JPS63189415A - Excellent radiation curable paint - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a radiation-curable coating material, which is used in particular when mixed with magnetic powder to produce magnetic recording media such as magnetic tapes and magnetic disks. The present invention relates to a radiation-curable paint that is suitably used as a magnetic paint.

[Conventional technology]

Generally, a magnetic recording medium has a magnetic layer formed by coating a support such as a polyester film with a magnetic paint consisting of magnetic powder, a polymer, a solvent, and various additives.

In recent years, a method has been developed in which a radiation-curable polymer having acrylic double bonds is used as the polymer used to prepare the above-mentioned magnetic paint, and a magnetic paint film made by mixing this with magnetic powder, solvent, etc. is cured by radiation irradiation. Are known.

JP-A-60-120765 discloses a terminal group having a polymerizable double bond obtained by using polyhydroxypolycarboxylic acid and/or polyhydroxysulfonic acid metal salt as at least a part of the chain extender. A magnetic paint is disclosed in which a radiation-curable polymer is an unsaturated polyurethane resin having two or more of the following.

As mentioned above, the unsaturated polyurethane resin disclosed in JP-A-60-120765 uses polyhydroxypolycarboxylic acid and/or polyhydroxysulfonic acid metal salt as at least a part of the chain extender. For,
It has a carboxylic acid component and/or a sulfonic acid metal salt component in its branch chain via a urethane bond.

However, as understood from the description of the resin manufacturing method described in, for example, line 17 of the lower right column to line 1) of the lower right column of the above publication, when a polyol is used as a part of the chain extender, No unsaturated polyurethane resin is disclosed which, if any, has sulfonic acid metal salts on average in all branched chain parts starting from each hydroxyl part of the polyol.

In addition, JP-A-61-228070 discloses a substantially linear molecular weight compound having a sulfonic acid metal salt and/or a sulfonic acid ammonium salt in the molecular chain and having a double bond at the end of the molecule. ,000 to 100,000 of a polyurethane resin is described.

According to the description in JP-A-61-228070, for example, on page 12, upper right column, lines 12 to 18, the purpose of the sulfonic acid metal salt and/or sulfonic acid ammonium salt is to improve the affinity for inorganic compounds such as magnetic substances. has been introduced into polyurethane resins. Also, the above-mentioned Japanese Patent Application Laid-Open No. 60-1207
According to the description in JP-A No. 65, for example, from line 6 to line 14 of the lower left column of 3, a sulfonic acid metal base is introduced into an unsaturated polyurethane resin for the purpose of improving the affinity for magnetic powder.

[Problem that the invention seeks to solve]

However, the above-mentioned conventional radiation-curable polymers have the problem of being difficult to provide sufficiently satisfactory practical durability and electromagnetic conversion characteristics when used to manufacture magnetic recording media. had.

The reason for this is not clear, but if the inventor considers it in relation to the present invention, the affinity of the sulfonic acid metal base present in the radiation-curable polymer molecular chain to the magnetic powder is The overall molecular chain structure of the radiation-curable polymer used is not sufficient compared to the alkylammonium sulfonate base;
This is thought to be caused by the distribution of the sulfonic acid metal base within the molecular chain or the viscosity of the magnetic paint containing the polymer and magnetic powder used.

Therefore, it is an object of the present invention to provide a radiation-curable coating material containing a novel radiation-curable polymer.

Another object of the present invention is to provide a radiation-curable coating material that provides a magnetic recording medium with excellent practical durability and electromagnetic characteristics.

Still another object of the present invention is to provide a radiation-curable coating material that provides a magnetic recording medium with a high magnetic powder filling rate and excellent surface smoothness.

Still another object of the present invention is to have low viscosity as a paint;
Radiation curing provides magnetic recording media with increased pot life and excellent practical durability, as well as simplifies the manufacturing process of magnetic recording media and reduces energy consumption for curing magnetic paints. Our goal is to provide paints with a high quality of color.

Further objects and advantages of the present invention will become apparent from the description below.

[Means for solving problems]

The objects and advantages of the present invention are, firstly, the following formula (1): R is a hydrogen atom or a methyl group; R is an alkylene group having 2 to 8 carbon atoms; R3 is an alkylene group having 2 to 20 carbon atoms; is a divalent hydrocarbon group; X is the following formula (1
)-a Here, R4 is an alkylene group having 2 to 4 carbon atoms, the definition of R3 is the same as above, n is a number of 1 to 30, and a unit represented by the following formula (1 )-b where R3 is an alkylene group having 2 to 4 carbon atoms, the definition of R3 is the same as above, and Rxh* R! 71 Rzs and R2 are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and may be the same or different, m and l are numbers from 1 to 30, and p is a number from 1 to 5. , is a group in which the units represented by these form a urethane bond in an arbitrary ratio, Q is a residue of a tetrahydric alcohol, and Y is a hydroxyl group or a group other than Y bonded to Q according to the above formula (1). This is achieved by a radiation-curable coating material containing a polymer represented by the following as a radiation-curable polymer component, provided that two or more of Y are not hydroxyl groups.

According to the present invention, secondly, in the above formula (1), X is a unit represented by the above formula (1) -a, (1) -
a unit represented by b, and...(1) -e, where R1 and R8 are alkylene groups having 2 or 3 carbon atoms, r and S are numbers from 1 to 20, and R3 is defined above. There is also provided a radiation-curable paint containing, as a radiation-curable polymer component, a polymer in which the units represented by: are groups forming urethane bonds in any proportion.

The definition of X in the above formula (1) is (1)-a and (1)
The above first paint consists of units represented by -b, and the second paint consists of units whose definition of X in formula (1) is (1) -a, 1-su and (1) -e. In the paint, the definition of X in the above formula (I) further includes the following formula (1) -C lh where R4 is -(-C)1. CH! Oh-, (CI, C
80 catties, CI.

CH3 where 2 and Z' are independently Cll3 or -c
n, co- CH3 -CHCHz- or a group represented by Hs, q is a number from 1 to 20, the definition of R1 is the same as above, R1' is a hydrogen atom or a methyl group, A unit represented by the following formula (1)-d, where the definitions of Rs, Rs and m are the same as above, and a unit selected from the group consisting of the unit represented by (
It may be included as any unit other than the units of 1) -a, (1) -b and (1) -e.

In the above formula (,1'), R is a hydrogen atom or a methyl group.

R3 is an alkylene group having 2 to 8 carbon atoms, examples include ethylene group, 1,2- or 1,3-propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc. It is. R2 is preferably an alkylene group having 2 to 3 carbon atoms.

R3 is a divalent hydrocarbon group having 2 to 20 carbon atoms, such as ethylene group, propylene group, tetramethylene group, hexamethylene group, phenylene group, cyclohexylene group, methylenebisphenylene group, methylenebiscyclohexylene group, Or it represents a divalent aliphatic, alicyclic or aromatic group of 02 to C2°, preferably C2 to cps, as shown by the structural formula.

X is a unit represented by the above formula (1) -a, a unit represented by -b, and optionally a unit represented by (1) -c and/or a unit represented by +1) -d in any proportion. Represents a group forming a urethane bond, or the composition is (1
) the unit represented by -a, +1) the unit represented by -, (1) the unit represented by -e and optionally +1) -C
It represents a group in which the units represented by and/or the units represented by (1)-d form a urethane bond in any proportion.

In formula (1)-a, R4 is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a 1.2- or 1,3-propylene group, a tetramethylene group, a butylene group, and the like. Further, the definition of R:l is the same as above, and n is a number from 1 to 30.

In formula (1) -b, R6 is an alkylene group having 2 to 4 carbon atoms, such as ethylene group, 1.2- or 1.3-propylene group, tetramethylene group, butylene group, etc. R
2b+R2? + RZll and R29 are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, such as methyl groups,
Ethyl group, propyl group, butyl group, pentyl group, 2-ethylhexyl group, hexyl group, heptyl group, octyl group, ethylhexyl group, etc., preferably hydrogen atom, ethyl group, propyl group, butyl group, 2-ethylhexyl group, etc. and may be the same or different. Furthermore, the definition of R2 is the same as above, and m and l are independently 1 to 3.
0, and p is a number from 1 to 5.

In formula (1)-c, R6 is -(CIIzCIlzO, C
I.

CH.

Here, Z and Z' are independently C1h or CHC
th- or a group represented by HI, and q is a number from 1 to 20.

Further, R1' is a hydrogen atom or a methyl group, and the definition of R3 is the same as above.

The definitions of Rz, Rs and m in formula (1)-d are as above.

Furthermore, in formula (1)-e, R7 and R8 are alkylene groups having 2 or 3 carbon atoms, such as ethylene group, 1.2-
or 1,3-propylene group, etc. In addition, the definition of R3 is as described above, and r and S are independently 1 to 2.
It is the number of 0.

In addition, in formula (1), Q is a tetrahydric alcohol residue,
For example, if the tetrahydric alcohol is pentaerythritol, Q is CH2 -C)I, -C-CH2- lb ", and the tetrahydric alcohol is N, N, N', N'
- If it is tetrahydroxypropylethylene diamine, Q is here, Z, Zt, 23 and Z4 are independently, and if the tetrahydric alcohol is a propylene oxide adduct of diglycerin, then Q is CHz O(Z+)- - CHO(Zz)X- C1)□ CI.

■ CH-0- (z3), - Cf1z-〇 (L) x- Here, 2. ．． 2. ．． 2. The definitions of and Z4 are the same as above, and X is a number from 1 to 4.

In formula (1), Y is a hydroxyl group or a group other than Y shown in formula (1) above. However, two or more of the three Y's in the above formula (1') must not be hydroxyl groups.

Next, a method for producing a polymer used in the radiation-curable coating material of the present invention will be explained using specific examples.

