JPS6090272A - Magnetic coating composition - Google Patents

Abstract

PURPOSE:To provide the titled composition for magnetic recording use, having excellent dispersibility of magnetic powder and heat resistance, etc., and containing an unsaturated polyurethane resin having plural terminal groups containing polymerizable double bond, and having a specific amount of a quaternary ammonium base. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.(wt.) of an unsaturated polyurethane resin having >=2 terminal groups having polymerizable double bond and >=0.05meq/g of quaternary ammonium terminal group (e.g. a resin containing a compound having >=2 active hydrogen atoms and >=1 tertiary amino groups as a polyol component) with (B) 50-2,000 pts. of magnetic powder (preferably, a ferromagnetic material such as Fe-Co alloy and having a specific surface area of >=30m<2>/g), and if necessary, (C) an ethylenic unsaturated compound and/or a solvent. EFFECT:Excellent hydrolysis resistance and abrasion resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to magnetic paints that are concerned not only with abrasion resistance, heat resistance, and hydrolysis resistance, but also with particular concern about the dispersibility of magnetic powder.
More specifically, the present invention relates to a magnetic paint suitable for curing with radiation such as an electron beam.

In recent years, magnetic materials for magnetic recording have been increasingly required to have higher performance, and in particular, there has been a strong demand for electrical properties with less wear. It is important to improve magnetic powders for the purpose of achieving the 2nd 1st goal.Recently, finer powders with higher saturation magnetization per unit volume1) and higher coercive force have been developed. Magnetic powders such as large metal powders are attracting attention and are being considered as ferromagnetic materials suitable for high-density magnetic recording. For example, according to the catalog of 7 Isa Co., Ltd. (USA), when using ferromagnetic powder with a specific surface area of 3 On+"/g or more, which can be determined from the amount of nitrogen adsorbed by the BET method, it exhibits particularly excellent electrical properties and has a high density. It is described that these magnetic powders are suitable for recording.On the other hand, the binder used is also an important factor when coating these magnetic powders on the support L on the tape.

In particular, if the dispersibility of magnetic powder is poor, it often impairs various performances, including electrical properties, such as generating M sound and reducing output. In particular, ferromagnetic powder with a large specific surface area often suffers from agglomeration of particles. Since magnetic powders are easily susceptible to adverse effects and the degree of such effects is large, one of the most important issues in achieving the above objective is to have a property as a binder that can better disperse magnetic powders. In addition, maintaining adhesion between the binder and the magnetic powder and between the binder and the base material base film or film mainly composed of polyester resin and fat, as well as heat resistance and abrasion resistance, are essential properties.

Conventionally, binders for paints containing magnetic powder include those using thermoplastic resins such as vinyl chloride copolymers, polyurethane, nitrocellulose, polyvinyl butyral, and saturated polyesters, as well as those using phenol, area, melamine,
Generally, thermosetting IJ1 resins such as epoxy are used, and additives such as dispersants, lubricants, abrasives, and antistatic agents are added as necessary. When thermoplastic resins are used as resins for these binders, they often do not have sufficient heat resistance and abrasion resistance. In addition, when thermosetting resin is used, the above-mentioned drawbacks can be overcome to a relatively satisfactory level, but on the other hand, it requires curing by heating for a long time in order to obtain the desired physical properties. Defects such as a decrease in surface smoothness of the magnetic layer and thermal deformation of the substrate base film are likely to occur, and furthermore, the total cost is adversely affected due to thermal energy costs and a prolonged manufacturing time. Furthermore, in order to improve the above-mentioned problems, a binder has been proposed to improve heat resistance and l1i4 abrasion resistance by adding compounds that can be cured through chemical reactions, such as incyanate compounds and epoxy compounds, to thermoplastic resins. However, in this case, the uniformity of the finally obtained magnetic material for magnetic recording is likely to be impaired due to the lack of storage stability.

