JP2022037865A - Method for producing active energy ray-curable water-soluble resin composition containing photochromic dye and coating composition, and cured article - Google Patents

Abstract

To provide a method for producing an aqueous solution or an emulsion of a resin composition which contains a photochromic dye and exhibits multi-functions.SOLUTION: A method for producing a photochromic dye-containing active energy ray-curable water-soluble resin composition includes: reacting a (meth)acrylic acid alkylene oxide addition compound or a one-terminal hydroxy group-containing polyalkylene glycol compound with a reactant obtained by reacting a hydroxyl group-containing (meth)acrylate compound with an isocyanate compound, and obtaining an urethane (meth)acrylate oligomer represented by formula (1); preparing an oligomer composition obtained by gently stirring or emulsifying an interface between the oligomer and water while adding the water to the oligomer; preparing a photochromic dye solution by dissolving a photochromic dye in an ethylenically unsaturated monomer; and dissolving the dye solution in an oligomer composition. Formula (1): (R1O-CONH)m-R2-(NHCO-OR3)n.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an active energy ray-curable water-soluble resin composition containing a photochromic dye, a coating composition, and a cured article.

For example, the forochromic material reversibly isomerizes between two states having different absorption spectra by irradiation with light, and is accompanied by a color change. Therefore, in recent years, it is expected that such materials will be used for various purposes such as dimming, optical memory, and holograms. On the other hand, since the photochromic material is oil-soluble (water-insoluble) due to its color-developing structure, it is difficult to use it as an aqueous solution or an emulsion.
On the other hand, a monomer obtained by copolymerizing a monomer that imparts photochromic properties with a monomer that imparts water solubility or the like (for example, Patent Document 1) is used by expressing a liquid crystal state in a bicolor dye using water as a solvent. (For example, Patent Document 2), a forochromic material emulsified with a surfactant, and the like have been proposed (for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 63-308014 Special Table 2018-3996 Gazette Japanese Unexamined Patent Publication No. 2019-3103

However, depending on the application, development of a material that not only is used as an aqueous solution or an emulsion, but also has various functions such as durability (water resistance, solvent resistance) and hard coat property. Is required.
The present disclosure discloses an active energy ray-curable water-soluble resin composition which not only contains a photochromic dye but also exhibits multiple functions and can be used as an aqueous solution or an emulsion, a method for producing the same, and a method for curing the active energy ray-curable water-soluble resin composition. It is an object of the present invention to provide a cured article.

The present application includes the following inventions.
(1) The hydroxyl group-containing (meth) acrylate compound n-molar ratio is reacted with the 1-molar ratio of the isocyanate compound having (m + n) isocyanate groups.
Next, the obtained reaction product was reacted with a (meth) acrylic acid alkylene oxide-added compound or a polyalkylene glycol compound containing a single-terminal hydroxyl group in an mmolar ratio.
Obtaining the urethane (meth) acrylate oligomer according to the formula (1),
A water-soluble urethane (meth) acrylate oligomer composition obtained by gently stirring or emulsifying the interface between the urethane (meth) acrylate oligomer and water while adding water to the urethane (meth) acrylate oligomer is prepared. ,
A photochromic dye solution is prepared by dissolving the photochromic dye in an ethylenically unsaturated monomer.
A method for producing an active energy ray-curable water-soluble resin composition containing a photochromic dye, which comprises dissolving the photochromic dye solution in the water-soluble urethane (meth) acrylate oligomer composition.
(R ¹ O-CONH) _m -R ^2- (NHCO-OR ³ ) n (1)
(During the ceremony,
R ¹ O- is a dehydrogenation residue of a polyalkylene glycol compound containing a hydroxyl group at one end or an alkylene oxide-added (meth) acrylic acid alkylene oxide compound.
R ² is a deisocyanate group residue of an isocyanate compound,
-OR ³ is a dehydrogenation residue of a hydroxyl group-containing (meth) acrylate compound,
Represents an integer of m and n = 1 to 50. However, m ≦ n. )
(2) The production method according to the above, wherein the ethylenically unsaturated monomer is water-soluble.
(3) The production method according to the above, wherein the ethylenically unsaturated monomer has a glass transition temperature of 100 ° C. or higher of the homopolymer thereof.
(4) The production method according to the above, wherein the photochromic dye is at least one selected from a spirobenzopyran derivative and a diarylethene derivative.
(5) The production method according to the above, wherein the isocyanate compound is a diisocyanate or a diisocyanate monomer polyisocyanate.
(6) The production method according to the above, wherein the one-terminal hydroxyl group-containing polyalkylene glycol compound is an alkoxypolyalkylene glycol.
(7) The production method according to the above, wherein the (meth) acrylic acid alkylene oxide-added compound is obtained by adding (meth) acrylic acid to alkylene oxide or mono (meth) acrylate-forming polyalkylene glycol.
(8) The production method according to the above, wherein the hydroxyl group-containing (meth) acrylate compound is hydroxyalkyl (meth) acrylates, polyol (meth) acrylates or alkylene oxide-added polyol (meth) acrylates.
(9) The production method according to the above, wherein the ethylenically unsaturated monomer is a (meth) acrylic acid compound or a vinyl group-containing compound.
(10) The (meth) acrylic acid compound is an acrylic acid amide, an alkyl (meth) acrylate, an aminoalkyl (meth) acrylate, a quaternary salt of an aminoalkyl (meth) acrylate, and an alkoxypolyalkylene glycol (meth). Acrylate, hydroxyalkyl (meth) acrylate, acid anhydride adduct of hydroxyalkyl (meth) acrylate, polyalkylene glycol di (meth) acrylate, alkyldiol di (meth) acrylate, polyol poly (meth) acrylate Class, at least one selected from alkylene oxide-added polyol poly (meth) acrylates, the vinyl group-containing compound is vinyl acetate, N-vinylacetamide, vinylpyrrolidone, vinylalkyl ethers, vinylsulfonic acid, vinylsulfonic acid salts. The production method according to the above, which is at least one selected from the above.
(11) The solid content ratio (weight ratio) of the water-soluble urethane (meth) acrylate oligomer composition, the ethylenically unsaturated monomer and the photochromic dye is 100: 5 to 300: 0.005 to 0.2 as described above. Manufacturing method.
(12) A coating composition containing an active energy ray-curable water-soluble resin composition containing a photochromic dye obtained by the above-mentioned production method.
(13) The coating composition according to the above, further comprising at least one photopolymerization initiator.
(14) The coating according to the above, wherein the photopolymerization initiator is 0.002 to 10 parts by weight with respect to 100 parts by weight of the total solid content of the water-soluble urethane (meth) acrylate oligomer composition and the ethylenically unsaturated monomer. Composition.
(15) A cured article having a film of the coating composition described above formed on the surface of the object to be coated and the object to be coated.

According to the present invention, an active energy ray-curable water-soluble resin composition which not only contains a photochromic dye but also exhibits multiple functions and can be used as an aqueous solution or an emulsion, and a method for producing the same. It is possible to provide a cured article obtained by curing the above.

