JP2005008866A - Electronic beam-curable resin for magnetic recording medium, method for producing the same, and the magnetic recording medium given by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an electronic beam-curable resin for a magnetic recording medium, having such high crosslinking properties as to be suitably used for the magnetic recording medium, capable of preventing increase in viscosity of a coating material, and gelling thereof, when a conventional heat-curable vinyl chloride-based resin or polyurethane-based resin is subjected to electronic beam-initiated modification, to provide a method for producing the electronic beam-curable resin, capable of easily forming the electronic beam-curable resin having the high crosslinking properties out of a conventional heat-curable resin, and to provide the magnetic recording medium of high performance, by using the electronic beam-curable resin. <P>SOLUTION: The electronic beam-curable resin for the magnetic recording medium is obtained by reacting a diisocyante (DI) with a hydroxy(meth)acrylate-based compound (HA) in a mol ratio of HA/DI of more than 1 and less than 2 to form a DI-HA adduct, and further reacting the DI-HA adduct with active hydrogen radicals of the vinyl chloride-based resin or polyurethane-based resin which has the active hydrogen radicals in its molecule. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electron beam curable resin for a magnetic recording medium, a method for producing the same, and a magnetic recording medium using the same, and more specifically, an electron beam curable resin having high crosslinkability that can be suitably used for magnetic recording medium applications. The present invention relates to a production method for obtaining a highly cross-linkable electron beam curable resin by subjecting a general thermosetting vinyl chloride resin or polyurethane resin to electron beam sensitive modification, and a magnetic recording medium using the same.

  Conventionally used resins for magnetic recording media include thermosetting resins and electron beam curable resins. Among these, the thermosetting resin takes a curing method in which an active hydrogen group represented by a hydroxyl group present in the resin is reacted with an isocyanate compound to crosslink the resin, while the electron beam curable resin is Then, an electron beam sensitive functional group represented by an acrylic double bond is introduced into the resin molecule, and the resin is crosslinked by electron beam irradiation.

  In general, examples of electron beam curable resins used for magnetic recording media include vinyl chloride resins and polyurethane resins. In the case of a vinyl chloride resin, the electron beam sensitive modification method includes tolylene diisocyanate (TDI) and 2-hydroxyethyl methacrylate (2-HEMA) with respect to the hydroxyl group in the thermosetting vinyl chloride resin containing a hydroxyl group. ) And a TDI adduct obtained by reacting with a cyclic acid anhydride with a hydroxyl group in a vinyl chloride resin and further reacting with an epoxy monomer having an acrylic double bond. There are a method (see Patent Document 2), a method in which 2-isocyanatoethyl (meth) acrylate (MOI) is reacted with a hydroxyl group in a vinyl chloride resin (see Patent Document 3), and the like.

  On the other hand, in the case of a polyurethane resin, a method of forming a radiation curable polyurethane resin by using a (meth) acrylate compound having a hydroxyl group in the molecule as a part of a raw material when synthesizing polyurethane (Patent Document) 4) and a method of producing a polyurethane having an isocyanate group at the end of the polymer and subsequently reacting an alcohol having an acrylic double bond (see Patent Document 5).

Patent Document 6 discloses the production of a radiation curable resin including a step of reacting a predetermined monohydroxy compound and a diisocyanate compound at a predetermined ratio for the purpose of obtaining a radiation curable resin excellent in curability and the like. A method is described.
Japanese Patent Publication No. 1-25141 (Claims) Japanese Patent No. 2514682 (claims, etc.) JP-A-4-67314 (Claims etc.) Japanese Patent No. 2610468 (claims, etc.) Japanese Examined Patent Publication No. 3-1727 (Claims) Japanese Patent Publication No. 1-81812 (Claims etc.)

  However, the conventional electronically sensitive modified products of vinyl chloride resin or polyurethane resin have not always had sufficient crosslinkability. Further, the methods described in Patent Document 1 and Patent Document 2 have a problem that the resin / paint is gelled and the dispersibility is lowered. Furthermore, when the hydroxyl group concentration in the resin is increased in order to improve the cross-linking property, there is a problem that the viscosity of the paint increases.

  Therefore, the object of the present invention is to prevent high viscosity and gelation of paints and to be used suitably for magnetic recording medium applications when electron-sensitive modification of existing thermosetting vinyl chloride resins or polyurethane resins. It is an object of the present invention to provide an electron beam curable resin for magnetic recording media. Another object of the present invention is to provide a method for producing such an electron beam curable resin, which can easily obtain an electron beam curable resin having high crosslinkability from an existing thermosetting resin. Another object of the present invention is to provide a high-performance magnetic recording medium by using such an electron beam curable resin.

