Ink set, glass product, and method for manufacturing the same

Abstract

To provide: an ink set which cannot only form a primer layer having high adhesiveness on a glass substrate but also form a colored layer having excellent hue reproducibility and fineness on the primer layer; a glass product which has characters and designs, having not only high adhesiveness but also excellent hue reproducibility and fineness, printed on the glass substrate using the ink set; and a production method thereof.SOLUTION: An ink set comprises: a primer ink containing an amino group-containing silane coupling agent and a hydroxyl group-containing (meth)acrylate; and a colored ink containing 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. A glass product has a primer layer formed from the primer ink and a colored layer formed from a colored ink laminated in this order on a glass substrate. A production method of the glass product comprises: printing a primer layer to form an uncured precursor layer; subsequently laminating the colored ink to form an uncured precursor layer; and thereafter subjecting the two layers to a curing reaction.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention particularly relates to an ink set suitable for printing characters, patterns, etc. on the surface of a glass substrate such as a glass bottle, a glass product having characters, patterns, etc. printed on the surface of a glass substrate using the ink set, and a method for manufacturing the same.

Background Art

[0002] For glass bottles for beverages or foods, it is common to attach a paper label printed with characters, patterns, etc. such as product names, or to wrap a shrink film printed with characters, patterns, etc. and heat-shrink it to make it adhere. However, recently, from the viewpoint of recycling, etc., there is a growing demand to omit paper labels and shrink films and directly print characters, patterns, etc. on the surface of glass bottles.

[0003] So far, for relatively simple characters and patterns with a small number of colors, they have sometimes been directly printed on the surface of glass bottles by a screen printing method or the like. However, with conventional printing methods such as the screen printing method, it has been difficult to print multi-color and complex characters, patterns, etc. comparable to those printed on paper labels or shrink films. In addition, conventional printing methods such as the screen printing method require a predetermined printing plate and are suitable for printing a large amount of fixed patterns, but are not suitable for printing in small quantities of multiple varieties or frequently changing patterns.

[0004] On the other hand, according to an inkjet printing method that does not require a printing plate and can directly print based on data created in a computer, it is possible to print multi-color and complex characters, patterns, etc. comparable to those printed on paper labels, etc. Also, according to the inkjet printing method, it is easy to handle printing in small quantities of multiple varieties or frequently changing patterns.

[0005] However, conventional inkjet inks do not have sufficient adhesion to the surface of glass bottles, particularly resistance to warm water, water when washing glass bottles prior to bottling beverages, etc., or warm water during retort processing of the entire glass bottle with food, etc. after bottling. Therefore, various studies have been conducted on inkjet inks capable of printing characters, patterns, etc. with excellent adhesion to glass substrates such as glass bottles (see, for example, Patent Document 1, etc.).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] Patent Document 1 describes an active energy ray-curable inkjet ink that contains a photo radical polymerization initiator and a radical polymerizable component and undergoes a curing reaction (radical polymerization reaction) upon irradiation with active energy rays such as ultraviolet rays. And in order to improve the adhesion of the cured product of the inkjet ink to the glass substrate, · As the radical polymerizable component, an alicyclic monofunctional (meth)acrylate having a predetermined glass transition temperature and a hydroxyl group-containing monofunctional (meth)acrylate are used in combination, · Further, a silane coupling agent is blended, and these are being studied.

[0008] Also, Patent Document 1 describes printing the above inkjet ink on the surface of a glass substrate, causing a curing reaction to form a primer layer, and then printing a colored layer such as characters and patterns using an arbitrary active energy ray-curable colored ink. According to such a configuration, for example, by coloring the primer layer white or the like, it is expected that the reproducibility of the color tone of the colored layer formed of a colored ink that is basically transparent or translucent and easily affected by the color tone of the base can be improved.

[0009] However, according to the inventor's study, as described in Patent Document 1, if the primer ink is first printed and cured to form a primer layer, and then the colored layer is printed using the colored ink, the adhesion of the colored layer to the primer layer may be insufficient. In order to improve the adhesion of the colored layer to the primer layer, first, an uncured precursor layer of the primer layer (hereinafter sometimes abbreviated as "primer precursor layer") is formed on the surface of the glass substrate using the primer ink.

[0010] Next, an uncured precursor layer of the colored layer (hereinafter sometimes abbreviated as "colored precursor layer") is formed thereon using the colored ink, and then it is desirable to irradiate both precursor layers with active energy rays and simultaneously cause a curing reaction. However, when the inkjet ink described in Patent Document 1 is used as the primer ink and combined with an arbitrary colored ink, in the above procedure, the color tone of the colored layer may not be sufficiently reproduced, or the fineness of characters, patterns, etc. constituting the colored layer may be reduced.

