JP2004300384A - Aqueous fluorescent resin composition and method for producing the same - Google Patents

Abstract

The present invention provides an aqueous fluorescent resin composition which can be suitably used for applications such as paints and inks capable of forming display articles and painted articles having excellent weather resistance, and a method for producing the same.
An ethylenically unsaturated monomer (a) having a functional group reactive to a carboxyl group and another ethylenically unsaturated monomer copolymerizable with the monomer (a) The monomer mixture (A) comprising the monomer (b) is emulsion-polymerized in an aqueous medium in the presence of the fluorescent colorant (B) to produce a fluorescent colorant-containing resin (C) emulsion, The emulsion and a water-soluble polymer compound (D) having a carboxyl group are mixed to react the functional group in the fluorescent colorant-containing resin (C) with the carboxyl group in the polymer compound (D). A method for producing an aqueous fluorescent resin composition.
[Selection diagram] None

Description

【００４３】
第１表に示す結果からも明らかように、本発明の製造方法で得られた実施例１〜５の水性蛍光樹脂組成物は、エタノール安定性、初期蛍光発色性及び耐候性の何れの性能にも優れていた。しかしながら、カルボキシル基に対して反応性がある官能基を有するエチレン性不飽和単量体（ａ）を含まない単量体混合物から得られた蛍光着色剤含有樹脂エマルションを用いた比較例１では、エタノール安定性が顕著に劣っており、耐候性も劣っていた。また、水溶性高分子化合物（Ｄ）を添加しなかった比較例２では、エタノール安定性が不十分であるだけでなく、耐候性も劣っていた。
【００４４】
【発明の効果】
本発明の製造方法で得られる本発明の水性蛍光樹脂組成物は、耐候性に優れた表示物、塗装物等を形成することのできる塗料やインク等の用途に好適に適用できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an aqueous fluorescent resin composition containing a fluorescent colorant and a method for producing the same, and more particularly, to a display material excellent in weather resistance, suitable for applications such as paints and inks capable of forming a coated product and the like. The present invention relates to an aqueous fluorescent resin composition applicable to the present invention and a method for producing the same.
[0002]
[Prior art]
In recent years, demands for fluorescent colorants for display items such as stickers and labels, painted objects, etc., mainly for exhibits in events and marine sports, warning displays, and the like.
When a fluorescent colorant is used in an aqueous paint or ink, a method of dispersing the fluorescent colorant using a water-soluble resin is known. However, the dispersion stability of paints and inks obtained by such a method is not sufficient, and the weather resistance (especially light resistance) of the display objects and coated objects obtained using such paints and inks is not sufficient. However, if it is continuously exposed to sunlight, there is a problem that the fluorescence decreases, discolors, or loses color (discoloration) in about six months.
[0003]
Further, a fluorescent colorant is dyed on fine particles obtained by emulsion polymerization of a monomer mixture containing a vinyl monomer having an acetoxy group, a phenyl group or a lower alkoxycarbonyl group and a vinyl monomer having a cyano group. It has been reported that weather resistance can be improved by using an aqueous ink containing the ink (see, for example, Patent Document 1).
[0004]
However, in the fine particles obtained by this method, since the fluorescent colorant is almost present on the particle surface, the stability of the particles when mixed with a water-soluble organic solvent such as alcohol used for controlling the drying speed is reduced. When the weather resistance under more severe conditions was required, the weather resistance was insufficient.
[0005]
[Patent Document 1]
JP 2002-121203 A
[Problems to be solved by the invention]
The present invention has been made in order to solve the problems of the conventional technology as described above, and is suitably applied to uses such as paints and inks capable of forming a display material having excellent weather resistance, a painted product, and the like. It is an object of the present invention to provide an aqueous fluorescent resin composition that can be used and a method for producing the same.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to achieve the above object, and as a result, in the presence of a fluorescent colorant, emulsion polymerization of a specific ethylenically unsaturated monomer mixture to obtain a fluorescent colorant-containing resin emulsion obtained. It has been found that the above object can be surely achieved by reacting with a specific water-soluble polymer compound, and the present invention has been achieved.