As the first step, a diol compound represented by the following general formula (a), where the definitions of R4 and n are the same as in the above formula (1)-a, and a compound represented by the following general formula (bl) (hereinafter (referred to as a specific sulfonic acid compound) where Rs+Rza+ Rzt+ Rze+ R29
, m, l and p are the same as in the following formula (1)-b, and if necessary, a compound represented by the following general formula (C) (hereinafter referred to as a specific hydroxyl compound) HOCI
ICHzORb CHzC1lOH Here, the definitions of R6 and R+' are the same as in the following formula (1)-c, and if necessary, a compound represented by the following general formula (d), HObeR3-0hll...
(The definitions of dlRl and m are the same as the above formula +1) - d, and the following formula (A) OCN R3NCO... (A) Here, the definition of R1 is the same as the above formula (I) It is made to react with a diisocyanate compound represented by , . In this first step reaction, a stoichiometric excess of the diisocyanate compound is used to generate urethane bonds and form a polymer having an isocyanate group at the end of the molecule. In the above first step, a compound CH represented by the following general formula (Q), where R7+R81r and S are defined as the above formula (1)-
The same as e can also be used together with -, in which case the above formula (1)
Polymers containing -e units can be formed. In the polymer, (1)-a, (1)-b, (
1) -c.

The units of (L)-d and (1)-e are, for example, randomly distributed.

In the second step, the following formula (B) CH,=CGOR20+1 ・CB
) Here, the definitions of R3 and R2 are the same as in the above formula (1). By reacting an acrylic or methacrylic compound having a hydroxyl group represented by stoichiometrically with approximately 2 equivalents of isocyanate groups, the molecule is A polymer is produced in which the units of the above formula (B) are bonded to the ends via urethane bonds.

In the third step, the remaining isocyanate groups of the polymer thus obtained and the tetrafunctional alcohol represented by the following formula (C)HO01), where the definition of Q is the same as in the above formula (1), are added. The radiation-curable polymer used in the present invention can be obtained by reacting with a compound and bonding them via a urethane bond.

The reaction in the first step is usually carried out using a catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyltin laurate, or triethylamine. These catalysts were used in a total amount of 100% of the starting materials used in the first step.
It is preferable to use about 0.01 to 1 part by weight. The reaction temperature is usually 30 to 80°C.

The reaction in the second step can be carried out in the presence of the same catalyst as above. The catalyst is preferably used in an amount of 0.01 to 1 part by weight per 100 parts of the polymer formed in the first step. The reaction in the second step is usually carried out at 30 to 80°C.

Further, the reaction in the third step can preferably be carried out under the same conditions as the reaction conditions in the second step.

The reactions in the first, second and third steps can be carried out sequentially without isolating the products of each step. When carrying out the reaction in each step, a solvent that does not inhibit the reaction, such as methyl ethyl ketone, cyclohexanone, tetrahydrofuran, toluene, methyl isobutyl ketone, dioxane, etc., can be used as necessary.

The diol compound (a) used in the first step is prepared by reacting adipic acid or a lower alkyl ester thereof with a corresponding diol such as ethylene glycol, propylene glycol, butanediol, or tetramethylene glycol according to a method known per se. It can be manufactured by

Moreover, among the specific sulfonic acid compounds), it can be produced by reacting the diol compound represented by the general formula (d) with sulfoisophthalic acids. Examples of sulfoisophthalic acids include 5-ammonium-sulfo-isophthalic acid, 5-diethylammonium-sulfo-isophthalic acid, 5-dipropylammonium-sulfo-isophthalic acid, and 5-dibutylammonium-sulfo-isophthalic acid.
Isophthalic acid, 5-(2-ethylhexyl)ammonium-sulfo-isophthalic acid, 5-ammonium-sulfo-isophthalic anhydride, 5-diethylammonium-sulfo-isophthalic anhydride, 5-'; propylammonium-sulfo-isophthalic anhydride Acid anhydride, 5-dibutylammonium-sulfo-isobutylene water Th, s-(2-
ethylhexyl)ammonium-sulfo-isophthal 1
m water TL, 5-ammonium-sulfo-isophthalic acid di-lower alkyl ester, 5-diethylammonium-sulfo-isophthalic acid di-lower alkyl ester, 5-dipropylammonium-sulfo-isophthalic acid di-lower alkyl ester, 5-dibutylammonium -Sulfo-isophthalic acid di-lower alkyl ester, 5-(2-ethylhexyl)ammonium-sulfo-isophthalic acid di-lower alkyl ester, etc., and examples of the lower alkyl ester include methyl ester, ethyl ester, etc. be able to.

By controlling the number of moles of raw materials during these reactions, the degree of polymerization (p in formula (bl)) of addition polymerization by esterification or transesterification can be controlled, and structural units derived from sulfoisophthalic acids in specific sulfonic acid compounds can be controlled. The reaction temperature for addition polymerization by esterification or transesterification is usually 40 to 2
As a catalyst for the esterification reaction at 20°C, preferably 50 to 180°C, bases such as pyridine and triethylamine, or acids such as sulfuric acid and para-toluenesulfonic acid can be used. In addition to the catalysts used in the esterification reaction, the catalysts used for the transesterification reaction include sodium acetate, manganese acetate, zinc acetate,
Salts of organic carboxylic acids such as calcium acetate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alcoholades such as sodium methylate and sodium ethylate, alkaline earth metal oxides or hydroxides, Organic titanium compounds such as zinc oxide, cadmium oxide, titanium isopropylate, titanium butyralate, etc. can be used.

The specific hydroxyl compound TCI is at least one type selected from acrylic and methacrylic compounds having a carboxyl group and acrylic and methacrylic compounds having a hydroxyl group per mole of a jepoxy compound containing two epoxy groups in one molecule. It is synthesized by reacting 1 mole or more of the compound and performing addition polymerization until the epoxy groups in the entire reaction system disappear. Examples of the jepoxy compound here include glycidyl ether of polyhydric phenol obtained by reacting bisphenol A and epichlorohydrin (hereinafter referred to as bisphenol A derivative); Glycidyl ether of alkylene oxide adduct of polyhydric phenol obtained by reacting shrimp with shrimp chlorohydrin (hereinafter referred to as bisphenol A alkylene oxide derivative); ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene Examples include glycidyl ether of a polyhydric alcohol obtained by reacting a polyhydric alcohol such as glycol or polytetramethylene glycol with epichlorohydrin.

The reaction temperature for the above addition polymerization is usually 20 to 130°C, preferably 40 to 70°C. As a catalyst for the reaction, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, etc. can be used. Preferably triethanolamine, N,N,N',N'-tetramethylethylenediamine, N,N-dimethylpiperazine,
N-methylmorpholine, boron trifluoride etherate can be used. The amount of these catalysts used is 0.01 to 5 parts by weight based on 100 parts by weight of the reaction raw materials.

The compound represented by the above formula (d+) is a polyethylene glycol, polypropylene glycol, etc., and is a compound that is easily available as a commercial product.

The compound represented by the above formula (e) is bisphenol A
These are ethylene oxide, polyethylene oxide, propylene oxide, or polypropylene oxide adducts, and are easily available commercially.

The above compound (al, (bl, (C1, +d), +1ll
) can be used alone or in combination of two or more.

As the diisocyanate compound (A), 2,4-toluene diisocyanate, 2,6-)toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p -phenylene diisocyanate, 3,3'-dimethyl-4,4
'-diphenylmethane diisocyanate), 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate), 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate,
Examples include isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), and the like.

In addition, examples of the acrylic or methacrylic compound (B) having a hydroxyl group used in the reaction of the second step include 2-hydroxyethyl (meth)acrylate, 2-
Examples include hydroxypropyl (meth)acrylate and 2-hydroxyoctyl (meth)acrylate.

Further, as the tetrafunctional alcohol compound used in the reaction in the third step, ethylene oxide of ethylene diamine, alkylene oxide adducts such as 1,2- or 1,3-propylene oxide, ethylene oxide of diglycerin, 1 , 2- or 1,3-propylene oxide, and pentaerythritol.

Thus, the radiation-curable polymer used in the present invention can be obtained by the method described above, but is not limited to the method described here.

In the present invention, the proportion of formula +1)-b in X in the radiation-curable polymer represented by formula (I) is preferably 0.0005 to 90% by weight, particularly preferably O, O
O25-70% by weight. If it exceeds 90% by weight, the solubility in general-purpose solvents such as toluene, methyl ethyl ketone, and methyl isobutyl ketone, which are commonly used as magnetic paints, tends to decrease, and the hygroscopicity of the paint film after being cured by radiation increases. This tends to lead to a decrease in coating film strength.

The proportion of ammonium sulfonate base and/or alkylammonium sulfonate base in the radiation-curable polymer represented by formula (1) is preferably 1.0XIO
-"equivalents/g to 1.3X10-"equivalents/g, particularly preferably from 5X10-"equivalents/g to 1X10-'equivalents/g.

Furthermore, X in the radiation-curable polymer represented by formula (I)
The proportion of the component represented by formula (1)-c in is preferably 95% by weight or less, particularly preferably 90% by weight or less. If it exceeds 95% by weight, the coating film cured by radiation as a paint will lose its flexibility, which is not preferable.

The ratio of the total amount of units represented by formulas (1)-a, (1)-d, and (1)-e to X in the entire radiation-curable polymer represented by formula (I) is 4.9995.
~99.5% by weight is preferred, and within this range (1) -
The proportions occupied by the units represented by a, (1)-d and (1)-e can be varied arbitrarily.

In the present invention, the radiation-curable polymer represented by formula (1) preferably has a number average molecular weight of about 10,000 to 100,000.

In the present invention, the mechanical properties of the coating film obtained by radiation curing the radiation curable polymer represented by formula (1) vary depending on the radiation curing conditions, etc., but usually the elastic modulus is 10.
kg/co! The breaking strength is 90 kg/cat or more, and the breaking elongation is 7% or more.

In the present invention, the radiation-curable polymer represented by formula (1) can be used in combination with other radiation-curable polymers and/or compounds having radiation-curable unsaturated bonds, if necessary. Other radiation-curable polymers include the following:

(1) A polymer that has an acrylic double bond at the molecular end and whose polymer skeleton is polyester, polyurethane, epoxy, polyether, polycarbonate, polyamide, etc.

(2) A polymer represented by the following general formula.

[In the formula, R1 is -CH:l or -CJs, and X is Rh.

CHt = CCOO (wherein, R1° is H or C8,l
), Z is 4 alkyl group, phenyl group or carbon number 1-4
(which may be the same or different, Y is a group having an acrylic or vinyl double bond), t is a number from 200 to 800, U is a number from 10 to 200, V is a number from O to 200, W is a number from 3 to 100, m is O
~50] (3) Hydrophilic group, e.g. -3o1
M", -0SOtM", I2 (wherein M' is a hydrogen atom, lithium atom, sodium atom, potassium atom or a hydrocarbon group, and R1) is a hydrocarbon group) at least one and two or more Polymers with acrylic double bonds such as polyester, polyether, polyurethane, epoxy, polybutadiene, polyamide, polycarbonate, etc.

