JPH0215570B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a radiation-curable paint, and in particular, it is suitable for use as a magnetic paint mixed with magnetic powder and used in manufacturing magnetic recording media such as magnetic tapes and magnetic disks. It relates to radiation-curable paints. [Prior Art] Generally, a magnetic recording medium has a magnetic layer formed by coating a support such as a polyester film with a magnetic paint consisting of magnetic powder, a polymer, a solvent, and various additives. In recent years, a radiation-curable polymer having acrylic double bonds has been 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. method is known. JP-A No. 58-32617 discloses that the polyester molecule contains about 0.2 to 30 mol% of a sulfonic acid metal salt based on the total carboxylic acid component, and the molecular part is chain-extended via a urethane bond. substantially linear with a terminal double bond and a molecular weight of about 1
An electron beam curable resin comprising a polyester polyurethane resin of 10,000 to 50,000 is described. As mentioned above, the resin described in JP-A-58-32617 has a sulfonic acid metal salt in the polyester portion of the polyester polyurethane resin. Furthermore, JP-A-60-120765 discloses that the chain extender is obtained by using polyhydroxypolycarboxylic acid and/or polyhydroxysulfonic acid metal salt as at least a part of the chain extender and has a polymerizable double bond. A magnetic paint is disclosed in which a radiation-curable polymer is an unsaturated polyurethane resin having two or more terminal groups. 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, page 5, lower left column, line 17 to page 5, lower right column, line 11 of the above publication, when a polyol is used as part of the chain extender, However, no unsaturated polyurethane resin is disclosed which has a sulfonic acid metal salt on average in all branched chain parts starting from each hydroxyl group part of the polyol. [Problems to be Solved by the Invention] However, when the above-mentioned conventional radiation-curable polymer is used to manufacture a magnetic recording medium,
There was a problem to be solved in that it was difficult to provide sufficiently satisfactory practical durability and electromagnetic conversion characteristics. The reason for this is not clear, but if the inventor considers it in relation to the present invention, the overall molecular chain structure of the radiation-curable polymer used, the distribution of the sulfonic acid metal salt within the molecular chain, or the This is thought to be due to the viscosity of the magnetic paint containing the polymer and magnetic powder. 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 provide a magnetic recording medium that has low viscosity as a paint, has an increased pot life, and has excellent practical durability, and also simplifies the manufacturing process of magnetic recording media. An object of the present invention is to provide a radiation-curable paint that achieves reductions in energy consumption for curing. Further objects and advantages of the invention will become apparent from the description below. [Means and effects for solving the problems] According to the present invention, the objects and advantages of the present invention are, firstly, the following formula () [Here, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 to 3 carbon atoms,
R ₃ is a divalent aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms, and X is represented by the following formula (1)-a [Here, R ₄ is an alkylene group having 2 to 4 carbon atoms, the definition of R ₃ is the same as above, and n is 1
~30 numbers. ] The unit represented by and the following formula (1)-b [Here, R ₅ is an alkylene group having 2 to 4 carbon atoms, the definition of R ₃ is the same as above, M is an alkali metal, m and l are numbers from 1 to 30, and p is It is a number from 1 to 5. ] is a group in which the units represented by form a urethane bond in an arbitrary ratio, Q is a residue of a tetrahydric alcohol, and Y
is a hydroxyl group or the above formula other than Y bonded to Q ()
This is the group shown inside. However, two or more of Y are not hydroxyl groups, and this can be achieved by a radiation-curable coating material containing a polymer represented by the following as a radiation-curable polymer component. Also, according to the present invention, secondly, the above formula ()
, X is a unit represented by the above formula (1)--a, (1)--a unit represented by b, and 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. There is also provided a radiation-curable paint containing, as a radiation-curable polymer component, a polymer represented by the above formula (), which is a group forming a urethane bond in proportion. The definition of X in the above formula () consists of units represented by (1)--a and (1)--b.
and the second paint consisting of units where X in the above formula () is represented by (1)--a, (1)--b and (1)--e, the above formula () The definition of X is further expressed by the following formula (1)-
c. Here, R ₆ is (-CH ₂ CH ₂ O) - _q ,

【formula】

(Here, Z and Z′ are independently

[expression] or

[Formula]. ) or, is a group represented by, q is a number from 1 to 20,
The definition of R ₃ is the same as above, R ₁ ' is a hydrogen atom or a methyl group, and the unit represented by the following formula (1)-d Here, the definitions of R ₃ , R ₅ and m are the same as above, and the unit selected from the group consisting of the units represented by is other than the units of ()-a, ()-b, and ()-e. may be included as any unit. In the above formula (), R ₁ is a hydrogen atom or a methyl group. R ₂ is an alkylene group having 2 to 3 carbon atoms, such as an ethylene group, 1,2- or 1,3-propylene group. R ₃ is a divalent aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms, such as ethylene group, propylene group, tetramethylene group, hexamethylene group, phenylene group, cyclohexylene group,
Methylenebisphenylene group, methylenebiscyclohexylene group, or structural formula

