KR20230038328A - 3D printing resin composition comprising fluorescent dye having urethane acrylate group and method for preparing of the composition - Google Patents

Abstract

The present invention relates to a 3D printing resin composition containing a fluorescent dye having a urethane acrylate group, capable of crosslinking, wherein the viscosity of the resin composition is suitable for 3D molding, and a 3D molded material realizes a fluorescent color with excellent light resistance and at the same time, shows the characteristic that the dye does not migrate to the outside even when left for a long time. The 3D printing resin composition of the present invention comprises (a) a mixture of a perylene-based red fluorescent dye having a urethane acrylate group and polyalkylene glycol-urethane diacrylate, (b) a urethane acrylate oligomer, (c) a reactive diluent containing an acryl group, and (d) a photocuring initiator.

Description

Photocurable resin composition for 3D printing containing a fluorescent dye having a urethane acrylate group and method for preparing the same

The present invention relates to a photocurable resin composition for 3D printing containing a red fluorescent dye and a method for preparing the same, and more particularly, to a resin composition for 3D printing using a perylene fluorescent dye having a urethane acrylate reactive group capable of crosslinking It relates to a technology for producing a urethane-based elastomer having excellent elasticity and light resistance and no migration.

The 3D printing industry has been growing rapidly in recent years, and 3D printing technology is creating a new paradigm in which consumers directly produce products based on their ideas. In particular, in the case of SLA (Stereolithography) and DLP (Digital Light Processing) methods using photocurable resins, they are widely applied to electronic parts, sensors, and bio devices because they have the advantage of being able to mold finely precise structures. A lot of research and development is being conducted to manufacture a flexible device using this photocuring method. In order to realize a product with excellent elasticity, a urethane acrylate oligomer having a high molecular weight among photocurable resin compositions is required. It should be included as a main ingredient. However, if the viscosity of the photocurable resin is too high, 3D printing molding itself is impossible, or even if it is molded, there is a problem in that a product that is excessively deformed compared to the originally planned shape is output.

In order to solve this high viscosity problem, low molecular weight monomers with low viscosity are usually used as reactive diluents, but when the content of these diluents increases, the final molded product becomes brittle and loses the characteristics of the elastomer. Although the method of lowering the viscosity by raising the temperature of the vat containing the photocurable resin has been reported in literature (Adv. Mater. 2017, 29, 1606000, Highly Stretchable and UV Curable Elastomers for Digital Light Processing Based 3D Printing), commercialized 3D It is difficult to apply to printing equipment. In addition, US patents US 10,316,213 B1 and WO 2020/131675 A1 disclose a dual-cure method. In this case, some photocurable monomers or oligomers are formed in the 3D molding step using blocked isocyanate or micro-capsule technology. It reacts to form an object having a desired shape (green state), and in the post curing step, when a temperature is applied to the 3D molding in a green state, for example, a condition different from the 3D molding condition, blocked isocyanate or micro-capsule contained in the molding Participating in this new chemical reaction, an additional high-molecular-weight elastomeric structure is created.

On the other hand, currently, in order to realize various colors of 3D molded products, a method of coloring after molding or dispersing in resin is used. In the case of coloring after molding, it is difficult to realize a high-quality color sense, and Problems such as dispersibility and uniformity arise. Moreover, in the case of photocurable resins for elastomers made of polymeric oligomers, the viscosity is very high, and it is very difficult to disperse the colorant. In addition, in the case of the photocuring 3D printing method, the time the resin is exposed to light increases, causing discoloration problems, and over time, a phenomenon in which the colorant is eluted to the surface (migration) may occur. This dissolution problem causes serious problems when applied to parts in contact with the human body or when molding bio-related products. In order to solve the dye elution problem, techniques for introducing an acrylic reactor to Perylene-based fluorescent dyes have been reported (Korean Registered Patent No. 10-1915865 and 10-2146616), and the manufacturing cost is too high due to a drop in purification yield during mass production. A problem was discovered. In particular, since the molecular weight of the perylene-based red fluorescent dye is very large, it is very difficult to obtain a crystal in a powder state with a molecular weight of 1,800 when a urethane acrylate reactor is introduced.

