JPH11140368A - Ultraviolet-curing phosphorescent ink and process for printing inorganic material therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curing phosphorescent ink with which an inorganic material can be continuously printed a lower temperature and a low cost. SOLUTION: There is provided an ultraviolet-curing ink which is applied to an inorganic material, containing a photopolymerizable resin mixture comprising at least one photopolymerizable prepolymer selected from the group consisting of polyester acrylates, polyurethane acrylates, polyether acrylates, polyester acrylates and polyurethane acrylates each of which has a molecular weight of 500-500,000, a photopolymerizable monomer and a photoinitiator, at least one member selected among epoxy resins and acrylic epoxy resins, at least one phosphorescent pigment and at least one silane coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable luminous ink and a method for printing on an inorganic material using the same.

[0002]

2. Description of the Related Art An ink using a luminous pigment that emits energy obtained by absorbing light of a specific wavelength as long-wave light such as visible light has been developed and is being put to practical use.

For example, a glaze obtained by mixing a lead-free frit, an inorganic phosphor or a phosphorescent material and a binder (JP-A-8-165)
No. 140) or a ceramic color composition obtained by mixing a low-melting glass powder, a luminous pigment, an inorganic pigment and an organic vehicle (Japanese Patent Application Laid-Open No. 9-142882). According to these technologies, glass, metal,
It is possible to form a coating film containing a luminous pigment on an inorganic material such as ceramics.

[0004]

However, the above glaze must be baked at a high temperature of 500 to 1300 ° C. before use. For this reason, sulfide-based pigments such as zinc sulfide and calcium sulfide, which are generally used as luminous pigments, may be deteriorated by oxidative decomposition of sulfides when baked at such a high temperature, In some cases, sufficient light emitting performance cannot be obtained. Even when a pigment other than a sulfide-based pigment is used, it is desirable that printing can be performed at a temperature as low as possible in order to eliminate the risk of deterioration.

On the other hand, although the firing temperature of the ceramic color composition is relatively low at 500 to 700 ° C., if the firing temperature can be further lowered, the production efficiency and the like can be improved. In particular, if the temperature can be further reduced,
Sulfide-based phosphorescent pigments, which may be oxidatively decomposed at high temperatures, can also be used effectively, and cost reduction can be achieved.

Accordingly, an object of the present invention is to provide an ultraviolet-curable luminous ink for inorganic materials which can be continuously printed at a lower temperature and at a lower cost.

[0007]

Means for Solving the Problems The present inventor has conducted research in view of the state of the art as described above, and as a result, has found that when a specific organic component is used together with a luminous pigment, the above object can be achieved. Under the heading, the present invention has finally been completed.

That is, the present invention relates to the following ultraviolet curable luminous ink and a method for printing on an inorganic material using the same.

1. A first invention is an ultraviolet curable ink applied to an inorganic material,
(1) (a) at least one photopolymerizable prepolymer selected from the group consisting of polyester acrylate, polyurethane acrylate, polyether acrylate, polyester acrylate and polyurethane acrylate having a molecular weight of 500 to 500,000; And (c) a photopolymerizable resin mixture comprising a photoinitiator,
(2) at least one kind of epoxy resin and acrylic epoxy resin, (3) at least one kind of luminous pigment and (4)
An ultraviolet curable luminous ink containing at least one silane coupling agent.

[0010] 2. Second invention An ultraviolet curable ink applied to an inorganic material,
(1) (a) a photopolymerizable prepolymer comprising an epoxy acrylate having a molecular weight of 500 to 500,000; (b) a photopolymerizable resin mixture comprising a photopolymerizable monomer and (d) a photoinitiator; and (2) at least an epoxy resin. One, (3)
An ultraviolet curable luminous ink containing at least one kind of luminous pigment and (4) at least one kind of silane coupling agent.

3. Third invention An ultraviolet curable ink applied to an inorganic material,
(1) (a) a photopolymerizable prepolymer composed of an epoxy acrylate having a molecular weight of 500 to 500,000, (b) a photopolymerizable resin mixture composed of a photopolymerizable monomer and (c) a photoinitiator, and (2) at least a phosphorescent pigment. An ultraviolet-curable luminous ink containing one kind and (3) at least one kind of a silane coupling agent.

