JPS63189414A - 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 containing acrylic double bonds is used as the polymer used to prepare the 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 polyhydroxycarboxylic acid and/or polyhydroxysulfonic acid metal salt as at least a part of the chain extender. , has a carboxylic acid component and/or a sulfonic acid metal salt component in its molecular chain via a urethane bond.

However, as can be understood from the description of the resin manufacturing method described in, for example, lines 17 to 11 of the lower right column of the Queen's Publication, there are some problems when polyols are used as part of the chain extender. However, no unsaturated polyurethane resin is disclosed which has a sulfonic acid metal salt on average in all branched chain parts starting from each hydroxyl group 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 above-mentioned JP-A-61-228070, for example, page 12, upper right corner 41j, lines 112 to 18, sulfonic acid metal salts and/or sulfonic acid ammonium salts are used for the purpose of improving the affinity for inorganic compounds such as magnetic substances. Introduced into polyurethane resin. Also, the above-mentioned Unexamined Patent Publication No. 60-1
According to the description in Japanese Patent Application No. 20765, for example, lines a6 to 14 of the third paragraph, 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 radiation-curable polymer has a problem that needs to be solved, in that when it is used to manufacture magnetic recording media, it is difficult to provide sufficiently satisfactory practical durability and electromagnetic conversion characteristics. It 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 Insufficient compared to alkylammonium sulfonate bases, and the overall molecular chain structure of the radiation-curable polymer used.
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 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 (I) (I) where R1 is a hydrogen atom or a methyl group; R is a carbon P is a divalent hydrocarbon group having 2 to 20 carbon atoms, and X is the following formula (11
-a Here, R4 is an alkylene group having 2 to 4 carbon atoms, the definition of R3 is the same as above, and n is a number from 1 to 50. RS is an alkylene group having 2 to 4 carbon atoms, the definition of R1 is the same as above, Rtb+ Iht+ RlII and R19 are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and they may be the same or different. m and l are numbers from 1 to 30, p is a number from 1 to 5, a group in which the units represented by form urethane bonds in any proportion, and Q is 4 and Y is a hydroxyl group or a group shown in the above formula (1) other than Y bonded to Q, provided that two or more of Y are not hydroxyl groups, This is achieved by means of a radiation-curable paint containing the indicated polymer as a radiation-curable polymer component.

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 R3 are alkylene groups having 2 or 3 carbon atoms, r and S are numbers from 1 to 20, and The definition is the same as above, and a radiation-curable coating material containing, as a radiation-curable polymer component, a polymer in which the units represented by the following are groups forming urethane bonds in any proportion is also provided.

The definition of X in the above formula (I) is (1)-a and (1)
-b, and the definition of X in formula (I) is (1)-a, (1)-b.
In the second paint consisting of units represented by (1) and -e, the definition of X in the above formula (1) further includes the following formula (11-c......(1 ) - Nikode R6 is (CHtCHzOh 1 Here, Z and Z' are independently or a group represented by , q is a number from 1 to 20, and R1 is the same as above, , l is a hydrogen atom or a methyl group, and a unit selected from the group consisting of units represented by (1
It may be included as any unit other than the units of 1-a, (1)-b, and (11-e).

In the above formula (L), R1 is a hydrogen atom or a methyl group.

Rt is an alkylene group having 2 to 8 carbon atoms, such as ethylene group, 1.2- or 1.3-propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, etc. be. R8 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 represents a divalent aliphatic, alicyclic or aromatic group of 02 to C26, preferably cg'''c+s, represented by the structural formula, etc. X is a unit represented by the above formula (1)-a, (
1) The unit represented by - and optionally the unit represented by (1) -c represents a group forming a urethane bond in any ratio, or the unit represented by (1) -a,
It represents a group in which a unit represented by (1)-b, a unit represented by (1)-e, and optionally a unit represented by (1)-c 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 is the same as above, and n is a number from 1 to 50.

In formula (1)-b, R1 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. Ih
&＋RZ'? + lR11 and RlQ are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, 2-ethylhexyl group, hexyl group, peptyl group, octyl group,
Ethylhexyl group, etc., preferably a hydrogen atom, ethyl group, propyl group, butyl group, 2-ethylhexyl group, etc., and may be the same or different. Furthermore, the definition of R5 is the same as above, and m and l are independently 1 to 1.
30, and p is a number from 1 to 5.

In formula (11-c, R6 is (CH2CH20)Q 1
Here, Z and Z' are independently CH, ct+s -cozctt= or -CHCH! - or is a group represented by these, and q is a number from 1 to 20.

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

Furthermore, in formula (1)-e, R1 and R 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.

Further, in formula (I), Q is a tetrahydric alcohol residue,
For example, if the tetrahydric alcohol is pentaerythritol, Q is CH.

-CH, -C-CH2- CH.

If the tetrahydric alcohol is N,N,N',N'-tetrahydroxyprobylethylenediamine, then Q is here, ZI + Zz, Zs and Z are independently, and the tetrahydric alcohol is If it is a propylene oxide adduct of diglycerin, Q is CHHz O(Z+), I- C) I O(Zz) , z2. The definitions of z3 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.

In the first step, a diol compound HO-(-R,0-h)I --- (a
) Here, 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 (b) (hereinafter referred to as a specific sulfonic acid compound) where Rs+ Rzb+ R1? + Rzs+ Rzq
＋ffL J! and p are defined by the above formula (11-b
and, if necessary, a compound represented by the following general formula (C) (hereinafter referred to as a specific hydroxyl compound), where the definitions of R4 and R,1 are the same as in the above formula (11-c). , is expressed as the following formula (A) OCN RI NCO (
A) Here, the definition of R1 is the same as in the above formula (I). It is reacted 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 first step, a compound represented by the following general formula (e), where R7+ R+++ r and S
The definition of % can also be used together with the above formula %, in which case the above formula (1)
Polymers containing -e units can be formed.

In the polymer, the formula (1) -a, (1) -
b, (1) -c.

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

In the second step, the following formula CB) RI CHz"-CCORzO) I is added to the polymer having an isocyanate group at the molecular end formed as described above.
...(B) Here, the definition of R and Rt is the above formula C
By reacting an acrylic or methacrylic compound having a hydroxyl group, which is the same as I), in a stoichiometrically equivalent amount of isocyanate groups, the above formula (B) is added to the molecular terminal.
This produces a polymer in which the units are linked via urethane bonds.

In the third step, the remaining isocyanate groups of the thus obtained polymer are combined with a tetrafunctional alcohol compound represented by the following formula (C), where the definition of Q is the same as in the above formula (I). react,
By bonding these together via urethane bonds, the radiation-curable polymer used in the present invention can be obtained.

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 based on 100 parts by weight 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 (al) used in the first step is polyethylene glycol, polypropylene glycol, or polytetramethylene glycol, and is a compound that can be easily obtained as a commercial product.