US Registered Patent US 10,316,213 B1 International Patent Publication WO 2020/131675 A1 Korea Patent No. 10-1915865 Korea Patent Registration 10-2146616

The problem to be solved by the present invention is to effectively synthesize a red fluorescent dye having a urethane acrylate reactive group, and to provide a resin composition for 3D printing that has excellent elasticity and light resistance and has no migration problem.

In order to solve the above technical problem, the present invention is (a) a mixture of a perylene-based red fluorescent dye having a urethane acrylate group and polyalkylene glycol-urethane diacrylate, (b) a urethane acrylate oligomer, (c) an acryl group It provides a photocurable resin composition for 3D printing comprising a reactive diluent and (d) a photocuring initiator.

In addition, the present invention comprises the steps of i) dissolving a perylene fluorescent dye having an alcohol group in polyalkylene glycol; ii) mixing and reacting an isocyanatoethyl acrylate solution with the dye solution; iii) preparing a red fluorescent dye having a urethane acrylate group and a polyalkylene glycol-urethane diacrylate mixture by evaporating the solvent after the reaction; and iv) mixing a urethane acrylate oligomer, a reactive diluent containing an acryl group, and a photocuring initiator with the mixture.

In addition, the present invention provides a fluorescent molded article manufactured by 3D printing using the photocurable fluorescent resin composition, characterized in that the elongation is 200% or more and the light fastness is 6th grade or higher.

In the present invention, a mixture in which red fluorescent dye having a urethane acrylate group is uniformly dissolved in polyalkyleneglycol-urethane diacrylate is first prepared, and 3D printing is performed using this mixture. Prepare a resin composition for use. Since red fluorescent dye having a urethane acrylate group is uniformly dissolved in the mixture at a high concentration (0.1 to 1.0% by weight), when appropriately mixed with a high viscosity urethane acrylate oligomer having a molecular weight of 4,000 to 20,000 and a reactive diluent, elasticity and A red fluorescent resin composition for 3D printing having excellent light resistance and no migration problem can be provided.

1 is a photograph confirming whether or not the 3D fluorescent elastomer moldings are eluted according to Examples and Comparative Examples of the present invention.

The present invention will be described in more detail through the following examples.

Since the fluorescent dye used in the resin composition for 3D printing of the present invention irradiates UV or 405 nm Blue-LED due to the nature of the 3D printing method, it must have excellent light fastness to these high energy lights. , Miscibility and solubility for monomers and oligomers must also be excellent in order to manufacture molded products of uniform color. In order to satisfy these conditions, in the present invention, a perylene-based red fluorescent dye (Red-UA) represented by the following [Chemical Formula 1] was synthesized and used. Since the compound of [Formula 1] has a urethane acrylate reactive group in a perylene skeleton having excellent light resistance, it has excellent compatibility with most monomers and oligomers used in photocurable 3D printing resin compositions.

[Formula 1]

The fluorescent dye of [Chemical Formula 1] can be synthesized according to the following [Scheme 1], but the molecular weight of Red-UA is too large to separate it into a pure solid in the final stage, which is particularly important in mass production. There is a problem in that the manufacturing cost rapidly increases due to a sharp drop in manufacturing cost.

[Scheme 1]

In order to solve the above problems, the present invention provides a method for preparing a photocurable resin composition for 3D printing by synthesizing a red fluorescent dye (Red-UA) in a mixture state as follows, and using the mixture obtained at this time, specifically i ) dissolving a perylene fluorescent dye having an alcohol group in polyalkylene glycol; ii) mixing and reacting an isocyanatoethyl acrylate solution with the dye solution; iii) preparing a red fluorescent dye having a urethane acrylate group and a polyalkylene glycol-urethane diacrylate mixture by evaporating the solvent after the reaction; and iv) mixing a urethane acrylate oligomer, a reactive diluent containing an acryl group, and a photocuring initiator with the mixture.

For example, perylene fluorescent dye (Red-UA) having a urethane acrylate group of [Formula 1] may be synthesized according to the following [Scheme 2].

