JPS63189416A - 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 a magnetic powder monopolymer, a solvent, and various additives.

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

JP-A No. 11560-120765 discloses an end 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 molecules.

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 above-mentioned publication, when a polyol is used as a 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 its molecular chain and a double bond at the molecular end. , Goo~100.000
A radiation-curable paint comprising a polyurethane urea resin is described.

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

[Problem that the invention seeks to solve]

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

The reason for this is not clear, but if the present 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 Furthermore, the overall molecular chain structure of the radiation-curable polymer to be used, the distribution of the sulfonic acid metal base within the molecular chain, or the magnetic properties of the polymer and magnetic powder to be used. This is thought to be caused by the viscosity of the paint.

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, that the following formula (I
) R□ is a hydrogen atom or a methyl group; R□ is an alkylene group having 2 to 8 carbon atoms; R3 is a divalent hydrocarbon group having 2 to 20 carbon atoms; Formula (1
)-a Here, R4 is an alkylene group having 2 to 4 carbon atoms or the formula -C
A group represented by H, CH20CH, CH, -, and R
The definition of 3 is the same as above.

n and n' are numbers from 1 to 30, a unit represented by the following formula (I)-b22, R5 is an alkylene group having 2 to 4 carbon atoms, and the definition of R1 is the same as above. , R2, R2'J, R*, 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 numbers from 1 to 30, p is a number from 1 to 5, the units represented by form a urethane bond in an arbitrary ratio, and Q is the remainder of the tetrahydric alcohol. group; 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 a radiation-curable paint containing 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 (I)-a.

(1) A unit represented by -b and the following formula (I)-e
Here, R1 and R are alkylene groups having 2 or 3 carbon atoms, and r and S are numbers from 1 to 20.

The definition of R3 is the same as above.

A radiation-curable coating material containing, as a radiation-curable polymer component, a monopolymer in which the units represented by the formula are groups forming urethane bonds in arbitrary proportions is also provided.

The definition of X in the above formula (I) is (1)-a and (1)
- The above first paint consisting of the units represented by the above, and the definition of X in the above formula (1) is (1)-a, (1)-
In the second paint consisting of units represented by b and (1)-e, the definition of X in the above formula (1) further includes:
It is a group represented by the following formula (1)-c or group 2, where 9 is a number from 1 to 20.

The definition of R8 is the same as above, RL' is a hydrogen atom or a methyl group.

and optionally a unit selected from the group consisting of the following formula (I), where R3, R, and m are the same as defined above, (I)
It may be included as any unit other than the units of -a, (I)-b and (1)-e.

In the above formula (1), R1 is a hydrogen atom or a methyl group.

R2 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. R2 is preferably an alkylene group having 2 to 3 carbon atoms.

R1 is a divalent hydrocarbon group having 2 to 20 carbon atoms.

For example, ethylene group, propylene group, tetramethylene group,
Hexamethylene group, phenylene group, cyclohexylene group, methylenebisphenylene group, methylenebiscyclohexylene group, or a divalent aliphatic or alicyclic group of 02 to C2°, preferably 02 to C2, represented by the structural formula, etc. formula or aromatic group.

X is a unit represented by the above formula (1)-a, a unit represented by (1)-b, and optionally a unit represented by (1)-c and/or a unit represented by (1)-d. Does it represent groups forming urethane bonds in proportion?

Or the unit represented by (1)-a, the unit represented by (1)-b, the unit represented by (1)-e, and optionally (
It represents a group in which the units represented by I)-c and/or the units represented by (I)-d form a urethane bond in any proportion.

In formula (1)-a, R4 is an alkylene group having 2 to 4 carbon atoms, such as ethylene group, 1.2- or 1.3-propylene group, tetramethylene group, butylene group, etc.
The definition of R1 is the same as above, and n and n' are independently numbers from 1 to 30. In formula (1)-b, R9 is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, , 2- or 1,3-propylene group, tetramethylene group, butylene group, etc. or a group represented by the formula -0)l, CHlOCH,C1,-. R2 Lv, R2゜ and Ro are hydrogen atoms or carbon atoms 1
-8 alkyl group, 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. They may be the same or different.

In addition, the definition of R3 is the same as above, m and Q are each independently a number from 1 to 30, p is a number from 1 to 5 and is -, a group represented by U, and q is a number from 1 to 20.

Further, R and / are hydrogen atoms or methyl groups, and the definition of R1 is the same as above.

The definitions of R1, Rs and m in formula (1)-d are as above.

Furthermore, in Formula 1 (I)-e, R7 and R are an alkylene group having 2 or 3 carbon atoms, such as an ethylene group.

1,2- or 1,3-propylene group, etc. Also R3
The definition of is as described above, and r and S are mutually independently numbers from 1 to 20.

In addition, in formula (1), Q is a tetrahydric alcohol residue,
For example, if the tetrahydric alcohol is pentaerythritol, Q is, and the tetrahydric alcohol is N, N, N', N'
-Tetrahydroxypropylethylenediamine, Q is the tetrahydric alcohol, and if the alcohol is a propylene oxide adduct of diglycerin, Q is here, 21.2. ．． 2. The definitions of and z4 are the same as above.

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

The first step is to prepare a diol compound represented by the following general formula (a), where the definitions of R4, n and n' are the same as in the above formula (1)-a, and a diol compound represented by the following general formula (b). compound (hereinafter referred to as specific sulfonic acid compound) where R5, Rxa % R2? -Rzs, 82m,
The definitions of m, 42 and p are the same as in the above formula (t)-b, and if necessary, a compound represented by the following general formula (c) (hereinafter referred to as a specific hydroxyl compound), where R
The definitions of 6 and R1' are the same as in formula (1)-c above.

and, if necessary, a compound represented by the following general formula (d) - Ho-(Rs-0)-H (d) The definitions of R5 and m are the same as in the above formula (1)-d,
is reacted with a diisocyanate compound represented by the following formula (A) OCN-R, -NCO.(A) where the definition of R3 is the same as in the above formula (I). 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) is used. Here, R1, R1, r and S are defined as the above formula (I)-
The same as 〇, can also be used together with -, in which case the above formula (1)
Polymers containing -e units can be formed.

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

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

In the second step, the polymer having isocyanate groups at the molecular ends formed as described above.

The following formula (B) Here, the definitions of 81 and R2 are the same as in the above formula (1).

It is expressed as An acrylic or methacrylic compound having a hydroxyl group is stoichiometrically approximately 17% of the isocyanate group.
By reacting with 2 equivalents, the above formula (
A polymer in which the units of B) are bonded via urethane bonds is produced.

In the third step, the remaining isocyanate groups of the thus obtained polymer are expressed by the following formula (C), where the definition of Q is the same as in the above formula (1).

React with a tetrafunctional alcohol compound represented by
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 copper naphthenate.

cobalt naphthenate, zinc naphthenate, n-lauric acid
It is carried out using a catalyst such as butyltin or triethylamine. These catalysts are preferably used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the total amount of starting materials used in the first step.The reaction temperature is usually 30 to 80°C.

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

Usually, it is 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.