  As a result of intensive studies to solve the above problems, the present inventors have found that the active hydrogen group of a vinyl chloride resin or polyurethane resin having an active hydrogen group in the molecule is converted to diisocyanate (DI) and hydroxy (meta ) In the modification to the electron beam curing type by reacting with a DI-HA adduct which is a reaction product with an acrylate compound (HA), the HA / DI molar ratio is within a predetermined range when the adduct is formed. As a result, it was found that an electron beam curable resin having high crosslinkability and stability was obtained, and the present invention was completed.

  That is, the electron beam curable resin for magnetic recording media of the present invention reacts diisocyanate (DI) with a hydroxy (meth) acrylate compound (HA) at a HA / DI molar ratio of greater than 1 and less than 2. The DI-HA adduct obtained by the above reaction is reacted with the active hydrogen group of a vinyl chloride resin or polyurethane resin having an active hydrogen group in the molecule. The diisocyanate (DI) is preferably isophorone diisocyanate (IPDI).

  The method for producing an electron beam curable resin for a magnetic recording medium according to the present invention comprises a diisocyanate (DI) and a hydroxy (meth) acrylate compound (HA), wherein the HA / DI molar ratio is greater than 1 and less than 2. Then, the obtained DI-HA adduct is reacted with a vinyl chloride resin or polyurethane resin having an active hydrogen group in the molecule.

  Furthermore, the magnetic recording medium of the present invention comprises a layer containing the electron beam curable resin for a magnetic recording medium on a nonmagnetic support.

  According to the present invention, an existing vinyl chloride resin or polyurethane resin having an active hydrogen group is used as a raw material for a magnetic recording medium having excellent crosslinkability and dispersibility while preventing thickening and gelation of a paint. An electron beam curable resin can be obtained, whereby a high-performance magnetic recording medium can be obtained.

Hereinafter, specific embodiments of the present invention will be described in detail.
The electron beam curable resin for a magnetic recording medium of the present invention is obtained by using a vinyl chloride resin or a polyurethane resin as a raw material and subjecting it to electron beam sensitive modification using a specific DI-HA adduct. is there.

  The raw material vinyl chloride resin or polyurethane resin used in the present invention may be an existing (general purpose) or novel resin, but has an active hydrogen group such as a hydroxyl group or a primary or secondary amine in the molecule. It is necessary to carry out the reaction.

  Such a resin is not particularly limited, but specific examples of the vinyl chloride resin include MR110, MR104, MR112, MR113 (manufactured by ZEON CORPORATION), Solvein A, Solvein TAO, Solvein MK6 (Nisshin Chemical Industry ( In addition, as polyurethane resins, ESTEN 5778P, ESTEN 5799P (manufactured by BF GOODRICH (Goodrich)), UR8700, UR8300 (manufactured by Toyobo Co., Ltd.), N-3167, N- 3301, TK501K (manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like.

  The compound DI-HA adduct used for reacting with the active hydrogen of these resins and electron beam sensitive modification of the resin is a reaction product of diisocyanate (DI) and hydroxy (meth) acrylate compound (HA). . Here, in the present invention, it is important to react the diisocyanate (DI) and the hydroxy (meth) acrylate compound (HA) at an HA / DI molar ratio of greater than 1 and less than 2. This HA / DI molar ratio is preferably 1.2 or more, more preferably 1.3 or more and less than 2. By setting the HA / DI molar ratio during the reaction of diisocyanate (DI) and hydroxy (meth) acrylate compound (HA) within the above range, thickening and gelation of the coating can be effectively prevented.

  On the other hand, when a DI-HA adduct is produced with a blending ratio deviating from the HA / DI molar ratio in the present invention as described in Patent Document 1, a large amount of unreacted diisocyanate remains in the reaction system. When the obtained adduct body is reacted with a resin, it leads to thickening and further gelation of the resin solution after the reaction. Moreover, since reaction is not performed smoothly, the crosslinkability of a resin film will also fall. Further, when such a resin is used to disperse the pigment, the dispersibility is lowered and the solvent resistance of the coating film is lowered. Patent Document 6 describes a technique of reacting a monohydroxy compound and a diisocyanate compound at a ratio of substantially less than 2.0 in the above reaction molar ratio in the adduct formation reaction. However, since an unreacted diisocyanate compound remains after the reaction, a step of removing it is essential. Therefore, this technique is significantly different from the present invention in that there is no remaining unreacted diisocyanate compound, and therefore does not require a step of removing the unreacted diisocyanate compound. Moreover, in the Example of patent document 6, only the manufacture example of resin of reaction molar ratio 1.0 is described, and this reaction molar ratio is outside the scope of the present invention.

