JP3019382B2 - New energy ray-curable resin composition - Google Patents

Description

The present invention relates to an energy ray-curable resin composition emulsified with a new and useful energy ray-curable resin.

More specifically, the present invention relates to an energy ray-curable resin composition obtained by emulsifying a synthetic resin with an unsaturated urethane compound having a specific alkali metal sulfonate in the molecule as an active ingredient.

The energy ray-curable resin composition of the present invention can be arbitrarily diluted with water, and is very useful for a wide range of uses such as coating materials, printing inks, photoresists and adhesives. And a water-based resin composition curable by energy rays such as

(Prior art) Resins that can be cured, especially those that can be cured by a radical polymerization reaction, include various products such as unsaturated polyester resins, vinyl ester resins (epoxy-acrylates), various oligoacrylates, and diallyl phthalate prepolymers. It is widely used because of its features in application fields.

However, the demand for water-based treatment in each application field, such as environmental pollution and improvement of working conditions, is increasing.

Therefore, resins that can be cured with ordinary energy rays (energy ray-curable resins) include, for example, non-ionic resins such as polyoxyethylene-based alkyl allyl ethers, alkyl ethers, alkyl esters, alkyl amines, and sorbitan derivatives. An aqueous resin composition is obtained by emulsification using a compound having a surface active effect such as a system; an anionic system such as sulfonate, sulfate or phosphate; or a cationic system such as quaternary ammonium or imidazoline.

However, various physical properties of the cured coating film are reduced due to the presence of such various surfactants.

(Problems to be Solved by the Invention) As described above, a resin composition which is water-based and can be cured by energy rays without deteriorating the performance in various applications at all is still obtained. Absent.

However, in view of the above-mentioned situation, the present inventors can use it for applications that cannot be satisfied with the existing emulsified aqueous resin, and furthermore, have water resistance, solvent resistance, chemical resistance and curability. Various studies have been made on the synthesis of a radical-curable resin composition having excellent properties such as an energy-ray-curable resin composition having an ethylenically unsaturated double bond and a sulfonate of an alkali metal, and optionally a urethane bond. When a resin is used to emulsify a synthetic resin other than this resin, it can be easily emulsified in water without using a normal emulsifier, and without deteriorating various properties of a cured coating film, to be aqueous. The present invention has been completed by finding out that the present invention can be fulfilled.

(Means for Solving the Problems) That is, the present invention basically provides a synthetic resin by using an energy ray-curable resin (A) having an ethylenically unsaturated double bond and a sulfonate of an alkali metal. The present invention provides an energy ray-curable resin composition which is an energy ray-curable resin composition obtained by emulsifying the resin into an energy ray-curable resin composition. Is what you do.

Here, the energy ray-curable resin (A) has a compound having an ethylenically unsaturated double bond and a functional group in a molecule, a sulfonate of an alkali metal, and a functional group which reacts with the functional group. It can be obtained by reacting a compound. Further, when the functional group is a hydroxyl group, an energy ray-curable resin having an ethylenically unsaturated double bond, a sulfonate of an alkali metal and a urethane bond in the molecule can be obtained by reacting an isocyanate compound. .

As the resin (A), any resin can be used as long as it has reacted the above-mentioned compounds, and among them, a polyvalent isocyanate compound [hereinafter referred to as (a-1)] is preferable. And a polyfunctional (meth) acrylate having at least one primary and / or secondary hydroxyl group in one molecule [hereinafter referred to as (a-2)], and at least one primary in one molecule. And / or a polyvalent isocyanate obtained by reacting a compound having both a secondary hydroxyl group and at least one alkali metal sulfonate (hereinafter referred to as sulfonate-containing polyol (a-3)) A so-called urethane (meth) obtained by reacting (a-1) with a mono-, di-, tri- or higher polyvalent (meth) acrylate (a-2).
Resins obtained by reacting the acrylate prepolymer with the above-mentioned sulfonate-containing polyol (a-3) are exemplified.

