JP2992866B2 - UV curable ink composition and method of printing inorganic material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, when printing on inorganic materials such as glass, ceramics, and metal, multicolor printing is continuously performed using an inorganic ink such as a glass enamel ink containing an inorganic pigment as a coloring component. After performing, it has been usually performed by firing at a high temperature of 500 ° C. or more. However, when an inorganic pigment is used as a coloring component, there is a problem that a print layer of a bright color cannot be formed. It is conceivable to use an organic pigment exhibiting a more vivid color in place of the inorganic pigment. However, since the organic pigment has poor heat resistance, it is impossible to form a printed layer by firing at a high temperature.

Therefore, when an organic pigment is used as a coloring component, a thermosetting epoxy ink (one-pack type) which can be fired or cured at a relatively low temperature of up to 200 ° C.
Organic inks such as two-pack type) are used. However, conventional organic inks such as thermosetting epoxy do not have a B-stage immediately after printing, so that continuous printing is impossible, and it takes a lot of time until printing is completed. .

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel ink composition for inorganic materials which can perform continuous printing at a relatively low temperature by using an organic pigment lacking heat resistance as a coloring material. Main purpose.

[0005]

The present inventor has conducted research in view of the state of the art as described above, and as a result, when a specific photopolymerizable mixture is used as a resin component, the above-mentioned prior art is used. Has been found to be substantially eliminated or greatly reduced.

That is, the present invention provides the following ultraviolet-curable ink composition and a method for printing an inorganic material using the same. In an ultraviolet curable ink composition applied to an inorganic material, (1) (a) polyester acrylate, polyurethane acrylate having a molecular weight of 500 to 500,000,
A photopolymerizable resin mixture comprising at least one photopolymerizable prepolymer selected from the group consisting of polyether acrylate, polyester acrylate, and polyurethane acrylate, (b) a photopolymerizable monomer, and (d) a photoinitiator; An ink composition containing a resin component comprising at least one of an epoxy resin and an acrylic epoxy resin, (3) at least one organic pigment, and (4) at least one silane coupling agent.

[0007] 2. Item 1. The ultraviolet-curable ink composition according to Item 1, wherein the photopolymerizable mixture is composed of (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) 90 to 10 parts by weight of a photopolymerizable monomer. An ink composition which is a mixture of (c) 0.01 to 10 parts by weight of a photoinitiator with respect to parts by weight.

[0008] 3. 3. The ultraviolet-curable ink composition according to item 1 or 2, wherein (1) the photopolymerizable resin mixture 1
(2) 0.05 to 30 parts by weight of resin component, (3) 1 to 40 parts by weight of at least one kind of organic pigment, and (4) at least one kind of silane coupling agent.
An ink composition comprising 0.01 to 10 parts by weight.

4. In an ultraviolet curable ink composition applied to an inorganic material, (1) (a) a molecular weight of 500 to 50
(B) a photopolymerizable resin mixture comprising (ii) a photopolymerizable monomer and (d) a photoinitiator; (2) a resin component comprising at least one epoxy resin; An ink composition containing at least one organic pigment and at least one silane coupling agent.

[0010] 5. Item 4. The ultraviolet-curable ink composition according to Item 4, wherein the photopolymerizable mixture has a total of 100 parts by weight of (a) 10 to 90 parts by weight of the photopolymerizable prepolymer and (b) 90 to 10 parts by weight of the photopolymerizable monomer. An ink composition which is a mixture of (c) 0.01 to 10 parts by weight of a photoinitiator with respect to parts by weight.

6. Item 6. The ultraviolet curable ink composition according to item 4 or 5, wherein (1) the photopolymerizable resin mixture 1
(2) 0.05 to 30 parts by weight of resin component, (3) 1 to 40 parts by weight of at least one kind of organic pigment, and (4) at least one kind of silane coupling agent.
An ink composition comprising 0.01 to 10 parts by weight.

7. In an ultraviolet curable ink composition applied to an inorganic material, (1) (a) a molecular weight of 500 to 50
(Ii) a photopolymerizable resin mixture comprising (ii) a photopolymerizable monomer and (d) a photoinitiator; (2) at least one organic pigment; and (3) a silane cup. An ink composition containing at least one ring agent.

8. Item 7. The ultraviolet-curable ink composition according to Item 7, wherein the photopolymerizable mixture is a total of 100 parts by weight of (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) 90 to 10 parts by weight of a photopolymerizable monomer. An ink composition which is a mixture of (c) 0.01 to 10 parts by weight of a photoinitiator with respect to parts by weight.