(4) A polymer represented by the following general formula.

(In the formula, RI4 and RI5 are aliphatic, alicyclic or aromatic hydrocarbon groups or derivative residues thereof, R14 may contain a -0- bond, and RI5 is -O-, -S
- or -SO, - bond may be included, RI& is a hydrogen atom or a methyl group, and y represents a number from 1 to 20) (5) Phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, Saturated polybasic acids such as sebacic acid and ethylene glycol, diethylene glycol, glycerin, trimethylolpropane, 1,2-propylene glycol, 1,3-butanediol, dipropylene glycol, 1.4-butanediol, 1.6-hexane Saturated polyesters obtained by ester bonding with polyhydric alcohols such as diol, pentaerythritol, sorbitol, glycerin, neopentyl glycol, 1,4-cyclohexane dimetatool, etc., or polymers obtained by modifying these polyesters with 5OsNa etc. are described later. A polymer that has been given radiation curability using a special technique.

(6) A polymer obtained by imparting radiation curability to polyvinyl alcohol, butyral polymer, acecool polymer, or formal resin by the method described later.

(7) A polymer obtained by imparting radiation curability to an epoxy polymer phenoxy resin obtained by reacting bisphenol A or brominated bisphenol A with epichlorohydrin or methylepichlorohydrin by a method described later.

(8) A polymer obtained by imparting radiation curability to a cellulose polymer such as nitrified cotton, cellulose acetobutyrate, ethyl cellulose, butyl cellulose, acetyl cellulose, etc. by the method described later.

(9) A polymer in which radiation curability is imparted to a polyfunctional polyether such as a polyether containing one or more hydroxyl groups by a method described later.

(10) A polymer obtained by imparting radiation curability to a polyfunctional polyester such as polycaprolactone by a method described later.

Cl1l Vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-vinyl propionate-vinyl alcohol copolymer, etc. A polymer that has been given radiation curability using the method described.

0 - At least a polyether ester polymer, a polyvinylpyrrolidone polymer, a polyvinylpyrrolidone-olefin copolymer, a polyamide polymer, a polyimide polymer, a phenol polymer, a spiroacecool polymer, an acrylic ester containing a hydroxyl group, and a methacrylic ester A polymer in which radiation curability is imparted to an acrylic polymer containing one type of polymer as a polymerization component using the method described later.

Next, a specific example of the method for imparting the above-mentioned radiation curability will be shown.

(1) One molecule of the thermoplastic polymer or these prepolymers having a hydroxyl group in the molecule is reacted with an isocyanate group of one or more molecules of a polyisocyanate compound, and then a functional group that reacts with the incyanate group and radiation curable React with one or more molecules of a monomer having an unsaturated double bond. Monomers having a functional group that reacts with an isocyanate group and a radiation-curable unsaturated double bond include 2-hydroxyethyl ester of acrylic acid or methacrylic acid, 2-
Ester monomers with hydroxyl groups such as hydroxypropyl ester or 2-hydroxyethyl ester; acrylic double bonds with active hydrogen that reacts with isocyanate groups such as acrylamide, methacrylamide, N-methylol acrylamide, etc. A monomer containing;
Allyl alcohol, maleic acid polyhydric alcohol ester compounds, mono- or diglycerides of long-chain fatty acids with unsaturated double bonds, etc. Contains active hydrogen that reacts with isocyanate groups and has radiation-curable unsaturated double bonds. Examples include monomers.

(U) Introducing an ester double bond by reacting one molecule of the above thermoplastic polymer having a hydroxyl group in the molecule or one molecule of these prepolymers with an acid or acid halide having one or more radiation-curable unsaturated double bonds. do. Examples of the acid or acid halide having a radiation-curable unsaturated double bond include acrylic acid, methacrylic acid, methacrylic acid chloride, acrylic acid chloride, acrylic acid bromide, and methacrylic acid bromide.

( I React with one or more body molecules. Examples of the monomer having a functional group that reacts with a carboxyl group and a radiation-curable unsaturated double bond include glycidyl acrylate and glycidyl methacrylate.

Two or more radiation-curable polymers other than the radiation-curable polymer represented by formula (1) can be used in combination, and the amount used is usually 100% of the radiation-curable polymer represented by formula (1). It is 4001 parts by weight or less.

Further, as compounds having a radiation-curable unsaturated bond, acrylic acid, ethyl acrylate, propyl acrylate, trimethylolproban triacrylate, pentaerythritol triacrylate, hydroxyethyl acrylate, phenoxyethyl acrylate, 2-ethylhexyl acrylate, dibromopropyl acrylate,
Acrylic acid or acrylic acid esters such as triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, penquerythritol triacrylate, adduct of isophorone diisocyanate and hydroxyethyl acrylate, trishydroxyethyl isocyanurate triacrylate; Acrylamide, acrylamides such as N-methylacrylamide, methacrylic acid, ethyl methacrylate, propyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, hydroxyethyl methacrylate, phenoxyethyl methacrylate, 2-ethylhexyl methacrylate, dibromopropyl methacrylate , methacrylic acid esters such as triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, trishydroxyethyl isocyanurate trimethacrylate; methacrylamide, such as methacrylamide, N-methylmethacrylamide Examples include vinylpyrrolidone, phosphoric acid ester having a radiation-curable unsaturated bond. Two or more of these compounds having one radiation-curable unsaturated bond can be used in combination, and the amount used is preferably 5 parts by weight per 100 parts by weight of the radiation-curable polymer represented by formula (1). ~90 parts by weight, more preferably 10 to 80 parts by weight.

Solvents used in preparing the radiation-curable paint of the present invention include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, and butyl acetate; methanol, ethanol, Alcohols such as isopropanol and butanol; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Aliphatic hydrocarbons such as hexane and heptane; Ethylene glycol dimethyl ether,
Examples include glycol ethers such as ethylene glycol monoethyl ether and dioxane, and these solvents may be used alone or as a mixture. The amount of these solvents used is usually 200 to 2,500 parts by weight per 100 parts by weight of the radiation-curable polymer represented by formula (1).

In addition, when preparing the radiation-curable paint of the present invention, caprylic acid, capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, lylunic acid, stearolic acid, lecithin acid, , a dispersant such as an organic titanium compound, an organic silane compound;
Lubricants such as molybdenum disulfide, graphite, silicone oil; Abrasives such as aluminum oxide, chromium oxide, silicon oxide; Conductive fine powder such as carbon black graft polymer; Natural surfactants such as saponin; Alkylene oxide type, glycerin Cationic surfactants such as higher alkylamines, quaternary ammonium salts, pyridine, phosphoniums, and sulfoniums; Carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, phosphoric esters Anionic surfactants containing acidic groups such as amino acids, aminosulfonic acids, amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino alcohols; Antistatic agents such as carbon black, diphosphoric acid, sulfamide, pyridine, dicyclohexylamine Rust inhibitors such as nitrite and cyclohexylammonium carbonate can be added.

Furthermore, the radiation-curable coating material of the present invention may optionally contain polyvinyl butyral, polyvinyl acecool, polyurethane, polyester, polyester having a sulfonic acid and/or metal base in the molecule, epoxy resin, epoxyurethane resin, polyvinyl chloride. , hinyl chloride-hinyl acetate copolymer, hydroxyl group-containing vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, hydroxyl group-containing vinyl chloride-vinyl propionate copolymer, vinyl chloride-vinyl acetate-acrylic acid Ester copolymer, hydroxyl group-containing vinyl chloride-vinyl acetate-acrylic ester copolymer, polyvinylidene chloride, maleic acid-containing vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinylidene chloride-acrylonitrile copolymer Polymer, vinylidene chloride-methacrylic acid ester copolymer,
Phenoxy resin, nitrocellulose, nitrified cotton, ketone resin, acrylic or methacrylic acid polymer or copolymer, acrylic ester or methacrylic ester polymer or copolymer, polyimide resin, 1,3-pentadiene resin, epoxidized 1.3-pentadiene resin,
Hydroxylated 1,3-pentadiene resin, acrylonitrile polymer or copolymer, acrylic ester-acrylonitrile copolymer, methacrylic ester-acrylonitrile copolymer, phenol-formalin resin, phenol-furfural resin, xylene-formalin resin, Urea resin, melamine resin, alkyd resin, acrylonitrile-butadiene styrene copolymer, etc. are blended.

When using the radiation-curable paint of the present invention as a magnetic paint, the magnetic powder to be mixed includes 7Pe, 03, Fe.
30n, T FezOz and Fe, iron oxide in an oxidation state intermediate between 04, Co-containing r FewO+ % Co-containing Pe5Oa, Co-containing γ-Fe, 0. and Fe5O
Iron oxide in an oxidation state intermediate to No. 4, iron oxide further containing a metal element such as a transition metal element, iron oxide with a coating layer mainly composed of Co oxide or hydroxide, The surface of Cry, CrO□ is reduced to Cr2
Examples include those in which an O3 layer is formed, metals such as Fex C0% Nt, alloys thereof, or metal elements such as typical metal elements or transition metal elements. These magnetic powders are usually used in an amount of 2 parts by weight per 100 parts by weight of the radiation-curable polymer represented by formula (1).
00 to 700 parts by weight are used.

When manufacturing magnetic recording media using the radiation-curable paint of the present invention as a magnetic paint, materials to be coated (substrate: base film) include, for example, polyesters such as polyethylene terephthalate; polyolefins such as polypropylene; cellulose triacetate, cellulose diacetate, etc. Cellulose derivatives such as acetate; polycarbonate; polyvinyl chloride; polyimide; non-magnetic metals such as aluminum and copper; and paper.