4. Fourth invention After applying the ultraviolet curable luminous ink according to the first to third inventions to an inorganic material and irradiating it with ultraviolet light, 80 to 20
A method for printing on an inorganic material, wherein the method comprises heating and curing at 0 ° C.

As described above, the inventions described in claims 1 to 3 are referred to as “first inventions”, and the inventions described in claims 4 to 6 are referred to as “second inventions”. The described invention will be described in detail as a "third invention" and the invention described in claim 10 as a "fourth invention". Regarding matters common to all inventions,
It may simply be referred to as “the present invention”. Further, in the present invention, components other than the phosphorescent pigment are collectively referred to as “organic components”.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION

1. First Invention The photopolymerizable resin mixture used in the ultraviolet curable luminous ink according to the first invention comprises (a) a molecular weight of 500 to 500,000.
At least one of a degree of photopolymerizable prepolymer, (b)
At least one kind of the photopolymerizable monomer and (c) at least one kind of the photoinitiator are essential components.

(A) Examples of the photopolymerizable prepolymer include the following: polyester acrylates ... oils, modified alkyds,
An acroyl group-introduced urethane compound based on a modified polyester or the like.

Polyurethane acrylate: polycarbonate acrylate, hydroxyl group-containing acrylate, reaction product of diisocyanate and hydroxyl group-containing material, etc.

Polyether acrylate type.

These photopolymerizable prepolymers include:
Polyester acrylates and polyurethane acrylates are more preferred.

(B) Examples of the photopolymerizable monomer include the following: Monofunctional monomer: 2-ethylhexyl acrylate;
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethylhexyl acryloyl phosphate, tetrahydrofurfuryl acrylate,
Acrylates of tetrahydrofurfuryl derivatives and the like.

Bifunctional monomers: dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,3-butanediol diacrylate, 1,4
-Butanediol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 400 diacrylate, hydroxypivalic acid ester neopentyl glycol diacrylate, 1,3
-Bis (3'-acryloxyethoxy-2'-hydroxypropyl) -5,5-dimethylhydantoin, diacrylate of hydroxypivalic acid ester neopentyl glycol derivative and the like.

Polyfunctional monomers: trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate and the like.

(C) Examples of the photoinitiator include the following: acetophenone type: diethoxyacetophenone, 2-acetophenone
Hydroxy-2-methyl-1-phenylpropane-1-
On, benzyl methyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, aryl ketone mixture, 2-methyl-2-morpholino (4-thio Methylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane, 2-hydroxy-2-
Oligomers of methyl-1- [4- (1-methylvinyl) phenyl] propane and the like.

Benzoin ether type: benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin isobutyl ether and the like.

Benzophenone type: benzophenone, o
-Methyl benzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4
'-Methyl-diphenyl sulfide, 3,3', 4
4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone,
4-benzoyl-N, N-dimethyl-N- [2- (1-
Oxo-2-propenyloxy) ethyl] benzenemethanium brimide, (4-benzoylbenzyl) trimethylammonium chloride and the like.

-Thioxanthone type: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,
4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9
-On mesochloride and the like.

Others: acylphosphine oxide,
2,2'-bis (o-chlorophenyl) -4,5,4
', 5'-tetraphenyl-1,2-biimidazole,
10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, titanocene compounds and the like.

Among these photoinitiators, acetophenones, benzophenones, acylphosphine oxides and the like are more preferable.

The mixing ratio of (a) the photopolymerizable prepolymer, (b) the photopolymerizable monomer, and (c) the photoinitiator in the photopolymerizable resin mixture is usually (a) 10 to 90% by weight of the photopolymerizable prepolymer. Part and (b) the photopolymerizable monomer 90 to 10
(C) about 0.01 to 10 parts by weight of a photoinitiator, and more preferably (a) 30 to 80 parts by weight of a photopolymerizable prepolymer, and (b)
(C) The photoinitiator is about 0.05 to 5 parts by weight based on 100 parts by weight in total of 70 to 20 parts by weight of the photopolymerizable monomer. When the former is excessive (that is, the latter is too small) in the mixing ratio of the photopolymerizable prepolymer and the photopolymerizable monomer, the workability at the time of printing the ink is reduced, while the former is too small. (That is, the latter becomes excessive), the strength of the coating film decreases. When the amount of the photoinitiator with respect to the photopolymerizable prepolymer and the photopolymerizable monomer is too small, the curing does not proceed sufficiently, whereas when the amount is too large, the internal curability decreases.