In the present specification, "(meth) acrylate", "(meth) acrylic acid" and the like are selected from the group consisting of "at least one selected from the group consisting of acrylate and methacrylate" and "the group consisting of acrylic acid and methacrylic acid, respectively". It means "at least one kind" and the like. In addition, the numerical range represented by "-" includes the numerical values before and after it. In the present specification, "solid content" means "heated residue" in the examples, and usually corresponds to "curing component concentration". Further, in the present specification, "part" means "part by weight". Further, the molecular weight means a weight average molecular weight, and indicates a value measured by the method described in paragraph 15.

[Manufacturing method of photochromic dye-containing active energy ray-curable water-soluble resin composition]
In the method for producing an active energy ray-curable water-soluble resin composition containing a photochromic dye in the present application (hereinafter, may be simply referred to as "dye-containing composition"),
(A) A water-soluble urethane (meth) acrylate oligomer composition is prepared, and also
(B) The photochromic dye is dissolved in an ethylenically unsaturated monomer to prepare a photochromic dye solution, followed by
(C) The photochromic dye solution is dissolved in a water-soluble urethane (meth) acrylate oligomer composition.
As described above, most photochromic dyes are oil-soluble (water-insoluble) due to their structure. Therefore, when applying a photochromic dye, it is possible to dissolve it in an organic solvent and apply it on a substrate for use. It is common. However, when an organic solvent is used, for example, when it is applied onto a plastic base material, the organic solvent may dissolve the base material. Furthermore, from the viewpoint of safety, it is preferable to use an aqueous solvent rather than an organic solvent.
Therefore, in the production method of the present invention, the obtained photochromic dye-containing active energy ray-curable water-soluble resin composition is in a state in which the photochromic dye is dispersed in the water-soluble resin composition. , Solution stability can be improved. Moreover, since it is water-soluble, it is easy to use. That is, as compared with the case where an organic solvent is used as the solvent, the dissolution of the plastic base material can be avoided, and the safety can be further ensured by not using the organic solvent. Furthermore, unlike conventional water-soluble photochromic polymers, it has excellent durability (water resistance, solvent resistance) of the cured coating film, and it also has excellent hard coat properties by appropriately compensating for scratch resistance, which can be said to be a weak point of plastics. Can be. In addition, it is possible to exhibit excellent characteristics such as optical transparency (total light transmittance, HAZE).

(A: Preparation of water-soluble urethane (meth) acrylate oligomer composition)
In order to prepare the water-soluble urethane (meth) acrylate oligomer composition in the present application, first, a urethane (meth) acrylate oligomer represented by the formula (1) is synthesized.
The urethane (meth) acrylate oligomer represented by the formula (1) is
The hydroxyl group-containing (meth) acrylate compound n-molar ratio was reacted with the 1-molar ratio of the isocyanate compound having (m + n) isocyanate groups.
Then, it can be obtained by reacting a (meth) acrylic acid alkylene oxide addition compound or a polyalkylene glycol compound containing a single-ended hydroxyl group in an mmolar ratio.
(R ¹ O-CONH) _m -R ^2- (NHCO-OR ³ ) _n (1)
(During the ceremony,
R ¹ O- is a dehydrogenation residue of a polyalkylene glycol compound containing a hydroxyl group at one end or an alkylene oxide-added (meth) acrylic acid alkylene oxide compound.
R ² is a deisocyanate group residue of an isocyanate compound,
R ³ O- is a dehydrogenation residue of a hydroxyl group-containing (meth) acrylate compound.
Represents an integer of m and n = 1 to 50. However, m ≦ n. )
Then, while adding water to the obtained urethane (meth) acrylate oligomer, the interface between the urethane (meth) acrylate oligomer and water is gently stirred. Thereby, a water-soluble urethane (meth) acrylate oligomer composition can be produced.

The emulsion obtained by the method for producing the water-soluble urethane (meth) acrylate oligomer composition described above in the present application has an extremely small average particle size and is stable for a long period of time (secondary aggregation does not occur). The coating film obtained by the composition containing the mixture can be a coating film having excellent water resistance, solvent resistance and scratch resistance. That is, it has the contradictory unique characteristics that it is water-soluble before curing, but has high water resistance when it becomes a cured product. Since such a coating film has excellent scratch resistance and antistatic properties, it is possible to protect the surface of a base material such as plastic, prevent dust absorption, and impart antibacterial properties. Further, since such a coating film has a hydrophilic group, it has excellent anti-fog properties, and can be used not only for plastics but also for anti-fog for eyeglasses, mirrors, etc., and also has dispersibility in water-based pigments. It can be good. Further, since the urethane (meth) acrylate oligomer itself has a relatively small molecular weight, it can also be used as a component of a water-soluble UV inkjet ink.

Examples of the isocyanate compound having (m + n) isocyanate groups include diisocyanates and polyisocyanates which are diisocyanate monomers.
Examples of the diisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (o-, m-, or p-) xylene diisocyanate, methylene bis (cyclohexyl isocyanate), and the like. Examples thereof include trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalenediocyanide, and norbornan diisocyanate. Examples of the polyisocyanates of the diisocyanate monomer include hexamethylene diisocyanate nulates, isophorone diisocyanate nulates, tolylene diisocyanate nulates, and burettes of these diisocyanates. Of these, hexamethylene diisocyanate nurates, isophorone diisocyanate nurates, and tolylene diisocyanate nurates, which have three or more isocyanate groups in one molecule, are more preferable.
The isocyanate compound may have a urethane structure in which an alcohol compound is added or a urea structure in which an amine compound is added to one or more isocyanate groups contained therein. When an alcohol compound and an amine compound are added to the isocyanate group, the number of functional groups per molecule of the isocyanate compound can be increased. Examples of the alcohol compound that can be added to the isocyanate group include ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Examples of the amine compound include diaminoethane, diaminopropane, tetramethylenediamine and the like. From the viewpoint of increasing the scratch resistance of the cured polymer, it is preferable to use these alcohol compounds and amine compounds having a small molecular weight per functional group.

Examples of the hydroxyl group-containing (meth) acrylate compound include hydroxyalkyl (meth) acrylates, polyol (meth) acrylates, alkylene oxide-added polyol (meth) acrylates, and the like. Examples of hydroxyalkyl (meth) acrylates include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyphenoxypropyl (meth) acrylate and the like. Examples of the polyol (meth) acrylates include glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Examples of the alkylene oxide-added polyol (meth) acrylate include alkylene oxide-added trimethylolpropane di (meth) acrylate, alkylene oxide-added pentaerythritol tri (meth) acrylate, and alkylene oxide-added dipentaerythritol penta (meth) acrylate. Can be mentioned.

When a hydroxyl group-containing (meth) acrylate compound is reacted with an isocyanate compound, a metal-based catalyst such as dibutyltin dilaurate and an amine-based catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7 are used for the purpose of accelerating the reaction. In the presence of a catalyst or the like, stirring is preferably performed in the temperature range of 50 ° C to 80 ° C, more preferably 60 ° C to 70 ° C.