【formula】

【formula】

【formula】

【formula】

It represents a C ₂ -C ₂₀ , preferably C ₂ -C ₁₅ divalent aliphatic, alicyclic or aromatic group represented by the following formula. X is a unit represented by the above formula (1)--a, (1)--a unit represented by b, and optionally a unit represented by (1)--c and/or (
)-d represents a group forming a urethane bond in any proportion, or ()-a unit, ()-b unit, (
It represents a group in which a unit represented by )-e and optionally a unit represented by ()-c and/or a unit represented by ()-d form a urethane bond in any proportion. In formula (1)-a, R ₄ is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a 1,2- or 1,3-propylene group, a tetramethylene group, or a butylene group. Further, the definition of R ₃ is the same as above, and n is a number from 1 to 30. In formula (1)-b, R ₅ 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. M is an alkali metal, such as sodium,
It is potassium. Further, the definition of R ₃ is the same as above, m and l are each independently a number from 1 to 30, and p is a number from 1 to 5. In formula (1)—c, R ₆ is (—CH ₂ CH ₂ O)— _q ,

【formula】

(Here, Z and Z′ are independently

[expression] or

[Formula]. ) or, It is a group represented by, and q is a number from 1 to 20.
Further, R ₁ ' is a hydrogen atom or a methyl group, and the definition of R ₃ is the same as above. The definitions of R ₃ , R ₅ and m in formula ()-d are as above. Further, in formula ()--e, R ₇ and R ₈ are alkylene groups having 2 or 3 carbon atoms, such as ethylene group, 1,2- or 1,3-propylene group. In addition, the definition of R ₃ is as described above, and r
and s are each independently a number from 1 to 20. Q is a tetrahydric alcohol residue, for example, if the tetrahydric alcohol is pentaerythritol, Q
teeth , and the tetrahydric alcohol is N, N, N', N'-
If it is tetrahydroxypropylethylenediamine, Q is It is. Y is a hydroxyl group or a group other than Y shown in the above formula (). However, two or more of the three Y's in the above formula () must not be hydroxyl groups. The radiation-curable coating material of the present invention contains a polymer represented by the above formula () as a radiation-curable polymer component. Next, a method for producing a polymer used in the radiation-curable coating material of the present invention will be explained using specific examples. As the first step, a diol compound represented by the following general formula (a) Here, the definition of R ₄ and n is the above formula () -
Same as a, and a compound represented by the following general formula (b) (hereinafter referred to as a specific sulfonic acid compound) Here, the definitions of R ₅ , M, m, l and p are the same as in the above formula ()-b, and if necessary, a compound represented by the following general formula (c) (hereinafter referred to as a specific hydroxy compound) Here, the definition of R ₆ and R ₁ ' is the above formula () - c
and, if necessary, a compound represented by the following general formula (d), HO( _-R5 -O) _-nH ...(d) _R5 and m definitions are the same as the above formula () - Same as d, is reacted with a diisocyanate compound represented by the above formula (A) OCN-R ₃ -NCO ... (A) where the definition of R ₃ is the same as in the above formula (). . 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) Here, the definitions of R ₇ , R ₈ , r and s are the same as in the above formula ()-e. In that case, they can also be used together, and in that case, a polymer containing units of the above formula ()-e can be formed. In the polymer, ()-a, ()-b,
The units of ()-c, ()-d, and ()-e are, for example, randomly distributed. In the second step, the polymer having an isocyanate group at the molecular end formed as described above,
Above formula (B) Here, the definitions of R ₁ and R ₂ are the same as in the above formula (). , the above formula (B) at the end of the molecule
This produces a polymer in which the units are linked via urethane bonds. In the third step, the remaining isocyanate groups of the thus obtained polymer and the above formula (c) Here, the definition of Q is the same as in the above formula, and the radiation-curable polymer used in the present invention can be prepared by reacting with a tetrafunctional alcohol compound represented by Obtainable. The reaction in the first step is usually performed using copper naphthenate,
It is carried out using a catalyst such as cobalt naphthenate, zinc naphthenate, n-butyltin laurate, or triethylamine. These catalysts are used in an amount of 0.01 to 100 parts by weight of the total amount of starting materials used in the first step.
It is preferable to use about 1 part by weight. The reaction temperature is
The temperature is usually preferably 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 based on 100 parts by weight of the polymer formed in the first step.
0.01 to 1 part by weight is used. The reaction in the second step is preferably carried out at 30-80°C. Further, the reaction in the third step can be preferably carried out under the same conditions as the reaction conditions in the second step. The reactions in the first, second and third steps can be carried out simultaneously 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, and dioxane, can be used as necessary. Diol compound (a) used in the first step above
can be produced by reacting adipic acid or a lower alkyl ester thereof with a corresponding diol according to a method known per se. Further, the specific sulfonic acid compound (b) can be produced by reacting the polyether diol compound represented by the general formula (d) with sulfoisophthalic acids. Examples of sulfoisophthalic acids include 5-sodium-sulfo-isophthalic acid, 5-potassium-sulfo-isophthalic acid, and 5-sulfoisophthalic acid.