Recently, a new curing method and a bangu ingredient used in it have been developed to solve various problems such as
A method has been proposed in which an unsaturated resin having an ethylenic double bond in its molecule is used and cured by radiation such as an electron beam. Many of the radiation-curable resins used are polyester resins, polyurethane resins, and epoxy resins (resins with ethylenic double bonds that can be polymerized by radiation, with a backbone of epoxy, etc.). There are β rays, γ rays, X rays, etc.The characteristics of these O (fats) and curing methods are listed in many known documents, for example (i) excellent storage stability when used as a magnetic paint; Therefore, there is almost no waste during use, and it is easy to handle before and after forming the coating.■ Since no or only a small amount of solvent is required for coating, it does not damage the base film and is also environmentally friendly. Preferable.■ Since it polymerizes and hardens as desired with very short irradiation and leaves no unreacted low molecular weight components, it causes almost no damage to the magnetic layer in the post-curing process. It also prevents thermal deformation, deterioration, etc. of the material base film. ■Since curing occurs through crosslinking, it is advantageous in terms of heat resistance and abrasion resistance, and it is also easy to add flexibility. ■ Especially conventional Compared to conventional methods, almost no thermal energy is required for heating,
The list ends with things like the fact that it can be manufactured in large quantities in a short period of time, which is very advantageous in terms of cost.

However, the currently proposed radiation-curable magnetic paints cannot be said to fully take advantage of these excellent features, and furthermore, the dispersibility of magnetic powder is significantly inferior to conventional products. The current situation is that there are many cases.

In particular, when using the aforementioned fine ferromagnetic powder, the strong cohesive force between the magnetic powders further deteriorates the dispersibility, impairing the smoothness of the magnetic layer surface and preventing the electrical properties required for high-density magnetic recording. In addition, the abrasion resistance is often poor.

The purpose of the present invention is to modify the unsaturated polyurethane resin itself as a binder to provide a cured product that has extremely excellent dispersibility of magnetic powder and also has excellent heat resistance, hydrolysis resistance, and abrasion resistance. Our goal is to provide magnetic paints that can.

The present invention relates to a magnetic coating composition containing an unsaturated polyurethane resin, a magnetic powder, and optionally an ethylenically unsaturated compound and/or a solvent (1.
+ Has a double polymer bond that allows the fat to polymerize - ] Has two or more terminal groups, and contains 0.05+ oeq of quaternary ammonium base
/g or more.

In the present invention, by using the above-mentioned specific unsaturated polyurethane resin, many hydrophilic quaternary ammonium bases are present in the molecular chain. γ-Fe20
．． ferromagnetic powders such as magnetic powders such as iron, chromium, nickel, cobalt, etc., or metal powders such as iron, chromium, nickel, cobalt, etc., or alloys thereof, resulting in a marked increase in dispersibility. .

The unsaturated polyurethane resin of the present invention is, for example, an organic polyisocyanate (A), a polyol (B), a compound (C) having two or more active hydrogens and at least one tertiary amine 7 group, and, if necessary, It can be obtained by treating a polyurethane obtained using a chain extender CD) with a quaternizing agent (1Σ). As another method, an organic polyisocyanate (A), a polyol (B), a chain extender having a molecular weight of 5001; It can also be obtained by treating polyurethane obtained using F) and, if necessary, a common chain extender (D), with a quaternizing agent (E). In addition, in the above, compound (C) or chain extender (
It is also possible to treat d) with a quaternizing agent (E) in advance.

Various organic polyisocyanates ()\) used in the present invention are exemplified, including polyphenylmethanoisocyanate (MDI), lylene diisocyanate (TI), and trilene diisocyanate (TI).
'0Dl), xylylene diisocyanate (XDI),
Diisocyanates such as naphthylene diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (11111), dicyclohexylmethane diisocyanate (IIMDI), lysine diisocyanate (Lull), triphenylmethane triisocyanate, Examples include polyisocyanates such as methylene polyphenylisocyanate (PAPI) and carbonimide-modified
More than one species can be used at the same time.

As the bipedal polyol (B), various polyester polyols, polyether polyols, and other polyols can be used. Examples of polyester polyols having 4 or more carbon atoms include adipic acid, superric acid, sebacic acid, and brassylic acid. -20 aliphatic carboxylic acids, terephthalic acid, isophthalic acid, etc. as acid components, aliphatic diols having 1 to 6 carbon atoms such as ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol, dipropylene glycol, etc. Etherglyfur, spiroglycols, etc.
Polyester polyols or polycaprolactone polyols containing N-furkylsialkane-lamine such as N-methyljetanolamine as a polyol component may be used. Specific examples include polybutylene adipate polyol, polybutylene adipate polyol, 7 dibate polyols such as polyethylene propylene adipate polyol, terephthalic acid polyols (e.g., Toyobo Co., Ltd., trade names Pylon RUX, Byron RV-20OL), polycaprolactone polyols (e.g., Gwicel Chemical, trade names Plaxel 212, Plaxel 220) etc. can be exemplified.

Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, and polyoxytetramethylene polyol.

In addition, polyols in the pond include polycarbonate polyols (e.g., Bayer AG, West Germany, product name DemataMoaen 2020E), polybutane polyols (e.g., Nippon Soda, product names G-1000, Ni-2000, G-300).
0, Idemitsu Petrochemical, trade name Poly bd R4511
Examples include °rL polypentadiene polyol, castor oil polyol, and the like. These polyols may be used alone or in combination of two or more.

Examples of the compound (C) having two or more active hydrogen atoms and at least one primary amino group include N-methyljetanolamine, N-methyljetanolamine,
N-butylnoethanolamine, bis-hydroxyethylpiperazine, N-phenyldiethanolamine, N
, N-dimethylamine/-2°2-bishydroxymethylethylamine, and polyesters containing N-furkyldialamine such as N-methyljetanolamine as a polyol component.

In the synthesis of the unsaturated polyurethane resin of the present invention, it is optional to use a chain extender (D) in addition to the above-mentioned components, and such chain extenders include, for example, 2- to 6-functional chain extenders with a molecular weight of 500 or less. Examples include polyols having a molecular weight of 500 or less and diamines having a primary or secondary terminal amino group. Suitable chain extenders include, for example, (,) ethyleneglyfur, diethyleneglyfur,
Polyols Cb such as propylene glycol, nobrobylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1゜4-cyclohexane dimetatool, xylylene glycol, etc. ) Diamines such as hydrazine, ethylene oxide, tetramethylene diamine, hexamethylene diamine, and 1,4-cyclohexane diamine (e) Alkanolamines such as ethanolamine, jetanolamine, and triethanolamine (d) Hydroquinone, pyrogallol, 4, Molecules obtained by adding propylene oxide and/or ethylene oxide to 4'-isopropylidene diphenol, aniline, and the polyols, diamines, and alkafuramines described in 1 above in any order. Examples include.

Examples of the quaternizing agent (E) include dialkyl sulfates such as dimethyl sulfate and dimethyl sulfate, methyl chloride, methyl iodide,
Eleven types of compounds can be used, including halogenated hydrocarbons such as ethyl bromide and pencil chloride, organic acids such as acetic acid, propionic acid, and monochloro^1 acid, and various non-sulfuric acids.

Also, a fi extender (I
As *'), the same compounds as those listed for the above compound (C) can be used.

The unsaturated polyurethane resin of the present invention is synthesized by various methods using the above-mentioned components. For example, polyisocyanate (A), polyol (13) and compound (C
), and then add a quaternizing agent (E) and react with it. Synthesize a terminal NCO prepolymer from (A) and (B), and react with this chain extender (F). Then, by the method of (reversing 1), (Δ) and (C) were synthesized 1) a prepolymer with terminal 1CO, and (I) was added to this.
Alternatively, a prepolymer with NCO terminals is synthesized from (A) and (B), while (F) and (B) are reacted.
Examples include a method in which E) is reacted in advance and both are reacted.

In the present invention, the ratio of each component can be appropriately determined from a wide range depending on the polyurethane, but usually the chemical equivalent ratio of NCO groups to active hydrogen is about 0.9 to 1.
4. The reaction is preferably carried out in a range of about 0.95 to 1.2, and the reaction is usually carried out at about 30 to 130°C, preferably about 40 to 120"C. The treatment with the quaternizing agent is generally preferably carried out at a temperature in the range of 40 to 100°C.

In the present invention, the concentration of quaternary ammonium base is 0.0
A concentration of 5n+eq/g or more is especially necessary to sufficiently disperse the ferromagnetic powder, and if this concentration is exceeded, aggregated magnetic powder tends to remain in the magnetic paint, and when it is made into a magnetic coating. -Poor two-hand lubricity (1), unable to exhibit sufficient electrical properties.