  Here, as a diisocyanate (DI) used as a raw material of such an adduct body, isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6- TDI), 1,4-xylene diisocyanate, hexamethylene diisocyanate, paraphenylene diisocyanate, etc. Among them, when isophorone diisocyanate (IPDI) is used, the crystallinity of the adduct is small and the subsequent modification is smooth. This is preferable because it goes forward. In the case of other diisocyanates, the crystallinity of the adduct is increased and the solubility in the reaction system is lowered, so that the reaction does not proceed smoothly and the viscosity tends to increase slightly. As a result, the dispersibility is slightly reduced.

  The hydroxy (meth) acrylate compound (HA), which is another raw material of the adduct body, is also simply referred to as a hydroxyacrylate compound and includes a hydroxyacrylate compound and a hydroxymethacrylate compound. Although such a compound is not particularly limited, specifically, 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl acrylate, hydroxydiethylene glycol methacrylate, butoxy Examples thereof include hydroxypropyl acrylate, phenoxyhydroxypropyl acrylate, hydroxypropyl dimethacrylate, glycidol dimethacrylate, glycerol dimethacrylate, monohydroxypentaerythritol triacrylate and the like.

  By reacting these DI-HA adducts with active hydrogen of a vinyl chloride resin or a polyurethane resin, electron beam sensitive modification of the resin is performed. The reaction is carried out in an organic solvent such as methyl ethyl ketone (MEK) or toluene. In this reaction, a urethanization catalyst such as dibutyltin dilaurate or tin octylate is usually added in an amount of 0.005 to 100 parts by mass of the total amount of reactants. The synthesis is preferably performed using 0.1 part by mass. This reaction temperature is preferably 30 to 80 ° C, more preferably 50 to 70 ° C.

  The electron beam curable resin thus produced can be used as a binder for a resin undercoat layer, an undercoat layer containing an inorganic pigment, a backcoat layer, and a magnetic layer in a magnetic recording medium. Hereinafter, these layers are also collectively referred to as “functional layers”. The usage form may be such an electron beam curable resin alone, or may be used in a mixed form with other resins typified by polyurethane resins.

  The irradiation amount when the electron beam curable resin of the present invention is crosslinked using an electron beam is preferably 1 to 10 Mrad, more preferably 3 to 7 Mrad. The irradiation energy (acceleration voltage) is preferably 100 kV or more.

  In the present invention, by using the electron beam curable resin as a binder for the functional layer, it is possible to obtain a high-performance magnetic recording medium having a functional layer having high crosslinkability and excellent solvent resistance. it can. The magnetic recording medium of the present invention only needs to be provided with a layer containing the electron beam curable resin of the present invention on a non-magnetic support, and other constituent materials, additives, etc. are not particularly limited. For example, the following materials can be used.

  The non-magnetic support can be appropriately selected from known resin films such as polyester, polyamide or aromatic polyamide, or laminated resin films thereof, and the thickness thereof is also within a known range and is not particularly limited. It shouldn't be.

  The ferromagnetic powder used for the magnetic layer is preferably an acicular ferromagnetic metal powder having an average major axis length of 0.15 μm or less, more preferably 0.03 to 0.10 μm. When the average major axis length exceeds 0.15 μm, the electromagnetic conversion characteristics (particularly, S / N and C / N characteristics) required for the magnetic recording medium tend not to be sufficiently satisfied. Further, hexagonal iron oxide powder such as barium ferrite can also be used. The plate ratio of the hexagonal iron oxide powder is preferably 2-7. Moreover, it is preferable that the average primary plate diameter by TEM observation is 10-50 nm. If it is larger than this, the magnetic layer surface tends to deteriorate.

  Such a ferromagnetic powder should just be contained about 70-90 mass% in a magnetic layer composition. If the content of the ferromagnetic powder is too large, the content of the binder is reduced, so that the surface smoothness due to calendering tends to be deteriorated. On the other hand, if the content is too small, a high reproduction output is difficult to obtain.