Above 1. The reactions of the second and third steps can be carried out sequentially without isolating the products of each step. When carrying out the reaction in each step, a solvent that does not inhibit the reaction, such as methyl ethyl ketone, cyclohexanone, tetrahydrofuran, toluene, methyl isobutyl ketone, dioxane, etc., can be used as necessary.

The diol compound (a) used in the first step can be produced by reacting caprolactone with a diol such as polyethylene glycol or polypropylene glycol according to a method known per se.

Further, the specific sulfonic acid compound (b) can be produced by reacting the diol compound represented by the general formula (d) with sulfoisophthalic acids. Examples of sulfoisophthalic acids include 1.

5-Ammonium-sulfo-isophthalic acid, 5-diethylammonium-sulfo-isophthalic acid, 5-dipropylammonium-sulfo-isophthalic acid, 5-dibutylammonium-sulfo-isophthalic acid, 5-(2-ethylhexyl)ammonium-sulfo - isophthalic acid,
5-Ammonium-sulfo-isophthalic anhydride, 5-
diethylammonium-sulfo-isophthalic anhydride,
5-dipropylammonium-sulfo-isophthalic anhydride, 5-dibutylammonium-sulfo-isophthalic anhydride, 5-(2-ethylhexyl)ammonium-
Sulfo-isophthalic 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-sulfoisophthalic acid di-lower alkyl ester, 5-(2-ethylhexyl)ammonium-sulfo-
Examples include isophthalic acid di-lower alkyl esters.

Note that examples of the lower alkyl ester include methyl ester, ethyl ester, and the like.

By controlling the number of moles of raw materials during these reactions, the degree of polymerization (P in formula (b)) of addition polymerization by esterification or transesterification can be controlled, and The content of scavenging units can be determined. The reaction temperature for addition polymerization by esterification or transesterification is usually 40 to
The temperature is 220°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, examples of catalysts used in the transesterification reaction include salts of organic carboxylic acids such as sodium acetate, manganese acetate, zinc acetate, and calcium acetate, sodium hydroxide, potassium hydroxide, etc. alkali metal hydroxides, alkali metal alcolades such as sodium methylate, sodium ethylate, alkaline earth metal oxides or hydroxides, organic titanium such as zinc oxide, cadmium oxide, titanium isopropylate, titanium butylade, etc. Compounds etc. can be used.

The specific hydroxyl compound (c) is at least one 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 performing addition polymerization until the epoxy groups in the entire reaction system disappear. Examples of the jepoxy compound here include glycidyl ether of polyhydric phenol obtained by reacting bisphenol A and epichlorohydrin (hereinafter referred to as bisphenol A derivative); Glycidyl ether of the fullylene oxide adduct of polyhydric phenol obtained by reacting the adduct with epichlorohydrin (hereinafter referred to as bisphenol A alkylene oxide derivative); ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene Examples include glycidyl ether of a polyhydric alcohol obtained by reacting a polyhydric alcohol such as glycol or polytetramethylene glycol with epichlorohydrin.

The reaction temperature for the above addition polymerization is usually 20 to 130°C.

As a catalyst for the zero reaction, which is preferably carried out at 40 to 70[deg.] C., tertiary amines, imidazoles, organic acid total salts, Lewis acids, amine complex salts, etc. can be used. Preferably triethanolamine, N, N, N'.

N'-tetramethylethylenediamine, N,N-dimethylpiperazine, N-methylmorpholine, and boron trifluoride etherate can be used. The amount of these catalysts used is 0.01 to 10 parts by weight of 1 reaction raw material.
5 parts by weight.

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

The compound represented by the above formula (e) is bisphenol A
It is ethylene oxide, polyethylene oxide, propylene oxide, or polypropylene oxide adduct, and is a compound that is easily available as a commercial product. The above compounds (a) and (b).

(c), (d), 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, oboro-phenylene diisocyanate, P- Phenyl diisocyanate, 3,3'-dimethyl-4,4
'-diphenylmethane diisocyanate, 4.4'-
Diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, influorone 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 , 2- or 1,3-propylene oxide and other alkylene oxide adducts, 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 formula (1)-b in X in the radiation-curable polymer represented by formula (I) is preferably from o,oos to 90% by weight, particularly preferably from 0.00 to 90% by weight. 0025-70% by weight. 90% by weight
If the temperature exceeds t, the solubility in general-purpose solvents such as toluene, methyl ethyl ketone, and methyl isobutyl ketone, which are commonly used as magnetic paints, tends to decrease. ! The hygroscopicity of the L film increases, which tends to cause a decrease in coating film strength.

The proportion of ammonium sulfonate base and/or alkylammonium sulfonate base in the radiation-curable polymer represented by formula (1) is preferably 1. OX10
-"equivalent/g to 1.3 x 10"" equivalent/g.

Particularly preferably 5 x 10-'' equivalents/g to I x 1
0-"equivalent/g.

The proportion of the component represented by formula (1)-c 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 formulas (1)-a, (1)-d, and (1)-e to X in the entire radiation-curable polymer represented by formula (1) is 4.9995. ~99.
5% by weight is preferred, and within this range (1)-a, (I
)-d and (1)-e can be arbitrarily determined.

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

In the present invention, the mechanical properties of the coating film obtained by radiation curing the radiation curable polymer represented by formula (1) vary depending on the radiation curing conditions, etc., but are usually 10 at an elastic modulus of 1.
kg/am2 or more, breaking strength of 90 kg/C♂ or more, and breaking elongation of 7% or more.

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

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

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

! R12 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an alkoxy group having 1 to 4 carbon atoms, and may be the same or different, and Y is a group having an acrylic or vinyl double bond. ), t is a number from 200 to 800, and U is 10
~ 200, V is a number from 0 to 200, W is a number from 3 to 100, m is a number from 0 to 50] (3) Parent tree group, for example -
503M', -0SO,M', -COOM', (in the formula,
A' is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom or a hydrocarbon group.

Polymers such as polyester, polyether, polyurethane, epoxy, polybutadiene, polyamide, polycarbonate, etc., having at least one (La is a hydrocarbon group) and two or more acrylic double bonds.

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

(In the formula, R14 and R□5 are aliphatic, alicyclic, or aromatic hydrocarbon groups, or derivative residues thereof.

Ro may contain a -〇- bond, and Rts is -〇-
1-S- or -SO3- bond may be included<-Rzs is a hydrogen atom or a methyl group, y represents an integer of 1 to 20) (5) Phthalic acid, isophthalic acid, terephthalic acid, succinic acid, Saturated polybasic acids such as adipic acid and sebacic acid and ethylene glycol, diethylene glycol, glycerin, trimethylolpropane, 1,2-propylene glycol, 1,3-butanediol, dipropylene glycol, 1,4-butanediol, 1° Saturated polyesters obtained by ester bonding with polyhydric alcohols such as 6-hexanediol, pentaerythritol, sorbitol, glycerin, neopentyl glycol, and 1,4-cyclohexane dimetatool, or these polyesters modified with So, Na, etc. A polymer that has been given radiation curability using the method described below.

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

(7) An epoxy polymer obtained by reacting bisphenol A or brominated bisphenol A with epichlorohydrin or methylepichlorohydrin; a polymer in which radiation curability is imparted to a phenoxy resin 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, vinyl chloride-vinyl acetate-maleic acid copolymer, vinyl chloride-vinyl propionate-vinyl alcohol copolymer A polymer that has been given radiation curability by combining with other methods as described below.