9. Item 7. The ultraviolet-curable ink composition according to item 7 or 8, wherein (1) the photopolymerizable resin mixture 1
(2) at least one kind of organic pigment 1 to 100 parts by weight
An ink composition comprising 40 parts by weight and 0.01 to 10 parts by weight of at least one of the silane coupling agents (3).

10. Item 10. A method for printing an inorganic material, comprising applying the ultraviolet-curable ink composition according to any one of Items 1 to 9 to an inorganic material, irradiating the material with ultraviolet light, and heating and curing at 80 to 200 ° C.

In the following, the inventions described in claims 1 to 3 will be referred to as the first invention of the present application, the inventions described in claims 4 to 6 will be referred to as the second invention of the present application, and the inventions described in claims 7 to 9 will be described. The invention will be described in detail as a third invention of the present application, and the invention described in claim 10 as a fourth invention of the present application. In addition, items common to all inventions may be simply referred to as the invention of the present application.

First Invention of the Present Application The photopolymerizable resin mixture used in the ultraviolet-curable ink composition according to the first invention of the present application comprises (a) a molecular weight of 500 to 500.
At least one of about 000 photopolymerizable prepolymers,
(B) at least one photopolymerizable monomer and (c)
At least one of the photoinitiators is an essential component.

Examples of the photopolymerizable prepolymer are as follows: polyester acrylates: oils, modified alkyds,
Acroyl group-introduced, based on modified polyester, and further urethanized.

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

Polyether acrylates.

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

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 monomer: 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 monomer: trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexacrylate, etc.

Examples of the photoinitiator are as follows: -acetophenone type: diethoxyacetophenone, 2-
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, acetophenone-based, benzophenone-based, acylphosphine oxide and the like are more preferred.

In the photopolymerizable resin mixture, (a) a photopolymerizable prepolymer, (b) a photopolymerizable monomer, and (c)
The mixing ratio of the photoinitiator is usually (a) 10 to 90 parts by weight of the photopolymerizable prepolymer and (b) 90 to 90 parts by weight of the photopolymerizable monomer.
(C) about 0.01 to 10 parts by weight of a photoinitiator, 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 ink composition according to the first invention of the present application contains a resin component comprising at least one of an epoxy resin and an acrylic epoxy resin. The epoxy resin is not particularly limited, bisphenol A type,
Novolak type, bisphenol F type, brominated epoxy resin and the like are exemplified, and those having a molecular weight of about 200 to 5,000 and an epoxy equivalent of about 100 to 1,000 are more preferable.
As an acrylic epoxy resin, the epoxy group of the above epoxy resin is esterified with acrylic acid,
One in which the functional group is an acryloyl group is exemplified.

In the ultraviolet curable ink composition of the first invention of the present application, a resin component comprising an epoxy resin and / or an acrylic epoxy resin is added in an amount of about 0.05 to 30 parts by weight based on 100 parts by weight of the photopolymerizable mixture. (More preferably about 1 to 20 parts by weight). When the amount of such a resin component is too small, the adhesive strength of the printed layer is reduced, while when it is excessive, the curability of the ink is reduced.

The coloring component to be added to the ultraviolet-curable ink composition according to the first invention of the present application is not particularly limited, and includes a fluorescent pigment, a thermochromic organic pigment, and the like, as long as they do not decompose or change under heating conditions after irradiation with ultraviolet light. A wide range of organic pigments can be used. The compounding amount of the organic pigment is usually about 1 to 40 parts by weight, more preferably about 5 to 30 parts by weight, based on 100 parts by weight of the photopolymerizable mixture. If the amount of the coloring component is too small, a predetermined color density cannot be obtained, while if it is too large, the strength of the coating film and the adhesive strength decrease.

The UV-curable ink composition according to the first aspect of the present invention contains at least one silane coupling agent in order to improve the 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) and the like.

Acrylic silane type: γ-methacryloxypropyltrimethoxysilane and the like.

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

-Aminosilane type: 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 ink composition according to the first invention of the present application is usually 0.01 to 1 with respect to 100 parts by weight of the photopolymerizable mixture.
It is about 0 parts by weight, more preferably about 0.05 to 5 parts by weight. If the amount of the silane coupling agent is too small, the adhesive strength is not sufficiently improved, while if it is too large, the printing characteristics are degraded.