Various types of magnetic powder can be used in the present invention, including iron, chromium, nickel, cobalt, alloys thereof, oxides thereof, and modified products thereof. Specific examples of oxides include γ-Fe20. , ferrite, magnetite, C'02, etc. Modified products include, for example, cobalt-doped γ-Fe20=, cobalt-doped Fe2O3 and Fe-2 beltride compounds, etc. It is also possible to use magnetic powders with various surface areas, especially when the specific surface area determined from the nitrogen VL photoresist amount by the BET method is 30 + n 2 /
When using a ferromagnetic powder of 8 or more, excellent electrical properties can be obtained. The blending amount of magnetic powder is unsaturated polyurethane (
h (preferably about 50 to 2000 ω parts to 100 ω 1 parts of fat).

In the present invention, the unsaturated polyurethane 1b1 resin can be synthesized in the absence of a solvent, in the presence of an organic solvent, or in the presence of an ethylenically unsaturated compound used as a crosslinking agent, which will be described later in section E. (Examples of solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl propionate, ethers such as dioxane and cellosolve acetate, dimethylformamide, and dimethyl sulfoxide. .

In the present invention, it is possible to mix various compounds within a range that does not impair the purpose of item 1. Specific examples of these compounds include unsaturated polyester resin, saturated polyester 4111,
resin, epoxy 48 (Ill), combination of these with (meth)acrylic acid, etc., polyurethane 484 an, diallyl phthalate resin, ketone resin, alkyl-nod resin, phenolic resin, rosin-modified phenol +111m
, rosin ester, maleic acid modified rosin ester, urea resin, melamine resin, polyamide T31 fin
, styrene-(meth)acrylic acid copolymer or its ester, poly(meth)acrylate, C1-9 petroleum resin, hydrogenated petroleum resin, polybutadiene, natural or synthetic rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer Resin, polyvinyl alcohol, wax, etc. are used. Further, these known compounds may be added before or during the reaction, as long as they interfere with the synthesis of the unsaturated borynerethane 1tJ1 fat of the present invention.

In the present invention, an ethylenically unsaturated compound can be used as a crosslinking agent, if necessary, when the unsaturated polyurethane resin described in item 1 is infarcted. Various known compounds can be used as ethylenically unsaturated compounds, but representative examples include styrene, vinyltoluene, chlorostyrene, t-butylstyrene, α-methylstyrene, divinylbenzene, acrylic acid, and methacrylic acid. , methyl, ethyl, isopropyl acrylic or methacrylic acid,
11-butyl, thi-butyl, a-ethylhexyl, 11
-nonyl, 11-decyl, lauryl, stearyl ester, etc., acrylic acid, τ1-butoxyethyl methacrylic acid, cyclohexynopephenoxyethyl, tetrahydrofurfuryl, glycidyl, allyl, benzyl, tribromophenyl, 2. :+-nochloroprovir, 3-
Chloro-2-hydroxypropyl, N, 1-methylaminoethylethylaminoethyl, N-L-butylaminoethyl ester, etc., ethylene glycol mo(meth)acrylate, propylene glycol mono(meth)acrylate, diethylene glycol 7 (meth)acrylate, dipropylene glycol mono(meth)acrylate, molecular weight (hereinafter referred to as +414) ZOO ~ 1000
polyethylene glycol mono(meth)acrylate,
HW200~1. 0 0 (l of polyethylene glycol monomethyl ether mono(meth)acrylate, H W 2 (l O~I 0 0 0 of polyethylene glycol mono(meth)acrylate, Ml1
1200-1000 polypropylene glycol monomethyl nitrate 7(meth)acrylate, M W 2
(1 (1-1000 polyethylene glycol moa ethyl ether mono(meth)acrylate, M1 tank 20
0-1000 polypropylene glycol monoethyl ether mono(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol:)(
meth)acrylate, l,3-propanediol(meth)acrylate, 1,4-butanediol(meth)
acrylate, neopentylglyfur di(meth)acrylate), j,6-hexaneol di(meth)acrylate-1, polyethylene glycol')(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerin di(meth)acrylate ) acrylate, glycerin tri(meth)acrylate, trimethylolethane (meth)acrylate, trimethylolethane tri(meth)acrylate-1, trimethylolpropane tri(meth)acrylate, acrylamide, N,N-dimethylacrylamide, N, Examples include N-ethyl acrylamide 1ζ, ethylene pyracrylamide, noaryl fucrate, triallyl isocyanurate, 77 tylfumarate, and vinyl acetate. However, if it is present during the urethanization reaction, ethylenically unsaturated compounds having active hydrogen among those listed in 1. above should be excluded.