Sodium-sulfo-isophthalic anhydride, 5-
Sodium-sulfo-di-lower alkyl isophthalate such as dimethyl or diethyl, 5-potassium-
Mention may be made of di-lower alkyl sulfo-isophthalates such as dimethyl or diethyl. 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 the constituent units can be determined. The reaction temperature for addition polymerization by esterification or transesterification is usually 40 to 220°C, preferably 50 to 180°C. Catalysts for the esterification reaction include bases such as pyridine and triethylamine, or sulfuric acid and paratoluene. Acids such as sulfonic 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 alcoholates such as sodium methylate and sodium ethylate, oxides or hydroxides of alkaline earth metals, organic titanium such as zinc oxide, cadmium oxide, titanium isopropylate, and titanium butyrate. Compounds etc. can be used. The specific hydroxyl compound (c) is at least selected from acrylic and methacrylic compounds having a carboxyl group and acrylic and methacrylic compounds having a hydroxyl group per mol of a diepoxy 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 diepoxy compound here include bisphenol A
Glycidyl ether of polyhydric phenol obtained by reacting alkylene oxide and epichlorohydrin: Alkylene oxide of polyhydric phenol obtained by reacting bisphenol A with alkylene oxide such as ethylene oxide or propylene oxide and epichlorohydrin. Glycidyl ether of adducts: Glycidyl ethers of polyhydric alcohols obtained by reacting epichlorohydrin with polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, and polytetramethylene glycol. Can be done. The reaction temperature of the above addition polymerization is usually 20 to 130℃,
Preferably it is 40-70°C. As a catalyst during the reaction, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amide complex salts, etc. can be used. Preferably triethanolamine, N, N, N',
N'-tetramethylethylenediamine, N,N-
Dimethylpiperazine, N-methylmorpholine,
Boron trifluoride etherate can be used. The amount of these catalysts used is 0.01 to 5 parts by weight per 100 parts by weight of the reaction raw materials. The compounds represented by formulas (d) and (e) above are compounds that are easily available as commercial products. As the diisocyanate compound (A), 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,
5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl Examples include phenylene diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), and the like. In addition, examples of the acrylic or methacrylic compound (B) having a hydroxyl group used in the reaction of the second step include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyoctyl ( Examples include meth)acrylate. Further, examples of the tetrafunctional alcohol compound used in the reaction in the third step include ethylenediamine alkylene oxide adduct, diglycerin alkylene oxide adduct, and the like. Thus, although the radiation-curable polymer used in the present invention can be obtained by the method described above, it is not limited to the method described here. The proportion of the component represented by formula (1)-b in the radiation-curable polymer used in the present invention is preferably 0.05 to 90% by weight, particularly preferably 0.1 to 70% by weight.
Weight%. Toluene, methyl ethyl ketone, which is commonly used as magnetic paint when it exceeds 90% by weight,
There is a strong tendency for the solubility in general-purpose solvents such as methyl isobutyl ketone to decrease, and the hygroscopicity of the coating film after being cured by radiation as a coating material increases, which tends to cause a decrease in coating strength. The content of the alkali metal sulfonate base contained in the radiation-curable polymer used in the present invention preferably ranges from 1.0×10 ^-7 equivalent/g to 1.3×10 ^-3 equivalent/g.
g, particularly preferably 2×10 ^-7 equivalent/g ~
1.0×10 ^-3 equivalent/g, especially 5×10 ^-7 equivalent/g
g to 1.0×10 ⁻³ equivalent/g. Further, the proportion of the component represented by formula (1)-c is preferably 95% by weight or less, particularly preferably 90% by weight or less.
% 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 undesirable. The ratio of the total amount of the components represented by formulas (1)-a, (1)-d, and (1)-e to the entire polymer is:
It is preferably 4.95 to 99.5% by weight, and within this range, the proportions of each component (1)-a, (1)-d, and (1)-e can be set arbitrarily. The radiation curable polymer used in the present invention preferably has a number average molecular weight of about 10,000 to 100,000. The mechanical properties of the coating film obtained by radiation curing the polymer used in the present invention vary depending on the radiation curing conditions, etc., but usually have an elastic modulus of 10 Kg/cm ² or more and a breaking strength of 90 Kg/cm ² Above, the elongation at break is 7% or more. The polymer used in the present invention 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 (a). [In the formula, R ₉ is -CH ₃ or -C ₂ H ₅ , X is

[Formula] (wherein R ₁₀ is H or CH ₃ ), Z is

[Formula] (R ₁₁ and R ₁₂ represent 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 an acrylic or vinyl ), t is 200
~800 integer, u is an integer from 10 to 200, v is 0~
200 integer, w is an integer from 3 to 100, m is an integer from 0 to 50] (3) Hydrophilic group, such as -SO ₃ M, -OSO ₃ M, -
COOM,