Further, the specific sulfonic acid compound (b) can be produced by reacting a diol compound represented by the general formula (a) with a sulfoisophthalic acid. Examples of sulfoisophthalic acids include 5-ammonium-sulfo-isophthalic acid and 5-diethylammonium-
Sulfo-isophthalic acid, 5-dipropylammonium-sulfoisophthalic acid, 5-dibutylammonium-sulfo-isophthalic acid, 5-(2-ethylhexyl)ammonium-sulfo-isophthalic acid, 5-ammonium-sulfoisophthalic acid Anhydride, 5-diethylammonium-sulfo-isophthalic anhydride, 5-dipropylammonium-sulfo-isophthalic anhydride, 5-dibutylammonium-sulfo-isophthalic anhydride, 5-
(2-ethylhexyl)ammonium-sulfo-isophthalic acid anhydride, 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,
Examples include ethyl ester.

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
The temperature is 20°C, preferably 50-180°C. As a catalyst for the esterification reaction, 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 (C) is at least selected from acrylic and methacrylic compounds having a carboxyl group and acrylic and methacrylic compounds having a hydroxyl group per mol of a jepoxy compound containing two epoxy groups in one molecule. It is synthesized by reacting one mole or more of one type of compound and conducting 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! conductor): addition of alkylene oxide such as ethylene oxide or propylene oxide to bisphenol A; Glycidyl ether (hereinafter referred to as bisphenol A alkylene oxide derivative) of an alkylene oxide adduct of polyhydric phenol obtained by reacting the compound with epichlorohydrin; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, Examples include glycidyl ether of a polyhydric alcohol obtained by reacting a polyhydric alcohol such as 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. Saltophiles include triethanolamine, N, and N.

N', N'-tetramethylethylenediamine, N.

N-dimethylpiperazine, N-methylmorpholine, boron trifluoride etherate can be used. The amount of these catalysts used is 0 per 100 parts by weight of the reaction raw materials.
．． 01 to 5 parts by weight.

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 compounds (a), (bl, (C), and (e)) 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.

Furthermore, 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 Examples include alkylene oxide adducts such as 2- or 1,3-propylene oxide, pentaerythritol, and the like.

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 units represented by 2(1)-b in X in the radiation-curable polymer represented by formula (1) is preferably from o,oos to 90% by weight, particularly preferably from 0.00 to 90% by weight. 0025-70% by weight.

If it exceeds 90% by weight, toluene, methyl ethyl ketone, methyl isobutyl ketone, which is commonly used as magnetic paint,
There is a strong tendency for the solubility in general-purpose solvents such as
Moreover, the hygroscopicity of the paint film after being cured by radiation increases, which tends to cause a decrease in the strength of the paint film.

The proportion of the ammonium sulfonate base and/or alkylammonium sulfonate base in the radiation-curable polymer represented by formula (I) is preferably from lXl0-'' equivalents/g to 1.3 X 10-3 equivalents/g. , particularly preferably 5X10-' equivalents/g to 1 to 10-3 equivalents/g
It is.

Furthermore, the proportion of the component represented by formula (1) -c in X in the radiation-curable polymer represented by formula (I) 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 formula (1) -a and (1) -e to X in the entire radiation-curable polymer represented by formula (I) is 4.9995 to 99.5% by weight. is preferable, and within this range, the proportions of the units represented by (1)-a and the units represented by (1)-e can be varied arbitrarily.

In the present invention, the radiation-curable polymer represented by formula (I) 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 (I) usually vary depending on the radiation curing conditions, etc., but usually have an elastic modulus of 1.
0 kg/cIa or more, breaking strength 90 kg/cd or more,
The elongation at break is 7% or more.

In the present invention, the radiation curable polymer represented by formula (1,) may be combined with other radiation curable polymers and/or as required.
Alternatively, it can be used in combination with a compound having a radiation-curable unsaturated bond. Other radiation-curable polymers include the following:

-(1) Has an acrylic double bond at the end of the molecule, and the polymer skeleton is polyester, polyurethane, epoxy,
Polymers such as polyethers, polycarbonates, polyamides, etc.

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

X Z [wherein R9 is -CH3 or -C2H, X is RIO CHzCCOO- (wherein RIO is H or CH3), Z
is Rat Si RIO (Rat and R12 represent an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a flukoxy group having 1 to 4 carbon atoms, and may be the same or different,
Y is a toad 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 0 to 200, W is a number from 3 to 100, m is a number from 0 to 5
(3) Hydrophilic group, such as -SO:1M', -050
3M', -COOM', (wherein M' is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom or a hydrocarbon group, and R11 is a hydrocarbon group) and at least one acryl group; Polymers with double bonds, such as polyester, polyether, polyurethane, epoxy, polybutadiene, polyamide, and polycarbonate.

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

RIS -0-CC-Cut (wherein RI4 and RIS are aliphatic, alicyclic or aromatic hydrocarbon groups or derivative residues thereof, RI4 may contain a -〇- bond<, Rts is -〇-1-8
- or -SO, - bond may be included, RIS 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, 1.4-7'tanediol, 1.6- Saturated polyesters obtained by ester bonding with polyhydric alcohols such as hexanediol, pentaerythritol, sorbitol, glycerin, neopentyl glycol, and 1,4-cyclohexane dimetatool, or polymers obtained by modifying these polyesters with So, Na, etc. A polymer that has been given radiation curability using the method described later.

(6) A polymer obtained by imparting radiation curability to polyvinyl alcohol, butyral polymer, acetal polymer, or formal resin by a 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.

(11) Vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl alcohol copolymer,
A polymer obtained by imparting radiation curability to vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-vinyl propionate-vinyl alcohol copolymer, etc. by the method described later.

(12) At least a polyether ester polymer, a polyvinylpyrrolidone polymer, a polyvinylpyrrolidone-olefin copolymer, a polyamide polymer, a polyimide polymer, a phenol polymer, a spiroacetal 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.

(I) 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 isocyanate group and a radiation-curable non-polymer are added. React with one or more molecules of a monomer having a saturated 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 having a hydroxyl group such as hydroxypropyl ester or 2-hydroxyoctyl ester Contains an acrylic double bond and has an active hydrogen that reacts with an isocyanate group such as niacrylamide, methacrylamide, N-methylol acrylamide, etc. Monomers: allyl alcohol, maleic acid polyhydric alcohol ester compounds, unsaturated di- and radiation-curable monomers that have active hydrogen that reacts with isocyanate groups such as mono- or di-glycerides of long-chain fatty acids with unsaturated double bonds. Examples include monomers containing heavy bonds.

(n) 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 molecules of 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.

(III) The above thermoplastic polymer having a carboxyl group in the molecule or a monomer 1 having a functional group that reacts with one or more carboxyl groups and a radiation-curable unsaturated double bond in one molecule of these prepolymers React with more than one molecule. 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 types of radiation-curable polymers other than the radiation-curable polymer represented by formula (I) can be used in combination, and the amount used is usually determined by the radiation-curable polymer represented by formula (1). The amount is 400 parts by weight or less per 100 parts by weight of the combined material.