[0008]
That is, the method for producing the aqueous fluorescent resin composition of the present invention comprises the step of co-polymerizing an ethylenically unsaturated monomer (a) having a functional group reactive with a carboxyl group with the monomer (a). A monomer mixture (A) comprising a polymerizable other ethylenically unsaturated monomer (b) is emulsion-polymerized in an aqueous medium in the presence of a fluorescent colorant (B) to contain a fluorescent colorant. A resin (C) emulsion is produced, and then the emulsion is mixed with a water-soluble polymer compound (D) having a carboxyl group to form the functional group and the polymer compound in the fluorescent colorant-containing resin (C). (D) reacting with a carboxyl group.
Further, the aqueous fluorescent resin composition of the present invention can be obtained by the above-mentioned production method.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be specifically described.
<Monomer mixture (A)>
The monomer mixture (A) used in the method for producing the aqueous fluorescent resin composition of the present invention comprises: an ethylenically unsaturated monomer (a) having a functional group reactive with a carboxyl group; And another ethylenically unsaturated monomer (b) copolymerizable with the monomer (a).
[0010]
As an ethylenically unsaturated monomer (a) having a functional group reactive to a carboxyl group, glycidyl (meth) acrylate or allyl glycidyl ether, an epoxy compound having two or more glycidyl groups, and an active hydrogen atom Monomers and oligomers having an epoxy group obtained by reaction with an ethylenically unsaturated monomer having the same; monomers and oligomers having an oxazoline group; and monomers and oligomers having an aziridine group.
[0011]
Other ethylenically unsaturated monomers (b) copolymerizable with the above-mentioned ethylenically unsaturated monomers (a) include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl ( (Meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, Stearyl (meth) acrylate, α-chloroethyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxy (Meth) acrylate monomers such as propyl (meth) acrylate; styrene monomers such as styrene, methylstyrene, chlorostyrene and methoxystyrene; 2-hydroxyethyl (meth) acrylate and 2 (3)- Monomers having a hydroxyl group such as hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, allyl alcohol and mono (meth) acrylate of polyhydric alcohol; amide groups such as (meth) acrylamide and maleamide Having an amino group such as 2-aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, and vinylpyridine Monomer; other N-methylol group Typical examples thereof include N-methylolacrylamide, vinyl acetate, vinyl chloride, and ethylene, butadiene, acrylonitrile, and dialkyl fumarate. Of course, only one of these may be used, or two or more of them may be appropriately mixed and used.
[0012]
In the method for producing the aqueous fluorescent resin composition of the present invention, as a part of the ethylenically unsaturated monomer (b), an ethylenically unsaturated monomer having a carboxyl group (b-1) and / or Ethylenically unsaturated monomers (b-2) having two or more polymerizable carbon-carbon double bonds in one molecule can also be used.
[0013]
Specific examples of the above-mentioned ethylenically unsaturated monomer having a carboxyl group (b-1) include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monoethyl maleate, and monoethyl itaconate. And the like.
[0014]
As the ethylenically unsaturated monomer (b-2) having two or more polymerizable carbon-carbon double bonds in one molecule, specifically, divinylbenzene, divinyl adipate, ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butylene Glycol di (meth) acrylate, 1,3-butyldi (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, diallylphthale , Triallyl di cyanurate, mention may be made of tetraallyloxyethane like. Of course, only one of these may be used, or two or more of them may be appropriately mixed and used.
[0015]
In the method for producing the aqueous fluorescent resin composition of the present invention, the monomer mixture (A) contains the above-mentioned ethylenically unsaturated monomer (a) in an amount of 0.1 to 10% by mass, and the balance is other ethylene. It is desirable that the polymer be composed of the unsaturated monomer (b). When the amount of the ethylenically unsaturated monomer (a) in the monomer mixture (A) is less than 0.1% by mass, the relative amount of the functional group in the resulting fluorescent colorant-containing resin (C) is reduced. The amount is smaller, that is, the number of reaction points with the carboxyl group in the water-soluble polymer compound is relatively reduced, and as a result, the stability when the resulting aqueous fluorescent resin composition is mixed with the water-soluble organic solvent is reduced. It is not preferable because it tends to be insufficient. Conversely, if it exceeds 10% by mass, the stability during polymerization tends to deteriorate, which is not preferable.