【formula】

【formula】

【formula】 【formula】 〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in the following examples, the molecular weight is a value determined by an osmotic pressure method. The structure of the compound is the result of analysis by infrared absorption spectrum and nuclear magnetic resonance (NMR) spectrum. The solution viscosity of the polymer in each example is the value (centipoise, cp) measured at 25°C for a 40% by weight solution in the solvent used in the synthesis of the polymer in each example.
It is. Example 1 (1) In a flask with a capacity of 1 equipped with a thermometer, a stirrer, and a reflux condenser, 74 g of 5-sodium-sulfo-isophthalic acid dimethyl ester, 400 g of polyethylene glycol (average molecular weight 400), and 1.0 g of sodium acetate were added. The mixture was added and 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 dimethyl 5-sodium-sulfo-isophthalate was not detected, indicating that the transesterification rate had progressed to almost 100%. It was judged. Furthermore, it was confirmed that unreacted polyethylene glycol was present. 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 polyethylene glycol, In the formula, R ₁₈ is a residue of polyethylene glycol (average molecular weight 400) excluding the OH groups at both ends, and n is 1.1. Moreover, the ratio of the compound shown in the above structure to unreacted polyethylene glycol was 55:45 (weight ratio). These mixtures are referred to as specific sulfonic acid compounds (). The hydroxyl equivalent of the specific sulfonic acid compound () was 3.28×10 ⁻³ equivalent/g. (2) Add 167.4 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone to a 2-volume flask equipped with a thermometer, stirrer, and reflux condenser.
After heating to ℃, add polyester diol (manufactured by Nippon Polyurethane Co., Ltd., Nipporan), which is a copolymer of adipic acid and butanediol, while being careful not to raise the temperature of the system through the dropping funnel.
409, 4002; Polyester diol ()
) 139.4 g, polyoxyethylene bisphenol A ether (manufactured by NOF Corporation, DA-
350F) 112.2g, acrylic acid adduct of bisphenol A propylene oxide derivative (Epoxy Ester 3002A, manufactured by Kyoeisha Yushi; hereinafter referred to as specific hydroxyl compound ()) 34.6g, specific sulfonic acid compound () 35.4g, cyclohexanone and methyl ethyl ketone 200g of mixed solvent
Drop a uniform mixture of
The reaction was carried out at 60°C for 4 hours. Next, 6.7 g of 2-hydroxyethyl acrylate was added to this, and after further reaction at 60°C for 2 hours, 4.3 g of a tetrafunctional alcoholic compound (Adeka Quadrol, manufactured by Asahi Denka) was added and the mixture was heated at 60°C.
The mixture was allowed to react for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (A).
The molecular weight and sulfonic acid sodium salt content of the polymer (A) are shown in Table 1. Example 2 187.3 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 500 g of cyclohexanone were added to a 2-volume flask equipped with a thermometer, stirrer, and reflux condenser.
After heating to 60°C, add 49.5 g of polyester diol () and polyoxyethylene bisphenol A ether (manufactured by NOF Corporation, DA-350F) while being careful not to raise the temperature of the system through the dropping funnel.
153.7g, specific hydroxyl compound () 65.6g,
A mixture of 33.5 g of the specific sulfonic acid compound () dissolved in 250 g of cyclohexanone was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. Next, 6.4 g of 2-hydroxyethyl acrylate was added to this, and after further reaction at 60°C for 2 hours, a tetrafunctional alcoholic compound (manufactured by Asahi Denka,
4.0 g of ADEKA QUODOROL) 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). The molecular weight and sulfonic acid sodium salt content of the polymer (B) are shown in Table 1. Example 3 In a 2 capacity flask equipped with a thermometer, stirrer and reflux condenser, 86.2 g of 2,4-toluene diisocyanate, 0.5 g of dibutyltin dilaurate,
After adding 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating it to 60°C, add
364.0 g of polyester diol, which is a copolymer of adipic acid and ethylene glycol (manufactured by Nippon Polyurethane Co., Ltd., Nipporan 4002; hereinafter referred to as polyester diol ()), polyoxyethylene bisphenol A ether (manufactured by Nippon Oil & Fats Co., Ltd., DA
-350F) 17.4g, specific sulfonic acid compound ()
A homogeneous mixture of 24.7 g of cyclohexanone and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the dropwise addition was completed, the mixture was reacted at 60° C. for 4 hours. Next, 4.7 g of 2-hydroxyethyl acrylate was added to this, and the reaction was further carried out at 60°C for 2 hours. Then, 3.0 g of a tetrafunctional alcoholic compound (manufactured by Asahi Denka, Adeka Quadrol) was added, and the reaction was carried out at 60°C for 4 hours. Made it react. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (C). Table 1 shows the molecular weight and sulfonic acid sodium salt content of the polymer (C). Example 4 (1) In a flask with a capacity of 1 equipped with a thermometer, a stirrer, and a reflux condenser, 78 g of 5-sodium-sulfo-isophthalic acid dimethyl ester, 422 g of polyethylene glycol (average molecular weight 200), 1.0 g of sodium acetate, Add 1.0g 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 dimethyl 5-sodium-sulfo-isophthalate was not detected, indicating that the transesterification rate was approximately 100%. It was judged. Furthermore, it was confirmed that unreacted polyethylene glycol was present. 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 polyethylene glycol, In the formula, R ₁₉ 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 36:64 (weight ratio).
These mixtures identify sulfonic acid compounds ()
shall be. The hydroxyl equivalent of the specific sulfonic acid compound () was 7.52×10 ⁻³ equivalent/g. (2) Add 114.3 g of 2,4-toluene diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ethyl ketone to a flask with a capacity of 2 equipped with a thermometer, stirrer, and reflux condenser, and heat to 60°C. After that, add polyester diol () while being careful not to raise the temperature of the system through the dropping funnel.