  As the binder resin for the magnetic layer, in addition to the electron beam curable resin of the present invention, conventionally known thermoplastic resins, thermosetting resins, other radiation curable resins, and mixtures thereof are preferably used. And should not be restricted in particular.

  The content of these binder resins used in the magnetic layer is preferably 5 to 40 parts by mass, particularly 10 to 30 parts by mass with respect to 100 parts by mass of the ferromagnetic powder. If the content of the binder resin is too small, the strength of the magnetic layer is lowered, and the running durability is likely to deteriorate. On the other hand, if the amount is too large, the content of the ferromagnetic metal powder is lowered, so that the electromagnetic conversion characteristics are lowered.

  As the crosslinking agent for curing these binder resins, for example, in the case of thermosetting resins, various known polyisocyanates can be mentioned, and the content of this crosslinking agent is 100 parts by mass of the binder resin. It is preferable to set it as 10-30 mass parts. Moreover, you may add dispersing agents, such as an abrasive | polishing material and surfactant, a higher fatty acid, and other various additives as needed in a magnetic layer.

  The coating material for forming the magnetic layer is prepared by adding an organic solvent to the above components. The organic solvent to be used is not particularly limited, and one or more of various solvents such as ketone solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexanone, and aromatic solvents such as toluene may be appropriately selected and used. Good. The addition amount of the organic solvent may be about 100 to 1100 parts by mass with respect to 100 parts by mass of the total amount of the solid content (ferromagnetic metal powder, various inorganic particles, etc.) and the binder resin.

  The thickness of the magnetic layer in the present invention is 3.0 μm or less, preferably 0.01 to 0.50 μm, more preferably 0.02 to 0.30 μm. If the magnetic layer is too thick, self-demagnetization loss and thickness loss increase.

  The nonmagnetic layer as the undercoat layer can be provided between the magnetic layer and the nonmagnetic support, thereby improving the electromagnetic conversion characteristics of the thinned magnetic layer. It helps to improve reliability.

As the nonmagnetic powder used in the nonmagnetic layer, various inorganic powders can be used. Preferably, acicular nonmagnetic powders such as acicular nonmagnetic iron oxide (α-Fe ₂ O ₃ ) are exemplified. Can do. In addition, various nonmagnetic powders such as calcium carbonate (CaCO ₃ ), titanium oxide (TiO ₂ ), barium sulfate (BaSO ₄ ), and α-alumina (α-Al ₂ O ₃ ) may be appropriately blended. In addition, it is preferable to use carbon black for the nonmagnetic layer. As such carbon black, furnace black for rubber, thermal black for rubber, black for color, acetylene black and the like can be used.

  The mixing ratio of carbon black and inorganic powder is preferably 100/0 to 10/90 by weight. When the blending ratio of the inorganic powder exceeds 90, a problem is likely to occur due to surface electrical resistance.

  As the binder resin for the non-magnetic layer, in addition to the electron beam curable resin of the present invention, as in the case of the magnetic layer, conventionally known thermoplastic resins, thermosetting resins, other radiation curable resins, and these Although a mixture etc. are used, a radiation curable resin is preferable among these.

  In the nonmagnetic layer of the present invention, if necessary, a dispersant such as a surfactant used in the magnetic layer, a lubricant such as a higher fatty acid, a fatty acid ester, a silicone oil, and other various additives are added. May be. In addition, the coating material for the nonmagnetic layer can be prepared using the same amount of organic solvent as that of the magnetic layer.

  The thickness of the nonmagnetic layer is preferably 2.5 μm or less, more preferably 0.1 to 2.3 μm. Even if this thickness is made larger than 2.5 μm, the improvement in performance cannot be expected. On the other hand, when a coating film is provided, the thickness tends to be uneven, the application conditions become severe, and the surface smoothness tends to deteriorate. .

  The back coat layer is provided as necessary for improving running stability and preventing the magnetic layer from being charged. The backcoat layer preferably contains 30 to 80% by mass of carbon black, and any carbon black that is normally used may be used as the carbon black. The thing similar to what is used can be used. In addition to carbon black, if necessary, nonmagnetic inorganic powders such as various abrasives used in the magnetic layer, dispersants such as surfactants, lubricants such as higher fatty acids, fatty acid esters, silicone oils, etc. Various additives may be added.

  The thickness of the back coat layer (after calendering) is 0.1 to 1.5 μm, preferably 0.2 to 0.8 μm. If this thickness exceeds 1.5 μm, the friction with the medium sliding contact path becomes too large, and the running stability tends to decrease. On the other hand, if the thickness is less than 0.1 μm, the coating film of the backcoat layer tends to be scraped when the medium is running.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following, “part” means “part by mass”, and “%” means “% by mass”.

