) 特開 平8−109244(JP,A) 特開 平6−295804(JP,A)   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuto Kawamata               6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo               Knee Co., Ltd. (72) Inventor Eiji Ota               6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo               Knee Co., Ltd.                (56) Reference JP-A-2001-76920 (JP, A)                 JP 2000-150226 (JP, A)                 JP-A-9-115714 (JP, A)                 Japanese Patent Laid-Open No. 11-150012 (JP, A)                 JP-A-8-109244 (JP, A)                 JP-A-6-295804 (JP, A)

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】非磁性支持体上に、強磁性粉末と結合剤を
主成分とする磁性塗料を塗布し、乾燥させて磁性層が形
成され、前記磁性層は面内方向に磁化容易軸を有し、か
つ磁化容易軸に沿って面内で磁化が交互に反転するよう
に多極着磁されている磁気吸着シートであって、 前記磁性塗料は、結合剤としてガラス転移点Tg≧80
(℃)の樹脂を、全結合剤のうちの5〜60重量%含有
し、 前記磁性塗料は、前記ガラス転移点Tg≧80(℃)の
樹脂を含む全結合剤を、前記強磁性粉末100重量部に
し8〜18重量部含有し、前記強磁性粉末の保磁力は700〜4000エルステッ
ド(Oe)であり、 前記磁性層の膜厚は0.03〜0.10mmであり、 全厚は0.08〜0.25mmであり、 前記強磁性粉末の平均粒径は0.5〜5μmである 磁気吸着シート。
1. A nonmagnetic support is coated with a magnetic coating material containing a ferromagnetic powder and a binder as main components and dried to form a magnetic layer. The magnetic layer has an easy axis of magnetization in the in-plane direction. A magnetic adsorption sheet which has a multi-pole magnetization and which is magnetized so that the magnetization is alternately inverted in the plane along the easy axis of magnetization, wherein the magnetic coating material has a glass transition point Tg ≧ 80 as a binder.
The resin of (° C.) is contained in an amount of 5 to 60% by weight based on the total amount of the binder, and the magnetic paint contains the total binder including the resin of the glass transition point Tg ≧ 80 (° C.). parts by weight <br/> pairs and contains 8-18 parts by weight, the coercive force of the ferromagnetic powder is from 700 to 4000 Erusute'
(Oe), the thickness of the magnetic layer is 0.03 to 0.10 mm, the total thickness is 0.08 to 0.25 mm, and the average particle diameter of the ferromagnetic powder is 0.5 to A magnetic adsorption sheet of 5 μm.
【請求項2】前記ガラス転移点Tg≧80(℃)の樹脂
は、セルロースアセテート系樹脂を含む 請求項1記載の磁気吸着シート。
2. The magnetic adsorption sheet according to claim 1, wherein the resin having a glass transition point Tg ≧ 80 (° C.) contains a cellulose acetate resin.
【請求項3】前記磁性塗料は、前記ガラス転移点Tg≧
80(℃)の樹脂を含む全結合剤を、前記強磁性粉末1
00重量部に対し15.4〜18重量部含有する 請求項1記載の磁気吸着シート。
3. The glass transition point Tg ≧
The total binder containing a resin of 80 (° C.) was added to the ferromagnetic powder 1
00 magnetic sticking sheet according to claim 1, wherein against the parts containing from 15.4 to 18 parts by weight.
JP2001240620A 2001-08-08 2001-08-08 Magnetic adsorption sheet Expired - Lifetime JP3429503B2 (en)

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