266.4g, polyoxyethylene bisphenol A ether (manufactured by NOF Corporation, DA-350F) 75.5
g, specific sulfonic acid compound () 6.8g, mixed solvent of cyclohexanone and methyl ethyl ketone
A uniform mixture of 200 g was added dropwise, and after the addition was completed, the reaction was carried out at 60° C. for 4 hours. Next, 21.2 g of 2-hydroxypropyl methacrylate was added to this and reacted at 60°C for 2 hours, and then 18.2 g of a tetrafunctional alcoholic compound (DG-500, manufactured by Asahi Denka) 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 Polymer (D).
Table 1 shows the molecular weight and sulfonic acid sodium salt content of the polymer (D). Example 5 (2) In a 2 capacity flask equipped with a thermometer, stirrer and reflux condenser, 132.4 g of isophorone 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,
While being careful not to raise the temperature of the system through the dropping funnel, add 27.7 g of polyester diol (manufactured by Nippon Polyurethane Co., Ltd., Nipporan 4040; hereinafter referred to as polyester diol ()), which is a copolymer of adipic acid and ethylene glycol, Oxypropylene bisphenol A ether (manufactured by NOF Corporation, DB-900) 237.2 g, methacrylic acid adduct of ethylene glycol diglycidyl ether derivative (manufactured by Kyoeisha Yushi Co., Ltd., epoxy ester 40EM: hereinafter referred to as specific hydroxyl compound ()) 57.6 g A homogeneous mixture of 44.3 g of a specific sulfonic acid compound () and 250 g of a mixed solvent of cyclohexanone and methyl ether ketone was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. Then, 2-hydroxyethyl acrylate
After adding 6.4 g and reacting at 60°C for 2 hours, a tetrafunctional alcoholic compound (manufactured by Asahi Denka,
DG-500) 6.9g was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (E).
The molecular weight and sulfonic acid sodium salt content of the polymer (E) are shown in Table 1. Example 6 (1) In a flask with a capacity of 1 equipped with a thermometer, a stirrer, and a reflux condenser, 105.9 g of acrylic acid and polypropylene glycol #400 diglycidyl ether (manufactured by Kyoeisha Yushi, Epolite 400p) were added.
After adding 394.1g and reacting at 60℃ 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 (). The main structure of the specific hydroxyl compound is as follows. (2) Add 156.8 g of 2,4-toluene diisocyanate and 0.5 g of dibutyltin dilaurate to a 2-capacity flask equipped with a thermometer, stirrer, and reflux condenser, heat to 60°C, and then pour the system through a dropping funnel. While being careful not to raise the temperature, add 83.8 g of polyester diol, a copolymer of adipic acid and butanediol (manufactured by Nippon Polyurethane Co., Ltd., Nipporan 4010; hereinafter referred to as polyester diol ()), and 57.0 g of a specific hydroxyl compound (). g, a uniform mixture of 184.0 g of specific sulfonic acid compound () and 250 g of tetrahydrofuran was added dropwise, and after the dropping was completed, the mixture was heated to 60°C.
The mixture was allowed to react for 4 hours. Next, 12.2 g of 2-hydroxypropyl methacrylate was added to this and reacted at 60°C for 2 hours, and then 6.2 g of a tetrafunctional alcoholic compound (Adeka Quadrol, manufactured by Asahi Denka) was added and the mixture was heated at 60°C.
The mixture was allowed to react for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (F).
Table 1 shows the molecular weight and sulfonic acid sodium salt content of the polymer (F). Example 7 (1) In a flask with a capacity of 1 equipped with a thermometer, a stirrer, and a reflux condenser, 35 g of 5-sodium-sulfo-isophthalic acid dimethyl ester, 465 g of polytetramethylene glycol (manufactured by DuPont, Terratan 650), 1.0 g of zinc acetate and 1.0 g of sodium acetate were added and 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 dimethyl 5-sodium-sulfo-isophthalate was not detected, indicating that the transesterification rate was approximately 100%. It was judged. 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, R ₂₀ is a residue of polytetramethylene glycol excluding the OH groups at both ends, and n is 1.4. Further, 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 (). The hydroxyl equivalent of the specific sulfonic acid compound () was 2.42×10 ⁻³ equivalent/g. (2) In a 2-capacity flask equipped with a thermometer, stirrer, and reflux condenser, add 105.9 g of isophorone diisocyanate and 0.5 g of dibutyltin dilaurate.
After adding 500g of a mixed solvent of cyclohexanone and methyl ethyl ketone and heating to 60℃,
While being careful not to raise the temperature of the system from the dropping funnel, add polyester diol () 117.9
g, polyoxypropylene bisphenol A ether (manufactured by NOF Corporation, DB-900) 106.1 g,
206.8g of specific sulfonic acid compound (206.8g), mixed solvent of cyclohexanone and methyl ether ketone
A uniform mixture of 250 g was added dropwise, and after the addition was completed, the reaction was carried out at 60° C. for 4 hours. Next, 5.8 g of 2-hydroxyethyl acrylate was added to this, and after reacting at 60°C for 2 hours, a tetrafunctional alcoholic compound (manufactured by Asahi Denka,
DG-500) 6.2g was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (G).
Table 1 shows the molecular weight and sulfonic acid sodium salt content of the polymer (G). Example 8 In a 2 capacity flask equipped with a thermometer, stirrer and reflux condenser, isophorone diisocyanate is added.
125.6g, dibutyltin dilaurate 0.5g, mixed solvent of cyclohexanone and methyl ethyl ketone
After adding 500g and heating to 60℃, add 191.8g of polyester diol (), 132.7g of specific hydroxyl compound (), and 39.6g of specific sulfonic acid compound () while being careful not to raise the temperature of the system from the dropping funnel. A homogeneous mixture of 250 g of a mixed solvent of cyclohexanone and methyl ether ketone was added dropwise, and after the addition was completed, the mixture was reacted at 60° C. for 4 hours. Next, 5.6 g of 2-hydroxypropyl methacrylate was added to this and reacted at 60°C for 2 hours, and a tetrafunctional alcoholic compound (manufactured by Asahi Denka,