[Scheme 2]

In the present invention, as shown in [Scheme 2], first, a hydroxyl-containing perylene red fluorescent dye (Red-OH) [Formula 2] is synthesized, and polytetramethylene glycol having a molecular weight of 1,000 to 4,000 at 40 to 60 ° C. PTMG) to prepare a mixture (Red-OH + polytetramethylene glycol) having a Red-OH concentration of 0.1 to 1.0% by weight. These mixtures are reacted with 2-Isocyanatoethyl acrylate in a THF solvent at a temperature of 60 to 70 ° C for about 1 hour. After completion of the reaction, when the solvent is removed by vacuum distillation, the mixture in which red-urethane acrylate having a urethane acrylate group is uniformly dissolved in polytetramethylene glycol-urethane diacrylate (PTMG-urethane diacrylate) is obtained with high can be obtained in yield. Further, in the present invention, polyalkylene glycol having a molecular weight of 1,000 to 4,000 such as polyethylene glycol and polypropylene glycol may be used alone or in combination instead of polytetramethylene glycol.

At this time, the content of the red fluorescent dye (Red-OH) in the mixture is preferably in the range of 0.1 to 1.0% by weight. If the concentration is more than 1.0% by weight, Red-OH is not sufficiently dissolved, so there is a high possibility that unreacted Red-OH exists in the final compound. It is not economical because the content of the Hal (Red-OH + polyalkylene glycol diacrylate) mixture increases. On the other hand, if the molecular weight of polyalkylene glycol is less than 1,000, it adversely affects the elastomer properties, such as reducing the elongation of the final 3D printing molded product. Occurs.

The present invention utilizes a mixture in which the red fluorescent dye having a urethane acrylate group is uniformly dissolved in the polyalkylene glycol-based urethane diacrylate, and has excellent elasticity and light resistance and has no migration problem. It is characterized by being able to provide a red fluorescent resin composition for 3D printing.

The photocurable resin composition for 3D printing according to the present invention is specifically, (a) a mixture of a perylene-based red fluorescent dye having a urethane acrylate group and polyalkylene glycol-urethane diacrylate, (b) a urethane acrylate oligomer, ( c) a reactive diluent containing an acryl group and (d) a photocuring initiator, and may optionally include (e) a light absorber if necessary.

The content of each component of the photocurable resin composition for 3D printing according to the present invention is, for example, (a) 0.1 to 1.0% by weight of red fluorescent dye (Red-urethane acrylate) having a urethane acrylate group having a molecular weight between 1,000 and 4,000 1 to 10% by weight of a mixture uniformly dissolved in polyalkylene glycol-based urethane diacrylate (b) 30 to 70% by weight of high-viscosity urethane acrylate oligomer having a molecular weight of 4,000 to 20,000 (c) Reactive type containing an acryl group 10 to 50% by weight of a reactive diluent, (d) 1 to 5% by weight of a photocuring initiator, and optionally (e) 0.1 to 2% by weight of a photoabsorber.

Polyether urethane acrylate, polyester urethane acrylate, etc. may be used as the urethane acrylate oligomer usable in the present invention. It is preferably at least 4,000 or more. A polymer oligomer having a molecular weight of 20,000 or more may be used, but in this case, the viscosity is too high, and thus it is difficult to prepare a resin composition and the 3D moldability is very poor. The content of the urethane acrylate oligomer in the resin composition is preferably 30 to 70% by weight. If the content is 30% by weight or less, it is difficult to secure properties of 200% or more in elongation, and if the content is 70% by weight or more, there is a problem in that the viscosity increases too much.

In addition, in the resin composition according to the present invention, the reactive diluent may be any low-viscosity monomer containing an acryl group capable of participating in a photocuring reaction, and for example, isobornyl acrylate, methyl acrylate ( methyl acrylate, ethyl acrylate, butyl acrylate, 4-hydroxybutyl acrylate, hexanediol diacrylate, diethylene glycol diacrylate (diethyleneglycol diacrylate), dipropylene glycol diacrylate, polyethylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate (butyl methacrylate), hexanediol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacylate ) may be selected and used at least one from the group consisting of, but is not particularly limited thereto. In the case of the input content of the monomer, which is a reactive diluent, 10 to 50% by weight is preferable, and it is adjusted according to the molecular weight and viscosity of the urethane acrylate oligomer.

In the photocurable resin composition according to the present invention, if the content of the reactive diluent is too low, such as 10% by weight or less, there is a limit to lowering the viscosity of the high-viscosity oligomer. characteristics are drastically reduced.