The UV-curable ink composition according to the present invention may be added, if necessary, with known ink compositions such as sensitizers, fillers, leveling agents, thixotropes, and thermal polymerization inhibitors. Agents can be added.

The ultraviolet-curable ink composition according to the present invention can be produced according to a conventional method. That is,
After the photopolymerizable resin mixture prepared in advance and the resin component are uniformly mixed, an organic pigment is added and uniformly dispersed. Then, prior to the printing operation, the mixture is obtained by adding a silane coupling agent to the mixture obtained above and mixing the mixture uniformly.

Second Invention of the Present Application The ultraviolet curable ink composition according to the second invention of the present application uses an 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 type as those mentioned as the resin component in the first invention of the present application can be used. However, the molecular weight is about 500 to 500,000.

Further, in the ultraviolet curable ink composition according to the second invention of the present application, the same epoxy resin (having the same molecular weight and epoxy equivalent) as that described in the first invention of the present application is used as a resin component.

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

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

Fourth invention of the present application The fourth invention of the present application is directed to a method of applying the present invention to 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. After applying the ink composition according to the third invention to form a print layer or a pattern layer, UV irradiation is performed, and then 80 to 2
It is carried out by heating at a temperature of about 00 ° C. (more preferably about 100 to 150 ° C.) for about 1 to 60 minutes (more preferably about 5 to 30 minutes) to cure.

[0049]

According to the ultraviolet curable ink composition of the present invention, continuous printing can be performed at a relatively low temperature while using an organic pigment lacking heat resistance as a coloring material. Also,
The formed printing or picture layer is excellent in adhesion, hot water adhesion and the like.

[0050]

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

The details of the materials used and the test methods performed are as follows.