The radiation used for crosslinking and curing the radiation-curable paint of the present invention includes electron beams, γ-rays, neutron beams, β-rays,
Examples include X-rays and X-rays, but electron beams are particularly preferred from the viewpoint of controlling the radiation dose and ease of introducing the radiation irradiation device into the manufacturing process. The electron beam used has an accelerating voltage of 100~ from the viewpoint of penetrating power.
It is preferable to use an electron beam accelerator of 750 KV, preferably 150 to 300 KV, and irradiate the coating film so that the absorbed dose of the electron beam is 0.5 to 20 megarads.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the following examples, the molecular weight is a value determined by an osmotic pressure method. Further, the structure of the compound is the result of analysis by infrared absorption spectrum and nuclear magnetic resonance (NMR) spectrum.

The solution viscosity of the polymer of each example is 25°C for a 40% by weight solution in the solvent used in the synthesis of the polymer in each example.
This is the value measured in centipoise (cp).

Example 1 (1) Capacity 1) with thermometer, stirrer and reflux condenser
Into a flask, add 77 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester 1 polyethylene glycol (
Average molecular weight 400) 423g and sodium acetate 1.0
g was added thereto, and the mixture was reacted at 130°C for 6 hours. When the obtained reaction product was analyzed by NMR spectrum, it was found that 5
Since no peak due to the proton of the methyl group of -ammonium-sulfo-isophthalic acid dimethyl ester was detected, it was determined that the transesterification rate had progressed to approximately 100%. Furthermore, it was confirmed that unreacted polyethylene glycol was present. Further, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMR spectrum, the reaction product was a mixture of a compound represented by the following structural formula and polyethylene glycol, and 0JHn (in the formula, R1 ) + is a residue of polyethylene glycol (average molecule (1400) excluding both terminal Oil groups, n
is 1.1. ) The ratio of the compound shown in the above structure to unreacted polyethylene glycol was 54:46 (weight ratio).

These mixtures are referred to as specific sulfonic acid compounds (1).

The hydroxyl equivalent of the specific sulfonic acid compound (1) is 3°29X
It was 10-3 equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
167.4 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to the flask and heated to 60°C. While paying attention to
Polyester diol, which is a copolymer of adipic acid and butanediol (manufactured by Nippon Polyurethane Co., Ltd., Niraporan 40)
09;Hereinafter referred to as polyester diol (1)) 13
9.4g 1 polyoxyethylene bisphenol A ether (DA 350F manufactured by NOF Corporation) 2.2g, acrylic acid adduct of propylene oxide derivative of bisphenol A (Kyoeisha Yushiso, Epoxy Ester 3002)
A; hereinafter referred to as specific hydroxyl compound (I)) 34.
6g, 35.3g of specific sulfonic acid compound (I), and 200g of a mixed solvent of cyclohexanone and methyl ethyl ketone.
A uniform mixture of these was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. Next, 6.8 g of 2-hydroxyethyl acrylate was added to this, and the reaction was further carried out at 60°C for 2 hours, followed by 4.3 g of propylene oxide adduct of ethylenediamine (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.).
was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no incyanate group remained in the system. The polymer thus obtained is referred to as Polymer (A). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (A).

Example 2 187.3 g of 4,4'-dicyclohexylmethane diisocyanate, dibutyltin dilaure-1-0,
After adding 5g and 500g of cyclohexanone and heating to 60°C, 49.5g of polyester diol (I) was added through the dropping funnel while being careful not to raise the temperature of the system.
, 153.7 g of polyoxyethylene bisphenol A ether (DA-350F manufactured by Japan Oil Co., Ltd.), 65.6 g of specific hydroxyl compound (1), and 33.4 g of specific sulfonic acid compound (I) were dissolved and mixed in 250 g of cyclohexanone. After dropping, the mixture was reacted at 60° C. for 4 hours. Next, 6.4 g of 2-hydroxyethyl acrylate was added to this, and the reaction was further carried out at 60°C for 2 hours, followed by the addition of 4.0 g of an ethylenediamine propylene oxide adduct (Jiryuka-type Adeca Quadrol).
The reaction was carried out at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system.

The polymer thus obtained is referred to as Polymer (B).

Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (B).

Example 3 86.2 g of 2,4-toluene diisocyanate was added to a 21 capacity flask equipped with a temperature needle, stirrer and reflux condenser.
After adding 0.5 g of dibutyltin dilaurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, the copolymer of adipic acid and ethylene glycol was added through the dropping funnel while being careful not to raise the temperature of the system. 364.0 g of Niraporan 4002 (hereinafter referred to as polyester diol (n)) manufactured by Polyester Diol Co., Ltd., 364.0 g of polyoxyethicine bisphenol A ether (DA-350F manufactured by NOF Corporation)
) 17.4g, specific sulfonic acid compound (I) 24.6g
and cyclohexanone and methyl ethyl ketone mixed solvent 2
Drop a homogeneous mixture of 00g, and after dropping, add 60g
The reaction was carried out at ℃ for 4 hours. Next, 4.7 g of 2-hydroxyethyl acrylate was added to this, and the reaction was further carried out at 60°C for 2 hours, followed by 3.0 g of propylene oxide adduct of ethylenediamine (Abcafodorol, manufactured by Asahi Denka).
g was added and reacted at 60°C for 4 hours. After the reaction is complete,
It was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system.

The polymer thus obtained is referred to as Polymer (C).

Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (C).

Example 4 (1) Capacity 1) with thermometer, stirrer and reflux condenser
Into a flask, add 77 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester 1 polyethylene glycol (
Average molecule ff1200) 423 g.

Add 1.0 g of sodium acetate and 1.0 g of zinc acetate,
The reaction was carried out at 130°C for 6 hours.

When the obtained reaction product was analyzed by NMR spectrum, a peak due to the proton of the methyl group of 5-ammonium-sulfo-isophthalic acid dimethyl ester was not detected, so it was determined that the transesterification rate had progressed to almost 100%. It was done. Furthermore, it was confirmed that unreacted polyethylene glycol was present.

Furthermore, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMR spectrum, the reaction product was a mixture of a compound represented by the following structural formula and polyethylene glycol, and SO, NH4 (in the formula , R19 is a residue of polyethylene glycol (average molecular weight 200) from which both terminal 01) groups have been removed. ) The ratio of the compound shown in the above structure to unreacted polyethylene glycol was 34:66 (weight ratio).

These mixtures are designated as specific sulfonic acid compound (II). The hydroxyl equivalent of specific sulfonic acid compound (II) is 7.6
It was 6×10-′ equivalents/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
2,4-toluene diisocyanate 1) in the flask.
4.3g, dibutyltin dilaurate 0.5g and mixed solvent of cyclohexanone and methyl ethyl ketone 550g
After adding and heating to 60°C, 266.4 g of polyester diol (II) and polyoxyethylene bisphenol A ether (DA-350F manufactured by NOF Corporation) were added while being careful not to raise the temperature of the system through the dropping funnel. 7
5.5g, specific sulfonic acid compound (II) 6.8g and mixed solvent of cyclohexanone and methyl ethyl ketone 20
Drop a uniform mixture of 0g, and after dropping, add 60g
The reaction was carried out at ℃ for 4 hours. Next, 21.2 g of 2-hydroxypropyl methacrylate was added thereto and the mixture was reacted at 60°C for 2 hours, followed by the addition of 18.2 g of propylene oxide adduct of diglycerin (DG-500, manufactured by Asahi Denka) and the reaction was carried out at 60°C. The reaction was allowed to proceed for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate a remained in the system. The polymer thus obtained is referred to as Polymer (D). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (D).

Example 5 132.4 g of isophorone diisocyanate, 0.5 g of dibutyltin dilaurate, and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to a 22-volume flask equipped with a thermometer, stirrer, and reflux condenser.
After heating to ℃, polyester diol (Niraporan 4040, manufactured by Nippon Polyurethane Co., Ltd., hereinafter referred to as polyester diol (III)), which is a copolymer of adipic acid and ethylene glycol, was added while being careful not to raise the temperature of the system from the dropping funnel. ) 27.7 g, polyoxypropylene bisphenol A ether (DB- manufactured by NOF Corporation)
900) 237.2g, methacrylic acid adduct of ethylene glycol diglyndyl ether derivative (manufactured by Kyoeisha Yushi, epoxy ester 40EM: hereinafter referred to as specified hydroxyl compound (old)) 57.6g, specified sulfonic acid compound (
A homogeneous mixture of 43.5 g of I[) and 250 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. then 2
-After adding 6.4 g of hydroxyethyl acrylate and further reacting at 60°C for 2 hours, 6.4 g of propylene oxide adduct of diglycerin (DG-500 manufactured by Asahi Denka) was added.
．． 9 g was added and reacted at 60°C for 4 hours. After the reaction is complete,
It was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (E). Table 1 shows the molecular weight of the polymer (E) and the content of ammonium sulfonate salt.

Example 6 (1) In a flask with a capacity of 1) equipped with a thermometer, a stirrer, and a reflux condenser, 105.9 g of acrylic acid and 394.1 g of polypropylene glycol #400 diglycidylether (manufactured by Kyoeisha Yushi, Evolai h400p) were added. was added and reacted at 60° C. for 6 hours, and it was confirmed by infrared absorption spectrum that there was no absorption of epoxy rings in the reaction product. This reaction product is designated as specific hydroxyl compound (III). The main structure of the specific hydroxyl compound is as follows.

■ C-C1h ■ H (2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
2.4-1-lene diisocyanate 15 in the flask
After adding 6.8 g and 0.5 g of dibutyltin dilaurate and heating to 60°C, add polyester diol (a copolymer of adipic acid and butanediol) while being careful not to raise the temperature of the system from the dropping funnel. Nippon Polyurethane Co., Ltd., Niraporan 4010 (hereinafter referred to as polyester diol (IV)) 83.8 g, specific hydroxy compound (I[I) 57.0 g, specific sulfonic acid compound (
II) A uniform mixture of 181.0 g and 250 g of tetrahydrofuran was added dropwise, and after the addition was completed, the mixture was heated at 60°C for 4 hours.
Allowed time to react. Next, 12.2 g of 2-hydroxypropyl methacrylate was added thereto and the mixture was reacted at 60°C for 2 hours. Then, 6.2 g of an ethylenediamine propylene oxide adduct (Asahi Denka, Abucafuodrol) was added and the mixture was reacted at 60°C. The reaction was allowed to proceed for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (F). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (F).