If only the typical examples of the polyvalent isocyanate compound (a-1) described above are exemplified, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, Diisocyanate compounds having an aromatic ring such as 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyl-diphenylmethane diisocyanate or 1,5-naphthalenediisocyanate; alicyclic rings such as dicyclohexylmethane diisocyanate or isophorone diisocyanate A diisocyanate compound of the formula: or an aliphatic diisocyanate compound such as hexamethylene diisocyanate or lysine diisocyanate, or a diisocyanate compound having an aromatic ring described above, which is obtained by hydrogenation. Isocyanate compounds, for example, hydrogenated xylylene diisocyanate or hydrogenated diphenylmethane-4,4'-diisocyanate;
A polyisocyanate compound obtained by subjecting each of these diisocyanate compounds to an addition reaction with a di- to hexavalent low-molecular alcohol represented by trimethylolpropane in a ratio of 2 equivalents of isocyanate groups to 1 equivalent of hydroxyl groups. Or a burette-type polyisocyanate compound obtained by reacting various diisocyanate compounds with water; or 2-isocyanatoethyl-2,
Trifunctional isocyanate compounds such as 6-diisocyanate hexanoate; and multimers obtained by subjecting various diisocyanate compounds to isocyanuration.

Next, if only typical examples of the above-mentioned polyfunctional hydroxyl group-containing (meth) acrylate (a-2) are given, only 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate ,
2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meta)
Acrylate, glycerin mono (meth) acrylate,
Examples include glycerin di (meth) acrylate, glycidyl (meth) acrylate- (meth) acrylic acid adduct, tris (2-hydroxyethyl) esocyanurate-di (meth) acrylate, and N-methylol (meth) acrylamide.

These polyfunctional hydroxyl group-containing (meth) acrylates (a-2) may be used alone or in combination of two or more to obtain various polyvalent isocyanate compounds (a-1) as described above and NCO. Equivalent / OH equivalent = 1.5-2.0, and having at least one (meth) acryloyl (oxy) group in one molecule, that is, acryloyl group, methacryloyl group, acryloyloxy group or methacryloyloxy group. One type of urethane (meth) acrylate prepolymer, which may be called an unsaturated urethane compound, is obtained.

Typical examples of such unsaturated urethane compounds or urethane (meth) acrylate prepolymers include reaction products of tolylene diisocyanate with 2-hydroxyethyl (meth) acrylate. The combination of more than one species may be
Of course.

Furthermore, as the sulfonate-containing polyol (a-3), for example, sodium dimethylsulfoisophthalate and an excess polyhydric alcohol are subjected to a transesterification reaction by a conventional method, and first, a sodium sulfonate-containing diol is used. And then subjecting the sodium sulfonic acid-containing diol and a dicarboxylic acid to an esterification reaction.

Only the typical examples of the above-mentioned polyhydric alcohols used in this case are ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, Pentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,
2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, neopentyl glycol hydroxypivalate, cyclohexane dimethylol, 1,4 -Cyclohexanediol,
Trimethylolethane, trimethylolpropane, glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, spiroglycol, tricyclodecanedimethylol, hydrogenated bisphenol A or carbonate diol, and further, Examples include polyester polyols obtained by an esterification reaction of the above-mentioned various di- or polyols with various known and commonly used carboxylic acids or acid anhydrides thereof as described below.

Particularly representative of such carboxylic acids or their anhydrides are maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hetonic acid,
Hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic acid, sebacic acid,
Azelaic acid, 2,2,4-trimethyladipic acid, terephthalic acid, 2-potassium sulfoterephthalic acid, 2-sodium sulfoterephthalic acid, isophthalic acid, 2-potassium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, 5-sodium Di-lower alkyl sulfoisophthalates (e.g., -dimethyl or -dimethyl, etc.),
Orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid An acid or an acid anhydride thereof is exemplified.