[0016]
When a part of the ethylenically unsaturated monomer (b) is the ethylenically unsaturated monomer (b-1) and / or the ethylenically unsaturated monomer (b-2), The monomer mixture (A) contains 0.1 to 10% by mass of the ethylenically unsaturated monomer (a), and further contains 0.1 to 6% by mass of the ethylenically unsaturated monomer (b-1). And / or 0.1 to 30% by mass of the ethylenically unsaturated monomer (b-2), and the remainder is desirably composed of another ethylenically unsaturated monomer (b).
[0017]
When the amount of the ethylenically unsaturated monomer (b-1) is less than 0.1% by mass, the weather resistance of a coating film obtained using such a composition is insufficiently improved, Conversely, if it exceeds 6% by mass, the stability during polymerization tends to deteriorate, which is not preferable. When the amount of the ethylenically unsaturated monomer (b-2) is less than 0.1% by mass, the weather resistance of the coating film obtained using such a composition is insufficiently improved. On the contrary, if it exceeds 30% by mass, the stability at the time of polymerization tends to deteriorate, which is not preferable.
[0018]
Fluorescent colorant (B)
The fluorescent colorant (B) used in the method for producing the aqueous fluorescent resin composition of the present invention is a colorant having a fluorescent property such as a fluorescent dye or a fluorescent pigment. As such a fluorescent dye or fluorescent pigment, various types of conventionally known fluorescent dyes or fluorescent pigments can be used.
[0019]
As the fluorescent dye, various fluorescent dyes can be suitably used as long as they are soluble in a solvent and not soluble in water. As such a fluorescent dye, for example, Brilliant sulfoflavine FF, Basic Yellow HG (Basic yellow HG), Eosine, Eosine, Rhodamine 6G, Rhodamine B (Rhodamine B) And the like can be mentioned as preferable ones.
[0020]
As the fluorescent pigment, for example, those which emit light by being excited by an electromagnetic wave can be mentioned as preferable examples. Specifically, 4,4,4-trifluoro-1- (2-thienyl)-is added to europium. Complexes in which one or more ligands such as 1,3-butanedione, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, tri-n-octylphosphine oxide are coordinated And 3- (2-quinolylmethylene) isoindoline-1-one, C.I. I. Basic Yellow 40, C.I. I. Fluorescing brightening agent 52, C.I. I. Fluorescent brightening agent 135 and the like.
[0021]
<Fluorescent colorant-containing resin (C) emulsion>
In the method for producing the aqueous fluorescent resin composition of the present invention, the monomer mixture (A) is emulsion-polymerized in an aqueous medium in the presence of the fluorescent colorant (B) to obtain a fluorescent colorant-containing resin (C) emulsion. To manufacture.
[0022]
About the compounding quantity of a fluorescent coloring agent (B), it is desirable that the mass ratio of a monomer mixture (A) and a fluorescent coloring agent (B) becomes 100: 0.1-10. If the relative amount of the fluorescent colorant (B) is less than the above range, the fluorescent coloring property becomes insufficient, which is not preferable. On the other hand, when the relative amount of the fluorescent colorant (B) is larger than the above range, the stability during polymerization is deteriorated, which is not preferable.
[0023]
In the method for producing the aqueous fluorescent resin composition of the present invention, the emulsion polymerization may be performed by a one-stage emulsion polymerization method or a multi-stage emulsion polymerization method according to a conventional method. Therefore, even if the obtained fluorescent colorant-containing resin (C) emulsion contains an emulsion polymer consisting of one phase, the emulsion containing two or more phases, ie, an emulsion consisting of the outermost phase and one or more internal phases, is obtained. It may contain a polymer.
[0024]
As a typical example of the emulsion polymerization method, a monomer mixture (A) is usually added at a temperature of 60 to 90 ° C. in water in the presence of an emulsifier and a polymerization initiator and, if necessary, a chain transfer agent and an emulsion stabilizer. A method in which emulsion polymerization is performed at a temperature and a method in which this emulsion polymerization is repeated a plurality of times can be cited.