Photopolymerizable prepolymer (hereinafter referred to as prepolymer)
Hereinafter) prepolymer I ... trademark "KAYARAD UX4101", manufactured by Nippon Kayaku Co., Ltd., a urethane acrylate, a weight average molecular weight 6700 ± 600, viscosity 400000 ± 20000c
ps (at 20 ° C.) Prepolymer II: Trademark “Kayarad UX6101”,
Urethane acrylate, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight 6900 ± 700, viscosity 330000 ± 12000
cps (at 20 ° C.) Prepolymer III Trademark “Kayarad UX710
1 ", Nippon Kayaku Co., Ltd., urethane acrylate, weight average molecular weight 8700 ± 900, viscosity 30000 ± 600
0 cps (at 20 ° C.) Prepolymer IV: Trademark “Kayarad UX8101”,
Nippon Kayaku Co., Ltd., urethane acrylate, weight average molecular weight 3400 ± 300, viscosity 7000 ± 1400 cps
(At 20 ° C.) Prepolymer V: Trade name “Aronix M1100”, manufactured by Toagosei Chemical Co., Ltd., urethane acrylate, weight average molecular weight about 2,000, viscosity 200,000 ± 30,000 cp
s (at 20 ° C.) Prepolymer VI: Trademark “Aronix M6200”,
Toagosei Chemical Co., Ltd., bifunctional polyester acrylate, viscosity 2500 ± 500 cps (at 20 ° C.) Prepolymer VII: trademark “ALONIX M710”
0 ", manufactured by Toagosei Chemical Co., Ltd., polyester acrylate, weight average molecular weight: about 1,000, viscosity: 80000 ± 12
000 cps (at 20 ° C.) Photopolymerizable monomer (hereinafter referred to as “monomer”) Monomer I. Trademark “Kayarad MANDA”, manufactured by Nippon Kayaku Co., Ltd., a reaction product of neopentyl glycol and hydroxypivalic acid, average molecular weight 312. "Kayarad R551", manufactured by Nippon Kayaku Co., Ltd., 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, average molecular weight 512 Monomer III: neopentyl glycol diallylate (NPGDA) Monomer IV: 1,6 -Hexanediol diacrylate (HDDA) photoinitiator (hereinafter referred to as initiator) Initiator I: trade name "Irgacure 651", manufactured by Ciba Geigy Co., Ltd., benzyl methyl ketal-based initiator II ... trade mark "Irgacure 907", Ciba Geigy Corporation ), 2-methyl-1- (4- (me Tylthio) phenyl) -2-morpholino-propane-1 initiator III: trademark "Kayacure BMS", manufactured by Nippon Kayaku Co., Ltd., 4-benzoyl-4'-methyl-diphenylsulfide initiator IV: trademark "Kayacure" DETX-S ", manufactured by Nippon Kayaku Co., Ltd., 2,4-diethyloxane initiator V: Trademark" Kayacure ITX ", Nippon Kayaku Co., Ltd.
2-chlorothioxanthone-based initiator VI (trademark "Darocur 1173", MERK)
2-hydroxy-2-methyl-1-phenyl-1-
On-type initiator VII: Trademark "Lucillin TPO", manufactured by BASF,
2,4,6-trimethylbenzoyldiphenylphosphine oxide epoxy resin and acrylic epoxy resin (hereinafter referred to as epoxy resin)
Shi called) epoxy I ... trademark "Epikote 807", Yuka Shell Co., Ltd., bisphenol F type epoxy resin, epoxy equivalent 166 to 175 epoxy II ... trademark "Epikote 828", produced by Yuka Shell Co., Ltd., bisphenol A Epoxy resin, epoxy equivalent 184 to 194, epoxy III: trademark "Epicoat 834", manufactured by Yuka Shell Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 230 to 270, epoxy IV: trademark "Kayarad R001", Nippon Kayaku ( Novolak type epoxy acrylate, theoretical molecular weight 650, viscosity 18000 ± 4000 cps (at2
0 ° C.) Epoxy V: trademark “Kayarad R131”, manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy acrylate,
Theoretical molecular weight 1100, viscosity 15000 ± 5000 cps
(At 20 ° C.) Epoxy VI: trademark “Kayarad R190”, manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy acrylate,
Theoretical molecular weight 1950, viscosity 22000 ± 5000 cps
(At 20 ° C.) Epoxy VII—trade name “Kayarad EX2320”, manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy acrylate, theoretical molecular weight 800, viscosity 45000 ± 5000c
ps (at 20 ° C.) Epoxy VIII—trademark “Photomer 3016”, manufactured by San Nopco Co., Ltd., bisphenol A type epoxy acrylate, viscosity 70,000-100,000 cps (at 20
C) Silane coupling agent (hereinafter referred to as silane) Silane I. Trademark "KBM303", manufactured by Shin-Etsu Chemical Co., Ltd.
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Silane II: Trademark “KBE402”, Shin-Etsu Chemical Co., Ltd.
Γ-glycidoxypropylmethyldiethoxysilane Silane III. Trademark “KBM602”, Shin-Etsu Chemical Co., Ltd.
N-β- (aminoethyl) -γ-aminopropyldimethoxysilane Silane IV: Trademark “KBM603”, Shin-Etsu Chemical Co., Ltd.
N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane silane V. Trademark “KBM703”, manufactured by Shin-Etsu Chemical Co., Ltd.
γ-chloropropyltrimethoxysilane Silane VI Trademark “KBM1003”, Shin-Etsu Chemical Co., Ltd.
Manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane silane VII trademark "KBM903"
Ltd., vinyltrimethoxysilane organic pigments (hereinafter referred to as pigment) Pigment I ... ® "HS-3 Cyanine Blue", Dainichi Seika Co., cyanine blue pigment II ... trademark "820 Series Green", Sterling Co., fluorescent pigments Pigment III: trademark "820 series pink", manufactured by Stirling, fluorescent pigment Pigment IV: trademark "TC powder black 15C",
Thermochromic pigment manufactured by Sakura Crepas Co., Ltd. Pigment V: Trademark "TC Powder Blue 15C", manufactured by Sakura Crepas Co., Ltd. Thermochromic pigment test method 1) Adhesion test (cross-cut tape peeling test) Formed on the workpiece 11 parallel cuts were made in each of the printed coating 1 cm ² vertically and horizontally at an interval of 1 mm with a cutter knife to form 100 grids, and then cellophane tape was stuck thereon and pulled. The number of remaining squares was checked. In the test results, "100/1
"00" indicates that all the cells remain, and "0/100" indicates that all the cells have been peeled off.

2) Warm Water Adhesion Test I After the printed workpiece was immersed in hot water at 80 ° C. for 30 minutes, the same cross-cut tape peeling test as described above was performed.

3) Hot 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.

Examples 1 to 5 and Comparative Examples 1 to 5 Using the various materials described above, ink compositions having the compositions shown in Table 1 were prepared.

In Table 1 and Table 3 below, the blending amounts of various materials are indicated by "parts by weight". Therefore,
For example, in the section of the prepolymer, "I: 50" means that 50 parts by weight of the prepolymer I shown above was blended, and the same applies to other materials.