Further, as compounds having a radiation-curable unsaturated bond, acrylic acid, ethyl acrylate, propyl acrylate, trimethylolpropane 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, pentaerythritol triacrylate, adducts 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 , triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, trishydroxyethyl isocyanurate trimethacrylate, and other methacrylic acid esters; methacrylamide, N-methylmethacrylamide, and other methacrylates; Examples include amides, vinylpyrrolidone, and phosphoric acid esters having radiation-curable unsaturated bonds. Two or more of these compounds having radiation-curable unsaturated bonds can be used in combination, and the amount used is preferably 5 to 90 parts by weight per 100 parts by weight of the radiation-curable paint body represented by formula (1). 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 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 , 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; amphoteric surfactants such as amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols; antistatic agents such as carbon black; phosphoric acid, sulfamide, pyridine, dicyclohexyl Rust inhibitors such as amine nitrite and cyclohexyl ammonium carbonate can be blended.

Furthermore, the radiation-curable coating material of the present invention may optionally contain polyvinyl butyral, polyvinyl acetal, polyurethane, polyester, polyester having a sulfonic acid and/or metal base in the molecule, epoxy resin, epoxyurethane resin, polyvinyl chloride, Vinyl chloride-vinyl 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,
Hydroxylation 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, magnetic powders to be mixed include γ-Fe2O3, Fe4
04, T Iron oxide with an oxidation state intermediate between FezO1 and Pe304, Co-containing r -Fe20. , Co-containing F
e404Co-containing γ-Fe20. Iron oxide with an oxidation state between and Fe3O4, 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. , C
rO□, CrO□ surface reduced to form Cr, O, layer, metals such as Fes Go, Ni, or alloys thereof, or these containing metal elements such as typical metal elements or transition metal elements Examples include those that have been made. These magnetic powders are usually used in an amount of 200 to 100 parts by weight per 100 parts by weight of the radiation-curable polymer represented by formula (I).
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 (base material: base film) include, for example, polyesters such as polyethylene terephthalate; polyolefins such as polypropylene; cellulose triacetate, cellulose. Cellulose derivatives such as diacetate; polycarbonate; polyvinyl chloride; polyimide; non-magnetic metals such as aluminum and copper;

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 Megaland.

〔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 in each example was determined at 25°C for a 40% solution in the solvent used in the synthesis of the polymer in each example.
This is the value measured in centivoise (cp).

Example 1 (1) Capacity 11 equipped 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) 423 g and sodium acetate 1.
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,
Since no peak due to the proton of the methyl group of 5-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. In addition, as a result of analyzing the reaction product by NMR spectrum fractionated by liquid chromatography, the reaction product was a mixture of a compound represented by the following structural formula and polyethylene glycol, (wherein RIM is It is a residue of polyethylene glycol (average molecular weight 400) with both terminal OH groups removed, and n is 1.
It is 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 (I). The hydroxyl equivalent of the specific sulfonic acid compound (1) was 3.29×10-“equivalent/g.

(2) Add 185.6 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of dichlorohexanone and methyl ethyl ketone to a 21-volume flask equipped with a thermometer, stirrer, and reflux condenser. After heating to 60"C, add 103.6 g of polytetramethylene glycol (Teratane 650, manufactured by DuPont) while being careful not to raise the temperature of the system from the dropping funnel.

128.3 g of polyoxyethylene bisphenol A ether (0A-350F manufactured by Nippon Oil & Fats Co., Ltd.), 38.4 g of acrylic acid adduct of bisphenol A propylene oxide derivative (epoxy ester 3002A manufactured by Kyoeisha Yushi Co., hereinafter referred to as specific hydroxyl compound (I)) A uniform mixture of 31.3 g of a specific sulfonic acid compound (t) and 250 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after completion of the dropwise addition, 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.
Add 4.3g of Asahi Denka's Adeka Quadrol) and heat at 60°C.
After the reaction was completed for 4 hours, it was confirmed by infrared absorption spectrum that no isocyanate groups 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 In a 21 capacity flask equipped with a temperature system, stirrer and reflux condenser, 208.2 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibutyltin dilaurate were added.
g and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added and heated to 600°C, and then polytetramethylene gel 5 recall (Teratane 650, manufactured by DuPont) was added while being careful not to raise the temperature of the system from the dropping funnel. 35.8g, polyoxyethylene bisphenol A ether (DA-350F manufactured by NOF Corporation) 1
70.8g, specific sulfonic acid compound (I) 37.3g,
A homogeneous mixture of 36.3 g of specific hydroxyl compound (1) and 250 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after completion of the dropwise addition, the mixture was reacted at 60°C for 4 hours. After adding 1 g of the mixture and reacting at 60° C. for 2 hours, 4.5 g of an ethylenediamine propylene oxide adduct (Abcafuodrol, manufactured by Asahi Denka Co., Ltd.) was added and the reaction was continued 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 82.0 g of 2,4-toluene diisocyanate was added to a 121-volume flask equipped with a temperature system, stirrer, and reflux condenser.
, by adding 0.5 g of dibutyltin laurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone.
After heating to 0°C, while being careful not to raise the temperature of the system through the dropping funnel, add 338.0 g of polytetramethylene glycol (PTMG100O manufactured by Mitsubishi Kasei) and polyoxypropylene bisphenol A ether (DB manufactured by NOF Corporation). -900), 25.0 g of the specific sulfonic acid compound (1), and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added dropwise, and after the completion of the dropwise addition, the mixture was reacted at 60°C for 4 hours. Next, 5.9 g of 2-hydroxypropyl methacrylate was added and the reaction was further carried out at 60°C for 2 hours, and then 3.0 g of propylene oxide adduct of ethylene oxide (Adeka Quadrol manufactured by Asahi Denka) was added and the reaction was carried out at 60°C for 4 hours. Made it 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 Polymer (C).

The molecular weight and sulfonic acid ammonium salt content of 3tlC (C) are shown in Table 1.

Example 4 (1) In a 1β flask equipped with a temperature system, a stirrer, and a reflux condenser, 77 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester, 423 g of polyethylene glycol (average molecular weight 200), and 1 portion of sodium acetate were added.
．． 0 g and 1.0 g of zinc acetate were added, and the mixture was reacted at 130° C. for 6 hours.

When the obtained reaction product was analyzed by NMR spectrum, no peak due to the proton of the methyl group of 5-ammonium-sulfoisophthalic acid dimethyl ester was detected, indicating that the transesterification rate was approximately 100%.
It was determined that it was progressing. Furthermore, it was confirmed that unreacted polyethylene glycol was present.