Further, caprolactone polyester polyols obtained by ring-opening polymerization of ε-caprolactone using a dihydric to hexahydric alcohol represented by ethylene glycol, neopentyl glycol or trimethylolpropane as an initiator; or ethylene oxide or propylene oxide And polyalkylene polyols obtained by ring-opening polymerization of various alkylene oxides with the above-mentioned alcohols.

These may be used alone or in combination of two or more.

The energy ray-curable resin thus obtained is not particularly limited in molecular weight, but usually has a molecular weight of about 1,000 to 5,000, and contains this energy ray-curable resin as an active ingredient, a so-called energy ray-curable resin composition, An aqueous resin composition that can easily emulsify another synthetic resin, preferably an energy-ray-curable resin, without using a conventional emulsifier, and that has high sensitivity and does not use an organic solvent. After curing, it is different from existing emulsifiers, it has a high molecular weight and is reactive, so it has water resistance, solvent resistance, chemical resistance, etc. It gives an excellent film.

Examples of synthetic resins that can be emulsified with the energy ray-curable resin include the following. :
Known solutions include unsaturated polyester resin, vinyl ester resin (epoxy acrylate), polyurethane acrylate resin, polyether acrylate resin, melamine acrylate resin, alkyd acrylate resin, and silicon acrylate resin.

Thus, the energy ray-curable resin composition obtained by emulsifying a synthetic resin in water with the obtained energy ray-curable resin of the present invention is further, if necessary, within a range not departing from the object of the present invention, in particular, Water-soluble, storage stability and water resistance, as long as it can maintain solvent resistance and chemical resistance, etc., known and conventional additives, especially
It does not prevent adding other types of water-soluble resins.

The energy ray referred to in the present invention is an electron beam, an α ray,
It is a general term for ionizing radiation and light such as β-rays, γ-rays, X-rays, neutron rays or ultraviolet rays.

In the present invention, when curing the resin composition of the present invention using ultraviolet rays as the energy rays, the wavelength is
A photo (polymerization) initiator that dissociates with ultraviolet rays of 1,000 to 8,000 angstroms to generate radicals should be used. As such a photo (polymerization) initiator, any known and commonly used one can be used. , Acetophenones, benzophenones, Michler's ketone, benzine,
Benzoyl benzoate, benzoin, benzoin methyl ethers, benzyl dimethyl ketanol, α-
Examples include acyloxime esters, thioxanthones, anthraquinones, and various derivatives thereof.

A known and commonly used photosensitizer can be used in combination with such a photo (polymerization) initiator. However, if only typical photosensitizers are exemplified, amines, urea and the like may be used. , Sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, or nitriles or other nitrogen-containing compounds.

(Action) The energy ray-curable resin composition obtained as described above is capable of easily emulsifying another synthetic resin or energy ray-curable resin with a sulfonate of an alkali metal, , Is a component that forms a coating film from a place where it is itself reactive, and does not adversely affect the coating film as in the past emulsifiers. It is possible to convert the line-curable resin composition to an aqueous form.

In addition, by having both an ethylenically unsaturated double bond and a urethane bond in the resin skeleton, the chemical resistance and solvent resistance of the coating film can be ensured through the action of both these bonds, and The substrate itself can be protected from physical or chemical influences from the surface, and can be instantaneously cured by irradiation with energy rays. A membrane can also be obtained.

(Examples) Next, the present invention will be described more specifically with reference examples, examples, applied examples, and comparative applied examples. In the following, all parts and percentages are by weight unless otherwise specified. There is.

Reference Example 1 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 1 mol of tolylene diisocyanate and 1 mol of 2-hydroxyethyl acrylate were subjected to a urethanization reaction by a conventional method to give a urethane acrylate terminal. To obtain an unsaturated urethane compound (a-2-1) having an unreacted isocyanate group.

Also, 295.sodium dimethyl sulfoisophthalate.
0 g and 3-methyl-1,5-pentanediol 590.0 g
Was added to 16.0 g of "Fascat 4100" (organic tin catalyst manufactured by M & T Corp., USA), and transesterification was carried out by a conventional method to have sodium sulfonate base in the molecule. A mixture of diol and 3-methyl-1,5-pentanediol was obtained.