(12) Polyether ester polymer, polyvinylpyrrolidone polymer, polyvinylpyrrolidone polymer 'Fin copolymer, polyamide polymer, polyimide polymer, phenol polymer, spiroacetal polymer, acrylic ester and methacrylic ester containing hydroxyl group A polymer obtained by imparting radiation curability to an acrylic polymer or the like containing at least one of the following as a polymerization component by the method described later.

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

(1) One molecule of the above-mentioned thermoplastic polymer or these prepolymers having a hydroxyl group in the molecule is reacted with an isocyanate group of one or more molecules of a polyisocyanate compound, and then a functional group that reacts with the incyanate group and radiation curing are applied. react with one or more molecules of a monomer having a sexually unsaturated double bond. Monomers having a functional group that reacts with an isocyanate group and a radiation-curable unsaturated double bond include hydroxyl groups such as 2-hydroxyethyl ester, 2-hydroxypropyl ester, or 2-hydroxyoctyl ester of acrylic acid or methacrylic acid. Ester monomers having: monomers having active hydrogen that reacts with isocyanate groups such as acrylamide, methacrylamide, and N-methylol acrylamide and containing acrylic double bonds; allyl alcohol, maleic acid polyhydric Alcohol ester compound.

Examples include monomers containing unsaturated double bonds that have active hydrogen that reacts with isocyanate groups, such as mono- or diglycerides of long-chain fatty acids that have unsaturated double bonds, and that have radiation curability.

(II) One molecule of the above thermoplastic polymer having a hydroxyl group in the molecule or one of these prepolymers is reacted with an acid or acid halide having one or more radiation-curable unsaturated double bonds to form an ester double bond. will be introduced. As the acid or acid palite having a radiation-curable unsaturated double bond,
Acrylic acid, methacrylic acid, methacrylic acid chloride,
Examples include acrylic acid chloride, acrylic acid bromide, and methacrylic acid bromide.

(m) 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 (1) can be used in combination, and the amount used is usually determined by one 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 a radiation-curable unsaturated bond 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 polymer 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,
Ethylene glycol monoethyl ether.

Examples include glycol ethers such as dioxane, and these solvents may be used alone or as a mixture. The amount of these solvents used is usually 200 to 25 parts by weight per 100 parts by weight of the radiation-curable polymer represented by formula (I).
00! ! It is a quantity part.

In preparing the radiation-curable paint of the present invention, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, lylunic acid, stearolic acid, lecithin acid, , a dispersant such as an organic titanium compound, an organic silane compound;
Lubricants such as molybdenum disulfide, graphite, silicone oil; Abrasives such as aluminum oxide, chromium oxide, silicon oxide; Conductive fine powder such as carbon black graft polymer; Natural surfactants such as saponin; Alkylene oxide type, glycerin Cationic surfactants such as higher alkylamines, quaternary ammonium salts, pyridine, phosphoniums, and sulfoniums; Carboxylic acids, sulfonic acids, and phosphoric acids.

Anionic surfactants containing acidic groups such as sulfate ester groups and phosphate ester groups; amino acids, aminosulfonic acids,
Surface active agents such as sulfuric acid or phosphoric acid esters of amino alcohols; antistatic agents such as carbon black; phosphoric acid, sulfamide, pyridine.

Rust inhibitors such as dicyclohexylamine nitrite and cyclohexylammonium 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 acid or methacrylic acid polymer or co'
□ Polymer, acrylic ester or methacrylic ester polymer or copolymer, polyimide resin, 1.
3-pentadiene resin, epoxidized 1,3-pentadiene resin, hydroxylated 1,3-pentadiene resin.

Acrylonitrile polymer or copolymer, acrylic ester-acrylonitrile copolymer, methacrylic ester-acrylonitrile copolymer, phenol-formalin resin, phenol-furfural resin, xylene, formalin resin, urea resin, melamine resin, alkyd resin , acrylonitrile-butadiene styrene copolymer, etc. are blended.

When using the radiation-curable paint of the present invention as a magnetic paint, the magnetic powder to be mixed includes γ-Fe, 0. .

Fe50 γ-Fe, O, and Fe, iron oxide in the oxidation state intermediate between 04, Co-containing y-Fe, O,, Co-containing F
eaO*, Co-containing γ-Fe, O, and Fe, 0
Iron oxide in an oxidation state intermediate to No. 4, iron oxide further containing a metal element such as a transition metal element, iron oxide with a coating layer mainly composed of cobalt oxide or hydroxide, By reducing the surface of CrO□, Cry, Cr,
Examples include metals such as Fe, Co, and Ni, alloys thereof, and metals containing metal elements such as typical metal elements or transition metal elements.

These magnetic powders are usually used in an amount of 200 to 700 parts by weight per 100 parts by weight of the radiation-curable polymer represented by formula (I).

The material to be coated (substrate: base film) when producing a magnetic recording medium using the radiation-curable paint of the present invention as a magnetic paint includes, for example, polyester such as polyethylene terephthalate; polyolefin such as polypropylene; and cellulose triacetate.

Examples include cellulose derivatives such as cellulose diacetate; polycarbonate; polyvinyl chloride; polyimide; non-magnetic metals such as aluminum and copper; and paper.

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

〔Example〕

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

In addition, in the following examples, 1 molecular weight is a value determined by an osmotic pressure method. Also, the structure of the compound.

These are the results of analysis by infrared absorption spectrum and nuclear magnetic resonance (NMR) spectrum.

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

Example I (1) Volume 11z 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) 423g and sodium acetate 1.0
g was added thereto, and the mixture was reacted at 130°C for 6 hours. When the obtained reaction product was analyzed by NMR spectrum, it was found that 5
Since no peak due to the proton of the methyl group of -ammonium-sulfo-isophthalic acid dimethyl ester was detected, it was determined that the transesterification rate had progressed to approximately 100%. Furthermore, it was confirmed that unreacted polyethylene glycol was present. Further, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMR spectrum, the reaction product was a mixture of a compound represented by the following structural formula and polyethylene glycol, (wherein R111 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 (1).

The hydroxyl equivalent of the specific sulfonic acid compound (1) is 3.29X
It was 10-3 equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
165.4 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to the flask and heated to 60 °C, and then the system temperature did not rise through the dropping funnel. While paying attention to
255.0 g of polycaprolactone diol (Plaxel 205AL manufactured by Daicel Corporation), 38.4 g of acrylic acid adduct of bisphenol A propylene oxide derivative (epoxy ester 3002A manufactured by Kyoeisha Yushi, hereinafter referred to as specified hydroxyl compound (1)), specified sulfonic acid compound A homogeneous mixture of 31.3 g of (I) 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.

Then, to this, 2-hydroxyethyl acrylate-1-6
, 0g was added, and the mixture was further reacted at 60°C for 2 hours.
Add 3.8 g of propylene oxide adduct of ethylenediamine (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) and heat at 60°C.
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 (A).

Table 1 shows the molecular weight and ammonium sulfonate content of m-coalescence (A).

Example 2 (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 fJ200) 423 g.