In addition, as a result of fractionating the reactive components using liquid chromatography and analyzing them using NMR spectroscopy, the reaction product was a mixture of a compound represented by the following structural formula and polyethylene glycol. R19 is a residue of polyethylene glycol (average molecular weight 200) with both terminal OR groups removed.) The ratio of the compound shown in the above structure to unreacted polyethylene glycol was 34:66 (weight ratio). A mixture of these was designated as the specific sulfonic acid compound (n).The hydroxyl equivalent of the specific sulfonic acid compound (n) was 7.66×10-'' equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
2.4-) Luene diisocyanate 12 into a flask of
3.1 g, dibutyltin dilaurate 0.5 g and mixed solvent of cyclohexanone and methyl ethyl ketone 50
After adding 0 g and heating to 60°C, add polypropylene glycol (Uniol D-400 manufactured by NOF Corporation) while being careful not to raise the temperature of the system from the dropping funnel.
114.8g, polyoxypropylene bisphenol A
Ether (NOF DB-900) 212.3 g
A homogeneous mixture of 157 g of specific sulfonic acid compound (II) and 250 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 heated at 60°C for 4 hours.
Allowed time to react.

Then, to this, 2-hydroxypropyl methacrylate)
After adding 22.8 g and reacting at 60°C for 2 hours, add a propylene oxide adduct of diglycerin (manufactured by Asahi Denka Co., Ltd.).
After the completion of the reaction in which 19.7 g of DG-500) was added and reacted at 60° C. for 4 hours, it was confirmed by infrared absorption spectrum that no isocyanate groups 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 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 92.8 g of 2.4-)luene diisocyanate was added.
After adding g, 0.5 g of dibutyltin dilaurate and 500 g of tetrahydrofuran and heating to 60°C, while being careful not to raise the temperature of the system from the dropping funnel,
Polypropylene glycol (UNIOL manufactured by NOF Corporation)
D-1200) 57.1g, specific sulfonic acid compound (
n) A uniform mixture of 205 g, 32.9 g of methacrylic acid adduct of ethylene glycol diglycidyl ether derivative (manufactured by Kyoeisha Yushi Co., Ltd., epoxy ester 40EM; hereinafter referred to as specific hydroxyl compound (II)) and 250 g of tetrahydrofuran was added dropwise. After the dropwise addition was completed, the mixture was reacted at 60° C. for 4 hours.

Next, 11.0 g of 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate) was added and the reaction was further carried out at 60°C for 2 hours.
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 (E).

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

Example 6 (1) Capacity 1N equipped with temperature needle, stirrer and reflux condenser
105.9 g of acrylic acid & 394.1 g of hypholypropylene glycol #400 diglycidyl ether (Kyoeisha Yushi Evolai 400p) were added to a flask, and after reacting at 60°C for 6 hours, infrared absorption spectroscopy revealed the reaction product. It was confirmed that there was no absorption of ball boxy rings in the material. This reaction product is converted into a specific hydroxyl compound (
m).

The main structure of the specific hydroxyl compound is as follows.

■ HCCHL Peek OH (2) Capacity 2N equipped with thermometer, stirrer and reflux condenser
of isophorone diisocyanate 121.3
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 polytetramethylene glycol (manufactured by DuPont) while being careful not to raise the temperature of the system from the dropping funnel. Terratan 650) 16.5
g, polyoxypropylene bisphenol A ether (
A homogeneous mixture of 205.8 g of DB-900 (manufactured by NOF Corporation), 103.7 g of a specific hydroxyl compound (I[[), 39.7 g of a specific sulfonic acid compound (n), and 250 g of a mixed solvent of cyclohexanone and methyl ethyl ketone. was added dropwise and reacted at 60°C for 4 hours.

Then, to this, 2-hydroxyethyl acrylate)5.
After adding 9 g and further reacting at 60°C for 2 hours,
4.2 g of propylene oxide adduct of diglycerin (DG-500, manufactured by Jiryuka) 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 CF).

The molecular weight and sulfonic acid ammonium salt content of the polymer CF) are shown in Table 1.

Example 7 (1) In a 1β capacity flask equipped with a thermometer, stirrer and reflux condenser, 8 g of 5-dibutylammonium-sulfo-isophthalic acid dimethyl ester 46'.

453.2 g of polytetramethylene glycol (manufactured by DuPont, Terratan 650), 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, a peak due to the proton of the methyl group of 5-dibutylammonium-sulfo-isophthalic acid dimethyl ester was not detected, indicating that the transesterification rate had progressed to approximately 100%. It was determined that there was. 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. R2゜ is OH at both ends of polytetramethylene glycol
The ratio of the compound shown in the above structure and unreacted polytetramethylene glycol was 34:66 (weight ratio). These mixtures are referred to as specific sulfonic acid compounds (III). The hydroxyl equivalent of the specific sulfonic acid compound (III) is 2.02X10'
″3 equivalent/g.

(2) Capacity 92N equipped with thermometer, stirrer and reflux condenser
123.7 of isophorone diisocyanate in a flask of
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, add the specific sulfonic acid compound (n[) 211.9g, polyoxyethylene bisphenol A ether (DA-350F, manufactured by NOF Corporation)
A homogeneous mixture of 49.3 g, polytetramethylene glycol (PTMG100O manufactured by Mitsubishi Kasei), 142.9 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 mixture was heated at 60°C for 4 hours.
Allowed time to react. Next, 8.3 g of 2-hydroxypropyl methacrylate was added and the reaction was further carried out at 60°C for 2 hours, followed by the addition of 4.2 g of propylene oxide adduct of ethylenediamine (Adoca Quodrol manufactured by Jiryuka) and the reaction was carried out at 60°C for 4 hours. Made it 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 Polymer (G).

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

Example 8 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 200.0 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibutyltin dilaurate were added.
g and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added and heated to 60°C, and then 47.8 g of specific sulfonic acid compound (III) and 47.8 g of specific hydroxyl compound ( II) 133.7g, polypropylene glycol (NOF Uniol D-400) 11
A uniform mixture of 5.9 g and 250 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.

This was then added with 2-hydroxypropyl methacrylate 5
．． After adding 6g and further reacting at 60°C for 2 hours,
Addition of propylene oxide to diglycerin ¥yJ (DG-500 manufactured by Jinmineka) Add 4.8 g and heat at 60℃ for 4 hours.
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 Polymer (H).

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

Example 9 103.8 g of isophorone diisocyanate, 0.5 g of diptyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to a 2β flask equipped with a thermometer, a stirrer, and a reflux condenser.
After heating to ℃, add 73.8 g of polypropylene glycol (NOF 01200) and polyoxypropylene bisphenol A ether (NOF DB-9) to the dropping funnel while being careful not to raise the temperature of the system.
00) 166.0 g, specific hydroxy compound (I[
I) 50.2g, specific sulfonic acid compound (m) 1
A uniform mixture of 21.6 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.