[0011] This is considered to be because the colored ink that forms the colored precursor layer printed on the primer precursor layer mixes with the primer ink during the curing reaction of both precursor layers, causing the color tone to change, or the colored ink seeps into the primer ink and the boundary becomes unclear. Patent Document 2 describes using an ink set of a white or clear primer ink and a colored ink, and making the surface tensions of the primer ink and the colored ink different in order to prevent bleeding between the primer ink and the colored ink and enhance the fineness of the colored layer.

[0012] Patent Document 2 also describes that printing on the surface of a glass substrate is possible using such an ink set. However, according to the inventor's study, the primer ink of the ink set of Patent Document 2 does not consider at all ensuring the adhesion to the surface of the glass substrate. Therefore, the adhesion of the primer layer made of the primer ink to the surface of the glass substrate is insufficient, and a primer layer having high adhesion cannot be formed on the surface of the glass substrate.

[0013] An object of the present invention is to provide an ink set capable of forming a primer layer having high adhesion to the surface of a glass substrate and forming a colored layer excellent in color reproducibility and fineness on the primer layer. Another object of the present invention is to provide a glass product printed with characters, patterns, etc. having high adhesion, excellent color reproducibility and fineness on the surface of a glass substrate using such an ink set, and a method for manufacturing the same.

Means for Solving the Problems

[0014] The present invention is (A) A primer ink containing an amino group-containing silane coupling agent and a hydroxyl group-containing (meth)acrylate as a radical polymerizable component, and having active energy ray curability, and (B) At least one colored ink containing 2-(2-vinyloxyethoxy)ethyl (meth)acrylate as a radical polymerizable component and having active energy ray curability. It is an ink set containing.

[0015] The present invention is also a glass product in which a primer layer made of the primer ink and a colored layer made of the colored ink are sequentially laminated on the surface of a glass substrate. Furthermore, the present invention is a method for manufacturing the glass product of the present invention, A step of printing the primer ink on the surface of the glass substrate by an inkjet printing method to form an uncured precursor layer of the primer layer, On the formed precursor layer, the colored ink is printed by an inkjet printing method to form an uncured precursor layer of the colored layer, and irradiating the both precursor layers with active energy rays to cause a curing reaction of the primer ink and the colored ink that form the both precursor layers, thereby forming the primer layer and the colored layer, A method for manufacturing a glass product including

Advantages of the Invention

[0016] According to the present invention, it is possible to provide an ink set capable of forming a primer layer having high adhesion to the surface of a glass substrate, and capable of forming a colored layer excellent in color reproducibility and fineness on the primer layer. Further, according to the present invention, there can be provided a glass product having high adhesion to the surface of a glass substrate and printed with characters, patterns, etc. excellent in color reproducibility and fineness, and a method for manufacturing the same, by using such an ink set.

Embodiments for Carrying Out the Invention

[0017] 《Ink Set》 As described above, the ink set of the present invention (A) A primer ink containing an amino group-containing silane coupling agent and a hydroxyl group-containing (meth)acrylate as a radical polymerizable component, and having active energy ray curability, and (B) At least one colored ink containing 2-(2-vinyloxyethoxy)ethyl (meth)acrylate as a radical polymerizable component and having active energy ray curability, characterized by including

[0018] The amino group-containing silane coupling agent contained in the primer ink of (A) in the above ink set is a silane compound having an Si-OR group as a hydrolyzable group and an amino group in the same molecule, and among these, the Si-OR group has high reactivity with respect to the surface of the glass substrate. That is, the Si-OR group reacts with moisture in the air or moisture on the glass surface and hydrolyzes to form Si-OH groups. These Si-OH groups form hydrogen bonds with the surface of the glass substrate in the primer precursor layer. Furthermore, during the curing reaction, the hydrogen bonds undergo a dehydration condensation reaction, and in some cases, stronger chemical bonds are formed between the primer layer after curing and the glass substrate.

[0019] In addition, the amino group has a high affinity for the radically polymerizable component. Among them, the amino group-containing (meth)acrylate with a hydroxyl group forms a hydrogen bond with the hydroxyl group in the molecule. Therefore, when the primer ink is printed on the surface of the glass substrate, in the printed primer precursor layer, the amino group-containing silane coupling agent is unevenly distributed at the interface with the glass substrate, and it functions to enhance the adhesion of the primer layer after curing to the surface of the glass substrate.

[0020] In addition, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate contained in the colored ink of (B) has a high curing rate, so it functions to increase the curing rate of the colored ink that forms the colored precursor layer printed on the primer precursor layer. Therefore, the colored ink can be solidified as quickly as possible during the curing reaction of both precursor layers, and it is possible to suppress the colored ink from mixing with the primer ink and changing the color, or bleeding and making the boundary unclear.