Example 7 (1) In a flask with a capacity of 1) equipped with a thermometer, a stirrer, and a reflux condenser, 46.8 g of 5-dibutylammonium-sulfo-isophthalic acid dimethyl ester and polytetramethylene glycol (manufactured by DuPont, Terratan) were added. 650
), 1.0 g of zinc acetate, and 1.0 g of sodium acetate, and the reaction was carried out at 130"C for 6 hours. When the obtained reaction product was analyzed by NMR spectrum, it was found that 5-dibutylammonium-sulfo- Since the peak due to the proton of the methyl group of isophthalic acid dimethyl ester is not detected, the transesterification rate is approximately 100.
It was determined that the disease had progressed by %. Furthermore, the presence of unreacted polytetramethylene glycol was also confirmed. Further, the reaction product was fractionated by liquid chromatography and analyzed by NMR spectrum, and the result was that the reaction product was a mixture of a compound represented by the following structural formula and polytetramethylene glycol, 503N)+2 (C4H9 ) 2 (In the formula, R2° is the residue of polytetramethylene glycol excluding the 0■ groups at both ends, and n is 1.4.)
``The ratio of the compound shown in the above structure to unreacted polytetramethylene glycol was 34:66 (weight ratio). These mixtures are referred to as specific sulfonic acid compounds (I[[). The hydroxyl equivalent of the specific sulfonic acid compound (I[I) was 2.02×10-” equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
into a flask of isophorone diisocyanate 105.9
After adding 0.5 g of dibutyltin dilaurate and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, add polyester diol (I
V) 1) 7.9 g.

A homogeneous mixture of 106.1 g of polyoxypropylene bisphenol A ether (DB-900 manufactured by NOF Corporation), 247.5 g of specific sulfonic acid compound (II[), and 250 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and the dropping was completed. Afterwards, the mixture was reacted at 60°C for 4 hours. Then, to this, 2-hydroxyethyl acrylate 5
．． After adding 8 g of the mixture and reacting at 60°C for 2 hours, a propylene oxide adduct of diglycerin (manufactured by Asahi Denka, DG-
500) was added and reacted at 60°C for 4 hours.

After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (G). The molecular weight and sulfonic acid dibutylammonium salt content of the polymer (C) are
Shown in the table.

Example 8 125.6 g of isophorone diisocyanate, 0.5 g of dibutyltin dilaurate, and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to a 21-volume flask equipped with a thermometer, stirrer, and reflux condenser.
After heating to ℃, polyester diol (I[[)
191.8g, specific hydroxyl compound (I[) 132
．． 7g, specific sulfonic acid compound (I [[) 39.6g and mixed solvent of cyclohexanone and methyl ethyl ketone 2
Drop 50g of the mixture evenly, and after dropping, add 6
The reaction was carried out at 0°C for 4 hours. Next, 5.6 g of 2-hydroxypropyl methacrylate was added to this and reacted at 60°C for 2 hours, and then 4.8 g of propylene oxide adduct of diglycerin (DG-500, manufactured by Asahi Denka) was added. The reaction was carried out at 60°C for 4 hours.

After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system.

The polymer thus obtained is referred to as Polymer (H).

Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of the polymer (1).

Example 9 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 121.4 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibutyltin dilaurate were added.
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, add 61.0 g of polyester diol (II) and 61.0 g of a specific hydroxyl compound (I [ [) 49.8 g, specific sulfonic acid compound (
I[[) 120.5g1 Polyoxypropylene bisphenol A ether (manufactured by NOF Corporation DB=900) 164
．． A uniform mixture of 6 g and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the dropwise addition was completed, the reaction was carried out at 600° C. for 4 hours. Then add 2-
Add 3.5g of hydroxypropyl methacrylate,
After reacting at 60°C for 2 hours, 1.8 g of an ethylenediamine propylene oxide adduct (Abcafuodrol, manufactured by Asahi Denka) was added, and the mixture was reacted at 60°C for 4 hours.

After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (J). Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of the polymer (J).

Example 10 (1) Capacity equipped with thermometer, stirrer and reflux condenser 1) 1
5-(2-ethylhexylammonium)-sulfo-isophthalic acid dimethyl ester in a flask of 167.
5g, polyethylene glycol (average molecular weight 1400) 3
32.5g, sodium acetate 1. Og and zinc acetate1.
0g was added and the reaction was carried out at 130°C for 6 hours. When the obtained reaction product was analyzed by NMR spectrum, it was found that 5-(2-ethylhexylammonium)-sulfo-
Since no peak due to the proton of the methyl group of isophthalic acid dimethyl ester was detected, it was determined that the transesterification reaction had progressed to approximately 100%. Furthermore, it was confirmed that there was no unreacted polyethylene glycol. Further, as a result of detailed analysis of the reaction product by NMR spectrum, it was found that the reaction product was a compound represented by the following structural formula.

0JHz CHzCHC1lzCHzCHzCH*Peek C1)z CHs (wherein, R21 is polyethylene glycol (average molecular 1
The above compound (which is the residue obtained by removing both terminal OH groups of 400) is designated as the specific sulfonic acid compound (IV).

The hydroxyl equivalent of the specific sulfonic acid compound (IV) is 1.7
It was 5×10-′ equivalents/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
4.1 g of 4.4'-dicyclohexylmethane diisocyanate 1), 0.5 g of dibutyltin dilaurate, and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to the flask and heated to 60°C, and then the temperature of the system rose from the dropping funnel. A uniform mixture of 342.1 g of polyester diol (1), 35.4 g of specific sulfonic acid compound (IV), and 250 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise while being careful not to cause the drop to drop. 'C for 4 hours. Next, 7.2 g of 2-hydroxyethyl acrylate was added thereto, and the mixture was further reacted at 60'C for 2 hours, followed by the addition of 4.6 g of propylene oxide adduct of ethylenediamine (Adeca Quadrol manufactured by Jiryuka Co., Ltd.). The mixture was reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer obtained in this way was converted into a polymer (
K). Table 1 shows the molecular weight of the polymer (K) and the content of 2-ethylhexylammonium sulfonic acid salt.

Example 1) In a 21 capacity flask equipped with a thermometer, stirrer and reflux condenser, 162.7 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibdeltin dilaurate were added.
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, add 177.4 g of polyester diol (1) and polyoxyethylene bisphenol A ether from the dropping funnel while being careful not to raise the temperature of the system. (DA-350 manufactured by Nihon Yushi Co., Ltd.
F)1) 0.7g, specific hydroxyl compound (1) 35
．． 3g, 2.7g of specific sulfonic acid compound (1) and 200g of mixed solvent of cyclohexanone and methyl ethyl ketone
A uniform mixture of these was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. Next, 6.9 g of 2-hydroxyethyl acrylate was added thereto, and the reaction was further carried out at 60°C for 2 hours, and then 4.4 g of an ethylenediamine propylene oxide adduct (Adeka Quadrol manufactured by Jiryuka Co., Ltd.) was added and the reaction was carried out at 60”C. The reaction was allowed to proceed for 4 hours. After the completion of the reaction, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer obtained in this manner is referred to as Polymer (M). Polymer ( The molecular weight and sulfonic acid ammonium salt content of M) are shown in Table 1.

Example 12 il+ In a capacity 1) flask equipped with a thermometer, stirrer and reflux condenser, 33.9 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester, polytetramethylene glycol (average molecular weight ff1lo00) 466,1
g and 1.0 g of zinc acetate were added thereto, and the mixture was reacted at 130'C for 6 hours. When the obtained reaction product was analyzed by NMR spectrum, a peak due to the proton of the methyl group of 5-ammonium-sulfo-isophthalic acid dimethyl ester was not detected, indicating that the transesterification rate was approximately 1.
It was determined that the disease had progressed to 00%. Furthermore, unreacted polytetramethylene glycol may also exist61) E
'2 = I did.

Further, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMR spectrum, the reaction product was a mixture of a compound having the following structural formula and polytetramethylene glycol, and 0JH4 (formula In the formula, R2□ is a residue of polytetramethylene glycol (average molecule 1tlo00) excluding both terminal 01) groups, and n is 2.0. ) The ratio of the compound shown in the above structure to unreacted polytetramethylene glycol was 41:59 (weight ratio). A mixture of these is referred to as a specific sulfonic acid compound (V). The hydroxyl equivalent of the specific sulfonic acid compound (V) is 1.42X10-
It was 3 equivalents/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
184.86 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to the flask and heated to 60°C, and then the system temperature did not rise through the dropping funnel. 75.6 g of polyester diol (U), polytetramethylene glycol (PTMG100O manufactured by Mitsubishi Kasei Corporation)
23.7 g, polyoxyethylene bisphenol A
161.3 g of ether (DA-400 manufactured by NOF Corporation),
2.1 g of specific sulfonic acid compound (V), 33.4 g of acrylic acid adduct of propylene glycol oxide derivative (epoxy ester 70 PA manufactured by Kyoeisha Yushi Co., hereinafter referred to as specific hydroxyl compound (TV)), and a mixed solvent of cyclohexanone and methyl ethyl ketone. A uniform mixture of 200 g was added dropwise, and after the dropwise addition was completed, the reaction was carried out at 60° C. for 4 hours. This is then added with 2-hydroxyethyl acrylate 1). After further reacting at 60°C for 2 hours, 7.4 g of propylene oxide adduct of ethylenediamine (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) was added.
was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (N). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (N).

Example 13 (1) Capacity 1) with thermometer, stirrer and reflux condenser
In a flask, 31.5 g of 5-dibutylammonium-sulfo-isophthalic acid dimethyl ester and polytetramethylene glycol (average molecular weight 2000) were added.
5 g, zinc acetate 1.0 g and sodium acetate 1.0 g
was added and reacted at 130°C for 6 hours. When the obtained reaction product was analyzed by NMR spectrum, it was found that 5-
Since no peak due to the proton of the methyl group of dibutylammonium-sulfo-isophthalic acid dimethyl ester was detected, it was determined that the transesterification rate had progressed to approximately 100%. Furthermore, the presence of unreacted polytetramethylene glycol was also confirmed. Further, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMR spectrum, it was found that the reaction product was a mixture of a compound represented by the following structural formula and polytetramethylene glycol. )9)z (wherein, R23 is a residue of polytetramethylene glycol (average molecular weight 2000) excluding both terminal OH groups,
n is 3.0. ) The ratio of the compound shown in the above structure to unreacted polytetramethylene glycol was 47:53 (weight ratio). These mixtures are designated as specific sulfonic acid compounds (Vl). The hydroxyl equivalent of the specific sulfonic acid compound (Vl) is 6.30X1
It was 0-' equivalent/g.