Then, to 821.0 g of this mixture, 292.0 g of adipic acid
Was added, and an esterification reaction was carried out by a conventional method to obtain a polyester diol (a-3-1) having a sodium sulfonate group in the molecule.

Thereafter, 1,027 g of (a-3-1) was charged into a flask newly equipped with a thermometer, a stirrer and a reflux condenser, and 0.5 g of di-n-butyltin diacetate was added thereto.
2-1) of 498 g was added and a urethanization reaction was carried out at 80 ° C. It was confirmed by infrared absorption spectrum analysis (hereinafter abbreviated as IR analysis) that no isocyanate groups remained. Hereinafter, this is abbreviated as resin (A-1).

Reference Example 2 295.0 g of sodium dimethylsulfoisophthalate was placed in a flask equipped with a thermometer, a stirrer and a reflux condenser.
And 472.0 g of 1,6-hexanediol, and 5.2 g of “Fascat 4100” were added thereto, and a transesterification reaction was carried out by a conventional method to obtain a diol having a sodium sulfonate group in the molecule and 1,1, A mixture with 6-hexanediol was obtained.

Then, to 703.0 g of this mixture, 292.0 g of adipic acid
Was added, and an esterification reaction was carried out by a conventional method to obtain a polyester diol (a-3-2) having a sodium sulfonate group in the molecule.

Separately, 1 mole of isophorone diisocyanate and 1 mole of pentaerythritol triacrylate are subjected to a urethanization reaction by a conventional method to obtain an unsaturated urethane compound (a-2-2) having an unreacted isocyanate group at the end of the urethane acrylate. ) Got.

Next, 178.0 g of tolylene diisocyanate and 1,674 g of (a-3-2) were added to a flask equipped with a thermometer, stirrer and reflux condenser, and 0.5 g of di-n-butyltin diacetate was added. In addition, a urethanization reaction was performed at 80 ° C. IR analysis confirmed that no isocyanate groups were present.

Further, 1234 g of (a-2-2) was added thereto, and a urethanization reaction was carried out at 80 ° C. until the isocyanate group disappeared to obtain a target energy ray-curable resin.

 Hereinafter, this is abbreviated as resin (A-2).

Reference Example 3 First, a free isocyanate group-containing unsaturated urethane compound (a-2-2) was prepared in the same manner as in Reference Example 1, except that an equivalent amount of hydroxyethyl methacrylate was used instead of hydroxyethyl acrylate. Get
Next, an intended energy ray-curable resin was obtained in the same manner as in Reference Example 2, except that the compound (a-2-2) was changed to be used.

 Hereinafter, this is abbreviated as resin (A-3).

Reference Example 4 A polyester obtained by condensing 3 mol of 3-methyl-1,5-pentanediol and 2 mol of adipic acid by a known method in a flask equipped with a thermometer, a stirrer and a reflux condenser. 1,148 g of a diol was charged, and 174 g of tolylene diisocyanate was added, followed by a urethanization reaction at 80 ° C. It was confirmed by IR analysis that no isocyanate group remained.

Further, here, 60 moles of a urethane acrylate prepolymer obtained by reacting 1 mole of 2-hydroxypropyl acrylate with 1 mole of tolylene diisocyanate.
8 g was added, and the urethanization reaction was performed at 80 ° C. Confirm that no isocyanate groups remain by IR analysis,
A transparent liquid target resin was obtained.

 Hereinafter, this is abbreviated as resin (C-1).

Reference Example 5 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, “Epiclon N-695” [a cresol-novolak-type epoxy compound manufactured by Dainippon Ink and Chemicals, Ltd .;
(Epoxy equivalent = 213), 3,195.0 g, 2,6-di-tert-butyl-4-methylphenol 12.8 g and hydroquinone monomethyl ether 1.3 g were further added, and acrylic acid 1,080.0 g and triphenylphosphine 12.8 g were further added. Was added thereto and reacted at a temperature of 110 ° C. until the acid value became 3 or less to obtain a reaction product (C-2).