Synthesis Example 1: Resin 1
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 372 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained IPDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 1 was obtained.

Synthesis Example 2: Resin 2
In a 1 liter three-necked flask, 330 parts of 2,4-tolylene diisocyanate (2,4TDI), 0.4 parts of dibutyltin dilaurate, 0. 2,6-di-tert-butyl-4-methylphenol (BHT). 24 parts were charged, and 372 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling at 60 ° C. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain a 2,4TDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained 2,4TDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 2 was obtained.

Synthesis Example 3: Resin 3
In a 1-liter three-necked flask, 319 parts of hexamethylene diisocyanate (HDI), 0.4 part of dibutyltin dilaurate, and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, While controlling at 60 ° C., 372 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise. After completion of the dropping, the mixture was taken out after stirring for 2 hours at 60 ° C. to obtain an HDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained HDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 3 was obtained.

Synthesis Example 4: Resin 4
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, While controlling at ° C., 372 parts of 2-hydroxyethyl methacrylate (2HEMA) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HEMA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained IPDI-2HEMA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 4 was obtained.

Synthesis Example 5: Resin 5
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 710 parts of monohydroxypentaerythritol triacrylate was added dropwise while controlling at 0 ° C. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-monohydroxypentaerythritol triacrylate adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 470 parts of the previously obtained IPDI-monohydroxypentaerythritol triacrylate adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 5 was obtained.

Synthesis Example 6: Resin 6
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) were charged, 60 372 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of Solvein TAO manufactured by Nissin Chemical Industry Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 2,6-di-tert-butyl-4-methylphenol (BHT) 0.09 part was charged, and after stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained IPDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 6 was obtained.

Synthesis Example 7: Resin 7
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 298 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained IPDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 7 was obtained.

Synthesis Example 8: Resin 8
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, While controlling at ° C., 322 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained IPDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption of the isocyanate group (2270 cm ⁻¹ ) in the IR spectrum, the resin 8 was obtained.

Synthesis Example 9: Resin 9
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 446 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 528 parts of the previously obtained IPDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 9 was obtained.

Synthesis Example 10: Resin 10
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 372 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) Then, after stirring at 70 ° C. for 3 hours, 68 parts of the IPDI-2HPA adduct obtained above was added. After stirring at 70 ° C. for 15 hours, after confirming disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 10 was obtained.

Synthesis Example 11: Resin 11
In a 1 liter three-necked flask, 330 parts of 2,4-tolylene diisocyanate (2,4TDI), 0.4 parts of dibutyltin dilaurate, 0. 2,6-di-tert-butyl-4-methylphenol (BHT). 24 parts were charged, and 372 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling at 60 ° C. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain a 2,4TDI-2HPA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 68 parts of the previously obtained 2,4TDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 11 was obtained.

Synthesis Example 12: Resin 12
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, While controlling at ° C., 372 parts of 2-hydroxyethyl methacrylate (2HEMA) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HEMA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) Then, after stirring at 70 ° C. for 3 hours, 68 parts of the IPDI-2HEMA adduct body obtained previously was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 12 was obtained.

Synthesis Example 13: Resin 13
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 298 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) Then, after stirring at 70 ° C. for 3 hours, 68 parts of the IPDI-2HPA adduct obtained above was added. After stirring at 70 ° C. for 15 hours, after confirming disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 13 was obtained.

Synthesis Example 14: Resin 14
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, While controlling at ° C., 322 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of Esten 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 part of 2,6-di-tert-butyl-4-methylphenol (BHT) And stirred at 70 ° C. for 3 hours, and then charged with 68 parts of the IPDI-2HPA adduct obtained above. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 14 was obtained.

Synthesis Example 15: Resin 15
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 446 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) Then, after stirring at 70 ° C. for 3 hours, 68 parts of the IPDI-2HPA adduct obtained above was added. After stirring at 70 ° C. for 15 hours, after confirming disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 15 was obtained.

Synthesis Example 16: Resin 16
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 248 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained IPDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption of the isocyanate group (2270 cm ⁻¹ ) in the IR spectrum, the resin 16 was obtained.