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

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

Furthermore, as a result of fractionating the reaction product using liquid chroma 1-gram and analyzing it by NMR spectrum, the reaction product was a mixture of a compound having the following structural formula and polyethylene glycol, and 03NH4 (formula (R19 is a residue of polyethylene glycol (average molecular weight 200) with both terminal OH groups removed.) The ratio of the compound shown in the above structure to unreacted polyethylene glycol was 34:66 (weight ratio).

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

What is the hydroxyl equivalent of the specific sulfonic acid compound (n)? , 66X
It was 10-' equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
185.9 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 500 g of cyclohexanone were added to the flask, heated to 60°C, and then heated to 60°C, taking care not to raise the temperature of the system through the dropping funnel. A mixture of 260.2 g of polycaprolactone diol (Plaxel 205AL manufactured by Daicel Corporation) and 31.0 g of specific sulfonic acid compound (II) dissolved in 250 g of cyclohexanone was added dropwise, and after the completion of the dropping, 6
The reaction was carried out at 0°C for 4 hours.

Then, to this, 2-hydroxyethyl acrylate 13
．． After adding 7 g and reacting at 60°C for 2 hours,
8.8 g of propylene oxide adduct of ethylenediamine (Adeka Quadrol manufactured by Jiryuka Co., Ltd.) was added and reacted at 60° C. for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no 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 92.8 g of 2.4-) luene diisocyanate was placed in a 21 capacity flask equipped with a thermometer, stirrer and reflux condenser.
, 0.5 g of dibutyltin dilaurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added.
After heating to 0℃, add polycaprolactone diol (
Plaxel 212 (manufactured by Daicel) 337.0 g, polyoxyethylene bisphenol A ether (DA-350F manufactured by NOF Corporation) 28.3 g, specific sulfonic acid compound (
1) A homogeneous mixture of 10.8 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 2-hydroxyethyl acrylate 18
．． After adding 7 g and reacting at 60°C for 2 hours,
20.2 g of propylene oxide adduct of diglycerin (DG500 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 (C).

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

Example 4 156.2 g of isophorone diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to a flask with a capacity of 21 equipped with a thermometer, a stirrer, and a reflux condenser at 60°C.
183.9 g of polycaprolactone diol (Plaxel 212 manufactured by Daicel Corporation), polyoxyethylene bisphenol A ether (DA manufactured by NOF Corporation), while being careful not to raise the temperature of the system through the dropping funnel.
-350F) 86.3g, specific sulfonic acid compound (I[
) and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added dropwise, and after the dropwise addition was completed, the mixture was reacted at 60° C. for 4 hours.

Then, to this, 2-hydroxypropyl methacrylate)
After adding 24.2 g and reacting at 60°C for 2 hours, a propylene oxide adduct of ethylenediamine (
Add 12.3 g of Adeka Quadrol made by Jiryuka and add 60
The reaction was carried out at ℃ 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 (D).

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

Example 5 (1) A container equipped with a thermometer, a stirrer and a reflux condenser
46.8 g of 5-dibutylammonium-sulfo-isophthalic acid dimethyl ester 1 Polytetramethylene glycol (manufactured by DuPont, Teratane 650) 4
53.2g, zinc acetate 1.0g and sodium acetate 1.
0g was added and reacted 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-dibutylammonium-sulfo-isophthalic acid dimethyl ester was detected, it was determined that the transesterification rate had progressed to approximately 100%. Furthermore, the presence of unreacted polytetramethylene glycol was also confirmed. In addition, the reaction products are fractionated by liquid chromatography and analyzed by NMR.
As a result of spectral analysis, the reaction product was a mixture of a compound represented by the following structural formula and polytetramethylene glycol, 5OJHz (C4H9)2 (wherein R2° is 0 at both ends of polytetramethylene glycol). (N is 1.4.) The ratio of the compound shown in the above structure to unreacted polytetramethylene glycol was 34:66 (weight ratio). These mixtures are referred to as specific sulfonic acid compounds (III). The hydroxyl equivalent of the specific sulfonic acid compound (III) is 2. o2X
It was 1o-3 equivalent/g.

(2) Volume 121 equipped with a thermometer, stirrer and reflux condenser
2,4-toluene diisocyanate 121 in a flask of
．． After adding 1 g of dibutyltin dilaurate, 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 polycaprolactone diol (Plaxel 205AL manufactured by Daicel Corporation) while being careful not to raise the temperature of the system from the dropping funnel. ))
143.8 g, polyoxyethylene bisphenol A
A homogeneous mixture of 5.9 g of ether (DA-350F manufactured by NOF Corporation), 202.4 g of specific hydroxyl compound (I), 10.0 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 reaction was carried out at 60° C. for 4 hours. Then 2-hydroxypropyl methacrylate)
After adding 9.8 g of the mixture and further reacting at 60°C for 2 hours, 8.5 g of a propylene oxide adduct of diglycerin (DG-500 manufactured by Jiryuka) 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 (E).

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

Example 6 132.0 g of isophorone diisocyanate, 0.5 g of dibutyltin dilaurate, and 500 g of tetrahydrofuran were added to a flask with a capacity of 21 equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 60°C. While being careful not to raise the temperature, add polycaprolactone diol (Plaxel 205AL manufactured by Daicel).
)) 7.6g1 Polyoxypropylene bisphenol A ether (DB-900 manufactured by NOF Corporation) 87.1g
A mixture of 8.24 g of specific hydroxyl compound (I) and 253.0 g of specific sulfonic acid compound (1) dissolved and mixed in 250 g of tetrahydrofuran was added dropwise, and after completion of the dropwise addition, the mixture was reacted at 60° C. for 4 hours. Next, 8.0 g of 2-hydroxypropyl methacrylate was added to this, and after reacting at 60°C for 2 hours, a propylene oxide adduct of ethylenediamine (Adeka Quadrol manufactured by Jiryuka Co., Ltd.) 4.
1 g was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system.

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

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

Example 7 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 124.3 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibutyltin dilaurate were added.
After adding 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, add polycaprolactone diol (Daicel Plaxel 21) from the dropping funnel while being careful not to raise the temperature of the system.
2) 189.3g, methacrylic acid adduct of ethylene glycol diglycidyl ether derivative (epoxy ester 40EMi manufactured by Kyoeisha Yushi Co., Ltd., hereinafter referred to as specific hydroxyl compound (n)), 23.3g, specific sulfonic acid compound (I
A uniform mixture of 18.4 g of I) and 250 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, 3.9 g of 2-hydroxyethyl acrylate was added to this, and the reaction was further carried out at 60°C for 2 hours.
) was added thereto, 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 (G).

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

Example 8 In a 21 capacity flask equipped with a thermometer, stirrer and reflux condenser, 80.8 g of 2.4-1-luene diisocyanate was added.
g, 0.5 g of dibutyltin dilaurate, and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added and heated to 60°C. 212) 186.
6g, specific hydroxyl compound (II) 5.7g, specific sulfonic acid compound (III) 246.2g, polyoxypropylene and suphenol A ether (NOF DB)
A homogeneous mixture of 14.9 g of -900) 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.