Example 1 A paint comprising the energy-curable resin composition of the present invention was mixed sufficiently by mixing the following components with the resin (A-1) obtained in Reference Example 1, followed by stirring. Was prepared.

Resin (A-1) 10 parts 1-Hydroxyhexyl phenyl ketone 3 parts Resin (C-1) 30 parts Water 30 parts Then, the above-obtained paint was applied to a water-sharpened tin plate at a thickness of 20 μm. Applied.

Next, after drying this in hot air of 80 ° C for 20 minutes,
Ultraviolet rays were irradiated from a height of 15 cm for 5 seconds with a high-pressure mercury lamp of 80 W to cure. Table 1 shows the results of performance evaluation tests performed on the respective coated plates.

Example 2 In the same manner as in Example 1 except that the same amount of the resin (A-2) obtained in Reference Example 2 was used instead of the resin (A-1), an energy ray-curable resin was used. A paint composed of a resin composition was obtained, applied, and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained.

Example 3 In the same manner as in Example 1 except that the same amount of the resin (A-3) obtained in Reference Example 3 was used instead of the performance (A-1), the energy ray-curable type was used. A paint composed of a resin composition was obtained, applied, and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained.

Example 4 In the same manner as in Example 1 except that the same amount of the resin (C-2) was used instead of the resin (C-1),
A paint comprising an energy ray-curable resin composition was obtained, applied, and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained.

Example 5 In the same manner as in Application Example 2, except that the same amount of the resin (C-2) was used instead of the resin (C-1),
A paint comprising an energy ray-curable resin composition was obtained, applied, and cured.

The same performance evaluation was performed on the coated plate, and the results shown in Table 1 were obtained.

Application Example 6 In the same manner as in Example 3 except that the same amount of the resin (C-2) was used instead of the resin (C-1),
A paint comprising an energy ray-curable resin composition was obtained, applied, and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained.

Comparative Example 1 In the same manner as in Example 1 except that the resin (A-1) was replaced with the use of 5 parts of sodium alkyldiphenyl ether disulfonate, the composition was composed of an energy ray-curable resin composition. A paint was obtained, applied and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained.

Comparative Example 2 In the same manner as in Example 1 except that the resin (A-1) was replaced by using 5 parts of polyoxyethylene nonylphenyl ether, a paint composed of an energy ray-curable resin composition was used. Obtained, applied and cured.

When the same performance evaluation was performed on the coated plate, the results shown in Table 1 were obtained.

The evaluation of various performances was performed in the following manner.

Water emulsifiability: 10 g of water was mixed with 10 g of the paint, and the appearance was visually judged.

◎: Completely emulsified and in one liquid ○: Partially agglomerated ×: Water and resin are separated without emulsification Curability: Coated after drying for 15 minutes at a film just 80 ° C. in hot air, a 80 / cm ² consisting becomes lower 15cm position of the high-pressure mercury lamp intensity, and passed through at a rate made 50 m / min, until the cure Are indicated by the number of passes.

Water resistance: The reduced film thickness (μm) after rubbing the cured coating film 20 times with a gauze soaked in ion-exchanged water was measured, and the judgment was made based on the magnitude.

◎: less than 5 μm ○: 5 to 10 μm △: 11 to 15 μm ×: more than 15 μm Solvent resistance: A gauze immersed in acetone was applied to the cured coating film.
The reduced film thickness (μm) after rubbing 20 times was measured, and the judgment was made based on the magnitude.

◎: less than 5 μm ○: 6 to 10 μm △: 11 to 15 μm ×: more than 15 μm Alkali resistance: The reduced film thickness after rubbing the cured coating film 20 times with a gauze soaked with a 10% aqueous sodium hydroxide solution (μ
m) was measured, and the judgment was made based on the magnitude.