DG-500) was added and reacted at 60°C for 4 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. The polymer thus obtained is referred to as Polymer (H). Table 1 shows the molecular weight and sulfonic acid sodium salt content of the polymer (H). Example 9 121.4 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 a flask with a capacity of 2 equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 60°C. After heating, add polyester diol () while being careful not to raise the temperature of the system from the dropping funnel.
61.0g, specific hydroxyl compound () 49.8g,
A homogeneous mixture of 100.7 g of a specific sulfonic acid compound (), 164.6 g of polyoxypropylene bisphenol A ether (manufactured by NOF Corporation, DB-900), and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise, and after the addition was complete, 4 at 600℃
Allowed time to react. Next, 3.5 g of 2-hydroxypropyl methacrylate was added to this, and after reacting at 60°C for 2 hours, a tetrafunctional alcoholic compound (manufactured by Asahi Denka,
1.8 g of Adeca Quadrol) 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 (J). The molecular weight and sulfonic acid sodium salt content of Polymer (J) are shown in Table 1. Comparative Example In a 2 capacity flask equipped with a thermometer, stirrer and reflux condenser, dimethyl terephthalate was added.
119.2g, dimethyl isophthalate 89.4g, 5-
Sodium dimethyl sulfoisophthalate 136.5g,
148.2g ethylene glycol, 203.4g neopentyl glycol and zinc acetate as catalyst
Prepare 0.025g and 0.003g of sodium acetate,
The transesterification reaction was carried out at 180-220°C for 3 hours. Then, 376.2 g of sebacic acid was added to give 200 g.
After reacting at ~240°C for 2 hours, the reaction system was heated to 30°C.
The pressure was reduced to 10 mmHg over a period of minutes. This reaction system was further subjected to a polycondensation reaction at a temperature of 250° C. for 2 hours under a pressure of 3 to 10 mmHg. The hydroxyl equivalent of the polyester polyol thus obtained is 4.7×10 ^-4
Equivalent amount/g. As a result of analyzing this polyester polyol by NMR spectrum, its composition was as follows. Terephthalic acid 20 mol%, isophthalic acid 15 mol%, sodium 5-sulfoisophthalate 5 mol%, sebacic acid 60 mol%,
50 mol% ethylene glycol and 50 mol% neopentyl glycol. Next, 33.8 g of 4,4'-dicyclohexylmethane diisocyanate, 0.5 g of dibutyltin dilaurate, and 550 g of a mixed solvent of cyclohexanone and methyl ketone were added to a flask with a capacity of 2 equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 60°C. After heating, a uniform mixture of 466.2 g of the polyester polyol obtained above and 200 g of a mixed solvent of cyclohexanone and methyl ethyl ketone was added dropwise through the dropping funnel, taking care not to raise the temperature of the system. , and reacted at 60°C for 4 hours. Next, 4.5 g of 2-hydroxyethyl acrylate was added to this, and the mixture was further reacted at 60°C for 2 hours. After the reaction was completed, it was confirmed by infrared absorption spectrum that no isocyanate groups remained in the system. Reference Example 1 A magnetic paint having the following composition was prepared in the following manner using the mixed solution of Polymer A obtained in Example 1 in cyclohexanone and methyl ethyl ketone, applied to a substrate, and cured by electron beam irradiation. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer A 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone 200 parts by weight Magnetic powder of the above composition, cyclohexanone, methyl ethyl ketone and 3 mm of the above composition were placed in a 500 ml aluminum can.
A diameter stainless steel ball (approximately 150 ml) was placed in the mixture, and the mixture was shaken for 2 hours using a paint conditioner manufactured by Red Devil Co., Ltd., USA. Next, a mixed solvent of cyclohexanone and methyl ethyl ketone of Polymer A was added and the mixture was further shaken for 4 hours, and then the stainless steel ball was removed to obtain a magnetic paint. Next, the above magnetic paint was immediately applied to 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, the magnetic powder was excluded, and Polymer A was coated on a glass plate to a dry film thickness of 40 to 60 μm. After drying overnight at room temperature, the accelerating voltage was set to 160 kilovolts, and 5 megarads was applied. The coating was cured at an absorbed dose of . Regarding magnetic paint, the following test (1) was conducted.
Regarding the hardened magnetic coating, tests (2) to (6) were conducted. For cured coatings that do not contain magnetic powder, see (7)
- (8) tests were conducted. In addition to the above, a cured coating film was prepared and the test (9) was conducted. The results are shown in Table 2. (1) Passage test: It was observed whether 100% of the magnetic paint could be passed through a filter with an average pore size 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 (manufactured by Murakami Color Research Institute). If the gloss is 70 to 90, ◎, 50 to
A score of 70 was marked as ○, a score of 30 to 50 was marked as △, and a score of 30 or less was marked as ×. (3) Surface observation: The surface of the cured magnetic coating was observed using a scanning electron microscope. The state in which no agglomeration of the magnetic powder was observed was marked as ◎, and the results were expressed in the following order as ○, △, and ×. (4) Adhesion test: Adhesive tape is pasted on the surface of the cured magnetic coating, and after it has adhered uniformly to the entire surface, it is peeled off momentarily and the condition is observed. The evaluation was made as follows: Completely peeled off: ×; Slightly peeled off: △; Almost no peeled off: ○; No peeling observed at all: ◎. (5) Powder shedding test: The cured magnetic coating was sieved 20 times on #1000 emery paper and the amount of powder shedding was measured. (6) Square ratio (Br/Bm): VSM-3 manufactured by Toei Kogyo Co., Ltd.