Subsequently, the reaction product obtained above is reacted with the (meth) acrylic acid alkylene oxide addition compound or the one-terminal hydroxyl group-containing polyalkylene glycol compound.
The (meth) acrylic acid alkylene oxide-added compound is preferably one in which (meth) acrylic acid is alkylene oxide-added or mono (meth) acrylated with polyalkylene glycol. The alkylene oxide adduct of (meth) acrylic acid is obtained by adding an alkylene oxide typified by ethylene oxide, propylene oxide, butylene oxide or the like to (meth) acrylic acid. It can also be synthesized from polyalkylene glycols typified by polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. The molecular weight of the (meth) acrylic acid alkylene oxide addition compound can be arbitrarily selected, but is preferably 900 or more, and more preferably 900 to 2000. From another point of view, the number of moles of alkylene oxide added is preferably 20 or more, and more preferably 20 to 35.
The one-terminal hydroxyl group-containing polyalkylene glycol compound is preferably alkoxy polyethylene glycols. Examples of alkoxypolyethylene glycols include methoxypolyethylene glycol, ethoxypolyethylene glycol, butoxypolyethylene glycol, polyethylene glycol monoallyl ether, polyethylene glycol monododecyl ether, polyethylene glycol monolaurate, and polyethylene glycol monooctyl ether. The molecular weight of the alkoxypolyethylene glycols can be arbitrarily selected, but is preferably 900 or more, and more preferably 900 to 2000. By using such a compound, the obtained water-soluble urethane (meth) acrylate oligomer composition can be made into a nonionic emulsion, and even when various additives are added to the coating composition or the like. , Impairment of emulsion properties such as aggregation, precipitation and separation can be prevented.

When the reaction product obtained above is reacted with a (meth) acrylic acid alkylene oxide-added compound or a one-terminal hydroxyl-containing polyalkylene glycol compound, the temperature is 50 ° C to 80 ° C in the presence of a metal-based catalyst such as dibutyltin dilaurate. Stirring is preferably in the range, more preferably in the temperature range of 60 ° C to 70 ° C.
The obtained urethane (meth) acrylate oligomer can have a resin content concentration of 100%. The weight average molecular weight of the urethane (meth) acrylate oligomer can be, for example, 5000 to 100,000, preferably 7,000 to 20,000. By setting such a weight average molecular weight, a composition having an appropriate viscosity can be obtained, self-emulsification is likely to occur, and the water-soluble composition can be easily prepared by using the composition. When a coating film or the like containing such a water-soluble composition is formed, a coating film having a high hardness can be obtained.
The weight average molecular weight means the weight average molecular weight in terms of standard polystyrene molecular weight, and is used in high performance liquid chromatography (manufactured by Showa Denko, "Shodex GPC system-11 type"), column: Shodex GPC KF-806L (exclusion limit molecular weight). : 2 x ^{107, separation range: 100 to 2 x 10 7 ,} theoretical number of stages: 10,000 stages / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) It can be measured by using it.

For example, when an isocyanate compound having (m + n) isocyanate groups is first reacted with a (meth) acrylic acid alkylene oxide-added compound or a polyalkylene glycol compound containing a single-terminal hydroxyl group, the polyalkylene glycol compound has a distribution in molecular weight. However, due to the presence of polyalkylene glycol containing not only one-terminal hydroxyl group but also two-terminal hydroxyl group, gelation often occurs. When gelation occurs, not only is a stable reaction not possible, but the obtained reactant is difficult to dissolve in water.
On the other hand, as described above, the isocyanate compound having (m + n) isocyanate groups is first reacted with the hydroxyl group-containing (meth) acrylate compound n molar ratio, and then the (meth) acrylic acid alkylene oxide-added compound or one-terminal hydroxyl group is reacted. By reacting the contained polyalkylene glycol compound, the polyalkylene glycol compound is bonded like a pendant to form a pendant type urethane acrylate structure, so that self-emulsification is possible.

Subsequently, water is added to the urethane (meth) acrylate oligomer represented by the formula (1) to produce a water-soluble urethane (meth) acrylate oligomer composition in the form of an emulsified aqueous solution.
Therefore, water is gradually added to the urethane (meth) acrylate oligomer obtained above. At this time, the obtained urethane (meth) acrylate oligomer is preferably maintained in a temperature range of, for example, 30 ° C to 80 ° C, and the temperature of the water to be added is also preferably adjusted to the same range, preferably 40 ° C. It is more preferable to set the temperature in the temperature range of about 70 ° C. or 40 ° C. to 60 ° C.
As the water to be added, various waters such as tap water, deionized water, ion-exchanged water, and distilled water can be used. It is preferable to add water by, for example, dropping or dividing it. In the case of partial addition, the single dose can be, for example, 50 to 200 parts with respect to 100 parts of the urethane (meth) acrylate oligomer, preferably 100 to 200 parts. The amount of water added is preferably such that the resin content concentration is 50% by weight or less, more preferably 10% by weight to 45% by weight, and 15% by weight to 40% by weight or 20% by weight to 40% by weight. More preferred. For example, the time required for adding water may be 5 minutes or more from the start to the end of water addition, preferably 5 minutes to 2 hours, and 10 minutes to 30 minutes or 15 minutes to. More preferably, it is 30 minutes.

Further, at the same time as the addition of water, it is preferable to dispose a stirring blade at the interface between them, that is, near the interface between the oligomer and water or slightly closer to the water side to stir. It is preferable that the stirring here is performed gently. In the stirring with the stirrer, the stirrer sinks to the bottom surface of the container and cannot be placed at the interface between the oligomer and the water, that is, the W / O interface. Therefore, the stirring blade may be placed near the interface between the oligomer and the water. It is preferable to stir using a stirrer capable of stirring. As the stirring blade, for example, a paddle blade can be used. The paddle blade can be arranged near the interface between the oligomer and water or slightly on the water side of the interface, and may have only one blade or may have two or more blades in multiple stages. May be. Examples of the gentle stirring include a rotation speed of 500 rpm or less, preferably 300 rpm or less, more preferably 200 rpm or less, and particularly preferably 100 rpm to 300 rpm or 100 rpm to 150 rpm.
Further, it is preferable to continue stirring even after the addition of water is completed. The stirring in this case may be different from the stirring during addition, but it is preferably performed as slowly as possible. After the addition of water is completed, for example, stirring is continued for 10 minutes or more, preferably 20 minutes or more, and more preferably 30 minutes or more. The rotation speed at this time also includes the same range as described above.