Then, to this, 2-hydroxyethyl acrylate) 3
．． After adding 8 g of the mixture and reacting at 60°C for 2 hours, 2.4 g of an ethylenediamine propylene oxide adduct (Adeka Quadrol manufactured by Jiryuka Co., Ltd.) was added and the reaction was carried out at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system.

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

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

Example 9 (1) 105.9 g of acrylic acid and 394.1 g of polypropylene glycol #400 diglycidyl ether (Evolite 400p manufactured by Kyoeisha Yushi Co., Ltd.) were added to a flask with a capacity of 1ρ equipped with a thermometer, a stirrer, and a reflux condenser. After reacting at 60° C. for 6 hours, it was confirmed by infrared absorption spectrum that there was no absorption of epoxy rings in the reaction product. This reaction product is designated as a specific hydroxyl compound (I[I).

Main structure of specific hydroxyl compound: "HCGHZ CH2=CHCOCHz C[l-Yamabei"H (2) Into a 2β flask equipped with a thermometer, stirrer and reflux condenser, 4,4'-dicyclohexylmethane diisocyanate 181. 9 g, dibutyltin dilaurate 0
．． After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, add polycaprolactone diol (Daicel Plaxel 2) while being careful not to raise the temperature of the system from the dropping funnel.
05AL), 241.4g, specific hydroxyl compound (
I[[) 43.3g, specific sulfonic acid compound (II)
A uniform mixture of 27.4 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, 3.6 g of 2-hydroxypropyl methacrylate was added to this, and after further reacting at 60°C for 2 hours, 1.8 g of propylene oxide adduct of ethylenediamine (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 (J).

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

Example 1O (11 volume fil equipped with thermometer, stirrer and reflux condenser)
5-(2-ethylhexylammonium)-sulfo-isophthalic acid dimethyl ester 167.
5g, polyethylene glycol (average molecular weight 400) 3
32.5g, sodium acetate 1.0g and zinc 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-(2-ethylhexyl)ammonium-sulfo-isophthalic acid dimethyl ester was detected, it was determined that the transesterification reaction had proceeded approximately 100%. Furthermore, it was confirmed that there was no unreacted polyethylene glycol.

Further, as a result of detailed analysis of the reaction product by NMR spectrum, it was found that the reaction product was a compound having the following structure.

GHzCHGHzC)lzclhcH:+CH,CH2 (wherein, RZI is polyethylene glycol (average molecular 1
The above compound (which is the residue obtained by removing both terminal OH groups of 400) is designated as the specific sulfonic acid compound (IV).

The hydroxyl equivalent of the specific sulfonic acid compound (IV) is 1.7
5X10-'Tru! /g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
163.8 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 500 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to the flask, heated to 60 °C, and then heated to 60 °C, taking care not to raise the temperature of the system through the dropping funnel. While paying attention to
A uniform mixture of 32.2 g of V) and 250 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, 7.3 g of 2-hydroxyethyl acrylate was added and the mixture was further reacted 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 2 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 and 2-ethylhexylammonium sulfonic acid salt content of the polymer (L).

Example 11 (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, 466 g of polytetramethylene glycol (average molecular weight 1000), 1 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, a peak due to the proton of the methyl group of 5-ammonium-sulfo-isophthalic acid dimethyl ester was not detected, indicating that the transesterification rate was approximately 100.
It was determined that the disease had progressed by %. Furthermore, the presence of unreacted polytetramethylene 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 was a mixture of a compound represented by the following structural formula and polytetramethylene glycol. In the formula, Rtz is a residue of polytetramethylene glycol (average molecular weight: 11,000) excluding @OH groups at both ends,
n is 2.0. ) The ratio of the compound shown in the above structure to unreacted polytetramethylene gelicol 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-
"Equivalent weight/g.

(2) Volume Wk2 equipped with a thermometer, stirrer and reflux condenser
177.7 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added to flask No. 1, and after heating to 60°C, the system was While being careful not to raise the temperature, 248.6 g of polycaprolactone ludiol (Plaxel 205AL manufactured by Daicel), 44.9 g of specific hydroxyl compound (I), and 0.0 g of specific sulfonic acid compound (v) were added.
A uniform mixture of 23 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 17.5 g of hydroxyethyl acrylate and further reacting at 60°C for 2 hours, 11.1 g of an ethylenediamine propylene oxide adduct (Adeka Quadrol manufactured by Jiryuka Co., Ltd.) was added and reacting at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (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 1 i equipped with a thermometer, a stirrer, and a reflux condenser, 31.5 g of 5-dibutylammonium-sulfo-isophthalic acid dimethyl ester and polytetramethylene glycol (average molecular weight 2000) were added.
8.5 g, zinc acetate 1.0 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-dibutylammonium-sulfo-isophthalic acid dimethyl ester was detected, it was determined that the transesterification rate had progressed to approximately 100%. Furthermore, the presence of unreacted polytetramethylene glycol was also confirmed. In addition, the reaction product was fractionated using liquid chromatography and analyzed using NMR spectroscopy. As a result, the reaction product was a mixture of a compound represented by the following structural formula and polytetramethylene glycol, and 5O3NH! (C4119)
z (wherein, Ro is a residue excluding the O1 group at both ends of polytetramethylene glycol (average molecular weight: 12,000),
n is 3.0. ) The ratio of the compound shown in the above structure to unreacted polytetramethylene glycol was 47:53 (weight ratio), and the mixture thereof was designated as a specific sulfonic acid compound (Vl). The hydroxyl equivalent of the specific sulfonic acid compound (VI) is 6.30XI
O-' equivalent/g.

(2) Volume 1 equipped with a thermometer, stirrer and reflux condenser
After adding 152.8 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone to a flask No. 121 and heating it to 60°C,
From the dropping funnel, while being careful not to raise the temperature of the system, add 177.4 g of polycaprolactone diol (Plaxel 212, manufactured by Daicel Corporation) and 4 g of polyoxyethylene bisphenol A ether (DA-350F, manufactured by NOF Corporation).
8.0g, specific hydroxyl compound (■) 81.4g,
A homogeneous mixture of 25.3 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, 8.5 g of 2-hydroxypropyl methacrylate was added to this, and after further reacting at 60°C for 2 hours, 7.4 g of propylene oxide adduct of diglycerin (DG-500 manufactured by Jiryuka Co., Ltd.) was added to the mixture. The reaction was carried out at ℃ for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer obtained in this way is a polymer (N
). Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of the polymer (N).

Example 13 (1) Capacity 11 equipped with thermometer, stirrer and reflux condenser
27.5 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester, 472.5 g of polyethylene glycol (average molecular weight 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 mixture was allowed to react 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, and 0JHa (in the formula, R24 is polyethylene glycol (average molecule 1
1000) with both terminal OH groups removed, n is 1
．． It is 0. ) The ratio of the compound shown in the above structure to unreacted polyethylene glycol was 43:57 (weight ratio).