The ultraviolet curable luminous ink according to the first invention contains a resin component comprising at least one of an epoxy resin and an acrylic epoxy resin. The epoxy resin is not particularly limited, and examples thereof include a bisphenol A type, a novolak type, a bisphenol F type, and a brominated epoxy resin, and have a molecular weight of about 200 to 5000 and an epoxy equivalent of 1
Those having about 100 to 1000 are more preferable. Examples of the acrylic epoxy resin include those obtained by esterifying the epoxy group of the epoxy resin with acrylic acid to convert the functional group into an acryloyl group.

In the ultraviolet curable luminous ink of the first invention, at least one of an epoxy resin and an acrylic epoxy resin is used as a resin component in an amount of about 0.05 to 30 parts by weight (more preferably 100 parts by weight of the photopolymerizable mixture). Is 1
To about 20 parts by weight). If the amount of the resin component is too small, the adhesive strength of the printed layer decreases, while if it is excessive, the curability of the ink decreases.

The luminous pigment to be added to the ultraviolet curable ink composition according to the first invention is not particularly limited, and known or commercially available pigments can be used. For example, in addition to sulfide pigments such as zinc sulfide and calcium sulfide, MAl ₂ O such as strontium aluminate (SrAl ₂ O ₄ )
₄ (M: Mg, Ca, Sr, Ba) pigments can also be used. Furthermore, using these inorganic compounds as host crystals,
A pigment to which a metal element (Cu, Mn, Bi, etc.) or a rare earth element (La, Pr, Gd, Sm, etc.) is added as an activator is also used. In the present invention, since printing at lower temperatures can be realized, a relatively inexpensive sulfide-based pigment can be effectively used as a phosphorescent pigment. That is, printing using a luminous pigment can be performed at low cost. Also, MA
If an l ₂ O ₄ pigment is used, excellent characteristics can be obtained. Note that a part of the phosphorescent pigment may be replaced with an organic pigment, an inorganic pigment, or the like as long as the effects of the present invention are not impaired.

In the present invention, it is desirable to add 50 to 200 parts by weight of the luminous pigment, especially to 100 parts by weight of the photopolymerizable mixture. Preferably it is about 80 to 150 parts by weight. By using a relatively large amount of the luminous pigment in combination with the above-mentioned photopolymerizable mixture or the like, excellent printability can be obtained at a lower temperature and good luminous properties or luminous performance can be obtained. In other words, it is possible to impart more excellent printability and the like to the phosphorescent pigment with a smaller amount of the organic component used.

The UV-curable ink composition according to the first invention contains at least one silane coupling agent in order to improve adhesion to an inorganic material serving as a printing substrate. Although it does not specifically limit as a silane coupling agent, the following things are illustrated.

Vinylsilane type: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxysilane)
etc.

Acrylic silane type: γ-methacryloxypropyltrimethoxysilane and the like.

Epoxysilane type: γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyldiethoxysilane and the like.

Aminosilanes: γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxylan, N-β- (aminoethyl) -γ-aminopropyltrimethoxylan, N-
Phenyl-γ-aminopropyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like.

Others: γ-mercaptopropyltriethoxysilane, γ-chloropropyltriethoxysilane and the like.

The amount of the silane coupling agent in the ultraviolet curable luminous ink according to the first invention is usually about 0.01 to 10 parts by weight, more preferably 0.05 to 10 parts by weight, per 100 parts by weight of the photopolymerizable mixture. About 5 parts by weight. When the amount of the silane coupling agent is too small, the adhesive strength is not sufficiently improved, while when the amount is too large, the printing characteristics deteriorate.