Synthesis Example 17: Resin 17
In a 1 liter three-necked flask, 330 parts of 2,4-tolylene diisocyanate (2,4TDI), 0.4 parts of dibutyltin dilaurate, 0. 2,6-di-tert-butyl-4-methylphenol (BHT). 24 parts was charged, and 248 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling at 60 ° C. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain a 2,4TDI-2HPA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 352 parts of the previously obtained 2,4TDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 17 was obtained.

Synthesis Example 18: Resin 18
In a 1 liter three-necked flask, 348 parts of tolylene diisocyanate (TDI), 0.4 parts of dibutyltin dilaurate, and 0.24 parts of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged. While controlling at 60 ° C., 260 parts of 2-hydroxyethyl methacrylate (2HEMA) was added dropwise. After completion of the dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain a TDI-2HEMA adduct.

Next, 630 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 272 parts of the previously obtained TDI-2HEMA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 18 was obtained.

Synthesis Example 19: Resin 19
A 3-liter three-necked flask was charged with 500 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 1250 parts of methyl ethyl ketone (MEK), 0.5 part of dibutyltin dilaurate, and 0.3 part of hydroquinone, and stirred at 70 ° C. for 3 hours. 25 parts of 2-isocyanatoethyl methacrylate were added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 19 was obtained.

Synthesis Example 20: Resin 20
A 3-liter three-necked flask was charged with 500 parts of MR110 manufactured by Nippon Zeon Co., Ltd., 725 parts of methyl ethyl ketone (MEK), and 725 parts of toluene, stirred at 80 ° C. for 3 hours, and then 21 parts of anhydrous 1,2-cyclohexanedicarboxylic acid. Was added. Next, the reaction is carried out at 80 ° C. until the characteristic absorption (1790 cm ⁻¹ and 1870 cm ⁻¹ ) of the acid anhydride disappears in the IR spectrum, and further 42 parts of anhydrous 1,2-cyclohexanedicarboxylic acid, 58 parts of glycidyl methacrylate, hydroquinone 0.05 part and 0.3 part of triethanolamine were gradually added and stirred at 80 ° C. for 20 hours. After confirming that the acid value was less than 4, the resin 20 was obtained.

Synthesis Example 21: Resin 21
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 496 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, ZEON Corporation MR110 630 parts, methyl ethyl ketone (MEK) 2291 parts, dibutyltin dilaurate 2.45 parts, 2,6-di-tert-butyl-4-methylphenol (BHT) 0.09 parts And stirred at 70 ° C. for 3 hours, and then, 528 parts of the previously obtained IPDI-2HPA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 21 was obtained.

Synthesis Example 22: Resin 22
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 248 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) Then, after stirring at 70 ° C. for 3 hours, 68 parts of the IPDI-2HPA adduct obtained above was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 22 was obtained.

Synthesis Example 23: Resin 23
Into a 1 liter three-necked flask, 424 parts of isophorone diisocyanate (IPDI), 0.4 part of dibutyltin dilaurate and 0.24 part of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged, 496 parts of 2-hydroxypropyl acrylate (2HPA) was added dropwise while controlling the temperature. After completion of dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain an IPDI-2HPA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) Then, after stirring at 70 ° C. for 3 hours, 68 parts of the IPDI-2HPA adduct obtained above was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 23 was obtained.

Synthesis Example 24: Resin 24
A 3-liter three-necked flask was charged with 500 parts of EST Good 5778P, 1250 parts of methyl ethyl ketone (MEK), 0.5 part of dibutyltin dilaurate, and 0.3 part of hydroquinone, and stirred at 70 ° C. for 3 hours. 25 parts of 2-isocyanatoethyl methacrylate were added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 24 was obtained.

Synthesis Example 25: Resin 25
In a 1 liter three-necked flask, 348 parts of tolylene diisocyanate (TDI), 0.4 parts of dibutyltin dilaurate, and 0.24 parts of 2,6-di-tert-butyl-4-methylphenol (BHT) are charged. While controlling at 60 ° C., 260 parts of 2-hydroxyethyl methacrylate (2HEMA) was added dropwise. After completion of the dropping, the mixture was stirred for 2 hours at 60 ° C. and taken out to obtain a TDI-2HEMA adduct.

Next, 630 parts of ESTEN 5778P manufactured by BF Goodrich, 2291 parts of methyl ethyl ketone (MEK), 2.45 parts of dibutyltin dilaurate, and 0.09 of 2,6-di-tert-butyl-4-methylphenol (BHT) After stirring at 70 ° C. for 3 hours, 68 parts of the previously obtained TDI-2HEMA adduct body was added. After stirring at 70 ° C. for 15 hours, after confirming the disappearance of the characteristic absorption (2270 cm ⁻¹ ) of the isocyanate group in the IR spectrum, the resin 25 was obtained.