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

The hydroxyl equivalent of the specific sulfonic acid compound (■) is 1.53X
It was 10-3 equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
2.4-Toluene diisocyanate 1 in a flask of
29.7g, dibutyltin dilaurate 0.5g and mixed solvent of cyclohexanone and methyl ethyl ketone 550
318.2 g of polycaprolactone diol whose main structure is represented by
A uniform mixture of 22.4 g of a specific hydroxyl compound (I [[), 0.6 g of a specific sulfonic acid compound (■), and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone] was added dropwise, and after the completion of the dropwise addition, it was heated at 60°C for 4 hours. Made it react. Next, 19.3 g of 2-hydroxybrobyl methacrylate was added to this, and the mixture was further reacted at 60°C for 2 hours, and then 9.8 g of an ethylenediamine propylene oxide adduct (Adeka Quadrol, manufactured by Jiryuka Co., Ltd.) was added and the mixture was heated to 60°C. The reaction was carried out at ℃ 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 ammonium sulfonate content of Polymer (0).

Example 14 (1) In a flask with a capacity of 11 equipped with a thermometer, a stirrer, and a reflux condenser, 167 g of 5-(2-ethylhexylammonium)-sulboisophthalic acid dimethyl ester was added.
．． 5g, polypropylene glycol (average molecular weight 400
), 1.0 g of zinc acetate, and 1.0 g of sodium acetate were added, and the mixture was reacted at 130° C. for 6 hours. When the obtained reaction product was analyzed by NMR spectrum,
Since no peak due to the proton of the methyl group of 5-(2-ethylhexylammonium)-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. Further, as a result of fractionating the reaction product by liquid chromatography and analyzing it by NMR spectrum, the reaction product was a mixture of a compound having the following structural formula and polypropylene glycol, CIIzC1lCHzCHzCHzCHzCH2CHf
f (wherein, Rzs is a residue of polypropylene glycol (average molecular weight 400) excluding both terminal OH groups, and n is 4
．． It is 5. ) The ratio of the compound shown in the above structure to unreacted polypropylene glycol was 70:30 (weight ratio).

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

The hydroxyl equivalent of the specific sulfonic acid compound (■) is 1.76x
It was lO bow equivalent/g.

(2) Capacity 21 equipped with thermometer, stirrer and reflux condenser
2.4-1-ruene diisocyanate 1 in a flask of
64.8g, dibutyltin dilaurate 0.5g and mixed solvent of cyclohexanone and methyl ethyl ketone 550
After adding 42.4 g of polycaprolactone ludiol, whose main structure is represented by the formula, from the dropping funnel while being careful not to raise the temperature of the system.
1 Polyoxyethylene bisphenol A ether (DA-350F manufactured by NOF Corporation) 43.0 g, acrylic acid adduct of propylene glycol diglycidyl ether derivative (70PA manufactured by Kyoeisha Yushi Co., Ltd.: hereinafter referred to as specific hydroxyl compound (rV)> 222 A homogeneous mixture of .7 g, 0.30 g of a specific sulfonic acid compound (■), 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. Hydroxypropyl methacrylate 14
．． After adding 5g and further reacting at 60°C for 2 hours,
12.5 g of a propylene oxide adduct of diglycidyl (DC-500 manufactured by Shikkeika 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 (P). Polymer (
The molecular weight and sulfonic acid 2-ethylhexylammonium salt content of P) are shown in Table 1.

Example 15 (1) Volume 1 equipped with a thermometer, stirrer and reflux condenser
33.9 g of 5-ammonium-sulfo-isophthalic acid dimethyl ester, 466.1 g of polypropylene glycol (average molecular weight: 311,000), and 1.0 g of sodium acetate were added to a No. 11 flask, 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, and 5OJL (wherein R2b is polypropylene glycol (average molecular weight 1000) excluding both terminal OH groups). (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 designated as specific sulfonic acid compounds (IX). The hydroxyl equivalent of the specific sulfonic acid compound (IX) is 1.4
It was 2×10 −3 equivalents/g.

(2) Container 11 equipped with a thermometer, stirrer and reflux cooling and cooling pipe
177.9 g of methacrylic acid and polyethylene glycol #200 diglycidyl ether (
Manufactured by Kyoeisha Yushi Co., Ltd., Nivolai l-200E) 320, 1
After the reaction was carried out at 60° C. for 6 hours, it was confirmed by infrared absorption spectrum that there was no absorption of epoxy rings in the reaction product. This reaction product is designated as a specific hydroxyl compound (V). The main structure of the specific hydroxyl compound is as follows.

OH3 ■ Cabinet CH.

! ■ OH (3 N) Isophorone diisocyanate (100 g) was added to a 21-volume flask equipped with a thermometer, stirrer, and reflux condenser.
．． After adding 5 g of dibutyltin dilaurate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, polycaprolactone whose main structure is represented by the formula was added through the dropping funnel while being careful not to raise the temperature of the system. Diol 278. 5
g1 Polyoxyethylene bisphenol A ether (DA-400F manufactured by NOF Corporation) 1 13.3 g, specific hydroxyl compound (V) 0.33 g, specific sulfonic acid compound (IX) 2.1 g, mixed solvent of cyclohexanone and methyl ethyl ketone 200 g A uniform mixture of these was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. This is then added with 3. 2-hydroxyethyl acrylate. 2g
After further reaction at 60°C for 2 hours, 2.1 g of an ethylenediamine propylene oxide adduct (Adeka Quadrol, manufactured by Jiryuka 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 (Q). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (Q).

Example 16 In a flask with a capacity of 21 equipped with a temperature needle, a stirrer, and a reflux inlet tube, 6 g of isophorone diisocyanate 162, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were added at 60°C.
155.7 g of polycaprolactone diol (Plaxel 205AL manufactured by Daicel Corporation) and polyoxyethylene bisphenol A ether (DA-350F manufactured by NOF Corporation) were added through the dropping funnel while being careful not to raise the temperature of the system. ) 97.7g, specific hydroxyl compound (I) 70.5g, specific sulfonic acid compound (I) 6
．． A uniform mixture of 4 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-
Hydroxyethyl acrylate 4. After adding 4 g of the mixture and reacting at 60°C for 2 hours, 2.8 g of an ethylenediamine propylene oxide adduct (ADEKA QUODOLOL manufactured by Jiryuka 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 (R).

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

Example 17 In a flask with a capacity of 21 equipped with a thermometer, a stirrer, and a reflux condenser, 171.7 g of 4,4'-diphenylmethane 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,
While being careful not to raise the temperature of the system, add polycaprolactone diol (Daicel Plaxel 212) 10
9.6g, polyoxyethylene bisphenol A ether (DA-350F manufactured by NOF Corporation) 146.2g, polyethylene glycol (PEG #400 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
) 23.2g, specific hydroxyl compound (1) 34.8
g, 0.36 g of specific sulfonic acid compound (I) and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone
A uniform mixture of these was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours.

This was then added with 2-hydroxyethyl acrylate 6,
After adding 8 g and further reacting at 60°C for 2 hours,
7.3 g of propylene oxide adduct of diglycerin (DG-500, manufactured by Jiryuka 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 (S). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (S).

Example 18 130.0 g of 4,4'-diphenylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and a mixed solvent of cyclohexanone and methyl ethyl ketone were placed in a 21-volume flask equipped with a thermometer, stirrer, and reflux condenser.
After adding 50g and heating to 60℃, from the dropping funnel,
Polycaprolactone diol whose main structure is represented by the formula 345.46, taking care not to increase the temperature of the system.
, polyoxyethylene glycol (P manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
EG#200) 4.1 g, specific sulfonic acid compound (I
A uniform mixture of 0.64 g of I) 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 added with 2-hydroxypropyl methacrylate 13.2
After further reacting at 60°C for 2 hours, 6.7g 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 Polymer (T). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (T).