(2) Volume 12j equipped with a thermometer, stirrer and reflux condenser
In the flask No. 2, 105.3 g of 4,4'-diphenonoC methane diisocyanate and 0 g of dibutyltin dilaurate were added.
．． 5 g and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added and heated to 60°C.
66.4 g of polyester diol (rV), polytetramethylene glycol (PTMG2000 manufactured by Mitsubishi Chemical Corporation)
1) 2.8 g, polyoxypropylene bisphenol A ether (DB-900 manufactured by NOF Corporation) 179.
1g, specific sulfonic acid compound (Vl) 0.62g and mixed solvent of cyclohexanone and methyl ethyl ketone 200g
Drop a homogeneous mixture of g, and after dropping,
The reaction was carried out at C for 4 hours. Next, 19.2 g of 2-hydroxypropyl methacrylate was added to this, and an additional 6 g of 2-hydroxypropyl methacrylate was added.
After reacting at 0°C for 2 hours, a propylene oxide adduct of diglycerin (DG-500 manufactured by Asahi Denka)16.
6g was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (0). Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of Polymer (0).

Example 14 (1) Capacity 1) with thermometer, stirrer and reflux condenser
27.5 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester, 472.5 g of polyethylene glycol (average molecular weight: 1,000), 1.0 g of zinc acetate, and 1.0 g of sodium acetate were added to a flask of 130 g.
The reaction was carried out at ℃ for 6 hours. The obtained reaction product was subjected to IJMR
As a result of spectrum analysis, it was determined that the transesterification rate had progressed to approximately 100% since no peak due to the proton of the methyl group of 5-ammonium-sulfo-isophthalic acid dimethyl ester was detected. Furthermore, it was confirmed that unreacted polyethylene glycol was present. Further, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMIII spectrum, the reaction product was a mixture of a compound represented by the following structural formula and polyethylene glycol, and 0JH4 (in the formula, R24 is the residue of polyethylene glycol (average molecular weight 1000) with both terminal OH groups removed, and n is 1
．． It is 0. ) The ratio of the compound shown in the above structure to unreacted polyethylene glycol was 43:57 (weight ratio).

These mixtures are designated as specific sulfonic acid compounds (■).

The hydroxyl equivalent of the specific sulfonic acid compound (■) is 1.53X
lo-' equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
176.2 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to the flask and heated to 60°C, and then the system temperature did not rise through the dropping funnel. While paying attention to
126.0 g of polyester diol (r), polyoxyethylene bisphenol A ether (DA manufactured by NOF Corporation)
-350F) 107.4g, specific sulfonic acid compound (
■) 20.9g, specific hydroxyl compound (II) 58
．． A uniform mixture of 6 g and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the dropwise addition was completed, the reaction was carried out at 60° C. for 4 hours. Then to this, 2-
After adding 7.2 g of hydroxypropyl methacrylate and further reacting at 60°C for 2 hours, a propylene oxide adduct of diglycerin (DC-500 manufactured by Asahi Denka) 6
．． 2g was added and reacted at 60°C for 4 hours. After the reaction is complete,
It was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (P). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (P).

Example 15 (1) Into a 1N flask equipped with a thermometer, stirrer and reflux condenser, 167 mL of 5-(2-ethylhexylammonium)-sulfo-isophthalic acid dimethyl ester was added.
．． 5g, polypropylene glycol (average molecular weight 400
), 1.0 g of zinc acetate, and 1.0 g of sodium acetate were added, and the mixture was reacted at 130° C. for 6 hours. When the obtained reaction product was analyzed by NMR spectrum, it was found that 5
-(2-Ethylhexylammonium)-sulfo-isophthalic acid dimethyl ester has no peak due to the proton of the methyl group, so the transesterification rate is approximately 1.
It was determined that the disease had progressed to 00%. Furthermore, the presence of unreacted polypropylene glycol was also confirmed. In addition, the reaction product is fractionated using liquid chromatography to obtain NMI? As a result of spectral analysis, the reaction product is a mixture of a compound represented by the following structural formula and polypropylene glycol, and 0Jt13 ■ CIl□CHCHzCHzCHz (JlzCHICH:
+ (wherein, R2S is a residue of polypropylene glycol (average molecular weight 400) excluding both terminal O1) groups, and n is 4.5. ) The ratio of the compound shown in the above structure to unreacted polypropylene glycol was 70:30 (weight ratio).

These mixtures are designated as specific sulfonic acid compounds (■).

The hydroxyl equivalent of the specific sulfonic acid compound (■) is 1.76
It was X10-3 equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
Into the flask, add isophorone diisocyanate 103.9
After adding 0.5 g of dibutyltin dilaure-1 and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60"C, add polyester diol (n [) 81.4g, polyoxypropylene bisphenol A ether (DB-400 manufactured by NOF Corporation) 36.6
g, 289.3 g of specific sulfonic acid compound (■) and 200 g of mixed solvent of cyclohexanone and methyl ethyl ketone
Drop a homogeneous mixture of
The mixture was allowed to react for 4 hours. Next, 9.4 g of 2-hydroxyethyl acrylate was added to this, and after further reaction at 60°C for 2 hours, 6.0 g of propylene oxide adduct of ethylenediamine (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) was added.
g and reacted at 60"C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained was used as a polymer (Q ). The molecular weight of the polymer (Q) and the content of 2-ethylhexyl ammonium sulfonic acid salt are shown in Table 1. Example 16 Tl) A container 1 equipped with a thermometer, a stirrer and a reflux condenser.
33.9 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester, 466.1 g of polypropylene glycol (average molecular weight 1000), and 1.0 g of sodium acetate were added to a flask containing N. When the obtained reaction product was analyzed by NMR spectrum, a peak due to the proton of the methyl group of 5-ammonium-sulfo-isophthalic acid dimethyl ester was not detected, indicating that the transesterification rate was approximately 100.
It was determined that the disease had progressed by %. Furthermore, the presence of unreacted polypropylene glycol was also confirmed. In addition, the reaction product was fractionated by liquid chromatography and NM
As a result of analysis by R spectrum, the reaction product was a mixture of the compound represented by the following structural formula and polypropylene glycol, SO,Nl+4 (wherein RZh is the 01) group at both ends of polypropylene glycol (average molecular weight 1000). is the residue excluding n
is 1.5. ) The ratio of the compound shown in the above structure to unreacted polypropylene glycol was 45:55 (weight ratio).

These mixtures are referred to as specific sulfonic acid compounds (X).

The hydroxyl equivalent of the specific sulfonic acid compound (X) is 1.42x
lO-'Right! /g.

(2) Volume ff1 equipped with a thermometer, stirrer and reflux condenser
lff flask, 177.9 g of methacrylic acid and 200 diglycidyl ether with polyethylene glycol (
Kyoeisha Yushisha Co., Ltd., Niporai) 200E) 320, 1 g
was added and reacted at 60° C. for 6 hours, and it was confirmed by infrared absorption spectrum that there was no absorption of epoxy rings in the reaction product. This reaction product is designated as a specific hydroxyl compound (V). The main structure of the specific hydroxyl compound is as follows.

CI (2=CC00CHz Ctl C)12 0
1 Large OHCth ■ C1)□ (3) Capacity 21 equipped with thermometer, stirrer and reflux condenser
flask, 145.9 g of 4,4'-diphenylmethane diisocyanate, 0.5 g of dibutyltin dilaurate.
After adding g and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, 165.9 g of polyester diol (1) and specific hydroxyl compound (V) were added from the dropping funnel while being careful not to raise the temperature of the system. 180.4g - Specific sulfonic acid compound (X)
A uniform mixture of 0.2 g and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the dropwise addition was completed, the reaction was carried out at 60° C. for 4 hours. Then to this, 2
- Add 4.7 g of hydroxyethyl acrylate and react at 60°C for 2 hours, then add 3.0 g of propylene oxide adduct of ethylenediamine (ADEKA QUODOLOL, manufactured by Jiryuka Co., Ltd.) and react at 60°C for 4 hours. Ta. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (R). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (R).

Example 17 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 82.8 g of 2.4-1-ruene diisocyanate) was added.
After adding 0.5 g of dibutyltin dilaurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, polyester diol (IV
) 286.0 g, specific hydroxyl compound (1)
92.9g, specific sulfonic acid compound (II) 3.7g and mixed solvent of cyclohexanone and methyl ethyl ketone 2
Drop a uniform mixture of 00g, and after the dropping is completed, 6
The reaction was carried out at 0°C for 4 hours. Next, 21.1 g of 2-hydroxyethyl acrylate was added to this, and an additional 60 g of 2-hydroxyethyl acrylate was added.
After reacting at 60° C. for 2 hours, 13.4 g of an ethylenediamine propylene oxide adduct (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) was added and reacting at 60° C. for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (S). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (S).

Example 18 In a 2P flask equipped with a thermometer, stirrer, and reflux condenser, 48.7 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibutyltin dilaurate were added.
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, 7.4 g of polyester diol (II) and polyoxyethylene bisphenol A ether ( DA-350F manufactured by NOF Corporation)
2.6g, specific hydroxyl compound (IV) 0.2g,
A homogeneous mixture of 447.5 g of specific sulfonic acid compound (VI) and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise.
Allowed time to react. Next, 4.3 g of 2-hydroxypropyl methacrylate was added thereto, and the reaction was further carried out at 60°C for 2 hours, followed by the addition of 3.7 g of propylene oxide adduct of diglycerin (DC-500 manufactured by Jiryuka Co., Ltd.) at 60°C. The mixture was allowed to react for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer obtained in this way is a polymer (T
). Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of the polymer (T).

Example 19 94.5 g of isophorone diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to a 21-volume flask equipped with a thermometer, stirrer, and reflux condenser.
After heating to ℃, polyester diol (I[1
) 19.2g, polyoxypropylene bisphenol A
Ether (DB-900 manufactured by NOF Corporation) 149.7
g, a homogeneous mixture of 46.1 g of specific hydroxyl compound (V), 0.7 g of specific sulfonic acid compound (■), and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the completion of the dropwise addition, the mixture was reacted at 60°C for 4 hours. I let it happen. Next, 9.7 g of 2-hydroxypropyl methacrylate was added to this, and the reaction was further carried out at 60°C for 2 hours, and then 8.3 g of propylene oxide adduct of diglycerin (manufactured by Jiryuka Co., Ltd., DC-500) was added and the mixture was heated to 60°C. ℃4
Allowed time to react. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as a polymer (U).

Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (U).

Example 20 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 171.7 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate.
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, add 70.6 g of polyester diol (1) and polyoxyethylene bisphenol A ether from the dropping funnel while being careful not to raise the temperature of the system. (DA-350F manufactured by Nihon Yushi Co., Ltd.
) 97.4g, specific hydroxyl compound (r) 120.
1g, 30.6g of specific sulfonic acid compound (1) and 200g of mixed solvent of cyclohexanone and methyl ethyl ketone
A uniform mixture of these was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. Next, 5.9 g of 2-hydroxyethyl acrylate was added to this, and after further reaction at 60°C for 2 hours, propylene oxide was added to ethylenediamine. l (Adeka Quadrol manufactured by Jiryuka Co., Ltd.) 3.
7 g was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (V). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (V).

Example 21 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 171.3 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibutyltin dilaurate were added.
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, 142.7 g of polyester diol (1), polyethylene glycol (average molecular Bt 400 ) 22.6g, polyoxyethylene hydaphenol A ether (DA-
350F) 1) 4.9g, specific hydroxyl compound (1)
) 35.4g, specific sulfonic acid compound (1) 1.8g and mixed solvent of cyclohexanone and methyl ethyl ketone 2
Drop a uniform mixture of 00g, and after the dropping is completed, 6
The reaction was carried out at 0°C for 4 hours. Next, 6.9 g of 2-hydroxyethyl acrylate was added to this, and the reaction was further carried out at 60°C for 2 hours.
．． 4 g was added and reacted at 60°C for 4 hours. After the reaction is complete,
It was confirmed by infrared absorption spectrum that no incyanate group remained in the system. The polymer thus obtained is referred to as a polymer (W). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (W).

Example 22 80.7 g of 2,4-toluene diisocyanate was added to a 2 liter flask equipped with a thermometer, stirrer and reflux condenser.
, 0.5 g of dibutyltin dilaurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added.
After heating to 0°C, add polyester diol (I[
I) 322.4g.

A homogeneous mixture of 69.2 g of specific hydroxyl compound (Il), 0.7 g of specific sulfonic acid compound (Il), and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the completion of the dropwise addition, the mixture was reacted at 60° C. for 4 hours. . Next, 14.5 g of 2-hydroxypropyl methacrylate was added thereto, and the mixture was further reacted at 60°C for 2 hours, after which 12.5 g of propylene oxide adduct of diglycerin (DG-500 manufactured by Jiryuka Co., Ltd.) was added and the mixture was reacted for 60 min. °C
The mixture was allowed to react for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (X). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (X).

Comparative Example 1 In a flask with a capacity of 21 equipped with a thermometer, a stirrer and a reflux condenser, 9.2 g of dimethyl terephthalate 1) 89.4 g of dimethyl isophthalate, 136.5 g of dimethyl 5-sodium sulfoisophthalate, ethylene glycol 148.2g1 Neopentyl glycol 203.4
g and 0.025 g of zinc acetate and 0.003 g of sodium acetate as catalysts, and heated to 180-220°C.
The transesterification reaction was carried out for 3 hours. Then, 376.2 g of sebacic acid was added and the mixture was heated at 200-240°C for 2 hours.
After reacting for 30 minutes, the reaction system was
The pressure was reduced to 1) g.

This reaction system was further heated at 250° C. under a pressure of 3 to lommHg.
The polycondensation reaction was carried out at a temperature of .degree. C. for 2 hours. The hydroxyl equivalent of the polyester polyol thus obtained was 4.7.
It was X10-' equivalent/g. As a result of analyzing this polyester polyol by NMR spectrum, its composition was as follows. 20 mol% terephthalic acid, 15 mol% isophthalic acid, 5 mol% sodium 5-sulfoisophthalate, 60 mol% sebacic acid, 50 mol% ethylene glycol and 50 mol% neopentyl glycol.

Next, a container 12 equipped with a thermometer, a stirrer and a reflux condenser
33.8 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ketone were added to the flask of No. 1, and after heating to 60°C, the temperature of the system rose through the dropping funnel. 466.2 g of the polyester polyol obtained above and 20 g of a mixed solvent of cyclohexanone and methyl ethyl ketone, being careful not to
Drop a uniform mixture of 0g, and after dropping, add 60g
The reaction was carried out at ℃ for 4 hours. Next, 4.5 g of 2-hydroxyethyl acrylate was added to this, and the mixture was further reacted at 60°C for 2 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no incyanate group remained in the system.

Reference Example 1 A magnetic paint having the following composition was prepared using the mixed solution of cyclohexanone and methyl ethyl ketone of Polymer A obtained in Example 1 in the following manner, applied to a substrate, and cured by electron beam irradiation.

Co-containing r-FezOi 80 ft
Quantity: Polymer A: 20 parts by weight (in terms of solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight of the magnetic powder in the above composition, cyclohexanone, and methyl ethyl ketone in a 500 IIll aluminum can (about 150 mj' diameter stainless steel pole)
and was shaken for 2 hours using a paint conditioner manufactured by Red Devil Co., Ltd., USA. Next, a mixed solution of cyclohexanone and methyl ethyl ketone of polymer A was added and the solution was further mixed with 4
After shaking for an hour, the stainless steel pole was removed to obtain a magnetic paint. Next, the magnetic paint was immediately applied onto a 15 μm thick polyester film to a dry film thickness of 6 μm, immediately subjected to magnetic field orientation treatment, dried overnight at room temperature, and then accelerated using an electrocurtain type electron beam accelerator. The magnetic coating was cured with a voltage of 160 kilovolts and an absorbed dose of 7 Megaland.

Similarly, in the above magnetic paint composition, excluding magnetic powder,
Polymer A was coated on a glass plate to a dry film thickness of 40 to 60 μm, and after drying overnight at room temperature, the coating was cured at an accelerated voltage of 160 kilovolts and an absorbed dose of 5 Megaland.

For the magnetic paint, the following test (1) was conducted, and for the cured magnetic coating, tests (2) to (6) were conducted.

In addition, for cured coatings that do not contain magnetic powder, (7) to (
8) was conducted.

Furthermore, a cured coating film was prepared separately from the above, and the test (9) was conducted.

The results are shown in Table 2.

(1) IP filtration test: It was observed whether the magnetic paint could be 100% filtered in 1 minute using a filter having an average pore size of 2 μm.

(2) Gloss: Measure the gloss of the cured magnetic coating film at a reflection angle of 45° using a digital gloss needle (Murakami Color Technology Research Institute type), and when the gloss is 70 to 90, ◎, and 50 to 70. When the value was 0130 to 50, it was evaluated as Δ, and when it was 30 or less, it was evaluated as ×.

(3) Surface observation: The surface of the cured magnetic coating was observed using a scanning electron microscope. A state in which no agglomeration of the magnetic powder was observed was marked as ◎, and the results were expressed in the following order as O1△ and ×.

(4) Adhesion test: Adhesive tape is pasted on the surface of the cured magnetic coating, and after it is evenly adhered to the entire surface, the condition is observed when it is instantly peeled off. The evaluation was made as follows: Completely peeled off: ×; Slightly peeled off: Δ; Barely peeled off: ○; No peeling observed at all: ■.

(5) Powder shedding test: The cured magnetic coating was shed 20 times on #1000 emery and the amount of powder shedding was measured.

(6) Square ratio (Br/8m): Toei Kogyo Nishi 5
Magnetic properties were measured using an M-3 model with an external magnetic field of 5.0000 e.

Residual magnetic flux density - Br, maximum residual magnetic flux density = Bm (7) Breaking strength, elongation, initial modulus: Cut out a strip-shaped test piece from the cured coating film. 0.5 cm + m x 10 cm
40-60 μm, measured at room temperature and a tensile speed of 50 m/min.

(8) Tetrahydrofuran (TIIF) extraction residue: The cured coating film was subjected to THF Soxhlet extraction for 24 hours, and the proportion of extraction residue was measured.

(9) Bending test: The polymer obtained in the example was coated on a polyester film with a thickness of 100 μm so that the dry film thickness was 40 to 50 μm, and after drying at room temperature overnight, an accelerating voltage of 160 kilovolts was applied. The clear film was cured at 5 Megaland. This clear film was cut into short pieces with a width of 1 cm for each polyester film of the substrate, and a bending test was conducted 20 times per second in which both ends were fixed and bent from the center, then immediately restored to the original state. The presence or absence of peeling or destruction of the clear film from the bent portion was observed. Those that withstood 500 hours of bending were rated as excellent.

Reference Example 2 A test was conducted in the same manner as in Reference Example 1 except that the composition of the paint was changed as follows. The results are shown in Table 2.

Co-containing T PezOi 80 parts by weight Polymer 8 20 parts by weight (solid fractionation 3E) Cyclohexanone 200 parts by weight Reference Example 3 Same as Reference Example 1 except that the composition of the paint was changed as follows. I conducted a test. The results are shown in Table 2.

Co-containing T FezO 180 parts by weight Polymer C 17 parts by weight (solid content equivalent) Trimethylolpropane triacrylate 3 parts by weight Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 4 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r FezOn' 80 parts by weight Polymer D 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 5 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r FezO3so parts by weight Polymer E 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 6 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r-Fe20. 8.0 parts by weight Polymer F 20 parts by weight (in terms of solid content) Tetrahydrofuran zooii parts Reference Example 7 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing T FezO 380 parts by weight Polymer G 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 8 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r-Fe20. 80 parts by weight Polymer H 20 parts by weight (calculated as solid content) Cyclohexanone and methyl ethyl ketone solvent
200 parts by weight Reference Example 9 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

CO-containing r FezO2 80 parts by weight Polymer J 17 parts by weight (calculated as solid content) Pentaerythritol triacrylate 3 parts by weight Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 10 The test was carried out in the same manner as in Reference Example 1 except that the composition of the coating material in Reference Example (2) was changed as follows. The results are shown in Table 2.