The magnetic properties were measured using a mold with an external magnetic field of 5000 Oe. Residual magnetic flux density = Br, maximum residual magnetic flux density = Bm (7) Breaking strength, elongation, initial modulus: Cut a strip-shaped test piece from the cured coating (0.5 cm
x 10 cm x 40 to 60 μm, measured at room temperature and 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: Polymer A obtained in Example 1 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 The clear film was cured with kilovolts and 5 megarads. This clear film was cut into 1 cm wide pieces along with the polyester film as a 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. It was checked whether the clear film peeled off or broke from the bent area. 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 γ-Fe ₂ O ₃ 80 parts by weight Polymer B 20 parts by weight (solid content equivalent) Cyclohexanone 200 parts by weight Reference Example 3 Same as Reference Example 1 except that the composition of the paint was changed as follows. The test was conducted on The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer C 17 parts by weight (solid content equivalent) Trimethylolpropane triacrylate
3 parts by weight Mixed solvent of cyclohexanone and methyl ethyl ketone 200 parts by weight Reference Example 4 A test was conducted in the same manner as in Reference Example 1 except that the composition of the coating material was changed as follows. The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer D 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone 200 parts by weight Reference Example 5 Reference Example 1 except that the composition of the paint was as follows. The test was conducted in the same manner as in Reference Example 1. The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer E 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone 200 parts by weight Reference Example 6 Reference Example 1 except that the composition of the paint was as follows. The test was conducted in the same manner as in Reference Example 1. The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer F 20 parts by weight (solid content equivalent) Tetrahydrofuran 200 parts by weight Reference Example 7 Same as Reference Example 1 except that the composition of the paint was changed as follows. The test was conducted on The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer G 20 parts by weight (solid content equivalent) Mixed solvent of cyclohexanone and methyl ethyl ketone 200 parts by weight Reference Example 8 Reference Example 1 except that the composition of the paint was as follows. The test was conducted in the same manner as in Reference Example 1. The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 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 Reference Example 1 except that the composition of the paint was as follows. The test was conducted in the same manner as in Reference Example 1. The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer J 17 parts by weight (solid content equivalent) Pentaerythritol triacrylate
3 parts by weight 200 parts by weight of a mixed solvent of cyclohexanone and methyl ethyl ketone Example 10 (1) In a 1 capacity flask equipped with a thermometer, stirrer and reflux condenser, 148 g of dimethyl 5-sodium-sulfo-isophthalate, polyethylene glycol ( 400 g of average molecular weight 400), 1.0 g of sodium acetate, and 1.0 g of zinc acetate were added, and the mixture was reacted at 130°C for 6 hours. The obtained reaction product
When analyzed by NMR spectrum, 5
-Sodium-sulfo-dimethyl isophthalate It was determined that the transesterification reaction had progressed to almost 100% since no peak due to the proton of the methyl group was detected. Furthermore, it was confirmed that there was no unreacted polyethylene glycol. Further, as a result of detailed analysis of the reaction product by NMR spectrum, it was found that the reaction product was a compound represented by the following structure. (In the formula, R ₁₈ is a residue of polyethylene glycol (average molecular weight 400) from which both terminal OH groups have been removed) The above compound is designated as a specific sulfonic acid compound (). The hydroxyl equivalent of the specific sulfonic acid compound () was 1.94×10 ^-equivalent /g. (2) Add 114.1 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 to a flask with a capacity of 2 equipped with a thermometer, stirrer, and reflux condenser.
After heating to 60℃, 342.1 g of polyester diol (), 32.0 g of specific sulfonic acid compound (), and 250 g of a mixed solvent of cyclohexanone and methyl ethyl ketone were uniformly mixed while being careful not to raise the temperature of the system through the dropping funnel. The mixture was added dropwise, and after the dropwise addition was completed, the mixture was reacted at 60°C for 4 hours. Next, 7.2 g of 2-hydroxyethyl acrylate was added to this, and the reaction was further carried out at 60°C for 2 hours, followed by the addition of 4.6 g of a tetrafunctional alcoholic compound (Adeka Quadrol manufactured by Asahi Denka).
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 (K). The molecular weight and sulfonic acid sodium salt content of polymer (k) are shown in Table 1. Reference Example 10 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 γ-Fe ₂ O ₃ 80 parts by weight Polymer K 20 parts by weight (solid content equivalent) Mixed solvent of methyl ethyl ketone and cyclohexanone 200 parts by weight Comparative reference example Reference example 1 except that the composition of the paint was as follows. The test was conducted in the same manner as in Reference Example 1. The results are shown in Table 2. Co-containing γ-Fe ₂ O ₃ 80 parts by weight Polymer obtained in comparative example 20 parts by weight (calculated as solid content) Mixed solvent of cyclohexanone and methyl ethyl ketone 200 parts by weight