Example 19 In a 21 volume flask equipped with a thermometer, stirrer and reflux condenser, 142.1 g of 4,4'-dicyclohexylmethane diisocyanate and 0.5 g of dibutyltin dilaurate were added.
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, 160.1 g of polycaprolactone diol whose main structure is represented by 2 was added from the dropping funnel while being careful not to raise the temperature of the system.
, polyoxypropylene bisphenol A ether (NOF DB-400) 80.4g, specific hydroxy compound (II) 27.8g, specific sulfonic acid compound (V)
A uniform mixture of 74.4 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 to this,
After adding 9.3 g of 2-hydroxyethyl acrylate and further reacting at 60°C for 2 hours, 5.9 g of an ethylenediamine propylene oxide adduct (ADEKA QODOROL, manufactured by Jiryuka Co., Ltd.) was added and reacted at 60°C for 4 hours. Ta.

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

The polymer thus obtained is referred to as a polymer (U).

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

Example 20 In a 2β capacity flask equipped with a thermometer, stirrer and reflux condenser, 83.3 g of isophorone diisocyanate,
Add 0.5 g of dibutyltin dilaurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone to 60
After heating to ℃, 226.6 g of polycaprolactone diol whose main structure is represented by the formula was added from the dropping funnel while being careful not to raise the temperature of the system.
2 polyoxypropylene and suphenol Aether)? (
A uniform mixture of 168.1 g of NOF DB-900), 2.0 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 dropwise addition was completed, the mixture was allowed to react at 60°C for 4 hours. Ta.

Next, 0.8 g of 2-hydroxypropyl methacrylate I was added to this, and the mixture was further reacted at 60°C for 2 hours, and then 9.3 g of propylene oxide adduct of diglycerin (DC-500 manufactured by Jiryuka Co., Ltd.) was added to the mixture. The reaction was carried out at ℃ for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (V). Table 1 shows the molecular weight and sulfonic acid dibutylammonium salt content of the polymer (V).

Example 21 In a 21 capacity flask equipped with a temperature needle, stirrer and reflux condenser, 132.9 g of 2,4-toluene diisocyanate was added.
After adding 0.5 g of dibutyltin dilaurate and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60°C, add polycaprolactone diol (Plaxel 205AL manufactured by Daicel) from the dropping funnel while being careful not to raise the temperature of the system. )258.4g
A homogeneous mixture of 92.4 g of polyoxypropylene bisphenol DA-400), 5.2 g of a specific sulfonic acid compound (■), 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 heated to 60°C. The mixture was allowed to react for 4 hours. This is then added to 2-hydroxyethyl acrylate 6, 1
After further reacting at 60° C. for 2 hours, 4.3 g of an ethylenediamine propylene oxide adduct (ADEKA QUODOLOL 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). Table 1 shows the molecular weight and ammonium sulfonate content of the polymer (W).

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, 36.5 g of dimethyl 5-sodium sulfoisophthalate, and 148 g of ethylene glycol were added. 2g, neopentyl glycol 20 3.
4 g and 0.025 g of zinc acetate and 0.003 g of sodium acetate as catalysts,
The transesterification reaction was carried out at ℃ for 3 hours. Then sebacic acid 3 7 6. Add 2 g to 200-24
After reacting at 0°C for 2 hours, the reaction system was depressurized to IQmmHg over 30 minutes.

This reaction system was further heated at 250°C under a pressure of 3 to lonHg.
The polycondensation reaction was carried out at a temperature of 2 hours. The hydroxyl equivalent of the polyester polyol thus obtained is 4.7X
It was 1t/g per 10-'. 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.
1 flask, 33.8 g of 4,4'-dicyclohexylmethane diisocyanate, dibutyltin dilaure-1
-0.5 g and 550 g of a mixed solvent of cyclohexanone and methyl ketone were added and heated to 60°C, and then 466.2 g of the polyester polyol obtained above and cyclohexanone were added while being careful not to raise the temperature of the system from the dropping funnel. and methyl ethyl ketone mixed solvent 20
Drop a uniform mixture of 0g, and after dropping, add 60g
The reaction was allowed to proceed for 4 hours at °C. Next, 4.5 g of 2-hydroxyethyl acrylate was added to this, and the mixture was further reacted at 60°C for 2 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no 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 rFe2038o parts by weight Polymer A 20 parts by weight (in terms of solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight of the magnetic powder in the above composition, cyclohexanone, methyl ethyl ketone, and 3 dragon diameter stainless steel poles (approximately 150 m
j7) and 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 coated on a glass plate to a dry film thickness of 40 to 60 μm, and after drying overnight at room temperature, the coating was cured at an accelerated voltage of 160 kilovolts and an absorbed dose of 5 Megaland.

For the magnetic paint, the following test T1) 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.

(11yp overstretch) It was observed whether 100% of the magnetic paint passed through a filter having an average pore diameter of 2 μm in 1 minute.

(2) Gloss: Measure the gloss of the cured magnetic coating film at a reflection angle of 45° using a digital gloss meter (Murakami Color Technology Research Division), and when the gloss is 70 to 90, ◎, and 50 to 70. ○, cases of 30 to 50 were rated Δ, and cases of 30 or less were rated ×.

(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 ○, △, and ×.

(4) Adhesion test: Adhesive tape is pasted on the surface of the cured magnetic coating, and after it is evenly adhered to the entire surface, the condition is observed when it is instantly peeled off. The evaluation was rated as × when the film was completely peeled off, △ when it was slightly peeled off, ◯ when it was hardly peeled off, and ◎ when no peeling was 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 was measured.

(6) Square ratio (Br/Bm): VSM- manufactured by Toei Kogyo KL
The magnetic properties were measured using a type 3 with an external magnetic field of 5,0000 e.

Residual magnetic flux density - Br, maximum residual magnetic flux density = Bm (7) Breaking strength, elongation, initial modulus: Cut out a strip-shaped test piece from the cured coating film. 0.5 cm x lOcI11 x
40-60 μm), measured at room temperature and at a tensile speed of 50 mm/min.

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

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

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

Co-containing r -Fe203 80 parts by weight Polymer 8 20! Parts (in terms of solid content) Cyclohexanone 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.

Co-containing T FezOz 80 parts by weight Polymer C 17 parts by weight (solid content equivalent) Trimethylolpropane triacrylate 3 parts by weight 5 Mixed solvent of cyclohexanone and methyl ethyl ketone 200 parts by weight Reference Example 4 In Reference Example 1, the composition of the paint was as follows. The test was conducted in the same manner as in Reference Example 1, except that . The results are shown in Table 2.

Co-containing r-Fe, 0. , 80 M polymer D 20 parts by weight (in terms of 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 -Fe, 03 80 parts by weight Polymer E 20! Volume (solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200! i-scape Reference Example 6 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 r -FezO 380 parts by weight Polymer F 20 parts by weight (in terms of solid content) Tetrahydrofuran 200 parts by weight Reference Example 7 The test was carried out in the same manner as in Reference Example 1 except that the composition of the paint was changed as follows. I did it. The results are shown in Table 2.