The ultraviolet curable luminous ink according to the present invention may contain a sensitizer, a filler, a leveling agent,
Known additives for the ink composition such as a thixotropic agent and a thermal polymerization inhibitor can be blended.

The ultraviolet curable luminous ink according to the present invention is
It can be manufactured according to a conventional method. For example, after a previously prepared photopolymerizable resin mixture and a resin component are uniformly mixed, a phosphorescent pigment is added and uniformly dispersed. Then, prior to the printing operation, a silane coupling agent is added to the mixture obtained above, and the mixture is uniformly mixed.

2. Second Invention The ultraviolet curable luminous ink according to the second invention uses epoxy acrylate (acrylic epoxy resin) as a photopolymerizable prepolymer used in a photopolymerizable resin mixture. As such an epoxy acrylate or acrylic epoxy resin, the same ones as those mentioned as the resin component in the first invention can be used.
However, the molecular weight is usually about 500 to 500,000.

In the ultraviolet curable luminous ink according to the second invention, the same epoxy resin (same molecular weight and epoxy equivalent) as in the first invention can be used as a resin component.

The mixing ratio of each component of the photopolymerizable resin mixture in the second invention and the mixing ratio of the resin component, the luminous pigment and the silane coupling agent to the photopolymerizable resin mixture are the same as those of the first invention. is there.

3. Third invention The third invention corresponds to the second invention in which the resin component is removed. Therefore, the components constituting the ink according to the third aspect of the invention and the mixing ratio thereof are the same as those of the second aspect of the invention except for the resin component.

4. Fourth invention The fourth invention is directed to a method of manufacturing the ink according to the first to third inventions on a surface of a substrate or a product (a glass cup, a mug, a cup, a dish or a plate, etc.) made of a predetermined inorganic material such as glass, ceramics, and metal. To form a printing layer or a pattern layer, and then irradiate with UV,
It is carried out by heating at a temperature of about 0 ° C. (more preferably about 100 to 150 ° C.) for about 1 to 60 minutes (more preferably about 5 to 30 minutes) to cure.

In particular, in the present invention, since printing can be performed at a low temperature of about 80 to 200 ° C., a sulfide pigment which is oxidatively decomposed at a high temperature can be effectively used as the luminous pigment of the present invention. In addition, even when a MAl ₂ O ₄ pigment is used, the original characteristics can be obtained as it is because it is not exposed to high temperatures.

[0048]

According to the ultraviolet curable luminous ink of the present invention, since less organic components are blended in the luminous pigment, continuous printing of the luminous pigment, which is difficult to print on inorganic materials, is performed at a relatively low temperature. be able to.

Further, the printing or picture layer formed is
It is excellent not only in luminous property or luminous performance but also in adhesiveness, hot water adhesiveness and the like. That is, excellent printability can be exhibited without lowering the intrinsic properties of the luminous pigment.

In particular, in the present invention, printing can be performed at a lower temperature, and a sulfide pigment which is easily oxidized and decomposed at a high temperature can be effectively used. As described above, since a relatively inexpensive sulfide pigment can be used, printing can be performed at lower cost. On the other hand, MAl ₂
Even when an O ₄ -based pigment is used, there is no risk of deterioration due to the fact that it is not exposed to a high temperature, and the original excellent characteristics can be effectively obtained.

[0051]

EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention.

Example 1 Ingredients shown in Table 1 were mixed and stirred to prepare an ink.

Table 1 Raw materials Compounding amount Phosphorescent pigment 70.0 parts Photopolymerizable prepolymer 50.0 parts Photopolymerizable monomer 1 30.0 parts Photopolymerizable monomer 2 20.0 parts Photoinitiator 1.0 part Epoxy Resin 5.0 parts Silane coupling agent 1.0 part Each of the raw materials shown in Table 1 was specifically the following.