[0025]
Further, as the emulsion polymerization method, a monomer batch charging method in which the monomer mixture (A) is charged all at once, a monomer dropping method in which the monomer mixture (A) is continuously dropped, a monomer mixture method, A pre-emulsion method in which (A), water and an emulsifier are previously mixed and emulsified and then added dropwise, or a method in which these are combined can be mentioned. Is a state in which the fluorescent colorant (B) is dissolved in the monomer mixture (A), and the mixed solution of the monomer mixture (A) and the fluorescent colorant (B) is dispersed in water. It is preferable to carry out emulsion polymerization.
[0026]
Examples of the emulsifiers include fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene nonylphenyl ether sulfonic acid. Salts, polyoxyethylene-polyoxypropylene glycol ether sulfate, anionic surfactants such as so-called reactive emulsifiers having a polymerizable carbon-carbon unsaturated double bond and a polymerizable carbon-carbon unsaturated double bond in the molecule A polyoxyethylene alkyl ether, a polyoxyethylene nonylphenyl ether, a sorbitan fatty acid ester, a polyoxyethylene fatty acid ester, a polyoxyethylene-polyoxypropylene block copolymer, or the aforementioned Nonionic surfactants such as reactive emulsifiers having a highly polymerizable carbon-carbon unsaturated double bond in the molecule; and cationic surfactants such as alkylamine salts and quaternary ammonium salts. Can be.
[0027]
As the above-mentioned polymerization initiator, compounds generally used in conventional radical polymerization can be used. For example, persulfates such as potassium persulfate and ammonium persulfate; 2,2′-azobis (2- Azo compounds such as aminodipropane) hydrochloride, 4,4'-azobis-cyanovaleric acid, and 2,2'-azobis (2-methylbutanamidooxime) dihydrochloride tetrahydrate; hydrogen peroxide And peroxides such as t-butyl hydroperoxide. Further, a redox system combined with a reducing agent such as L-ascorbic acid, sodium thiosulfate, and ferrous sulfate can also be used.
[0028]
Examples of the chain transfer agent include long-chain alkyl mercaptans such as n-dodecyl mercaptan, aromatic mercaptans, and halogenated hydrocarbons.
Examples of the above emulsion stabilizer include polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl pyrrolidone, and the like.
[0029]
<Water-soluble polymer compound (D)>
In the method for producing the aqueous fluorescent resin composition of the present invention, the emulsion containing the fluorescent colorant-containing resin (C) obtained as described above is mixed with the water-soluble polymer compound (D) having a carboxyl group. The functional group in the fluorescent colorant-containing resin (C) is reacted with the carboxyl group in the polymer compound (D) to produce an aqueous fluorescent resin composition.
[0030]
As the water-soluble polymer compound (D), any polymer compound containing a carboxyl group and being water-soluble can be suitably used. For example, one or two or more compounds in the above-mentioned ethylenically unsaturated monomer (b) and one or two kinds in the above-mentioned ethylenically unsaturated monomer (b-1) having a carboxyl group A water-soluble polymer compound obtained by copolymerizing the above compound with an arbitrary ratio; by polymerizing one kind of compound in the above-mentioned ethylenically unsaturated monomer (b-1) having a carboxyl group A water-soluble polymer compound obtained by copolymerizing the obtained water-soluble polymer compound or two or more compounds at an arbitrary ratio; a water-soluble natural polymer compound having a carboxyl group such as carboxymethyl cellulose and keratin; be able to.
[0031]
As a method of mixing the fluorescent colorant-containing resin (C) emulsion with the water-soluble polymer compound (D), after the emulsion polymerization reaction of the fluorescent colorant-containing resin (C) emulsion is completed, the emulsion polymerization temperature (normally, It is desirable that the aqueous solution of the water-soluble polymer compound (D) is dropped into the emulsion maintained at 60 to 90 ° C. over a certain period of time, and the heated state is further maintained for a certain period of time. The aqueous solution of the water-soluble polymer compound (D) may be added dropwise while the emulsion of the fluorescent colorant-containing resin (C) is heated again. However, there is no problem even if the aqueous solution of the water-soluble polymer compound (D) is added to the unheated fluorescent colorant-containing resin (C) emulsion. Further, the addition method may be batch addition instead of dropping.