Particularly preferred among the above crosslinking agents are compounds represented by the general formula % (in the formula, A represents an alkylene group or haloalkylene group having 2 to 4 carbon atoms), and specific examples include ethylene glycol, propylene Glycol, 1,3-propanediol, 1,2-butanediol, 1.

Examples include monomethacrylates such as 3-butanediol and 1,4-butanediol, and 3-chloro-2-hydroxypropyl methacrylate.

In the present invention, the weight ratio of the unsaturated polyurethane 4, AJ resin and the ethylenically unsaturated compound is preferably 0 to 95:5, more preferably 50:50 to 20, where the latter is 30.

To ensure stable storage of the magnetic paint of the present invention, a known thermal polymerization inhibitor can be added. For example, ``hydroquinone, mo/-te+・L-butylhydroquinone, 2,5-di-Lerl-butylhydroquinone, hydroquinone monomethyl ether, catechol,
+1 Lert. -Butylcatefur, benzo Anon,
2,5-n'-1. erL-butylbenzenequinone, 2
．． 5-ji7koru p-penzokin/n, 2,6-shi L
Examples include erL-butyl-p-cresol and picric acid. It is desirable that these thermal polymerization inhibitors prevent only the thermal polymerization reaction (dark reaction) without inhibiting the photocuring reaction. 0.001 to 2.
It is desirable that the amount is 5% by weight, preferably in the range of 0.005 to 1% by weight. Furthermore, in the present invention, commonly used additives such as dispersants, lubricants, abrasives, and antistatic agents can be added as necessary.

The magnetic paint of the present invention can be obtained by mixing the above-mentioned components by various known methods, for example, using a mixer, roll mill, ball mill sand mill, high-speed impeller, etc.

The magnetic paint of the present invention is applied to supports in various forms such as tapes, sheets, cards, disks, and drum chopsticks. The support usually has a thickness of about 5-50μ, preferably about 10-50μ.
Approximately 40 μm is preferable, and polyesters such as polyethylene terephthalate, polyolefins such as polypropylene, cellulose derivatives such as cellulose acetate, polycarbomide, etc. are preferably used as the thickness. Various methods can be used to apply the magnetic paint onto the support, such as impregnation coating, air doctor coating, air knife coating, flade coating, reverse roll two 1, gravure foot, cast coating, and spray coating. can. After coating, the magnetic powder may be subjected to a treatment to orient it if necessary, or dried if it contains a general solvent. 'C, drying time is about 10~40μ
It is good to set it as about 1 to 5 minutes, preferably about 1 to 5 minutes. Further, if necessary, surface smoothing treatment can be performed during or after curing, and the material can be cut into a desired shape.

The magnetic paint of the present invention can be cured by a known method. For example, when curing with an electron beam, an acceleration voltage of 1
00-1000KeV, preferably 150-300KeV
Using an electron beam irradiation device of V, in an inert gas atmosphere, the total absorbed dose is 0.5 to 20 Mrad, preferably 2 to 15
A cured product can be obtained by irradiating at 8 rad. In addition, in the present invention, the hardening means of the pond, for example, a method using thermal energy such as infrared rays, high frequency waves, or microwaves, that is, a method of heating, a force method of curing with ultraviolet rays emitted from a mercury lamp, a xenon lamp, etc., or a method of curing with X-rays, gamma rays, etc. It is also possible to use other methods of curing by irradiating with radiation.

In the present invention, when using high-energy ionizing radiation such as electron beams, X-rays, and γ-rays, which have the effect of being absorbed by substances and emitting secondary electrons, it is not necessary to add a polymerization initiator. However, when curing by other heating or ultraviolet rays, it is preferable to add a thermal polymerization initiator or a round polymerization initiator. Examples of these thermal or mechanical polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, cumene hydroperoxide, ter
Hydroperoxides such as L-butyl peroxide, alkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, etc.
erL-butylbaroxylaure), tert-'7'
Examples include peroxy esters such as + ruberoxybenzoate, and azo compounds such as azobisiso7thyronitrile.