Next, 2-hydroxyethyl acrylate 2.9
After adding 1.8 g of propylene oxide adduct of ethylenediamine (Adeka Quadrol manufactured by Jiryuka Co., Ltd.) and reacting for 2 hours at 60°C, 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 (11 Bottle equipped with thermometer, stirrer and reflux condenser [11
of 5-(2-ethylhexylammonium)-sulfo-isophthalic acid dimethyl ester into a flask.
g 1 polyethylene glycol (average molecular weight 400)
332.5 g, 1.0 g of sodium acetate, and 1.0 g of zinc acetate were added, 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-(2-ethylhexyl)ammonium-sulfo-isophthalic acid dimethyl ester was not detected, indicating that the transesterification reaction had proceeded approximately 100%. It was determined that 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 having the following structure.

CHzcHcHzcHzcHzCHx C+1zCtlz (In the formula, Ihl is a residue of polyethylene glycol (average molecular weight 400) from which the 011 groups at both ends are removed) The above compound is designated as a specific sulfonic acid compound (IV). The hydroxyl equivalent of the specific sulfonic acid compound (IV) is 1.75
It was 10-'' equivalent/g.

(2) Capacity 2 with thermometer, stirrer and reflux condenser
148.5 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of diptyltin dilaurate, and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to the flask in Step 1, and the mixture was heated to 60°C.
Add 307.1 g of polytetramethylene glycol (Teratane 650 manufactured by DuPont) while being careful not to raise the temperature of the system from the dropping funnel.

35.4 g of specific sulfonic acid compound (II/) and 250 g 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, 7.3 g of 2-hydroxyethyl acrylate was added thereto and the reaction was further carried out at 60°C for 2 hours, and then 4.6 g of an ethylenediamine propylene oxide adduct (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) was added and reacted at 60°C for 4 hours. 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 Polymer (L). Table 1 shows the molecular weight of the polymer (L) and the content of 2-ethylhexylammonium sulfonic acid salt.

Example 11 In a 2E flask equipped with a thermometer, a stirrer, and a reflux condenser, 182.4 g of 4-4'-dicyclohexyl diisocyanate, 0.5 g of dibutyltin dilaurate, and 55 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added.
After adding 0 g and heating to 60°C, add polytetramethylene glycol (PTMG100O manufactured by Mitsubishi Kasei) 97 through the dropping funnel while being careful not to raise the temperature of the system.
．． 1 g, polyoxyethylene bisphenol A ether (DA-350F manufactured by NOF Corporation) 184.0 g,
A uniform mixture of 33.6 g of specific hydroxyl compound (1), 34.4 g of specific sulfonic acid compound (I), and 200 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. Ta. Next, 11.4 g of 2-hydroxyethyl acrylate was added to this, and after further reacting at 60°C for 2 hours, a propylene oxide adduct of ethylenediamine (
Add 7.2 g of Adeka Quadrol (manufactured by Jiryuka Co., Ltd.) and 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 thus obtained is referred to as Polymer (M). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (M).

Example 12 (1) In a flask with a capacity of 11 equipped with a thermometer, a stirrer, and a reflux condenser, 33.9 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester and 466.1 g of polytetramethylene glycol (average molecular weight 11000) were added. and 1.0 g of zinc acetate were added, 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, so it was determined that the transesterification rate had progressed to almost 100%. Ta. Furthermore, the presence of unreacted polytetramethylene 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 a compound represented by the following structural formula and polytetramethylene glycol, (wherein Ro represents both terminals O of polytetramethylene glycol (average molecular weight 1000).
It is a residue excluding the H group, and n is 2.0. ) The ratio of the compound shown in the above structure to unreacted polytetramethylene glycol was 41:59 (weight ratio). These mixtures are referred to as specific sulfonic acid compounds (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
In a flask, add 140.1 g of 4,4'-dicyclohexyl diisocyanate, dibutyltin dilaure).
After adding 0.5 g and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, pour the mixture into the dropping funnel, taking care not to raise the temperature of the system.
Polytetramethylene glycol (PTMG manufactured by Mitsubishi Kasei Corporation)
2000) 216.0 g, polyoxyethylene and suphenol A ether (NOF DA400) 88
．． 9 g, acrylic acid adduct of propylene glycol ethylene oxide it form (epoxy ester 70PA manufactured by Kyoeisha Yushi Co., Ltd.; hereinafter referred to as a specific hydroxyl compound (IV
) 34.1g, specific sulfonic acid compound (v) 1
．． A uniform mixture of 9 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 11.7 g of hydroxyethyl acrylate and further reacting at 60°C for 2 hours, a propylene oxide adduct of diglycerin (DG-500 manufactured by Mineka Co., Ltd.) was added.
) 12.6g 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 (N). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (N).

Example 13 (1) Capacity 11 equipped with thermometer, stirrer and reflux condenser
31.5 g of 5-dibutylammonium-sulfo-isophthalic acid dimethyl ester - polytetramethylene glycol (average molecular weight FF 12000) 468.
5 g, zinc acetate 1゜Og and acetic acid) IJum 1,
Og was added 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-dibutylammonium-sulfo-isophthalic acid dimethyl ester was not detected, so it was determined that the transesterification rate had progressed by approximately 1OO%. It was done. Furthermore, the presence of unreacted polytetramethylene 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 a compound represented by the following structural formula and polytetramethylene glycol, (wherein R23 is 0 at both ends of polytetramethylene glycol (average molecular weight 2000)) Residues except one group, 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) Capacity 1N equipped with thermometer, stirrer and reflux condenser
177.9 g of methacrylic acid and 320.1 g of polyethylene glycol 11200 diglycidyl ether (manufactured by Kyoeisha Yushi Co., Ltd., Evolite 200B)
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 the specific hydroxyl compound (V).The main structure of the specific hydroxyl compound is as follows.

H2 (3) Capacity 21 equipped with thermometer, stirrer and reflux condenser
flask, 125.8 g of 4,4'-diphenylmethane 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 polytetramethylene glycol (PTMG300 manufactured by Mitsubishi Kasei Corporation) from the dropping funnel while being careful not to raise the temperature of the system.
0) 100.7 g, polyoxypropylene and suphenol A ether (DB-900 manufactured by NOF Corporation) 1
85.4g, specific hydroxy compound (V) 61.7g,
A homogeneous mixture of 0.93 g of a specific sulfonic acid compound (Vl) 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 heated at 60°C for 4 hours.
Allowed time to react. Next, 15.6 g of 2-hydroxyethyl acrylate was added thereto, and the mixture was further reacted at 60°C for 2 hours, and then 9.9 g of a propylene oxide adduct of diethylamine (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) was added and the mixture was heated 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 obtained in this way was converted into a polymer (
0). Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of Polymer (0).

Example 14 (capacity 1 with 11 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 1000), 1.0 g of zinc acetate and 1.0 g of sodium acetate were added to a flask, and the mixture was heated at 130°C. The reaction was allowed to proceed 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%. Ta. 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, (in the formula, lh4 is OH at both ends of polyethylene glycol (average molecular weight 1000)
It is a residue excluding a group, and n is 1.0. ) 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 (■) was 1.53 x 10-' equivalent/g.