[0032]
About the compounding amount of the fluorescent colorant-containing resin (C) emulsion and the water-soluble polymer compound (D), the mass ratio of the fluorescent colorant-containing resin (C) and the water-soluble polymer compound (D) is 100: 1 to 1 It is desirable that the amount be 10,000. When the compounding amount of the water-soluble polymer compound is less than 1 by mass ratio, the stability and weather resistance when the obtained aqueous fluorescent resin composition is mixed with a water-soluble organic solvent such as alcohols is insufficient. This is not preferred because of the tendency to occur. On the other hand, when it exceeds 10,000, the resulting aqueous fluorescent resin composition is not preferable because the fluorescent coloring property of the obtained aqueous fluorescent resin composition becomes insufficient.
[0033]
【Example】
Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited to these Examples. In Examples and Comparative Examples, “parts” and “%” are values based on mass.
[0034]
<Preparation of aqueous solution of water-soluble polymer compound (D-1)>
After charging 100 parts of methyl ethyl ketone into a four-neck separable flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, the temperature was raised to 78 ° C. while replacing the inside of the flask with nitrogen. Thereafter, a mixture obtained by dissolving 1 part of azobisisobutyronitrile in a monomer mixture composed of 30 parts of styrene, 30 parts of n-butyl acrylate and 40 parts of methacrylic acid was continuously dropped over 3 hours. The temperature was further increased, and the mixture was aged while stirring under reflux for 2 hours, and then cooled to 30 ° C., and then dimethylethanolamine and ion-exchanged water were added. Next, methyl ethyl ketone was removed by an evaporator to prepare a polymer compound (acid value: 260 mg KOH / g) (D-1) aqueous solution having a pH of 8.0 and a nonvolatile content of 30%.
[0035]
<Preparation of aqueous solution of water-soluble polymer compound (D-2)>
Except that a monomer mixture consisting of 40 parts of methyl methacrylate, 40 parts of n-butyl acrylate, and 20 parts of methacrylic acid was used, the same procedure as in the method for producing the aqueous solution of the polymer compound (D-1) was carried out. Thus, an aqueous solution of a polymer compound (acid value 130 mgKOH / g) (D-2) having a pH of 8.0 and a nonvolatile content of 30% was prepared.
[0036]
<Example 1>
178 parts of ion-exchanged water, 1 part of sodium bicarbonate and 1 part of Emal 10N (manufactured by Kao Corporation) [sodium lauryl sulfate] were placed in a four-neck separable flask equipped with a stirrer, a thermometer, a cooling pipe and a dropping device. Each was charged and heated to 80 ° C. while replacing the inside of the flask with nitrogen. Thereafter, 1 part of potassium persulfate was added, and 206 parts of methyl methacrylate, 142 parts of butyl acrylate, 7 parts of glycidyl methacrylate, and 4,4,4-trifluoro-1- () were stirred and mixed in a separate container in advance. A fluorescent colorant-containing monomer emulsion composed of 4 parts of (2-chenyl) -1,3-butanedione / europium complex compound, 6 parts of emal 10N and 178 parts of ion-exchanged water was continuously dropped over 3 hours. Subsequently, 119 parts of the above resin aqueous solution (D-1) was continuously dropped over 30 minutes. Thereafter, 35 parts of a 1% aqueous solution of ammonium persulfate was added dropwise over 30 minutes, and the mixture was aged at 80 ° C. for 2 hours while stirring to obtain an aqueous fluorescent resin composition having a solid concentration of 40%.
[0037]
<Examples 2 to 5 and Comparative Examples 1 and 2>
Composition of monomer mixture (A), blending amount of fluorescent colorant (B), composition of monomer mixture used for preparation of water-soluble polymer compound (D), and addition of water-soluble polymer compound (D) An aqueous fluorescent resin composition having a solid content of 40% was obtained in the same manner as in Example 1 except that the amounts were changed as shown in Table 1.
[0038]
The aqueous fluorescent resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated for ethanol stability, initial fluorescent coloring and weather resistance of the coating film according to the following evaluation methods.
<Ethanol stability>
50 parts of ethanol was mixed with 10 parts of each aqueous fluorescent resin composition, and the appearance of the solution state after 24 hours was visually evaluated according to the following criteria.