In addition, polymerization accelerators such as metal soaps such as copal Y and manganese for the above-mentioned ketone peroxides, or reducing amines for the hydroperoxides described in 1 above may also be used in combination.

As described above, the magnetic paint of the present invention is characterized by containing as a binder an unsaturated polyurethane resin containing a hydrophilic quaternary ammonium base in the molecular chain.
The dispersibility of the magnetic powder in the oil is extremely good, and the resulting magnetic paint has significantly improved heat resistance, hydrolysis resistance, and abrasion resistance, and has excellent electrical properties and durability. It is a magnetic material for magnetic recording.

A detailed explanation will be given below with reference to synthesis examples and examples. still,
A simple part or % indicates a part or % by weight.

Synthesis Example 1 IPDI (152,5B) was placed in a reactor equipped with a stirrer and heated to 80°C.
Molecule fi1860) 424.9B, DemataMoaen 202
0 E (molecular weight 2000) 2: + 0, 08
, oxane 381.2ε, 7tilutin dilaure)
0.32 g of 81 solution was gradually added dropwise, heated to 90°C and reacted for about 3 hours, and then 2-hydroxyethyl acrylate (11) 39.1. , hydroquinone 1
．． After 74 g of the mixed solution was similarly added dropwise and reacted for about 2.5 hours, 20.0 h of N-methylnoethanolamine was added. After reacting for about 2 hours, lower the liquid temperature to 60°C, add 21.2 g of dimethyl sulfate little by little, and react for about 2 hours to obtain a solid content of 70% and a quaternary ammonium base in the solid content. An unsaturated polyurethane tjl fat solution (1) having a concentration of 0.19 meq/g was obtained.

Synthesis Example 2 An unsaturated polyurethane resin solution (II) was prepared in the same manner as in Synthesis Example 1 except that the quaternization treatment with dimethyl sulfuric acid was not performed.

Examples 1-2 and Comparative Examples 1-2 Using the unsaturated polyurethane resin solutions obtained in the above synthesis examples, the compositions shown in Table 1 were mixed and kneaded in a ball mill for 40 hours to obtain magnetic paints. .

Each of the obtained magnetic paints was applied onto a polyester film using a doctor blade and a trowel, and then heated in an oven at 80°C +4
11 Trowel 3 minutes 1' Jl After drying, curtain bee 11
Using a type of electron beam irradiation device, an acceleration voltage of 150Ke
The coating film was cured by irradiation with a beam current of 10 V and a beam current of 10 + n8 so as to cover the irradiation beam of 5t&d.

After curing, the surface gloss of the magnetic coating film was measured using a gloss meter (Toyosei 1AS-6) to examine the dispersibility of the magnetic powder.
o). The better the dispersibility, the better the light 11< property.

In addition, in the table, PI is unsaturated polyurethane resin solution, I
I E HA l hydroxyethyl methacrylate,
IIPM8 (±hydroxyethyl methacrylate, I)
8 is IIF, an ester of H8 and phosphoric acid, ``a mixture of 2-methacryloxyethyl phosphate and 7 (2-methacryloxyethyl) phosphate,'' 1 is trimethylolpropane triacrylate, and MIEK is methyl ethyl ketone. .

Also magnetic 4!1. Powder A is Fe with a specific surface area of 48+n7/6
-co gold alloy B has a cowsγ of 32 m 2/'H
-Fe, , On, (blasphemy same 221o77'6) γ-Fe
,0. shows.

In the adhesion test, cellophane tape was adhered to the magnetic coating at a weight of 5 kg and then suddenly peeled off, and the degree of peeling was evaluated on a 3-grade scale.

○: Peeling 81F area ()% △: 0 0 to 25% 10
The weight loss (+ns) when making 0 reciprocations was measured.