(2) Volume ff1 equipped with a thermometer, stirrer and reflux condenser
Into a 2j2 flask were added 230.2 g of 4,4'-diphenylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heated to 60°C. While being careful not to rise,
Polyethylene glycol (PEG#2 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
00) 147.8 g, polyethylene glycol (PEGItlOOO manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 69.3 g, polyoxypropylene bisphenol A ether (DB-400 manufactured by NOF Corporation) 19.4 g, specific sulfonic acid compound (■) A uniform mixture of 20.3 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-hydroxypropyl methacrylate) 7
．． After adding 0g and further reacting at 60°C for 2 hours,
6.1 g of propylene oxide adduct of diglycerin (DG-500, manufactured by Jinminaka Co., Ltd.) 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 (P). Polymer (P
) and the ammonium sulfonate salt content are shown in Table 1.

Example 15 (1) Capacity 11 equipped with thermometer, stirrer and reflux condenser
5-(2-ethylhexylammonium)-sulfo-isophthalic acid dimethyl ester in a flask of 167.
5 g, polypropylene glycol (average molecular weight 40
0) 332.5g, zinc acetate 1. After adding Og and 1.0 g of sodium acetate, 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)-
Since no peak due to the proton of the methyl group of sulfo-isophthalic acid dimethyl ester was detected, it was determined that the transesterification rate had progressed to approximately 100%. Furthermore, the presence of unreacted polypropylene glycol was also confirmed. In addition, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMR spectrum,
The reaction product is a mixture of a compound represented by the following structural formula and polypropylene glycol, CHzCHCHzCHzCHzCllz1hCHa (wherein R□ is a residue of polypropylene glycol (average molecular weight 400) excluding one group at both terminals). Yes, 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 (Vl). The hydroxyl equivalent of the specific sulfonic acid compound (■) is 1.76
xlO-' equivalent/g.

(2) Volume M equipped with a thermometer, stirrer and reflux condenser
In a flask No. 21, 104.6 g of 2,4-toluene diisocyanate, 0.5 g of dibutyltin laurate, and a mixed solvent of cyclohexanone and methyl ethyl ketone were added.
After adding 50g and heating to 60℃, from the dropping funnel,
While being careful not to raise the temperature of the system, add polyethylene glycol (PEG #400 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 80
．． 2g, polyoxyethylene bisphenol A ether (D^-350F manufactured by NOF Corporation) 3.5g, specific hydroxy compound N) 35.8g, specific sulfonic acid compound (■
A uniform mixture of 258.5 g of ) and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the dropwise addition was completed, the mixture was reacted at 60° C. for 4 hours. This is then followed by 2-hydroxypropyl methacrylate IL6.
After further reacting at 60°C for 2 hours, 5.9g of a propylene oxide adduct of diethylamine (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 isocyanate groups remained in the system.

The polymer thus obtained is referred to as Polymer (Q). Table 1 shows the molecular weight and 2-ethylhexylammonium sulfonic acid salt content of the polymer (Q).

Example 16 (1) Capacity 11 equipped with thermometer, stirrer and reflux condenser
33.9 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester and 466.1 g of polypropylene glycol (average molecular weight 1000) were added to a flask.

1.0 g of sodium acetate was added, 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 10.
It was determined that the disease had progressed to 0%. Furthermore, the presence of unreacted polypropylene glycol was also confirmed. Also,
The reaction product was fractionated by liquid chromatography and N
As a result of analysis by MR spectrum, the reaction product was a mixture of a compound represented by the following structural formula and polypropylene glycol, (wherein RZ6 is 0 at both ends of polypropylene glycol (average molecular weight 1000)) except for one group. is a residue, 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
It was 10 bow equivalents/g.

(2) Volume ff1 equipped with a thermometer, stirrer and reflux condenser
In a 2F flask, 113.0 g of 2,4-toluene diisocyanate, 0.5 g of dibutyltin laurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone.
After adding and heating to 60°C, add polyethylene glycol (PEGI100O manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 255 through the dropping funnel while being careful not to raise the temperature of the system.
．． 8 g, polyoxyethylene bisphenol A ether (Nippon Oil Co., Ltd. A-350F) 50.9 g, and specific hydroxyl compound (I[) 71.4 g.

A homogeneous mixture of 0.2 g of the specific sulfonic acid compound (X) and 200 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. Next, 5.7 g of 2-hydroxypropyl methacrylate was added thereto, and the reaction was further carried out at 60°C for 2 hours. Then, 2.9 g of a propylene oxide adduct of diethylamine (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) was added and the mixture was heated 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 obtained in this way was converted into a polymer (
R). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (R).

Example 17 In a 21 capacity flask equipped with a thermometer, stirrer and reflux condenser, 192.9 g of isophorone diisocyanate was added.
, 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℃, add polypropylene glycol (
A uniform mixture of 201.2 g of NOF D-400), 59.9 g of a specific hydroxyl compound (IV), 2.2 g of a specific sulfonic acid compound (IV), and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise. After the dropwise addition was completed, the mixture was reacted at 60° C. for 4 hours. This was then added with 2-hydroxyethyl acrylate 2
After adding 1.2 g and reacting at 60°C for 2 hours,
22.9 g of propylene oxide adduct of diglycerin (DG-500 manufactured by Asahi Denka 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 isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (S). Polymer (
Table 1 shows the molecular weight and 2-ethylhexylammonium sulfonic acid salt content of S).

Example 18 In a 2β capacity flask equipped with a thermometer, stirrer and reflux condenser, 144.2 g of isophorone diisocyanate was added.
, 0.5 g of dibutyltin laurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added.
After heating to 0℃, add polypropylene glycol (
NOF D-700) 106.7 g, polyoxypropylene bisphenol A 1-te JL/ (NOF DB-400) 54.2 g, specific hydroxyl compound (V) 55.6 g, specific sulfonic acid Compound(
1) A homogeneous mixture of 131.1 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 mixture was reacted at 60'C for 4 hours. Next, 4.4 g of 2-hydroxypropyl methacrylate was added thereto, and the reaction was further carried out at 60"C for 2 hours. Then, 3.8 g of propylene oxide adduct of diglycerin (DG-500 manufactured by Asahi Denka Co., Ltd.) was added and the mixture was heated at 60"C. After the reaction was completed for 4 hours, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system.The polymer obtained in this way is referred to as Polymer (T).Polymer ( Table 1 shows the molecular weight and ammonium sulfonate content of T).

Example 19 In a 2i capacity flask equipped with a thermometer, stirrer and reflux condenser, 120.9 g of 4,4'-dicyclohexylmethane diisocyanate and 0.9 g of dibutyltin laurate were added.
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60'C, polypropylene glycol (D-1000 manufactured by NOF Corporation) 9 was added from the dropping funnel while being careful not to raise the temperature of the system.
9.4 g, polyoxypropylene bisphenol A
Ether (DB-900 manufactured by NOF Corporation) 265.2g
A homogeneous mixture of 1.8 g of specific sulfonic acid compound (VI) and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after completion of the dropwise addition, the mixture was reacted at 60° C. for 4 hours. Next, 7.7 g of 2-hydroxyethyl acrylate was added thereto, and the reaction was further carried out at 60°C for 2 hours, and then 4.9 g of an ethylenediamine propylene oxide adduct (ADEKA QUODOLOL manufactured by Jiryuka Co., Ltd.) was added thereto and reacted at 60°C for 4 hours. 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 obtained in this way is a polymer (U
). Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of the polymer (U).