・ Phosphorescent pigment “GSS” (trade name, manufactured by Nemoto Special Chemical Co., Ltd., a pigment using zinc sulfide as a host crystal and copper as an activator) Manufactured by Yakuhin Co., Ltd.
Urethane acrylate, weight average molecular weight 6700 ± 60
0, viscosity 400,000 ± 20,000 cps (at20
° C)-Photopolymerizable monomer 1 Trade mark "Kayarad MANDA", manufactured by Nippon Kayaku Co., Ltd., a reaction product of neopentyl glycol and hydroxypivalic acid, average molecular weight 312 Photopolymerizable monomer 2-Photoinitiator Trademark "Irgacure 907" ”, Manufactured by Ciba Geigy,
2-methyl-1- (4- (methylthio) phenyl) -2
-Morpholino-propane-1 type-Epoxy resin "Epicoat 828", manufactured by Yuka Shell Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 184-1
94-Silane coupling agent trademark "KBM603", manufactured by Shin-Etsu Chemical Co., Ltd., N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane Next, using the obtained ink, a printing layer is formed on a glass substrate by a screen printing method, and then irradiated with ultraviolet light, and then at 150 ° C. for 30 minutes. Heat treatment was performed.

Example 2 Raw materials shown in Table 2 were mixed and stirred to prepare an ink.

Table 2 Raw materials Compounding amount Phosphorescent pigment 70.0 parts Photopolymerizable prepolymer 1 20.0 parts Photopolymerizable prepolymer 2 70.0 parts Photopolymerizable monomer 10.0 parts Photoinitiator 1 0.1 Part Photoinitiator 2 0.9 part Epoxy resin 5.0 parts Silane coupling agent 1.0 part In addition, each raw material shown in Table 2 specifically used the following.

-Luminescent pigment: Product name "N night light G-300F", Nemoto Special Chemical Co., Ltd.
Strontium aluminate activated with dyspium, europium, etc.) Photopolymerizable prepolymer 1 Trademark "Kayarad UX4101", manufactured by Nippon Kayaku Co., Ltd.
Urethane acrylate, weight average molecular weight 6700 ± 60
0, viscosity 400,000 ± 20,000 cps (at20
° C) ・ Photopolymerizable prepolymer 2 Trademark “Aronix M7100”, Toagosei Chemical Co., Ltd.
Made, polyester acrylate, weight average molecular weight about 10
00, viscosity 80000 ± 12000 cps (at 20
° C) Photopolymerizable monomer 1,6-hexanediol diacrylate (HDDA) Photoinitiator 1 Trademark “Kayacure DETX-S”, manufactured by Nippon Kayaku Co., Ltd.
2,4-diethyloxane photoinitiator 2 Trademark “Irgacure 907”, manufactured by Ciba Geigy Co., Ltd.
2-methyl-1- (4- (methylthio) phenyl) -2
-Morpholino-propane-1 type-Epoxy resin "Epicoat 828", manufactured by Yuka Shell Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 184-1
94-Silane coupling agent trademark "KBM603", manufactured by Shin-Etsu Chemical Co., Ltd., N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane Next, using the obtained ink, a printing layer is formed on a glass substrate by a screen printing method, and then irradiated with ultraviolet rays, and then at 150 ° C. for 30 minutes. Heat treatment was performed.

Test Example 1 The following tests were performed on the printed coating films obtained in Examples 1 and 2. For comparison, printing formed in the same manner as in Example 1 except that an organic pigment (trade name “HS-3 Cyanine Blue” manufactured by Dainippon Seika Co., Ltd.) was used instead of the phosphorescent pigment of Example 1. The same test was performed on the coating film (Comparative Example 1). (1) Adhesion test (cross-cut tape peeling test) Eleven parallel cuts were made vertically and horizontally at an interval of 1 mm with a cutter knife on 1 cm ² of the printed coating film formed on the workpiece, and 100 grids were cut. After forming a square cell, a cellophane tape was stuck thereon and pulled to check the number of remaining square cells. Table 3 shows the results. In the test results, “100/100” indicates that all the cells remain, and “0/100” indicates that all the cells have been peeled.

(2) Warm Water Adhesion Test I The printed workpiece was immersed in hot water at 80 ° C. for 30 minutes, and then subjected to the same cross-cut tape peeling test as described above. Table 3 shows the results.

(3) Warm Water Adhesion Test II The printed workpiece was immersed in hot water at 80 ° C. for 120 minutes, and then subjected to the same cross-cut tape peeling test as described above. Table 3 shows the results.