[0057]

[Table 1]

Note 1: 2 parts by weight of N-methyldiethanolamine was blended as a sensitizer.

After forming a printing layer on a glass substrate by a screen printing method using the obtained ink composition,
The coating was heated and cured under the conditions shown in Table 2 after irradiation with ultraviolet rays. Table 2 also shows the results of the various tests described above.

[0060]

[Table 2]

From the results shown in Table 2, it is clear that the UV curable ink composition according to the present invention has excellent properties.

Examples 6 to 15 Using the various materials described above, ink compositions having the compositions shown in Table 3 were prepared. In addition, the compounding amount of various materials in Table 3 means "part by weight".

[0063]

[Table 3]

After forming a printing layer on a glass substrate by a screen printing method using the obtained ink composition,
The coating was heated and cured under the conditions shown in Table 4 after irradiation with ultraviolet rays. Table 4 also shows the results of the various tests described above.

[0065]

[Table 4]

The results shown in Table 4 clearly show the excellent properties of the ultraviolet-curable ink composition according to the present invention.

Examples 16 to 19 Using the above various materials, ink compositions having the compositions shown in Table 5 were prepared. In addition, the compounding amount of various materials in Table 5 means "part by weight".

[0068]

[Table 5]

After forming a printing layer on a glass substrate by a screen printing method using the obtained ink composition,
The coating was heated and cured under the conditions shown in Table 6 after irradiation with ultraviolet rays. Table 6 also shows the results of the various tests described above.

[0070]

[Table 6]

The results shown in Table 6 clearly show the excellent properties of the ultraviolet-curable ink composition according to the present invention.

Claims (10)

(57) [Claims] 1. An ultraviolet-curable ink composition applied to an inorganic material, comprising: (1) (a) 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. (B) a photopolymerizable resin mixture comprising a photopolymerizable monomer and (d) a photoinitiator; (2) at least one of an epoxy resin and an acrylic epoxy resin; And (4) an ink composition containing at least one organic pigment and (4) at least one silane coupling agent. 2. The ultraviolet-curable ink composition according to claim 1, wherein the photopolymerizable mixture comprises (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) a photopolymerizable monomer 90.
(C) an ink composition which is a mixture obtained by mixing 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. 3. The ultraviolet curable ink composition according to claim 1, wherein (1) the photopolymerizable resin mixture 100
(2) 0.05 to 30 parts by weight of at least one of epoxy resin and acrylic epoxy resin based on part by weight, (3)
1 to 40 parts by weight of at least one kind of organic pigment and (4)
At least one of silane coupling agents 0.01 to 10
An ink composition comprising parts by weight. 4. An ultraviolet curable ink composition 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) a photopolymerizable monomer, and (d) a photopolymerizable monomer. Ink composition containing (2) at least one kind of epoxy resin, (3) at least one kind of organic pigment, and (4) at least one kind of silane coupling agent . 5. The ultraviolet-curable ink composition according to claim 4, wherein the photopolymerizable mixture comprises (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) a photopolymerizable monomer 90.
(C) an ink composition which is a mixture obtained by mixing 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. 6. The ultraviolet curable ink composition according to claim 4, wherein (1) the photopolymerizable resin mixture 100
At least one kind of (2) epoxy resin per part by weight.
05 to 30 parts by weight, (3) at least one kind of organic pigment 1
To 40 parts by weight and (4) 0.01 to 10 parts by weight of at least one kind of a silane coupling agent. 7. An ultraviolet curable ink composition 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) a photopolymerizable monomer, and (d) a photopolymerizable monomer. An ink composition containing a photopolymerizable resin mixture comprising a photoinitiator, (2) at least one organic pigment, and (3) at least one silane coupling agent. 8. The ultraviolet-curable ink composition according to claim 7, wherein the photopolymerizable mixture comprises (a) 10 to 90 parts by weight of a photopolymerizable prepolymer and (b) a photopolymerizable monomer 90.
(C) an ink composition which is a mixture obtained by mixing 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. The ultraviolet curable ink composition according to claim 7, wherein (1) the photopolymerizable resin mixture 100
(2) at least one kind of organic pigment is 1 to 40 parts by weight
An ink composition comprising 0.01 parts by weight of at least one kind of the silane coupling agent and (3) a silane coupling agent. 10. An inorganic material comprising applying the ultraviolet-curable ink composition according to any one of claims 1 to 9 to an inorganic material, irradiating it with ultraviolet light, and heating and curing at 80 to 200 ° C. Printing method.