Example 20 In a flask with a capacity of 21 equipped with a temperature needle, a stirrer, and a reflux condenser, 180.1 g of 4,4'-dicyclohexyl diisocyanate, 0.5 g of dibutyltin dilaurate, and 5 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added.
After adding 50g and heating to 60℃, from the dropping funnel,
Polytetramethylene glycol (PTMG100O manufactured by Mitsubishi Chemical Corporation) was added while being careful not to raise the temperature of the system.
132.7 g, polyoxyethylene bisphenol A
Ether (0A-350F manufactured by Nippon Oil & Fats Co., Ltd.) 100.8
g, a uniform mixture of 48.2 g of specific hydroxyl compound (1), 1.5 g of specific sulfonic acid compound (1), 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 heated at 60°C for 4 hours. Made it react. Next, 18.8 g of 2-hydroxyethyl acrylate was added to this, and after further reaction at 60°C for 2 hours, 11.9 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 is completed, it is determined by infrared absorption spectrum that no isocyanate groups remain in the system at T11! Approved. 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 flask with a capacity of 21 equipped with a thermometer, a stirrer, and a reflux condenser, 213.7 g of 4,4'-dicyclohexyl diisocyanate, 0.5 g of dibutyltinlaurate, and 5 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added.
After adding 50g and heating to 60℃, from the dropping funnel,
While being careful not to raise the temperature of the system, add polytetramethylene glycol (Teratane 650 manufactured by DuPont) 1
5.5 g, polyethylene glycol (PEG #400 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 78.9 g, specific sulfonic acid compound (I) 2.7 g, specific hydroxy compound (II)
A uniform mixture of 171.2 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 mixture was reacted at 60° C. for 4 hours. This was then added with 11.0 g of 2-hydroxyethyl acrylate.
The mixture was further reacted at 60°C for 2 hours, and then 7.0 g of an ethylenediamine propylene oxide adduct (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 isocyanate groups remained in the system. The polymer thus obtained is referred to as a polymer (W). Polymer (W
) and the ammonium sulfonate salt content are shown in Table 1.

Comparative Example 1 In a flask with a capacity of 21 equipped with a thermometer, a stirrer, and a reflux condenser, 119.2 g of dimethyl terephthalate, 89.4 g of dimethyl isophthalate, 136.5 g of dimethyl 5-sodium sulfoisophthalate, and 14B of ethylene glycol were added. , 2g1 neopentyl glycol 203.
4 g, 0.025 g of zinc acid and 0.025 g of sodium acetate.
003g was charged, and the transesterification reaction was carried out at 180 to 220°C for 3 hours. Then, 376.2 g of sebacic acid
After adding and reacting at 200 to 240°C for 2 hours,
The reaction system was depressurized to 10 mHg over 30 minutes.

This reaction system was further heated to 250" under a pressure of 3 to 10 Hg.
The polycondensation reaction was carried out at a temperature of C for 2 hours. The hydroxyl equivalent of the polyester polyol thus obtained was 4.7.
X 10-' 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, capacity 2 equipped with thermometer, stirrer and 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 in Step 1, and after heating to 60°C, the temperature of the system was raised through the dropping funnel. The poly-varnish mixture obtained above was added dropwise while being careful not to cause any splashing, and after the dropwise addition was completed, the mixture was allowed to react at 60° C. for 4 hours. Next, 4.5 g of 2-hydroxyethyl acrylate was added to this and the mixture was further heated at 60°C.
The mixture was allowed to react for 2 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups 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 Fe20z 80 parts by weight Polymer A 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight 500ml
Magnetic powder of the above composition, cyclohexanone,
Methyl ethyl ketone and 150 ml of 3 mm mm stainless steel pole were added thereto, and the mixture was shaken for 2 hours in a paint conditioner manufactured by Red Devil, USA. Next, a mixed solution of Polymer A, cyclohexanone and methyl ethyl ketone, was added and the mixture was further shaken for 4 hours, after which 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 at a voltage of 160 kilovolts and an absorbed dose of 7 megarads.

Similarly, in the above magnetic paint composition, excluding magnetic powder,
Polymer A was applied to the glass substrate to a dry film thickness of 40 to 60 μm, and after drying overnight at room temperature, the coating film 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.

+11 Filtration test: It was observed whether magnetic paint could be 100% filtered in 1 minute using a filter with 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 meter (manufactured by Murakami Color Research Institute), and when the gloss is 70 to 90, ◎, and 50 to 70. When the value was 0130 to 50, the value was Δ2.If the value 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 of 0, Δ, 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. Evaluations were made as follows: Completely peeled off: ×; Slightly peeled off: Δ; Barely peeled off: O1; No peeling observed at all: ◎.

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

(6) Square ratio (Br/8m): Toei Kogyo KK VS
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 = B
m(7) Breaking strength, elongation, initial modulus: Cut out a strip-shaped test piece from the cured coating film.
c11×40-60 μm), measured at room temperature and at a pulling rate of 50 dragons/min.

(8) Tetrahydrofuran (THF) extraction residue: The cured coating film was subjected to THF Soxhlet extraction for 24 hours,
The percentage 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 1 cm short pieces along with the polyester film of the substrate, and a bending test was performed in which both ends were fixed and bent from the center, then immediately restored to the original state 20 times per second. The presence or absence of peeling or destruction of the clear film from the site 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 r FezO180 superimposed part Polymer 8 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 3 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.

80 parts by weight of Co-containing r -Fetus 17 parts by weight of polymer C (calculated as solid content) 3 parts by weight of trimethylolpropane triacrylate 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 FezO 380 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 -FezOz 80 parts by weight Polymer 2 20 parts by weight (in terms of solid content) 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 T Fe20z 80 parts by weight Polymer F 20 parts by weight (solid content equivalent) Tetrahydrofuran 200 t 1 part Reference Example 7 The 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 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 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 [γ-FezO, + 80 parts by weight Polymer H 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
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 -FezOi 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 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-Fete, 80 parts by weight Polymer L 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 11 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 F13zO+ so parts by weight Polymer M 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 12 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 -Fet03 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 r-pe, o,, so parts by weight Polymer 0 20 parts by weight (calculated as 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-Fe, 0. 80 parts by weight Polymer P 20 parts by weight (calculated as 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 Fe40* 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.