By emulsifying by such an emulsification method (phase inversion emulsification), the obtained emulsion has an extremely small average particle size and high storage stability. Further, when the emulsion is used as a coating composition, for example, as a radiation-curable coating film after coating and drying, the obtained coating film has good leveling property, extremely high water resistance, and is cured. It is possible to obtain a coating composition having contradictory properties that the former oligomer is water-soluble but the cured coating film has high water resistance. It has been confirmed that this is due to the uniform particle size of the urethane (meth) acrylate oligomer in the obtained water-soluble urethane (meth) acrylate oligomer composition. For example, in the particle size distribution of the emulsion particles, the particle size of the cumulative 50% of the particles is 100 nm or less. Further, the particle size of 50% is preferably 60 nm or less, more preferably 50 nm or less, and even more preferably 10 nm to 45 nm. Further, those having a 95% integrated diameter of particles of 150 nm or less can be mentioned. Further, the 95% particle size is preferably 140 nm or less, more preferably 120 nm or less, and even more preferably 30 nm to 115 nm. Further, from another viewpoint, those having an arithmetic mean diameter of 110 nm or less can be mentioned. Further, it is preferably 100 nm or less, more preferably 70 nm or less, and even more preferably 10 nm to 60 nm.
These are the values obtained by measuring the particle size distribution of the emulsion with a dynamic light scattering type particle size distribution measuring device (LB-500) manufactured by HORIBA, Ltd.

The water-soluble urethane (meth) acrylate oligomer composition does not exclude the inclusion of an organic solvent. For example, as the organic solvent, ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol and butanol are not excluded. , Acetone, methyl isobutyl ketone, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves, diacetone alcohol and the like may be contained. In this case, 50 parts or less is preferable, and 10 parts or less is more preferable with respect to 100 parts by weight of the entire composition.

(B: Preparation of photochromic dye solution)
Any known photochromic dye can be used. Among them, an oil-based dye is preferable because the effect of the present invention can be more exerted. Examples of the oily dye here include those having a solubility in water at a temperature of 20 ° C. of less than 1 g / l.
Examples of the dye include inorganic compounds such as tungsten oxide (WO ₃ ) and silver halide (for example, AgBr); spirobenzopyran-based, spiroxazine-based, spiropyran-based, azobenzene-based, flugide-based, chromene-based, diarylethene-based, and azo. Examples thereof include organic dyes of anthraquinone type, merocyanine type, styryl type, azomethine type, quinone type, quinophthalone type, perylene type, indigo type, tetrazine type, stilben type and benzidine type. US Pat. No. 2,40877, JP-A-2002-527786, JP-A-2-28154, JP-A-62-288830, WO94 / 22850 pamphlet, WO96 / 14596 pamphlet, etc. May be. Of these, spirobenzopyran-based and diarylethene-based photochromic materials are preferable, and diarylethene-based photochromic materials are more preferable. In particular, these are such that molecules of all colors can be obtained by introducing substituents and condensed rings, that it is easy to design molecules that are stable in both colorless and colored forms that do not return to heat at room temperature, and that not only solutions but also crystals. However, it shows stable photochromism.
As a spirobenzopyran-based photochromic material,
1', 3'-Dihydro-8-methoxy-1', 3', 3'-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2'-[2H] indole] (CAS RN 1498-89- 1), 1,3,3-Trimethylindolinonaphthospirooxazine (CAS RN 27333-47-7), 1- (2-Hydroxyethyl) -3,3-dimethylindolino-6'-itrobenzopyrylospiran (CAS RN 16111-07-2), 1, 3,3-Trimethylindolinobenzopyrylospiran (CAS RN 1485-92-3), 1,3,3-Trimethylindolino-8'-methoxybenzopyrylospiran (CAS RN 13433-31-3), 1,3,3-Trimethylindolino-6'-nitrobenzopyrylospiran (CAS RN 13433-31-3) CAS RN 1498-88-0), 1,3,3-Trimethylindolino-β-naphthopyrylospiran (CAS RN 1592-43-4), 1,3,3-Trimethylindolino-6'-bromobenzopyrylospiran (CAS RN 16650-14-9) ) Etc. can be mentioned.
Diarylethene-based photochromic materials include 2,3-Bis (2,4,5-trimethyl-3-thienyl) maleimide (CAS RN 220191-36-6) and 2,3-Bis (2,4,5-trimethyl). -3-thienyl) maleic Anhydride (CAS RN 112440-47-8), 1,2-Bis (2,4-dimethyl-5-phenyl-3-thienyl) -3,3,4,4,5,5- hexafluoro-1-cyclopentene (CAS RN 172612-67-8), cis-1,2-Dicyano-1,2-bis (2,4,5-trimethyl-3-thienyl) ethene (CAS RN 112440-46-7) ), 1,2-Bis [2-methylbenzo [b] thiophen-3-yl] -3,3,4,4,5,5-hexafluoro-1-cyclopentene (CAS RN 137814-07-4), 1, 2-Bis [2-methylbenzo [b] thiophen-3-yl] -3,3,4,4,5,5-hexafluoro-1-cyclopentene (CAS RN 137814-07-4) and the like can be mentioned.

Examples of the ethylenically unsaturated monomer include (meth) acrylic acid compounds and vinyl group-containing compounds.
Examples of the (meth) acrylic acid compound include acrylic acid amides, alkyl (meth) acrylates, aminoalkyl (meth) acrylates, quaternary salts of aminoalkyl (meth) acrylates, alkoxypolyalkylene glycol (meth) acrylates, and the like. Hydroxyalkyl (meth) acrylates, acid anhydride additives of hydroxyalkyl (meth) acrylates, polyalkylene glycol di (meth) acrylates, alkyldiol di (meth) acrylates, polyol poly (meth) acrylates, alkylene Examples thereof include oxide-added polyol poly (meth) acrylates. Examples of the vinyl group-containing compound include vinyl acetate, N-vinylacetamide, vinylpyrrolidone, vinylalkyl ethers, vinyl sulfonic acid, salts of vinyl sulfonic acid and the like. These may be used alone or may use two or more kinds.

Examples of acrylic acid amides include (meth) acryloylmorpholine and dimethylaminoalkyl (meth) acrylamide. Examples of aminoalkyl (meth) acrylates include diethylaminoethyl (meth) acrylates. Examples of the quaternary salt of aminoalkyl (meth) acrylate include alkylaminopropyldimethyl-2-hydroxyethylammonium salt and the like. Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and the like. Examples of alkoxypolyalkylene glycol (meth) acrylates include methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate. Examples of hydroxyalkyl (meth) acrylates include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like. Examples of the acid anhydride adduct of hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate phthalic anhydride adduct, hydroxyethyl (meth) acrylate succinic anhydride adduct, and hydroxyethyl (meth) acrylate tetrahydrophthalic anhydride phthalic anhydride. Acid adduct, hydroxyethyl (meth) acrylate phthalic anhydride adduct, hydroxypropyl (meth) acrylate phthalic anhydride adduct, hydroxypropyl (meth) acrylate succinic anhydride adduct, hydroxypropyl (meth) acrylate tetrahydroanhydride Examples thereof include phthalic acid adducts, hydroxypropyl (meth) acrylate hexahydrophthalic anhydride adducts and the like. Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. Examples of the alkyldiol di (meth) acrylate include butanediol di (meth) acrylate and hexanediol di (meth) acrylate. Examples of the polyol poly (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. .. Examples of the alkylene oxide-added polyol poly (meth) acrylates include alkylene oxide-added trimethylolpropane tri (meth) acrylate, alkylene oxide-added pentaerythritol tri (meth) acrylate, and alkylene oxide-added pentaerythritol tetra (meth) acrylate alkylene oxide. Examples thereof include added pentaerythritol hexa (meth) acrylate. Examples of vinyl alkyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, amyl vinyl ether, 2-ethylhexyl vinyl ether and the like.