The photoinitiator included in the photocurable resin composition for 3D printing according to the present invention may use a commonly used radical photoinitiator, specifically, for example, phenylphosphineoxide, monoacrylphosphine, alpha a-hydroxyketone, acetophenoe, benzyldimethyl ketal, mrthylidynetrisdimethylaniline, sulfoniumphosphonate, benzoyl sulphide, At least one may be selected from the group consisting of benzophenone and aminobenzoate, but is not particularly limited thereto. The content of the initiator is appropriate to be 1 to 5% by weight, and depending on circumstances, a photoabsorber that controls penetration depth may be added in the range of 0.1 to 2% by weight.

The viscosity of the photocurable resin composition for 3D printing according to the present invention is preferably 500 to 3,000 cps at room temperature, more preferably 1,000 to 2,000 cps. It is very difficult to maintain a viscosity of 1,000 cps or less while securing properties of elongation of 200% or more, and if too much reactive diluent is added for low viscosity, the final molding becomes hard, making it difficult to secure elastomer properties. On the other hand, if the viscosity is more than 2,000 cps, it is very advantageous to secure the elasto properties, but the 3D printing work becomes very difficult. Resin with high viscosity adheres to the surface of the molding, making it difficult to clean. In general, various problems such as the shape of the output being much larger than the desired size or the formation of the desired structure due to clogging of fine holes occur.

Meanwhile, in the present invention, a molded article may be manufactured by a 3D printing method using the photocurable resin composition. It can be applied to various 3D printing devices, and, for example, a molded product can be manufactured by SLA (Stereolithography) and DLP (Digital Light Processing) methods.

The molded article manufactured by 3D printing using the photocurable resin composition according to the present invention has an elongation of 200% or more and a light fastness of 6 or more, which is very excellent.

The present invention will be described in more detail through the following examples. However, the following examples are presented by way of example to aid understanding of the present invention and should not be construed as limiting the scope of the present invention thereto.

<Synthesis Example 1> Synthesis of Perylene Red dye having -OH group (compound Red-OH)

1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid dianhydride (1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid dianhydride) (Compound Red-1) 10g, 2,6-diisopropylaniline (2,6-diisopropylaniline) (2,6-diisopropylaniline) (2,6-diisopropylaniline) (2,6-diisopropylaniline) 16.67g and propionic acid (propionic acid) (propionic acid) (propionic acid) (propionic acid) (propionic acid) (propionic acid) (250ml) was heated to 80 degrees and left at this temperature for 17 hours. After cooling to room temperature, crystals were precipitated using water, which was filtered and dried (Red-2). After mixing 5 g of dried powder with 8.14 g of 4-hydroxyphenylethyl alcohol and 4.07 g of K ₂ CO ₃ with 100 ml of DMF, the mixture was heated to 120 degrees and stirred for 12 hours. After cooling the reactant to room temperature, crystals were precipitated using methanol, which was filtered and dried.

<Synthesis Example 2> Synthesis of Perylene Red dye having a urethane acrylate group (compound Red-UA)

After mixing 20.46 g of Red-OH with 200 g of PGMEA and 0.04 g of methoxy phenol, the temperature was raised to 80 ° C. After diluting 12.4 g of 2-Isocyanatoethyl acrylate in 20 g of PGMEA, it was added and reacted for 12 hours. After confirming the completion of the reaction by FT-IR, it was cooled to room temperature and PEGMA was removed by distillation under reduced pressure to obtain a sticky red compound. It was confirmed through MALDI/TOF that the compound had a molecular weight of 1,876, and the reaction yield was 14%.

<Synthesis Example 3> Synthesis of PTMG-4000 urethane diacrylate (PTMG-400 UDA)

450 g of PTMG-4000 was mixed with 200 g of THF and 0.23 g of methoxy phenol, and then heated to 65°C and maintained for 1 hour. After diluting 31.75 g of 2-Isocyanatoethyl acrylate in 20 g THF, it was further added and reacted for 12 hours. After confirming the completion of the reaction by FT-IR, it was cooled to room temperature, and THF and PEGMA were removed through distillation under reduced pressure to obtain compound PTMG-4000. got the UDA. The molecular weight was confirmed through GPC, and the reaction yield was 92%.