Table 3 Adhesiveness Hot Water Adhesion Test I Hot Water Adhesion Test II Example 1 100/100 100/100 100/100 Example 2 100/100 100/100 100/100 Comparative Example 1 0/100 Coating As can be seen from Table 3, Comparative Example 1 in which a large amount of an organic pigment was added did not have adhesion, water resistance, etc., whereas the same amount of a phosphorescent pigment was added. In Example 1 or Example 2, excellent adhesion and water resistance are obtained.

Claims (10)

[Claims] 1. An ultraviolet-curable ink applied to an inorganic material, which is selected from the group consisting of (1) (a) polyester acrylate, polyurethane acrylate, polyether acrylate, polyester acrylate and polyurethane acrylate having a molecular weight of 500 to 500,000. (B) a photopolymerizable resin mixture comprising a photopolymerizable monomer and (c) a photoinitiator; (2) at least one type of an epoxy resin and an acrylic epoxy resin; And (4) an ultraviolet curable luminous ink containing at least one luminous pigment and (4) at least one silane coupling agent. 2. A photopolymerizable mixture comprising (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) a photopolymerizable monomer 90.
2. The ultraviolet curable luminous ink according to claim 1, which is a mixture of (c) 0.01 to 10 parts by weight of a photoinitiator with respect to a total of 100 parts by weight of 10 to 10 parts by weight. (3) 0.05 to 30 parts by weight of at least one of an epoxy resin and an acrylic epoxy resin, and (3) at least one of 50 to 50 parts by weight of a photopolymerizable resin mixture. 3. The ultraviolet curable luminous ink according to claim 1, wherein 200 parts by weight and (4) at least one of silane coupling agents of 0.01 to 10 parts by weight are blended. 4. An ultraviolet-curable ink applied to an inorganic material, comprising: (1) (a) a photopolymerizable prepolymer comprising an epoxy acrylate having a molecular weight of 500 to 500,000;
(B) at least one of (2) a photopolymerizable resin mixture comprising a photopolymerizable monomer and (d) a photoinitiator;
A UV curable luminous ink containing a seed, (3) at least one kind of luminous pigment, and (4) at least one kind of silane coupling agent. 5. A photopolymerizable mixture comprising (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) a photopolymerizable monomer 90.
The ultraviolet curable luminous ink according to claim 4, which is a mixture of 0.01 to 10 parts by weight of (c) a photoinitiator with respect to 100 parts by weight in total of 10 to 10 parts by weight. 6. An epoxy resin (2) of at least one of 0.05 to 3 (1) per 100 parts by weight of the photopolymerizable resin mixture.
0 parts by weight, (3) at least one kind of phosphorescent pigment 50 to 20
The ultraviolet curable luminous ink according to claim 4, wherein 0 parts by weight and 0.01 to 10 parts by weight of at least one kind of the silane coupling agent (4) are blended. 7. An ultraviolet-curable ink applied to an inorganic material, comprising: (1) (a) a photopolymerizable prepolymer comprising an epoxy acrylate having a molecular weight of 500 to 500,000;
(C) a photopolymerizable resin mixture comprising a photopolymerizable monomer and (c) a photoinitiator; (2) at least one kind of a luminous pigment; and (3) at least one kind of a silane coupling agent. ink. 8. A photopolymerizable mixture comprising (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) a photopolymerizable monomer 90.
8. The ultraviolet curable luminous ink according to claim 7, which is a mixture of (c) 0.01 to 10 parts by weight of a photoinitiator with respect to 100 parts by weight in total of 10 to 10 parts by weight. 9. (1) 50 to 200 parts by weight of at least one kind of a luminous pigment and (3) 0.01 to 10 parts by weight of at least one kind of a silane coupling agent per 100 parts by weight of a photopolymerizable resin mixture. The ultraviolet curable luminous ink according to claim 7, wherein the luminous ink is blended. 10. An inorganic material, comprising applying the ultraviolet curable luminous ink according to any one of claims 1 to 9 to an inorganic material, irradiating the ultraviolet light, and then heating and curing at 80 to 200 ° C. Printing method.