Example 1
(Evaluation 1) Crosslinkability evaluation After forming a film of resin 1 with a thickness of 30 μm on a release film, the film was cured by irradiation with an electron beam of 6 Mrad under the condition of an acceleration voltage of 200 kV. Next, the resin film after electron beam curing was peeled off from the release film, and the gel fraction was measured under the following conditions.

<Gel fraction measurement conditions>
Solvent: Methyl ethyl ketone (MEK)
Extraction conditions: MEK Boiling extraction time: 5 hours Extraction was performed under the above conditions, the weight of the resin film before and after extraction was measured, and the gel fraction was calculated from the difference.

(Evaluation 2) Evaluation of crosslinkability and dispersibility of pigment and magnetic powder-containing coating In each of three types of systems, metal magnetic powder, α-iron oxide / carbon black mixed system, and carbon black, each is dispersed in a resin. As the crosslinkability evaluation of the cross-linked sample, solvent resistance was evaluated. Moreover, the surface roughness (Ra) was measured as dispersibility evaluation.

(1) Evaluation of metal magnetic powder
Preparation of magnetic paint sample Metallic magnetic powder (Fe / Co / Al / Y = 100/10 / 5.2 / 2.0 (weight ratio))
100 parts (Hc = 145.6 kA / m (1830 Oe), σs = 130 Am ² / kg, BET specific surface area = 57 m ² / g, average major axis length = 0.10 μm)
Resin 1 70 parts MEK 120 parts Toluene 120 parts Cyclohexanone 70 parts The above composition was kneaded and then dispersed in a sand grinder mill to prepare a magnetic paint.

Next, the obtained magnetic coating material was applied on a polyethylene terephthalate (PET) film having a thickness of 6.1 μm so as to have a dry film thickness of 1.5 μm, dried at a drying temperature of 100 ° C., and then subjected to a linear pressure of 2.9. A calender treatment was performed at × 10 ⁵ N / m and a temperature of 90 ° C., followed by electron beam (EB) irradiation (6 Mrad) to prepare a cured magnetic coating film.

(2) Evaluation of α-iron oxide / carbon black mixed pigment
Preparation of nonmagnetic paint sample Nonmagnetic powder: 80 parts of acicular α-Fe ₂ O ₃ (average minor axis diameter = 18 nm, aspect ratio = 6.1, pH = 8.9)
20 parts of carbon black (Mitsubishi Chemical Corporation: # 850B) (average particle size = 16 nm, BET specific surface area = 200 m ² / g, DBP oil absorption = 70 ml / 100 g)
Resin 1 70 parts MEK 120 parts Toluene 120 parts Cyclohexanone 70 parts The above composition was kneaded and then dispersed in a sand grinder mill to prepare a nonmagnetic paint.

Next, the obtained nonmagnetic coating material was applied onto a 6.1 μm thick PET film so as to have a dry film thickness of 1.5 μm, dried at a drying temperature of 100 ° C., and then subjected to a linear pressure of 2.9 × 10 ^5. A calendar process was performed at N / m and a temperature of 90 ° C., followed by EB irradiation (6 Mrad) to prepare a cured non-magnetic coating film.

(3) Evaluation of carbon black
Preparation of carbon black paint sample 100 parts of carbon black (manufactured by Colombian Carbon: Conductex SC, average particle diameter = 20 nm, BET specific surface area = 220 m ² / g)
Carbon black 1 part (manufactured by Colombian Carbon: Sevacarb MT average particle size = 350 nm, BET specific surface area = 8 m ² / g)
Resin 1 330 parts MEK 350 parts Toluene 350 parts Cyclohexanone 170 parts The above composition was kneaded and then dispersed in a sand grinder mill.

Next, a carbon black paint was applied on a 6.1 μm thick PET film so as to have a dry film thickness of 1.5 μm, dried at a drying temperature of 100 ° C., and then a linear pressure of 2.9 × 10 ⁵ N / m. Then, a calendar treatment was performed at a temperature of 70 ° C., followed by EB irradiation (6 Mrad) to prepare a film of a cured carbon black paint.

About each film | membrane sample produced with the above method, solvent resistance was evaluated with the following method and reference | standard.
(1) A cotton swab dipped in MEK was used.
(2) The film was rubbed with a cotton swab.
(3) Count how many times the film was rubbed.
(4) 15 times or more: ◎
10 times or more and less than 15 times: ○
5 times or more and less than 10 times: △
1 to less than 5 times: ×
It was.