Among them, the (meth) acrylic acid compound or the vinyl group-containing compound has antistatic properties, and is a quaternary of (meth) acryloylmorpholine, vinylpyrrolidone, dimethylaminoalkyl (meth) acrylate, and dimethylaminoalkyl (meth) acrylate. More preferably, it is a salt, dimethylaminoalkyl (meth) acrylamide, N-vinylacetamide, vinyl sulfonic acid and vinyl sulfonate.

The method for dissolving the photochromic dye in the ethylenically unsaturated monomer is not particularly limited, and examples thereof include adding the photochromic dye to the ethylenically unsaturated monomer and stirring the dye. In this case, for example, it may be heated to room temperature to 80 ° C., preferably 40 ° C. to 70 ° C. or 50 ° C. to 60 ° C.
The ratio (parts by weight) of the ethylenically unsaturated monomer / photochromic dye is preferably 0.001 part to 4 parts of the photochromic dye with respect to 100 parts of the ethylenically unsaturated monomer, and 0.005 part. ~ 0.3 part is more preferable.

(C: Dissolution of photochromic dye solution in water-soluble urethane (meth) acrylate oligomer composition)
The method for dissolving the photochromic dye solution in the water-soluble urethane (meth) acrylate oligomer composition is not particularly limited, and the photochromic dye solution is added to the water-soluble urethane (meth) acrylate oligomer composition and stirred. Can be mentioned. In this case, for example, it may be heated to room temperature to 80 ° C., preferably 40 ° C. to 70 ° C. or 50 ° C. to 60 ° C.
The ratio (ratio of solid content) of the photochromic dye solution to the water-soluble urethane (meth) acrylate oligomer composition was 5 to 300 parts of the photochromic dye solution to 100 parts of the solid content of the water-soluble urethane (meth) acrylate oligomer composition. It is preferable to add parts so as to form parts, and more preferably 50 parts to 250 parts.

[Coating composition]
The photochromic dye-containing active energy ray-curable water-soluble resin composition obtained by the method for producing a photochromic dye-containing active energy ray-curable water-soluble resin composition in the present application may optionally be an ethylenically unsaturated monomer or a photopolymerization initiator. , A photopolymerization initiator, an antistatic agent and the like can be contained in the coating composition. Among them, those containing a photopolymerization initiator are preferable.
However, these components are added to and / or the photochromic dye solution at the time of preparing the above-mentioned photochromic dye solution and / or at the time of dissolving the photochromic dye solution in the water-soluble urethane (meth) acrylate oligomer composition. It may be added to the water-soluble urethane (meth) acrylate oligomer composition of the solution. In that case, these components may be added simultaneously or sequentially to the water-soluble urethane (meth) acrylate oligomer composition and / or to the photochromic dye solution and mixed.
The ethylenically unsaturated monomer is used in the preparation of the above-mentioned photochromic dye solution, but is obtained when the photochromic dye solution is dissolved in the water-soluble urethane (meth) acrylate oligomer composition and / or finally obtained. It may also be added in the dye-containing composition obtained. However, since the photopolymerization initiator and the like are relatively oil-soluble, it is preferable to add and dissolve them in the ethylenically unsaturated monomer of the photochromic dye solution, and then add and mix them with the water-soluble urethane (meth) acrylate oligomer. Further, when the ethylenically unsaturated monomer is separately added to the water-soluble urethane (meth) acrylate oligomer composition and / or the dye-containing composition, the mass ratio to the photochromic dye mentioned in the preparation of the photochromic dye solution is within the range. It is preferable to add in.
In other words, with respect to 100 parts (solid content 30% by weight) of the water-soluble urethane (meth) acrylate oligomer composition, 3 parts to 300 parts are mentioned, 5 parts to 300 parts are preferable, and 10 parts to 200 parts are more. preferable. However, the amount of the ethylenically unsaturated monomer here includes the amount of the ethylenically unsaturated monomer used in the preparation of the photochromic dye solution described later.

When a photopolymerization initiator is added to the coating composition, the curing component of the coating composition [solid content of water-soluble urethane (meth) acrylate oligomer composition + ethylenically unsaturated monomer] is 0. 1 to 10 parts are mentioned, 0.5 to 10 parts are preferable, 2 to 8 parts are more preferable, and 3 to 5 parts are particularly preferable.
When the photopolymerization initiator is added to the photopolymerization initiator, 0.1 to 100 parts of the photopolymerization initiator may be mentioned with respect to 100 parts of the photopolymerization initiator.
When an antistatic agent is added to the coating composition, 0 to 30 parts are mentioned, preferably 0.01 to 20 parts, based on 100 parts (solid content: 30% by weight) of the coating composition. 0.05 to 10 parts is more preferable, and 0.1 to 5 parts is particularly preferable.

The photopolymerization initiator crosslinks and / or crosslinks the urethane (meth) acrylate oligomer and the ethylenically unsaturated monomer by irradiating with active energy rays, for example, by adding to the dye-containing composition and / or the coating composition. Alternatively, it can be polymerized to form a cured polymer. This cured polymer exhibits excellent scratch resistance, surface hardness, and adhesion to a plastic substrate.
For example, when a single-terminal hydroxyl group-containing polyalkylene glycol compound having no polymerizable functional group is used when synthesizing a urethane (meth) acrylate oligomer, if the ratio of this compound is increased, the curability decreases during cross-link polymerization. Hardness also tends to decrease. Therefore, it is preferable that the molar ratio of the one-terminal hydroxyl group-containing polyalkylene glycol compound is equal to or less than the molar ratio of the hydroxyl group-containing (meth) acrylate compound. The larger the molecular weight of the polyalkylene glycol chain, the greater the antistatic effect when cross-linked and polymerized, but the hardness tends to decrease. Further, the larger the number of functional groups of the hydroxyl group-containing (meth) acrylate compound, the higher the hardness at the time of cross-linking polymerization, and conversely, the smaller the number, the lower the hardness. By adjusting these, a cured polymer having an appropriate hardness can be obtained.

The photopolymerization initiator is not particularly limited as long as it generates a radical by the action of light, and for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2. -Methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2- Methylpropane-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-Morphorinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4- Benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanson, 2-chlorthioxanson, 2-methylthioxanson, 2,4-dimethylthioxanson, isopropylthioxanson, Phenylquinone, Dibenzosverone, 2-Ethylanthraquinone, 4', 4 "-diethylisophthalofenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester , Acylphosphine oxide, methylphenylglycorate, benzyl, 9,10-phenanthrene quinone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and the like.