【table】

[Table] The average composition of polymers (A) to (H), (J) and (L) in Examples 1 to 10 above is shown in Table 3 below using the parameters of the above formula (). As shown. Note that v, w, x, y, and z each indicate the number of units in the formulas ()-a, ()-b, ()-c, ()-d, and ()-e.

【table】

【table】

【table】

Claims (1)

[Claims] 1. The following formula () [Here, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 to 3 carbon atoms,
R ₃ is a divalent aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms, and X is represented by the following formula (1)-a [Here, R ₄ is an alkylene group having 2 to 4 carbon atoms, the definition of R ₃ is the same as above, and n is 1
~30 numbers. ] The unit represented by the following formula (1)-b [Here, R ₅ is an alkylene group having 2 to 4 carbon atoms, the definition of R ₃ is the same as above, M is an alkali metal, m and l are numbers from 1 to 30, and p is It is a number from 1 to 5. ] The unit expressed as , and the following formula (1) as necessary.
-c [Here, R ₆ is (-CH ₂ CH ₂ O)-q,
【formula】 (Here, Z and Z' are independently [formula] or [formula].) Or, is a group represented by, q is a number from 1 to 20,
The definition of R ₃ is the same as above, and R ₁ ' is a hydrogen atom or a methyl group. ] The unit expressed as , and the following formula (1) as necessary.
-d [Here, the definitions of R ₃ , R ₅ and m are the same as above. ] is a group in which the units represented by form a urethane bond in an arbitrary ratio, Q is a residue of a tetrahydric alcohol, and Y
is a hydroxyl group or a group shown in the above formula () other than Y bonded to Q. However, two or more of Y are not hydroxyl groups. A radiation-curable coating material containing a polymer represented by the following as a radiation-curable polymer component. 2 The following formula () [Here, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 to 3 carbon atoms,
R ₃ is a divalent aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms, and X is represented by the following formula (1)-a [Here, R ₄ is an alkylene group having 2 to 4 carbon atoms, the definition of R ₃ is the same as above, and n is 1
~30 numbers. ] The unit represented by the following formula (1)-b [Here, R ₅ is an alkylene group having 2 to 4 carbon atoms, the definition of R ₃ is the same as above, M is an alkali metal, m and l are numbers from 1 to 30, and p is It is a number from 1 to 5. ] The unit expressed by the following formula (1) - e [Here, R ₇ and R ₈ are alkylene groups having 2 or 3 carbon atoms, r and s are numbers from 1 to 20, and the definition of R ₃ is the same as above. ] The unit expressed as , and the following formula (1) as necessary.
-c [Here, R ₆ is (-CH ₂ CH ₂ O) - _q ,
【formula】 (Here, Z and Z' are independently [formula] or [formula].) Or, is a group represented by, q is a number from 1 to 20,
The definition of R ₃ is the same as above, and R ₁ ' is a hydrogen atom or a methyl group. ] The unit expressed as , and the following formula (1) as necessary.
-d [Here, the definitions of R ₃ , R ₅ and m are the same as above. ] is a group in which the units represented by form a urethane bond in an arbitrary ratio, Q is a residue of a tetrahydric alcohol, and Y
is a hydroxyl group or a group shown in the above formula () other than Y bonded to Q. However, two or more of Y are not hydroxyl groups. A radiation-curable coating material containing a polymer represented by the following as a radiation-curable polymer component.