◎: less than 5 μm ○: 6 to 10 μm △: 11 to 15 μm ×: more than 15 μm Heat resistance: After drying the freshly applied coating film in hot water at 80 ° C. for 15 minutes, 80 / cm ² Pass 10 times under a high-pressure mercury lamp at a speed of 50 m / min 10 times below the high-pressure mercury lamp of high intensity, then place the cured coating film thus obtained in a heating furnace at 200 ° C for 20 seconds, and immediately apply the coating film. The gauze was pressed against the surface, the gauze was peeled off after cooling, and the state of change of the coated surface was visually determined.

◎: No change was observed. ○: A trace of gauze was slightly formed on the coating film. ×: The coating was melted and peeled off with the gauze. As is clear from the results shown in this table, The energy ray-curable resin compositions obtained by emulsifying with an energy ray-curable resin can be freely cured at room temperature or under heat, and can be freely cured with energy rays. Compared to those obtained using a conventional energy ray-curable resin with an ester structure, the curability is much better, and the resulting cured coating has water resistance, solvent resistance, chemical resistance, etc. It is also excellent in heat resistance, and is extremely useful for various applications that can be made aqueous with an alkali metal sulfonate. .

(Effect of the Invention) The energy ray effect type resin composition emulsified by the energy ray effect type resin of the present invention is one liquid,
Since it can be diluted with water, it has no influence on the environment or working process, and there is no factor that causes a dark reaction.

Therefore, long-term stability is ensured.

In addition, the resin composition of the present invention has high sensitivity, and it is possible to easily emulsify a wide variety of synthetic resins and convert it into an aqueous resin composition. It is extremely useful in a wide range of applications, especially as a coating agent, a photoresist, a printing ink, a plate-making material, etc., because of its excellent properties, chemical resistance and heat resistance.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09D 175/16 C09D 175/16 C09J 175/16 C09J 175/16 G03F 7/027 513 G03F 7/027 513 (56) References Special features JP-A-62-22865 (JP, A) JP-A-62-22866 (JP, A) JP-A-62-1112665 (JP, A) JP-A-2-20981 (JP, A) JP-A-59-77624 (JP, A) JP, A) JP-A-3-17113 (JP, A) JP-A-3-168209 (JP, A) JP-A-2-41380 (JP, A) JP-A-4-91162 (JP, A) JP JP-A-62-112666 (JP, A) JP-A-62-112667 (JP, A) JP-A-63-10820 (JP, A) JP-A-58-32617 (JP, A) JP-A-58-32618 (JP) , A) JP-A-4-31422 (JP, A) JP-A-3-199227 (JP, A) (58) Field (Int.Cl. ^7, DB name) C08F 283/00 - 283/01 C08F 290/00 - 290/14 C08F 299/00 - 299/08 C08L 1/00 - 101/14 C08G 18/00 - 18 / 87 C08G 59/00-59/72 C09D 1/00-201/10

Claims (4)

(57) [Claims] An energy ray-curable resin composition obtained by emulsifying a synthetic resin in water with an energy ray-curable resin (A) having an ethylenically unsaturated double bond and a sulfonate of an alkali metal. 2. The energy ray-curable resin according to claim 1, wherein the energy ray-curable resin (A) having an ethylenically unsaturated double bond and an alkali metal sulfonate further has a urethane bond in the molecule. Composition. 3. An energy ray-curable resin (A) having an ethylenically unsaturated double bond and a sulfonate of an alkali metal, comprising a polyvalent isocyanate compound and at least one primary compound per molecule. And / or at least one (meth) acrylate having a secondary hydroxyl group in one molecule.
The energy ray-curable resin according to claim 1 or 2, which is obtained by reacting a compound having both primary and / or secondary hydroxyl groups and at least one alkali metal sulfonate. Composition. 4. The energy ray-curable resin composition according to claim 1, wherein the synthetic resin is an energy ray-curable resin (B) other than the energy ray-curable resin (A).