：: No gelation, no generation of aggregates and precipitates.
×: Gelation or aggregates / precipitates are generated.
[0039]
<Initial fluorescent color development of coating film>
An aqueous solution obtained by diluting each aqueous fluorescent resin composition to a solid concentration of 10% was applied to art paper using a 4 mil applicator and dried at room temperature. The fluorescent property when this coating film was irradiated with black light was visually evaluated according to the following criteria.
A: Sufficient fluorescent coloring property.
：: Fluorescent.
×: No fluorescent coloring.
[0040]
<Weather resistance>
After irradiating the coating film for evaluating the initial fluorescence coloring property of the above-mentioned coating film with a fade meter for 10 hours, the fluorescence coloring property when irradiating the black light again is visually observed, and the initial fluorescence coloring property of the coating film is determined. In comparison, evaluation was made according to the following criteria.
：: No change.
：: slight decrease.
X: There is a clear decrease.
[0041]
The abbreviations of the raw materials shown in Table 1 have the following meanings.
MMA: methyl methacrylate n-BA: n-butyl acrylate GMA: glycidyl methacrylate MAA: EGDMA methacrylate: ethylene glycol dimethacrylate ST: styrene Also, in Table 1, the composition and water solubility of the monomer mixture (A) The composition of the polymer compound (D) is shown in%, the amount of the fluorescent colorant added is% with respect to the amount of the monomer mixture (A), and the ratio of (C) :( D) is a mass ratio. .
[0042]
[Table 1]

[0043]
As is evident from the results shown in Table 1, the aqueous fluorescent resin compositions of Examples 1 to 5 obtained by the production method of the present invention exhibited excellent performance in any of ethanol stability, initial fluorescent coloring property and weather resistance. Was also excellent. However, in Comparative Example 1 using a fluorescent colorant-containing resin emulsion obtained from a monomer mixture containing no ethylenically unsaturated monomer (a) having a functional group reactive to a carboxyl group, The ethanol stability was significantly poor and the weather resistance was also poor. In Comparative Example 2 in which the water-soluble polymer compound (D) was not added, not only the ethanol stability was insufficient but also the weather resistance was poor.
[0044]
【The invention's effect】
The aqueous fluorescent resin composition of the present invention obtained by the production method of the present invention can be suitably applied to applications such as paints and inks capable of forming a display material, a coated product, and the like having excellent weather resistance.

Claims (6)

An ethylenically unsaturated monomer (a) having a functional group reactive to a carboxyl group, and another ethylenically unsaturated monomer (b) copolymerizable with the monomer (a) ) Is emulsion-polymerized in the presence of a fluorescent colorant (B) in an aqueous medium to produce a fluorescent colorant-containing resin (C) emulsion. And mixing the functional group in the fluorescent colorant-containing resin (C) with a carboxyl group in the polymer compound (D) by mixing with a water-soluble polymer compound (D) having a group. Of producing an aqueous fluorescent resin composition. The monomer mixture (A) contains the monomer (a) in an amount of 0.1 to 10% by mass, and the remainder comprises another ethylenically unsaturated monomer (b). A method for producing an aqueous fluorescent resin composition of the above. Part of the ethylenically unsaturated monomer (b) has a carboxyl group and has two or more polymerizable carbon-carbon double bonds in one molecule. A monomer mixture (A) containing 0.1 to 10% by mass of the monomer (a) and 0.1% by mass of the monomer (b-1); 2 to 6% by mass and / or 0.1 to 30% by mass of the monomer (b-2), and the balance consists of another ethylenically unsaturated monomer (b). A method for producing the aqueous fluorescent resin composition according to the above. The aqueous fluorescent resin according to any one of claims 1 to 3, wherein the monomer mixture (A) and the fluorescent colorant (B) are used in an amount of 100: 0.1 to 10 by mass. A method for producing the composition. The aqueous fluorescent resin composition according to any one of claims 1 to 4, wherein the fluorescent colorant-containing resin (C) and the polymer compound (D) are used in a mass ratio of 100: 1 to 10,000. Method of manufacturing a product. An aqueous fluorescent resin composition obtainable by the production method according to claim 1.