In particular, in order to better exert the function as a dye-containing composition, it is preferable to use a photopolymerization initiator having water solubility or water dispersibility. Examples of such a photopolymerization initiator include 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-onemethylochloride (manufactured by Octel Chemicals, Inc., "Quantacure". QTX "), 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (manufactured by Ciba Specialty Chemicals," Irgacure 2959 "), etc. Among them, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (manufactured by Ciba Specialty Chemicals, "Irgacure 2959") Is more preferable.

Photopolymerization initiators include, for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Mihiler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethyl benzoic acid, 4-dimethylaminobenzoic acid. Ethyl acid, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxane Son and the like can be mentioned.

The antistatic agent acts synergistically with the antistatic effect of the cured polymer when cross-linked and polymerized, and can significantly improve the antistatic effect. By setting the antistatic agent in the following range, for example, a sufficient antistatic effect can be exhibited without leaking the antistatic agent from the cured polymer when cross-linked polymerization is performed.
Examples of the antistatic agent include a cationic antistatic agent for a quaternary ammonium salt, an aliphatic sulfonate, a higher alcohol sulfate ester salt, a higher alcohol alkylene oxide adduct sulfate ester salt, a higher alcohol phosphoric acid ester salt, and a higher alcohol alkylene. Examples thereof include at least one anionic antistatic agent selected from an oxide adduct phosphate ester salt, a higher alcohol alkylene oxide adduct, and at least one nonionic antistatic agent selected from a polyalkylene glycol fatty acid ester. Of these, a cationic antistatic agent is preferable.

The coating composition further includes fillers, dyes, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, defoamers, leveling agents, thixotropic agents. , Antioxidants, flame retardants, antistatic agents, fillers, reinforcing agents, matting agents, cross-linking agents and the like may be blended. As these, any of those usually used in the art may be used.

The object to be coated with the coating composition includes plastics (for example, polyolefin resins such as polyethylene, polypropylene and polycyclopentadiene, polycarbonates, polyesters, ABS resins, acrylic resins and the like), glass, paper, wood and cement. Such as a base material can be mentioned.
When the coating composition is applied to the surface of the object to be coated, the thickness thereof may be 1 μm to 50 μm, preferably 5 μm to 20 μm. Further, before irradiating with the active energy ray, in a temperature range of more than 60 ° C., preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and 100 ° C. or lower, 1 minute to 5 minutes, preferably 3 minutes to 5 minutes. It is preferable to dry for a minute.
Then, for example, the coating composition can be crosslinked / polymerized by irradiating with light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, and active energy rays such as X-rays and γ-rays.
The crosslinked / polymerized coating composition can, for example, integrally form a layer having photochromism performance and hardcourt performance that develops color with ultraviolet rays. That is, as described above, by drying at a relatively high temperature and in a short time, the leveling property of the surface of the coating film is improved and the steel wool resistance can be improved. It also has antistatic properties.
Therefore, the coating composition can form various coatings such as paints, adhesives, adhesives, adhesives, release agents, inks, protective coating agents, anchor coating agents, magnetic powder coating binders, sandblasting coatings, and plate materials. Very useful as a material. Further, it can be used as a dimming material, an ultraviolet indicator, a memory material for an optical signal, a display material, a toy, a material for controlling the amount of light such as a glass curtain, a photosensitive material that can be repeatedly used in the process of producing a photographic plate for printing, and the like.
The article to which the coating composition is applied and cured has excellent scratch resistance and antistatic properties, so that it is possible to protect the surface of a base material such as plastic and prevent dust absorption. In addition, it has excellent anti-fog properties and can be used not only for plastics but also for anti-fog such as eyeglasses and mirrors. In this case, the coating composition may be cured by active energy rays and / or heat and molded into a plastic lens or the like, may be applied to the surface of the lens or the like, or may be applied to an optical sheet or film or the like. It may be attached to the lens surface.

Hereinafter, embodiments of the present invention will be described in detail.
Synthesis Example 1: Water-soluble urethane (meth) acrylate oligomer composition (manufacturing of urethane (meth) acrylate oligomer composition)
159 g (0.29 mol) of hexamethylene diisocyanate trimer (isocyanate group content 23%), 2,6-di in a four-necked flask equipped with a thermometer, agitator, water-cooled condenser, and dry air inlet. -Tert-Butyl cresol 0.6 g and dibutyl tin dilaurylate 0.02 g were charged. To this, at 70 ° C., about 1 is charged with dipentaerythritol pentaacrylate (0.58 mol) (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 59.8 mgKOH / g) as 545 g). It was added dropwise over time and reacted at 70 ° C. for 4 hours. When the residual isocyanate group reached 1.7%, the mixture was cooled to 60 ° C.
Further, 643.9 g (0.30 mol) of polyethylene glycol monomethyl ether (weight average molecular weight 989.59, hydroxyl value 56.7 mgKOH / g) was added dropwise at 55 ° C. in about 1 hour. When the reaction started, it generated a lot of heat, so it was cooled at any time. When the heat generation has almost disappeared, the mixture is heated to 70 ° C. and reacted for 3 hours to measure the infrared absorption spectrum of the oligomer. When the absorption spectrum of the isocyanate group (2280 cm ^-1 ) disappears, the reaction is terminated and the urethane acrylate is used. Oligomers were obtained (resin concentration 100%).
The weight average molecular weight of the obtained urethane acrylate oligomer was 12,000.

(Emulsification)
300 g of the urethane acrylate oligomer obtained above is kept at 60 ° C., and 700 g of ion-exchanged water at room temperature (25 ° C.) is added dropwise or divided into 5 portions (initial 400 g, 100 g added every 30 minutes) (phase inversion emulsification method). While doing so, the mixture was stirred near the interface (W / O interface) between the oligomer and the ion-exchanged water with a paddle blade. The stirring at this time was performed at 100 to 150 rpm. When the resin content concentration reached 30%, the dropping was completed to obtain an emulsion. Then, stirring was maintained for 30 minutes to obtain a water-soluble urethane (meth) acrylate oligomer composition.
The pH of the obtained water-soluble urethane (meth) acrylate oligomer composition was 4 to 5, the heating residue (hereinafter, also referred to as "resin concentration") was 30% by weight, and the viscosity at 25 ° C. was 10 mPa · S. rice field.
The heating residue and viscosity are values measured by the following methods.

(Remaining heating)
Accurately measure the weight of the aluminum dish (diameter about 50 mm) (Ag), put about 1.5 g of the sample on the aluminum dish, quickly spread it as evenly as possible with a glass rod, spread it to the bottom, and then measure the mass accurately. (Bg). The aluminum dish is dried in an electric constant temperature dryer at 105 ° C to 110 ° C for 3 hours. The aluminum dish is taken out of the dryer, allowed to cool to room temperature, and then its weight is accurately measured (Cg).
Heating residue (%) = 100 × {(CA) / (BA)}
Here, A is the weight of the aluminum plate (g), B is the weight of the aluminum plate including the sample before drying (g), and C is the weight of the aluminum plate including the sample after drying (g).
(viscosity)
Take about 400 ml of the sample in a wide-mouthed bottle, cover it, put it in a constant temperature bath adjusted to the temperature "specified in the quality standard", and leave it for 4 hours or more to adjust the temperature of the sample. In the B-type rotational viscometer, put the rotor "specified in the quality standard", which is kept at the predetermined temperature ± 0.2 ° C, into the sample so that air bubbles do not adhere, attach the rotor to the viscometer, and mark the line. Adjust the liquid level to. Set to the number of revolutions "specified in the quality standard", rotate the viscometer, and read the pointer reading after 1 minute.
Viscosity (mPa · S) = pointer reading × X
Here, X is a viscosity conversion multiplier (according to the conversion table attached to the B-way rotational viscometer).