Table 1 Example Comparative example formulation (parts) 12123 Synthesis example No l' l II II IIpu < parts)
143143 143143143II E HΔ
80 7 (11,5100+111) 18 15 8
0 70 1) 8 18 5 10 T-IP-L 8 105 MILK 255 2':35 265 280 2
35 Magnetism A 660 G] 0 Powder B 620' 7X5 615 Surface gloss 94 95 27 31 47 Adhesion test ○ ○ △ Δ Δ Powder falling amount (title) 0.5 0.4 2.3 2.1
1] Synthesis Example 3
920) 367°08, Plaxel 210 (molecular weight 10
00) 444.8g, ') Butylsustaining -7 ure-
) 0.23H1MEK295.2gノjJ7. The combined solution was gradually added dropwise to react for about 3 hours, and then 71.
A mixed solution of 68 and hydroquinone 2.24B was added dropwise, and the mixture was reacted for about 2.5 hours. 35.63B of N-methylnoethanolamine was added dropwise to this, and after reacting for about 2 hours, the solution was poured down and 37.7g of dimethyl sulfuric acid was added.
By adding a little bit of, an unsaturated polyurethane tree III with a solid content of 80% and a quaternary ammonium salt basicity in the solid content of 0.25n+eq/g! (I'll get it.

Synthesis Example 4 MDI (171,88) was placed in a stirrer (-1) reactor, heated to 80°C, and Vyron R11X (molecular weight 2000) t387,2ε, MEK400.2.
A mixed solution of 0.17H of dibutyltinnolaurate was gradually added dropwise and reacted for about 3 hours, 1.87 g of dibutyltinnolaurate was added in the same manner and reacted for another 3 hours, and then N- Phenyldiethyl 7-lamine 17.2
After slowly adding 2 liters of B,l,4-phytanediol and reacting for about 2 hours, it was cooled to 60°C, and dimethyl sulfate]1.858 was added little by little until the solid content was 70.
%, primary ammonium base concentration in solid content is 0.1
0 meq/g unsaturated polyurethane 1b1 fat solution (IV
) Synthesis Example 5 Synthesis Example 31, but without adding dimethyl sulfate, unsaturated polyurethane (31 fat solution (V)
Ta.

Synthesis Example 6 In Synthesis Example 4, noethyleneglyfur was added instead of N-phenylnoethanolamine, and an unsaturated polyurethane solution (Vl) was obtained.

Examples 3 to 6 and Comparative Examples 3 to 7 1'*9 inferior (l value 3) Example 1
Obtain magnetic paint in the same manner as above. Obtain htko61ya1.
The properties of the ≦□porous materials were examined in the same manner. In addition, Table 1 Koori Te 1) 148 is ethyl methacrylate, IID8 is 1
．． 6-A'IF monool diacrylate, S8 (above) is an ester of IIF, M8 and Cono1, representing 2-7 tacryloxyethyl succinate.

Table 2 Example formulation (parts) 34'56 Synthesis example No. m Ill Ill IVPU (parts)
125 125 125 143IIEHA 75 7
0 85 11PMA 110 5E 8 10 25 111) 15 1+IS 8 5 Old: 320' 355: (25290 Magnetic 8615 Powder 11 685 730 635 Surface gloss 100 too 98 95 Adhesion test
0 0 0 0 powder drop 8) 0.2 0.2 (1st, 30th, 5th
3 Table comparison Example formulation (parts) 4 5 6 7 :3 Synthesis example No. V V V ■Vl pu (parts) 125 125 ] 25 143 143
11ENA 80 45 75 15 +1PM 8 85 3 (12,58°E148 1°11+18 15 t.

S8 55 HEK 395 440 420 345 310 Magnetic A 600 700 Powder 8665 C635 (i65 Surface likelihood 32 48 35 3 S adhesion test ○
○ ○ Δ ○ Powder falling amount (tn2) 1.0 1.1 1.7 1.5
0.9 (or more) Procedural amendment (voluntary) October 31, 1982 2. Name of the invention: magnetic coating composition 3. Relationship with the person making the amendment: Patent applicant (314) Toyo Tire & Rubber Industries, Ltd. 4 , Agent Address: 1-2-8 Maru Building, Sonezaki, Kita-ku, Osaka 530 Telephone: 06 (365) 0170 (Main) (8153) Patent Attorney 1 Iwao Mura: 5, Date of Amendment Order Voluntary 6, Increase due to amendment Contents of invention number correction J Specification - Page 8, bottom line and page 53, line 6, 1 polyol (B) and J, respectively, are 1 polyol (13)
, ethylenically unsaturated compound (U) having active hydrogen, 1
I will correct it.

2. On page 12, line 8 of the specification, the phrase "Can be done." should be corrected as follows:

Verify it with 1.