Co-containing r FezOz 80 parts by weight Polymer K 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 1) A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r-Fe. 0. 8 0 parts by weight Polymer M 20 parts by weight (in terms of solid content) Mixture of cyclohexanone, methyl, and tilketone Solvent 200 parts by weight Reference Example 12 Reference Example 1 except that the composition of the coating material in Reference Example 1 was changed as follows. The test was conducted in the same manner. The results are shown in Table 2.

Co containing r Fetch 80 parts by weight Polymer N 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 13 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing 7-FezO 380 parts by weight Polymer 0 20 parts by weight (in terms of solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 14 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r FezO: + go parts by weight Polymer P 20 parts by weight (in terms of solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 15 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r -Fe, Oz 80 parts by weight Polymer Q 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 16 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r FezO 180 parts by weight Polymer R 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 17 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r Part by weight of FezO18o Polymer s 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 18 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r Fe2O* so parts by weight Polymer 7 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 19 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r -F13203 80 parts by weight Polymer U 20 parts by weight (calculated as solid content) Mixed container of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 20 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing T F'etO* ao parts by weight Polymer V 20 parts by weight (calculated as solid content) Cyclohexanone and methyl ethyl ketone solvent
200 parts by weight Reference Example 21 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing T Fe202 so parts by weight Polymer W 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 22 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r FezOz 80 parts by weight Polymer
200 parts by weight Comparative Reference Example A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing 7 Fe20i 80 parts by weight Polymer obtained in Comparative Example 1 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Table 1 [Effects of the Invention] The present invention has the following effects.

(1) The radiation-curable coating material of the present invention provides a magnetic recording medium with excellent practical durability and electromagnetic conversion characteristics.

(2) The radiation-curable paint of the present invention provides a magnetic recording medium with a high magnetic powder filling rate and excellent surface smoothness.

(3) The radiation-curable coating material of the present invention provides a magnetic recording medium with low viscosity, increased pot life, and excellent practical durability.

(4) The cured coating film of the radiation-curable paint of the present invention is not only excellent in mechanical properties, but also has excellent adhesion to substrates such as magnetic recording media.

(5) The radiation-curable paint of the present invention has excellent cross-linking properties upon radiation irradiation, so that it can be cross-linked and cured with sufficient radiation dose at a low radiation dose, and a cured coating film with excellent solvent resistance can be obtained. The energy required to cure the film can be reduced.

(6) The magnetic paint obtained by blending magnetic powder into the radiation-curable paint of the present invention has extremely good affinity with the magnetic powder to be blended, and the magnetic powder can be easily dispersed in the paint. The blending ratio of magnetic powder inside can be greatly improved. Therefore, the radiation-curable coating material of the present invention can be used to prepare a magnetic coating material that can produce a magnetic recording medium with excellent magnetic conversion characteristics.

(7) Even if the coating film of the radiation-curable paint of the present invention improves the crosslinking density by increasing the radiation dose,
A cured coating film with appropriate flexibility and surface hardness can be obtained, and magnetic tapes and floppy disks can be obtained when used as a magnetic coating in the production of magnetic tapes and floppy disks, which are a type of magnetic recording medium. This makes it possible to obtain a highly durable magnetic tape with less magnetic powder falling off and less modulation noise.

Agent: Patent attorney: Comrade Iwamiya Procedural guide (spontaneous) Director of the Japan Patent Office: Kunio Ogawa 1. Indication of weight 1988 Patent application No. 012629 2. Title of invention: Excellent radiation-curable paint 3 , Relationship with the case of the person making the amendment Patent applicant address 2-1) 24 Tsukiji, Chuo-ku, Tokyo
Name (417) Japan Synthetic Rubber Co., Ltd. 4
, Agent 11 Poison, I, I 5. Date of amendment order Voluntary 6. Number of inventions increased by amendment None 7. Subject of amendment Scope of claims and detailed description of invention column 8. Amendment Content 1 and the scope of claims are amended as shown in the attached sheet.

1), (1) The description in the following sections of the specification (before amendment) is amended as shown in (after amendment).

(2) Formula (1)-b on page 14 of the specification is corrected as follows.

(3) Formula (b) on page 23 of the same book is corrected as follows.

(4) Add ``, polytetramethylene glycol'' between ``polypropylene glycol'' and ``r, etc.'' on page 32, line 2 of the same book.

(5) The formula in the fourth line from the bottom of page 56 of the same book is corrected as follows.

(6) Correct the formula in the first line from the bottom of page 79 of the circular as follows.

LiIzL+13" Claims (after amendment) "1. The following formula (1) R1 is a hydrogen atom or a methyl group; R2 is an alkylene group having 2 to 8 carbon atoms; R1 is 2 having 2 to 20 carbon atoms is a valent hydrocarbon group; X is the following formula (1
)-a The definition of R1 is the same as above.

n is a number from 1 to 30.

The units represented by the following formula (1)-b are represented by the following formula (1)-b, where R6 is an alkylene group having 2 to 4 carbon atoms.

The definition of R1 is the same as above, and R2, Ruff, Rts and Ro are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be the same or different.

m and 30 are numbers from 1 to 30, p is a number from 1 to 5, and if necessary, a group represented by the following formula (1)- or I-J'+3 , q is a number from 1 to 20, and R3
The definition is the same as above.

R1/ is a hydrogen atom or a methyl group.

The unit represented by and, if necessary, the following formula (1) - where the definitions of R1, R1 and m are the same as above.

is a group in which units represented by form urethane bonds in arbitrary proportions; Q is a residue of a tetrahydric alcohol; and Y is a hydroxyl group or a group other than Y bonded to Q in the above formula (1). A radiation-curable coating material containing a polymer represented by the following as a radiation-curable polymer component, provided that two or more of Y are not hydroxyl groups.

2. The following formula (1) R1 is a hydrogen atom or a methyl group; R2 is a fullkylene group having 2 to 8 carbon atoms; R3 is a divalent hydrocarbon group having 2 to 20 carbon atoms; X is the following: Formula (1
)-a Here, R4 is an alkylene group having 2 to 4 carbon atoms, the definition of R5 is the same as above, n is a number from 1 to 30, and the unit represented by the following formula (g -b Here, L is an alkylene group having 2 to 4 carbon atoms.

The definition of R3 is the same as above, and Roam L7- R18 and Ls are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be the same or different.

m and sad are numbers from 1 to 30, p is a number from 1 to 5.

A unit represented by the following formula (1)-e, where R7 and R8 are alkylene groups having 2 or 3 carbon atoms, r and S are numbers from 1 to 20, and the definition of R3 is the same as above. , and optionally a group represented by the following formula (1)- or 1, where q is a number from 1 to 20, and R3
The definition is the same as above.

R□' is a hydrogen atom or a methyl group, and if necessary, the following formula (1) - where R3, R6
The definitions of and m are the same as above, and the units represented by form a urethane bond in any proportion; Q is a residue of a tetrahydric alcohol; and Y is a hydroxyl group or A group shown in the above formula (1) other than the bonded Y, provided that two or more of Y are not hydroxyl groups,

Claims (1)

[Claims] 1. The following formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼... (I) Here, R_1 is a hydrogen atom or a methyl group; R_2 is an alkylene having 2 to 8 carbon atoms R_3 is a divalent hydrocarbon group having 2 to 20 carbon atoms; , R_4 is an alkylene group having 2 to 4 carbon atoms, the definition of R_3 is the same as above, n is a number from 1 to 30, a unit represented by the following formula (1)-b ▲ Formula, There are chemical formulas, tables, etc.▼...(1)-b Here, R_5 is an alkylene group having 2 to 4 carbon atoms, the definition of R_3 is the same as above, and R_2_6, R_2_7, R_2_8 and R_2_9 are hydrogen atoms. or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, m and l are numbers from 1 to 30, p is a number from 1 to 5, and a unit represented by, and necessary According to the following formula (1)-c
▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1)-c Here, R_6 is -(CH_2CH_2O)-_q, -(
CH_2CHO) -_q, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Here, Z and Z' are independently ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas , there are chemical formulas, tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ , q is a number from 1 to 20, and the definition of R_3 is the same as above, R_1' is a hydrogen atom or a methyl group, and if necessary, the following formula (1)-d
▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1)-d Here, the definitions of R_3, R_5 and m are the same as above, and the units represented by form urethane bonds in arbitrary proportions. Q is a residue of a tetrahydric alcohol; and Y is a hydroxyl group or a group shown in the above formula (I) other than Y bonded to Q, provided that two or more of Y are A radiation-curable paint containing a polymer represented by the following as a radiation-curable polymer component, which is not a hydroxyl group. 2. The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) Here, R_1 is a hydrogen atom or a methyl group; R_2 is an alkylene group having 2 to 8 carbon atoms; R_3 is It is a divalent hydrocarbon group having 2 to 20 carbon atoms; ~4 alkylene group, the definition of R_3 is the same as above, n is a number from 1 to 30, the unit represented by the following formula (1)-b ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...(1)-b Here, R_5 is an alkylene group having 2 to 4 carbon atoms, the definition of R_3 is the same as above, and R_2_6, R_2_7, R_2_8 and R_2_9 are hydrogen atoms or C1 to 8 an alkyl group, which may be the same or different, m and l are numbers from 1 to 30, p is a number from 1 to 5, a unit represented by the following formula (1) -e ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) -e Here, R_7 and R_8 are alkylene groups with 2 or 3 carbon atoms, r and s are numbers from 1 to 20, The definition of R_3 is the same as above, the unit represented by and the following formula (1)-c as necessary
▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1)-c Here, R_6 is -(CH_2CH_2O)-_q, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where Z and Z' are independently ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or, ▲Mathematical formulas , chemical formulas, tables, etc. ▼ is a group represented by , q is a number from 1 to 20, the definition of R_3 is the same as above, R_1' is a hydrogen atom or a methyl group, a unit represented by , and the following formula (1)-d as necessary
▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1)-d Here, the definitions of R_3, R_5 and m are the same as above, and the units represented by form urethane bonds in arbitrary proportions. Q is a residue of a tetrahydric alcohol; and Y is a hydroxyl group or a group shown in the above formula (I) other than Y bonded to Q, provided that two or more of Y are A radiation-curable paint containing a polymer represented by the following as a radiation-curable polymer component, which is not a hydroxyl group.