Synthesis Example 2: Photochromic dye solution To 100 parts of acryloylmorpholine as an ethylenically unsaturated monomer, 0.032 parts of a spiropyran-based photochromic dye (TPC-0144, manufactured by Yamada Chemical Co., Ltd.) was added as a photochromic dye at 60 ° C. It was heated and dissolved to obtain a photochromic dye solution.
Synthesis Example 3: Photochromic Dye Solution To 100 parts of N, N-dimethylacrylamide as an ethylenically unsaturated monomer, 0.08 part of a spiropyran-based photochromic dye (TPC-0144, manufactured by Yamada Chemical Co., Ltd.) was added as a photochromic dye to 60 parts. It was heated and dissolved at ° C to obtain a photochromic dye solution.

Example 1
With respect to 100 parts of the solid content of the water-soluble urethane (meth) acrylate oligomer composition (resin concentration: 30% by weight) obtained in Synthesis Example 1, 50 parts of an ethylenically unsaturated monomer and 0.016 parts of a photochromic dye were added. The forochromic dye solution obtained in Synthesis Example 2 was added and dissolved by heating at 60 ° C. to obtain an active energy ray-curable water-soluble resin composition containing a photochromic dye (resin content). Concentration: 39% by weight).

Example 2
Instead of acryloylmorpholine, which is an ethylenically unsaturated monomer of Example 1, N, N-dimethylacrylamide was mixed and dissolved in the same manner as in Synthesis Example 2 to obtain a photochromic dye solution, which was further used. An active energy ray-curable water-soluble resin composition containing a photochromic dye was obtained in the same manner as in Example 1 (resin concentration 39% by weight).

Example 3
With respect to 100 parts of the solid content of the water-soluble urethane (meth) acrylate oligomer composition (resin concentration: 30% by weight) obtained in Synthesis Example 1, 200 parts of an ethylenically unsaturated monomer and 0.04 part of a photochromic dye were added. The forochromic dye solution obtained in Synthesis Example 3 was added and dissolved by heating at 60 ° C. to obtain an active energy ray-curable water-soluble resin composition containing a photochromic dye (resin content). Concentration: 56% by weight).

Comparative Example 1
Spiropyran-based photochromic dye (TPC-0144, Yamada Chemical Co., Ltd.) in 100 parts of the solid content of the water-soluble urethane (meth) acrylate oligomer composition (resin concentration: 30% by weight) except for the ethylenically unsaturated monomer of Example 1. (Manufactured by) 0.04 part was added and mixed and dissolved at 60 ° C. to obtain an active energy ray-curable water-soluble resin composition (resin concentration 30% by weight).
Comparative Example 2
0.03 part of spiropyran-based photochromic dye (TPC-0144, manufactured by Yamada Chemical Co., Ltd.) was added to 100 parts of N, N-dimethylacrylamide as an ethylenically unsaturated monomer, mixed and dissolved at 60 ° C., and then water-soluble urethane (TPC-0144, manufactured by Yamada Chemical Co., Ltd.). Ion-exchanged water was added in place of the acrylate oligomer composition to obtain an active energy ray-curable water-soluble resin composition (resin concentration 40% by weight).

Test Example A
The active energy ray-curable water-soluble resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 obtained above were evaluated as follows.
(Solution stability of emulsified aqueous solution)
The above active energy ray-curable water-soluble resin composition was kept at 60 ° C. and stirred with a stirrer for 10 minutes, and then the obtained emulsified aqueous solution was allowed to stand at room temperature and 60 ° C. for 1 month for layer separation and sedimentation. The presence or absence was visually confirmed. Those without layer separation and sediment were uniform aqueous solutions and were evaluated as stable. The comparative example in which the emulsified aqueous solution was not obtained was judged to be insoluble, and the stability of the emulsified aqueous solution was not evaluated. The results are shown in Table 1.

Example 4: UV-curable water-soluble resin coating agent Photopolymerization of the water-soluble urethane (meth) acrylate oligomer compositions obtained in Examples and Comparative Examples, an ethylenically unsaturated monomer, and a total solid content of 100 parts. 4 parts of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (Ciba Specialty Chemicals, "Irgacure 2959") as an initiator Addition and mixing were carried out to obtain UV-curable water-soluble resin coating agents, respectively.

Test Example B
The UV curable water-soluble resin coating agent obtained above was evaluated as follows.
(Photochromism performance)
The coating agents using the urethane (meth) acrylate oligomer compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were respectively applied on an ABS plate using a # 16 bar coater to obtain a film thickness after drying. It was coated to a thickness of 10 μm and dried at 80 ° C. for 3 minutes. Then, using an electrodeless lamp H bulb, ultraviolet irradiation was performed at a line speed of 5.4 m / min, an irradiation amount of 600 mJ / cm ² , and a peak illuminance of 1,500 mW / cm ² . At this time, it was visually observed that the color was developed in red and then the color was extinguished when left to stand for one day under shading. Table 1 shows ◯ as having photochromism performance when the color is developed under UV → the color is erased under shading.
In addition, with the coating agent of Comparative Example 2, repelling occurred in the coating to the ABS plate, and it could not be applied uniformly.
(Adhesion to the base material)
The coating agents using the urethane (meth) acrylate oligomer compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were applied to various plastic panels on various plastic panels, respectively. Using No. 16, the film was applied so that the film thickness after drying was 10 μm, and the film was dried at 80 ° C. for 3 minutes. Then, using an electrodeless lamp H bulb, ultraviolet irradiation was performed at a line speed of 5.4 m / min, an irradiation amount of 600 mJ / cm ² , and a peak illuminance of 1,500 mW / cm ² to form a cured coating film.
According to JIS K5400, 100 2 mm grids were formed on the cured coating film, and an adhesion test was performed with cellophane tape. The peeling state of the grid was observed and evaluated by the number of remaining squares.
(Scratch resistance)
10 reciprocations of steel wool (# 0000) with a load of 500 g applied to the coating film on an easily adhesive PET film (Toyobo A4300, 125 μm) obtained to test the adhesion to the substrate. It was done by rubbing. The state of the scratch was evaluated by visual observation and is shown in Table 1.
(Pencil hardness)
A coating agent using the urethane (meth) acrylate oligomer compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was applied onto an easily adhesive PET film (Toyobo A4300, 125 μm) using a # 16 bar coater. The film was applied so that the film thickness after drying was 10 μm, and the film was dried at 80 ° C. for 3 minutes. Then, using an electrodeless lamp H bulb, ultraviolet rays were irradiated at a line speed of 5.4 m / min, an irradiation amount of 600 mJ / cm ² , and a peak illuminance of 1,500 mW / cm ² to form a cured coating film. For the cured coating film, the pencil hardness was measured according to JIS K5400.
(Curing shrinkage)
A coating film was formed in the same manner as in the pencil test, and immediately after curing, the coating film was cut into a film thickness of 10 μm, 10 cm × 10 cm square, and left overnight. The flip-up heights of the four end faces were measured, and the average value was calculated. The values are shown in Table 1 (unit: mm). If it is less than 1.5 cm, it passes.
(Flexibility (mandrel test))
A coating film was formed in the same manner as in the pencil test, and the flexibility of the dried cured coating film until it cracked was measured with a mandrel tester. Table 1 shows a diameter (mm) φ that does not cause cracks in the coating film.
(optical properties)
A coating film was formed in the same manner as in the pencil test, and the dried cured coating film (on the easy-adhesive PET (A-4300)) was measured for total light transmittance, HAZE and YI with a Konica Minolta spectrocolorimeter CM-3600A. did. The results are shown in Table 1.
Total light transmittance: 89% or more passed (A-4300: 89.34 above),
HAZE: Passed 1.0 or less (A-4300: 0.70 above),
YI (after color development): 1.5 or less passed (A-4300: 1.0 above).
(Rubbing test: water resistance, solvent resistance)
A coating film is formed in the same manner as in the pencil test, and a drop of water, ethanol, and methyl ethyl ketone (MEK) is dropped on the dried cured coating film (on the easy-adhesive PET (A-4300)), and a load of about 1 kg is applied with gauze. I rubbed it 10 times. The presence or absence of change in the coating film when visually observed was evaluated.