Further, as an evaluation of surface roughness, measurement was performed under the following conditions.
Measuring instrument: Taylor Hobson Talystep system Measurement conditions: Filter conditions 0.18-9Hz
Stylus 0.1 × 2.5μm special stylus
Stylus pressure 2mg
Measurement speed 0.03mm / sec
Measurement length 500μm

Example 2
A film sample was prepared in the same manner as in Example 1 except that the resin 2 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 3
A film sample was prepared in the same manner as in Example 1 except that the resin 3 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 4
A film sample was prepared in the same manner as in Example 1 except that the resin 4 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 5
A film sample was prepared in the same manner as in Example 1 except that the resin 5 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 6
A film sample was prepared in the same manner as in Example 1 except that the resin 6 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 7
A film sample was prepared in the same manner as in Example 1 except that the resin 7 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 8
A film sample was prepared in the same manner as in Example 1 except that the resin 8 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 9
A film sample was prepared in the same manner as in Example 1 except that the resin 9 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 10
A film sample was prepared in the same manner as in Example 1 except that the resin 10 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 11
A film sample was prepared in the same manner as in Example 1 except that the resin 11 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 12
A film sample was prepared in the same manner as in Example 1 except that the resin 12 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 13
A film sample was prepared in the same manner as in Example 1 except that the resin 13 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 14
A film sample was prepared in the same manner as in Example 1 except that the resin 14 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Example 15
A film sample was prepared in the same manner as in Example 1 except that the resin 15 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 1
A film sample was prepared in the same manner as in Example 1 except that the resin 16 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 2
A film sample was prepared in the same manner as in Example 1 except that the resin 17 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 3
A film sample was prepared in the same manner as in Example 1 except that the resin 18 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 4
A film sample was prepared in the same manner as in Example 1 except that the resin 19 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 5
A film sample was prepared in the same manner as in Example 1 except that the resin 20 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 6
A film sample was prepared in the same manner as in Example 1 except that the resin 21 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 7
A film sample was prepared in the same manner as in Example 1 except that the resin 22 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 8
A film sample was prepared in the same manner as in Example 1 except that the resin 23 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 9
A film sample was prepared in the same manner as in Example 1 except that the resin 24 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 10
A film sample was prepared in the same manner as in Example 1 except that the resin 25 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

Comparative Example 11
300 g of MR110 manufactured by Nippon Zeon Co., Ltd. was dissolved in 700 g of methyl ethyl ketone (MEK) to prepare a resin solution 1. A film sample was prepared in the same manner as in Example 1 except that the resin solution 1 was used instead of the resin 1, and the same evaluation was performed.

Comparative Example 12
300 g of ESTEN 5778P manufactured by BF Goodrich was dissolved in 700 g of methyl ethyl ketone (MEK) to prepare a resin solution 2. A film sample was prepared in the same manner as in Example 1 except that the resin solution 2 was used instead of the resin 1 in Example 1, and the same evaluation was performed.

  The HI / DI molar ratio at the time of synthesizing the resin, diisocyanate (DI), hydroxy (meth) acrylate compound (HA) and DI-HI adduct used in Examples 1 to 15 and Comparative Examples 1 to 12 is shown in Table 1 below. It summarizes and shows. The evaluation results are shown in Tables 2 to 5 below.

Claims (4)

  A DI-HA adduct obtained by reacting diisocyanate (DI) with a hydroxy (meth) acrylate compound (HA) at a HA / DI molar ratio of greater than 1 and less than 2, and active in the molecule An electron beam curable resin for a magnetic recording medium, which is obtained by reacting the active hydrogen group of a vinyl chloride resin or a polyurethane resin having a hydrogen group.   2. The electron beam curable resin for magnetic recording media according to claim 1, wherein the diisocyanate (DI) is isophorone diisocyanate (IPDI).   Diisocyanate (DI) and hydroxy (meth) acrylate compound (HA) are reacted at a HA / DI molar ratio of greater than 1 and less than 2, and then the resulting DI-HA adduct and intramolecular A method for producing an electron beam curable resin for a magnetic recording medium, comprising reacting an active hydrogen group with a vinyl chloride resin or a polyurethane resin.   A magnetic recording medium comprising a layer containing the electron beam curable resin for a magnetic recording medium according to claim 1 on a nonmagnetic support.