<Synthesis Example 4> (Red-UA + PTMG-4000 UDA) Synthesis of Mixed Oligomer

After mixing 4.5 g of Red-OH and 450 g of PTMG-4000 with 200 g of THF and 0.23 g of methoxy phenol, the mixture was heated to 65°C and maintained for 1 hour. After diluting 32.5 g of 2-Isocyanatoethyl acrylate in 20 g THF, it was further added and reacted for 12 hours. UA + PTMG-4000 UDA) mixed oligomers were prepared. It was confirmed through GPC that PETMG-4000 UDA was synthesized (yield: 87%), and UV-Vis. It was confirmed that the yield was 85% by measuring the concentration of the red dye through a spectrophotomer. Whether or not a urethane acrylate reactor was introduced into Red-OH was confirmed by preparing a 3D printing molding using the mixed oligomer prepared above and conducting a dissolution test (see evaluation example).

<Example 1>

200 g of urethane acrylate having a molecular weight of 15,000 (Pluto's product name PL-4500), 325 g of PTMG-4000 UDA prepared through (Synthesis Example 3), 400 g of isobornyl acrylate, 20 g of TPO initiator, 5 g of BBOT, and (Synthesis Example 4 A photocurable resin composition for 3D printing was prepared by mixing 50 g of the mixed oligomer (Red-UA + PTMG-4000 UDA) prepared through (Red-UA + PTMG-4000 UDA).

<Example 2>

It is the same as Example 1 except that 525 g of PTMG-4000 UDA prepared in Synthesis Example 3 was used instead of urethane acrylate having a molecular weight of 15,000.

<Example 3>

Synthesis Example 4 is the same as in Example 1 except for using (Red-UA + PEG-4000 UDA) prepared by adding PEG-4000 instead of PTMG-4000.

<Example 4>

It is the same as Example 1 except that 4-hydroxybutyl acrylate was used instead of isobornyl acrylate.

<Comparative Example 1>

Same as Example 1 except that 525 g of PEG-4000-UDA prepared by adding PEG-4000 instead of PTMG-4000 in Synthesis Example 4 was used instead of urethane acrylate having a molecular weight of 15,000 and PTMG-4000-UDA .

<Comparative Example 2>

(Red-UA + PTMG-4000 UDA) Examples except that 0.5 g of Red-UA prepared through Synthesis Example 2 and 49.8 g of PTMG-400-UDA prepared through Synthesis Example 3 were used instead of the mixed oligomer. Same as 1.

<Comparative Example 3>

It is the same as Comparative Example 2 except for using the Red-OH dye prepared through Synthesis Example 1 instead of Red-UA.

<Comparative Example 4>

It is the same as Comparative Example 2 except that Solvent Red 26 dye was used instead of Red-UA.

<Comparative Example 5>

It is the same as Example 1 except that 825 g of PTMG-4000 UDA prepared through Synthesis Example 3 was used instead of urethane acrylate having a molecular weight of 15,000 and isobornyl acrylate was reduced to 100 g.

<Evaluation example>

The viscosity of the photocurable resin compositions prepared in Examples 1-4 and Comparative Examples 1-3 was measured at room temperature using a Brookfield viscometer (spindle #62, rpm = 3), and 3D molding was carried out by Carima's DLP Equipment (product name IM-96) was used. In order to evaluate the elastomer characteristics of 3D moldings, KS M 6518 standard specimens were prepared and elongation was measured. If it was printed larger than the real thing, it was marked with an X. On the other hand, in the case of dissolution, the molded specimen was immersed in the IPA solution and stirred at room temperature for 24 hours, and then the state of the solution was checked and evaluated. In the case of light fastness, daylight fastness was measured in accordance with the KS K0700 (Xenon/Carbon-arc) standard, and it was marked with O for grade 6 or higher and X for grade 6 or lower, and the test results are summarized in Table 1 below.