表１中、ＡＣＭＯは、アクリロイルモルフォリン（ＫＪケミカルズ社製）、
ＤＭＡＡは、Ｎ，Ｎ－ジメチルアクリルアミド（ＫＪケミカルズ社製）を表す。
表１中、（）は固形分を表す。［］は水溶性ウレタンアクリレート組成物の固形分を１００部とした場合の重量部を表す。

In Table 1, ACMO is acryloylmorpholin (manufactured by KJ Chemicals),
DMAA represents N, N-dimethylacrylamide (manufactured by KJ Chemicals).
In Table 1, () represents the solid content. [] Represents a part by weight when the solid content of the water-soluble urethane acrylate composition is 100 parts.

Claims (15)

The hydroxyl group-containing (meth) acrylate compound n-molar ratio was reacted with the 1-molar ratio of the isocyanate compound having (m + n) isocyanate groups.
Next, the obtained reaction product was reacted with a (meth) acrylic acid alkylene oxide-added compound or a polyalkylene glycol compound containing a single-terminal hydroxyl group in an mmolar ratio.
Obtaining the urethane (meth) acrylate oligomer according to the formula (1),
A water-soluble urethane (meth) acrylate oligomer composition obtained by gently stirring or emulsifying the interface between the urethane (meth) acrylate oligomer and water while adding water to the urethane (meth) acrylate oligomer is prepared. ,
A photochromic dye solution is prepared by dissolving the photochromic dye in an ethylenically unsaturated monomer.
A method for producing an active energy ray-curable water-soluble resin composition containing a photochromic dye, which comprises dissolving the photochromic dye solution in the water-soluble urethane (meth) acrylate oligomer composition.
(R ¹ O-CONH) _m -R ^2- (NHCO-OR ³ ) n (1)
(During the ceremony,
R ¹ O- is a dehydrogenation residue of a polyalkylene glycol compound containing a hydroxyl group at one end or an alkylene oxide-added (meth) acrylic acid alkylene oxide compound.
R ² is a deisocyanate group residue of an isocyanate compound,
-OR ³ is a dehydrogenation residue of a hydroxyl group-containing (meth) acrylate compound,
Represents an integer of m and n = 1 to 50. However, m ≦ n. ) The production method according to claim 1, wherein the ethylenically unsaturated monomer is water-soluble. The production method according to claim 1 or 2, wherein the ethylenically unsaturated monomer has a glass transition temperature of the homopolymer of 100 ° C. or higher. The production method according to any one of claims 1 to 3, wherein the photochromic dye is at least one selected from a spirobenzopyran derivative and a diarylethene derivative. The production method according to any one of claims 1 to 4, wherein the isocyanate compound is a diisocyanate or a diisocyanate monomer polyisocyanate. The production method according to any one of claims 1 to 5, wherein the one-terminal hydroxyl group-containing polyalkylene glycol compound is an alkoxypolyalkylene glycol. The present invention according to any one of claims 1 to 6, wherein the (meth) acrylic acid alkylene oxide addition compound is obtained by adding (meth) acrylic acid to alkylene oxide or mono (meth) acrylate of polyalkylene glycol. Manufacturing method. The production according to any one of claims 1 to 7, wherein the hydroxyl group-containing (meth) acrylate compound is hydroxyalkyl (meth) acrylates, polyol (meth) acrylates, or alkylene oxide-added polyol (meth) acrylates. Method. The production method according to any one of claims 1 to 8, wherein the ethylenically unsaturated monomer is a (meth) acrylic acid compound or a vinyl group-containing compound. The (meth) acrylic acid compound includes acrylic acid amides, alkyl (meth) acrylates, aminoalkyl (meth) acrylates, quaternary salts of aminoalkyl (meth) acrylates, alkoxypolyalkylene glycol (meth) acrylates, and the like. Hydroxyalkyl (meth) acrylates, acid anhydride additives of hydroxyalkyl (meth) acrylates, polyalkylene glycol di (meth) acrylates, alkyldiol di (meth) acrylates, polyol poly (meth) acrylates, alkylene At least one selected from oxide-added polyol poly (meth) acrylates, the vinyl group-containing compound is selected from vinyl acetate, N-vinylacetamide, vinylpyrrolidone, vinylalkyl ethers, vinylsulfonic acid, and vinylsulfonic acid salts. The production method according to claim 9, which is at least one type. Claim 1 in which the solid content ratio (weight ratio) of the water-soluble urethane (meth) acrylate oligomer composition, the ethylenically unsaturated monomer, and the photochromic dye is 100: 5 to 300: 0.005 to 0.2. The manufacturing method according to any one of 10. A coating composition containing an active energy ray-curable water-soluble resin composition containing a photochromic dye obtained by the production method according to any one of claims 1 to 11. The coating composition according to claim 12, further comprising at least one photopolymerization initiator. Claim 12 or 13 in which the photopolymerization initiator is 0.002 to 10 parts by weight with respect to 100 parts by weight of the total solid content of the water-soluble urethane (meth) acrylate oligomer composition and the ethylenically unsaturated monomer. The coating composition according to. A cured article comprising a film of the coating composition according to any one of claims 12 to 14 formed on the object to be coated and the surface of the object to be coated.