In the present invention, various compounds can be used as the active hydrogen-containing ethylene saturated compound ((j), but its II (on the front side, ethylene glycol, propylene glycol, 1,3-furopane) A- Le, 1.3-
7tanol, 1,4-phthane) 4-l, mono(meth)acrylate of dihydric alcohols such as ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol,) limethylolethane, trimethylol, Mono- and (meth)acrylates of trihydric alcohols such as methylol butypan, glycerin, etc., alcohols of 4IITli or more such as pentaerythritol)
and tri(meth)acrylate, and these can be used singly or in combination of two types. -13 Specification, page 33, second line from the bottom] Comparative Example 3
-7" has been corrected to 1 Comparative Examples 4-8".

(hereinafter referred to as ``2'') Procedural Amendment Imported January 17, 1982 Patent Application No. 1'98825 2 Title of Invention Magnetic Coating Composition 3 Related to the Person Making the Amendment Case 0 Patent Applicant (814) Toyo Tire & Rubber Industries Co., Ltd. 4. Voluntary action by the agent 6. The number of inventions to be increased due to the amendment 7. Contents of the amendment subject to the amendment 1. The scope of the patent claims will be corrected as shown in the attached document.

2. The words ``electricity'' in the second line from the bottom of the second specification, lines 9 and 14 on page 3, line 124 on page 7, and line 2 on page 17 will be corrected to ``magnetism.''

3, page 8, line 4 "Double bond" should be corrected to "Double bond J."

4. On page 13, lines 2, 3, and 6-7, and on page 14, line 15, the words "chain extender" will be corrected to "chain extender."

5. Correct the text “(B)J” to “(B), ethylenically unsaturated compound (U)” in No. 2, page 15 of the same document.

6. In the same page, page 15, line 4 and lines 8 to 9, ``r(T3)J'' will be corrected to ``Giant B) and (U)''.

7. In the same page 15, No. 2, "Synthesize," should be corrected to "Synthesize, and then add (U) to synthesize urethane."

Claims (1) A magnetic paint comprising an unsaturated polyurethane resin, a magnetic powder, and optionally an ethylenically unsaturated compound and/or a solvent, wherein the unsaturated polyurethane resin is a polymerizable double layer. has two or more terminal groups with a bond, and a fourth
A magnetic paint whose W characteristic is that it contains 0.05 meq/g or more of grade ammonium base.

(2) Part or all of the polyol component of the unsaturated polyurethane resin is a compound having two or more active hydrogens and at least one tertiary amine 7 group.
Magnetic paint described in section.

(3) The unsaturated polyurethane resin is obtained using a chain extender having a molecular weight of 500 or less and having two or more active hydrogen atoms and at least one tertiary amine 7 group. Magnetic paint described in section.

(4) The magnetic paint according to claim 3, wherein the chain extender is treated with a quaternizing agent in advance.

(5) The ethylenically unsaturated compound has the following general formula CI.

The magnetic paint according to claim 1, characterized by a compound represented by C112=C-Coo-^-011 (wherein A represents a fullkylene group having 2 to 4 carbon atoms or a 10 alkylene group).

(6) The magnetic paint according to claim 1, wherein the magnetic paint is cured by radiation.

Claims (6)

[Claims] (1) In a magnetic paint containing an unsaturated polyurethane resin, a magnetic powder, and optionally an ethylenically unsaturated compound and/or a solvent, the unsaturated polyurethane 134 resin has an end group having a polymerizable dipolymer bond. A magnetic paint having two or more quaternary ammonium bases and containing 0.05 meq/g or more of quaternary ammonium bases. (2) Part or all of the polyol component of the unsaturated polyurethane 01 resin has two or more active hydrogen atoms and at least one
Individual 3rd class Ami/! i! The magnetic paint according to claim ptS1, which is a compound having i. (3) The above-mentioned unsaturated polyurethane I81 resin is synthesized using a chain extender having a molecular weight of 500 or less and having two or more active hydrogen atoms and at least one tertiary amino acid. The magnetic paint according to claim 1. (4) The magnetic paint according to claim 3, wherein the Jn chain extender is treated with one quaternizing agent in advance. (5) Claim 1, wherein the ethylenically unsaturated compound is a compound represented by the following general formula % (Formula ΦA represents an alkylene group or haloalkylene group having 2 to 4 carbon atoms) magnetic paint. (6) The magnetic paint according to claim 1, wherein the magnetic paint is cured by radiation.