As can be seen in Examples 1 to 4, when the photocurable resin composition for 3D v-printing is prepared with the composition according to the present invention, the room temperature viscosity is maintained at 1,000 to 2,000 cps, and the elastomer of red color having an elongation of 200% or more It can be seen that is molded, and it can be seen that the urethane acrylate introduced into the red dye is chemically bonded to the polymer chain so that no elution occurs even when immersed in a solvent for a long time. (FIG. 1) On the other hand, in the case of using only the soft urethane acrylate oligomer PEG-4000-DA (Comparative Example 1), it was found that all other properties were excellent, but the elongation was insufficient, making it unsuitable for use as an elastomer. When using Red-OH (Comparative Example 3) or solvent Red 26 (Comparative Example 4), which are dyes without a rate reactive group, it can be seen that dissolution properties and light resistance are not excellent. In addition, when Red-UA and PTMG-4000-UA were synthesized and used instead of the mixed oligomer (Comparative Example 2), the process is complicated and economical. On the other hand, when too much soft oligomer is added (Comparative Example 5), it can be seen that the viscosity is too high and the moldability is very poor.

Claims (15)

(a) a mixture of a perylene-based red fluorescent dye having a urethane acrylate group and polyalkylene glycol-urethane diacrylate, (b) a urethane acrylate oligomer, (c) a reactive diluent containing an acryl group, and (d) photocuring A photocurable resin composition for 3D printing comprising an initiator. According to claim 1,
The photocurable resin composition for 3D printing, characterized in that the perylene-based red fluorescent dye having a urethane acrylate group is a compound represented by the following [Formula 1].
[Formula 1]

According to claim 1,
The polyalkylene glycol is a photocurable resin composition for 3D printing, characterized in that selected from polytetramethylene glycol, polyethylene glycol and polypropylene glycol or mixtures thereof having a molecular weight in the range of 1,000 to 4,000. According to claim 1,
The mixture of (a) a perylene-based red fluorescent dye having a urethane acrylate group and polyalkylene glycol-urethane diacrylate is a photocurable resin for 3D printing, characterized in that in the range of 1 to 10% by weight based on the total weight of the resin composition composition. According to claim 1,
The content of the perylene-based red fluorescent dye having a urethane acrylate group is a photocurable resin composition for 3D printing, characterized in that the range of 0.1 to 1.0% by weight based on the mixture of polyalkylene glycol-urethane diacrylate. According to claim 1,
The urethane acrylate oligomer is a photocurable resin composition for 3D printing, characterized in that selected from high viscosity polyether urethane acrylate or polyester urethane acrylate or a mixture thereof having a molecular weight of 4,000 or more. According to claim 1,
The (b) urethane acrylate oligomer is a photocurable resin composition for 3D printing, characterized in that the range of 30 to 70% by weight based on the total resin composition. According to claim 1,
The reactive diluent containing the acrylic group is isobornyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 4-hydroxybutyl acrylate, hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol Diacrylate, polyethylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol A photocurable resin composition for 3D printing, characterized in that at least one selected from the group consisting of dimethacrylate. According to claim 1,
The (c) reactive diluent containing an acrylic group is a photocurable resin composition for 3D printing, characterized in that in the range of 10 to 50% by weight based on the total resin composition. According to claim 1,
The (e) photocurable resin composition for 3D printing, characterized in that it further comprises a light absorber. According to claim 1,
A photocurable resin composition for 3D printing, characterized in that the viscosity of the resin composition ranges from 500 to 3,000 cps at room temperature. i) dissolving a perylene fluorescent dye having an alcohol group in polyalkylene glycol;
ii) mixing and reacting an isocyanatoethyl acrylate solution with the dye solution;
iii) preparing a red fluorescent dye having a urethane acrylate group and a polyalkylene glycol-urethane diacrylate mixture by evaporating the solvent after the reaction; and
iv) A method for preparing a photocurable resin composition for 3D printing comprising mixing a urethane acrylate oligomer, a reactive diluent containing an acryl group, and a photocuring initiator with the mixture. According to claim 12,
The method for producing a photocurable resin composition for 3D printing, characterized in that the perylene fluorescent dye having an alcohol group is a compound of the following [Formula 2].
[Formula 2]

A fluorescent molding manufactured by 3D printing using the photocurable fluorescent resin composition according to claim 1. According to claim 14,
The fluorescent molding, characterized in that the elongation of the molding is 200% or more, and the light fastness is 6 or more.

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