380 parts by weight of Co-containing r-Fez0 20 parts by weight of polymer R (calculated as solid content) 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 Vetos 80 parts by weight Polymer 3 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 -Fetus 80 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-Fe, 0. 80 parts by weight Polymer U 20 parts by weight (calculated as solid content) Mixed solvent 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 -FezOi 80 parts by weight Polymer V 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
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 -FezO* 80 parts by weight Polymer W 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
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 r -FezO 380 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 Table 1 (continued) [Effects of the Invention] The present invention has the following effects.

fil 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 coating material 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 not only has excellent mechanical properties but also excellent adhesion to substrates such as magnetic recording media.

(5) The radiation-curable paint of the present invention has excellent crosslinking properties upon radiation irradiation, so that it can be sufficiently crosslinked and cured with low radiation irradiation vAI, 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 of the present invention, in which magnetic powder is blended with the magnetic paint, has extremely good affinity with the magnetic powder that is blended, and the magnetic powder can be easily dispersed in the paint. , and the blending ratio of magnetic powder in the paint can be greatly improved. Therefore, the radiation curable paint of the present invention is
A magnetic coating material that can be used to produce a magnetic recording medium with excellent magnetic conversion characteristics can be prepared.

(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 the magnetic tape and floppy disk obtained when used as a magnetic coating in the production of magnetic tape and floppy disk, which are a type of magnetic recording medium. Therefore, it is possible to obtain a highly durable magnetic tape with less magnetic powder falling off and less modulation noise.

Agent Patent Attorney Shushi Iwamiya Proceedings 7 City Authorization (Spontaneous) August 5, 1985 1. Indication of the case 1988 Patent Application No. 012828 2. Name of the invention Radiation-curable paint 3. Amendments made Relationship with the patent case Patent applicant address 2-11-24 Tsukiji, Chuo-ku, Tokyo
Name (417) Japan Synthetic Rubber Co., Ltd. 4
, Agent address: 10th floor, Kojimachi Garden Building, 2-3 Kojimachi, Chiyoda-ku, Tokyo 102 (03) 237-191
7 Name Patent Attorney (8430) Comrade Iwamiya,
f, 1, '5, Date of amendment order Voluntary 6, Number of inventions increased by amendment None 7, Subject of amendment
The scope of claims and 8. Contents of amendment ① of the specification and the scope of claims are amended as shown in the attached sheet.

n, (1) The descriptions in the following sections of the specification (before amendment) are amended as shown in (after amendment).

(2) Formula (1)-S on page 13 of the same book is amended as follows.

(3) The formulas in the second and third lines of page 35 of the same book are corrected as follows.

(4) The formula on page 50, line 5 of the same book is corrected as follows.

(5) The formula on page 55, line 11 of the same book is corrected as follows.

(6) The formula on page 61, line 10 of the same book is corrected as follows.

(7) The formula on page 66, line 9 of the same book is corrected as follows.

Shit12Lt13J (8) The formula on page 70, line 3 of the same book is corrected as follows.

(9) Correct the formula in the first line from the bottom of page 72 of the circular as follows.

(10) The formula on page 76, line 9 of the same book is corrected as follows.

(11) The formula on page 79, line 3 of the same book is corrected as follows.

Shi II, LJI,
J(12) The formula in the second line from the bottom of page 81 of the same book is corrected as follows.

503NH,J Claims (after amendment) "1. The following formula (I)' where R is a hydrogen atom or a methyl group; R2 is an alkylene group having 2 to 8 carbon atoms; R3 is an alkylene group having 2 to 8 carbon atoms; It is a divalent hydrocarbon group of 2 to 20, and X is the following formula (1)
-a Here, R4 is an alkylene group having 2 to 4 carbon atoms.

The definition of R1 is the same as above, n is a number from 1 to 50, The unit represented by the following formula (1)-b In the varnish, R6 is an alkylene group having 2 to 4 carbon atoms.

The definition of R1 is the same as above, Rzsq R2t, R2゜ and R1 are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and may be the same or different, m and Q are 1 to 30 is the number of

P is a number from 1 to 5, a unit represented by the following formula (1) or, as necessary.

is a group represented by, q is a number from 1 to 2o, and R
The definition of 1 is the same as above, R, / is a hydrogen atom or a methyl group, and the units represented by form a urethane bond in an arbitrary ratio; Q is the remainder of a tetrahydric alcohol. and Y is a hydroxyl group or a group shown in the above formula (1) other than Y bonded to Q, provided that two or more of Ys are not hydroxyl groups.

A radiation-curable coating material containing a polymer represented by the following as a radiation-curable polymer component.

2. 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 a divalent hydrocarbon group having 2 to 20 carbon atoms, or the following formula ( 1)
-a, the definition of R3 is the same as above, n is a number from 1 to 50, a unit represented by the following formula (1) -b2, and R5 is an alkylene group having 2 to 4 carbon atoms; Yes, R3
The definition of is the same as above, R2?R2? , R2m 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 Q are numbers from 1 to 30, and p is a number from 1 to 5. A unit represented by the following formula (1)-e, where R7 and R, are fullylene groups having 2 or 3 carbon atoms, r and S are numbers from 1 to 2o, and R3 is defined as above. A unit represented by the same formula (1) or, if necessary, a group represented by the following formula (1), where q is a number from 1 to 20.

The definition of R1 is the same as above, and R,/ is a hydrogen atom or a methyl group.

A group in which 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 other than Y bonded to Q in the above formula (I). This is the group shown in However, two or more of Y shall not be hydroxyl groups,

Claims (1)

[Claims] 1. 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 a divalent hydrocarbon group having 2 to 20 carbon atoms; and X is the following: formula(
1)-a ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1)
-a Here, R_4 is an alkylene group having 2 to 4 carbon atoms, the definition of R_3 is the same as above, and n is a number from 1 to 50. A 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 is a hydrogen atom 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, and p is a number from 1 to 5, represented by units, and the following formula (1)-c as necessary ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼・・・・・・・・・
(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. ▼ Here , Z and Z′ are independently ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Or, it is a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where q is a number from 1 to 20, and R_
The definition of 3 is the same as above, R_1' is a hydrogen atom or a methyl group, and the units represented by 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 shown in the above formula (I) other than Y bonded to Q, provided that two or more of Y are not hydroxyl groups. A radiation-curable paint containing a curable polymer component. 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 a divalent hydrocarbon group having 2 to 20 carbon atoms; and X is represented by the following formula (
1)-a ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1)
-a Here, R_4 is an alkylene group having 2 to 4 carbon atoms, the definition of R_3 is the same as above, and n is a number from 1 to 50. A 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 is a hydrogen atom 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, and p is a number from 1 to 5, represented by The unit shown is the following formula (1)-e ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1)
-e Here, R_7 and R_8 are alkylene groups having 2 or 3 carbon atoms, r and s are numbers from 1 to 20, and the definition of R_3 is the same as above. 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, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ 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 ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Or, it is a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where q is a number from 1 to 20, and R_
The definition of 3 is the same as above, R_1' is a hydrogen atom or a methyl group, and the units represented by 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 as shown in the above formula (I). Provided that two or more of Y are not hydroxyl groups. A radiation-curable paint containing a polymer represented by the following as a radiation-curable polymer component.