Co-containing r -FezO+ 80 parts by weight Polymer G 20 parts by weight (calculated as 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 r Fezes 80 parts by weight Polymer H 20 parts by weight (solid content equivalent) 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 PezOz 8 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 Fezes 80 parts by weight Polymer L 20 parts by weight (calculated as solid content) Mixed solvent of methyl ethyl ketone and cyclohexanone
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 -FeJ3 80 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 T FezO: + 8o 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 -Fe, Oi 80 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 T FezO3so parts by weight Polymer P 20 parts by weight (solid content equivalent) 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 Fezes ao weight part Polymer Q 20 weight parts (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 16 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing T -FetCh 80 parts by weight Polymer R 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Reference Example 17 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2.

Co-containing r-Fe, 0. 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 FezO 380 parts by weight Polymer 7 20 parts by weight (in terms of 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 pezO,, goo amount part polymer 0
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 -Fe, 0. 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 r FezO 380 parts by weight Polymer W 20 parts by weight (solid content equivalent) 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, 80 parts by weight Polymer obtained in Comparative Example 1 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone
200 parts by weight Table 1 [Effects of the Invention] The present invention has the following effects.

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

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

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

(7) Even if the coating film of the radiation-curable paint of the present invention improves the crosslinking density by increasing the radiation dose,
A cured coating film with appropriate flexibility and surface hardness can be obtained, and the magnetic tape and floppy disk obtained when used as a magnetic coating in the manufacture 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 Procedural Amendment (Sealed) 1. Indication of the case 1982 Patent application No. 012830 2 Name of the invention Radiation curable paint 3 Person making the amendment Relationship to the case Patent applicant address 2-11-24 Tsukiji, Chuo-ku, Tokyo
Name (41?) Japan Synthetic Rubber Co., Ltd. 8
, Contents of the amendment■, The scope of the claims will be amended as shown in the attached sheet.

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

(2) "Polypropylene glycol, etc." on page 30, lines 3 to 4 of the specification is corrected to "polypropylene glycol, polytetramethylene glycol, etc."

(3) Formula (1)-a on page 12 of the same book is corrected as follows.

(4) Formula (1)-b on page 13 of the circular is amended as follows.

(5) Formula (1)-e on page 14 of the same book is corrected as follows.

(6) The formula in the fifth line from the bottom of page 51 of the same book is corrected as follows.

(7) The formula on page 80, line 4 of the same book is corrected as follows.

Claims (after amendment) rt, 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 carbonized group having 2 to 20 carbon atoms It is a hydrogen group; X is the following formula ([
)-a Here, R4 is an alkylene group having 2 to 4 carbon atoms or the formula -C
A group represented by H, CH, OCH, Ctl, -,
The definition of R1 is the same as above.

n and n' are numbers from 1 to 30, a unit represented by the following formula (1)-b, R2 is an alkylene group having 2 to 4 carbon atoms, and R1
The definition of is the same as above, R2 Li, R2, and RSS are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and may be the same or different, m and Ω are 1 The number is ~30.

p is a number from 1 to 5, and if necessary, the following formula (,1)-
〇 or ul.

It is a group represented by, and q is a number from 1 to 20.

The definition of R1 is the same as above.

R1/ is a hydrogen atom or a methyl group, and optionally a unit represented by the following formula (1), where the definitions of R1, R1 and m are the same as above, in any proportion is a group forming a urethane bond; Q is a residue of a tetrahydric alcohol; and Y is a hydroxyl group or a group shown in the above formula (1) other than Y bonded to Q; 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.

2. The following formula (1) R1 is a hydrogen atom or a methyl group; R2 is carbon! I! L2-8 is an alkylene group; R1
is a divalent hydrocarbon group having 2 to 20 carbon atoms; X is the following formula (1)-a, where R4 is an alkylene group having 2 to 4 carbon atoms or the formula -C
A group represented by H2CH20C)I, CH2-, the definition of R1 is the same as above, n and n' are numbers from 1 to 30, a unit represented by the following formula (I)-b, where R2 is an alkylene group having 2 to 4 carbon atoms, the definition of R3 is the same as above, and R2, nxt, Ls and R1 are a hydrogen atom or an alkylene group having 1 carbon number.
~8 alkyl groups, which may be the same or different, and m and Q are numbers from 1 to 30.

p is a number from 1 to 5, a unit represented by the following formula (1)-e, where R7 and R1 are alkylene groups having 2 or 3 carbon atoms, and r and S are numbers from 1 to 20; , R3 have the same definitions as above, and if necessary, a group represented by the following formula (1), and q is a number from 1 to 20.

The definition of R3 is the same as above; is 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 of the above formula ( 1) The group shown in , provided that two or more of Y are not hydroxyl groups,

Claims (1)

[Claims] 1. The following formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼... (I) Here, R_1 is a hydrogen atom or a methyl group; R_2 is an alkylene having 2 to 8 carbon atoms R_3 is a divalent hydrocarbon group having 2 to 20 carbon atoms; , R_4 is an alkylene group having 2 to 4 carbon atoms or the formula -
A group represented by CH_2CH_2OCH_2CH_2-, the definition of R_3 is the same as above, n and n' are numbers from 1 to 30, a unit represented by the following formula (I)-b ▲ Numerical formula, chemical formula, table etc.▼(I)-b Here, R_5 is an alkylene group having 2 to 4 carbon atoms, and R
The definition of _3 is the same as above, R_2_6, R_2_7, R_2_8 and R_2_9 are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and may be the same or different, m and l are 1 -30, p is a number from 1 to 5, and if necessary, the following formula (I) -
c ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)-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 ▲ Mathematical formulas, chemical formulas, tables, etc. etc. ▼ is a group represented by , 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 if necessary, the following formula (I) -
d ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)-d Here, the definitions of R_3, R_5 and m are the same as above, and the units represented by are groups forming urethane bonds in any proportion. Yes; 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 polymer represented by the following as a radiation-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 with 2 to 8 carbon atoms; R_3
is a divalent hydrocarbon group having 2 to 20 carbon atoms; 2 to 4 alkylene groups or formula-
A group represented by CH_2CH_2OCH_2CH_2-, the definition of R_3 is the same as above, n and n' are numbers from 1 to 30, a unit represented by the following formula (I)-b ▲ Numerical formula, chemical formula, table etc.▼(I)-b Here, R_5 is an alkylene group with 2 to 4 monoprimes, and R
The definition of _3 is the same as above, R_2_6, R_2_7, R_2_8 and R_2_9 are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and may be the same or different, m and l are 1 ~30, p is a number from 1 to 5, the unit represented by the following formula (I)-e ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I)-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. )−
c ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)-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 ▲ Mathematical formulas, chemical formulas, tables, etc. etc. ▼ is a group represented by , 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 if necessary, the following formula (I) -
d ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) - d Here, the definitions of R_3, R_5 and m are the same as above, and the units represented by form a urethane bond in any proportion. Yes; 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 polymer represented by the following as a radiation-curable polymer component.