[0021] Also, if the colored ink sinks to the interface between the primer precursor layer and the glass substrate, the concentration of the amino group-containing silane coupling agent unevenly distributed at the interface decreases, and its function is inhibited, which may reduce the adhesion of the primer layer to the surface of the glass substrate. On the other hand, since the colored ink of (B) solidifies quickly as described above, it does not sink to the interface between the primer precursor layer and the glass substrate and inhibit the function of the amino group-containing silane coupling agent, nor does it reduce the adhesion of the primer layer to the surface of the glass substrate.

[0022] Therefore, according to the ink set of the present invention containing the primer ink of (A) and the colored ink of (B), a primer layer having high adhesion to the surface of the glass substrate can be formed, and a colored layer having better color reproducibility and fineness than the current situation can be formed on the primer layer. 〈(A) Primer Ink〉 As described above, the primer ink contains an amino group-containing silane coupling agent and a hydroxyl group-containing (meth)acrylate as a radical polymerizable component.

[0023] (Amino Group-Containing Silane Coupling Agent) As the amino group-containing silane coupling agent, in the same molecule having a silane as the basic skeleton, as described above, · A hydrolyzable group that hydrolyzes by a sol-gel reaction and reacts with the surface of the glass substrate, · An amino group having a high affinity for the radical polymerizable component and reacting with the hydroxyl group of the hydroxyl group-containing (meth)acrylate, Various silane compounds having the above can be used.

[0024] Specific examples of the amino group-containing silane coupling agent include, but are not limited to, the following various compounds. N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane.

[0025] One or more of these amino group-containing silane coupling agents can be used. Among them, as the amino group-containing silane coupling agent, an amino group-containing silane coupling agent having a phenyl group in the molecule, particularly N-phenyl-3-aminopropyltrimethoxysilane, is preferable.

[0026] Generally, a precursor layer composed of an ink having active energy ray curability tends to shrink in volume during the curing reaction, and the same applies to a primer precursor layer composed of a primer ink and a colored precursor layer composed of a colored ink. In particular, when the primer precursor layer and the colored precursor layer printed thereon are simultaneously subjected to a curing reaction, if the primer precursor layer shrinks greatly in volume, gaps are likely to occur at the interface between the two layers.

[0027] Then, warm water, water, etc. easily penetrate into the generated gaps, and peeling may easily occur between the cured primer layer and the colored layer. On the other hand, if an amino group-containing silane coupling agent having a phenyl group in the molecule is selected and used, due to the steric hindrance of the phenyl group, the volume shrinkage amount during the curing reaction of the primer precursor layer can be reduced.

[0028] And it is possible to prevent gaps from occurring at the interface between the primer precursor layer and the colored precursor layer, and to make peeling less likely to occur between the cured primer layer and the colored layer. The proportion of the amino group-containing silane coupling agent is preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more, in the total amount of the primer ink, and preferably 1.5% by mass or less, particularly preferably 1.3% by mass or less.

[0029] If the proportion of the amino group-containing silane coupling agent is less than this range, the effect of enhancing the adhesion of the primer layer to the surface of the glass substrate may not be sufficiently obtained. On the other hand, when the proportion of the amino group-containing silane coupling agent exceeds the above range, the proportion of the radical polymerizable component is relatively insufficient, the film strength of the primer layer may decrease, and accordingly, the adhesion of the primer layer to the surface of the glass substrate may decrease.

[0030] On the other hand, by setting the proportion of the amino group-containing silane coupling agent within the above range, it is possible to sufficiently enhance the adhesion of the primer layer to the surface of the glass substrate while suppressing a decrease in the film strength of the primer layer. (Radical polymerizable component) As the radical polymerizable component, as described above, at least a hydroxyl group-containing (meth)acrylate is used.

[0031] As the hydroxyl group-containing (meth)acrylate, various (meth)acrylates having a hydroxyl group in the molecule can be used. Specific examples of the hydroxyl group-containing (meth)acrylate include, but are not limited to, the following various compounds. 4-Hydroxybutyl acrylate (4HBA), 2-Hydroxyethyl acrylate (2HEA), 2-Hydroxypropyl acrylate (2HPA), 2-Hydroxyethyl methacrylate (2HEMA), 2-Hydroxypropyl methacrylate (2HPMA).

[0032] One or more of these hydroxyl group-containing (meth)acrylates can be used. In particular, 4-Hydroxybutyl acrylate is preferable. Since 4-Hydroxybutyl acrylate has a long crosslinking chain, it can improve the flexibility of the primer layer and further enhance the adhesion of the primer layer to the surface of the glass substrate.

[0033] In addition, as the radical polymerizable component, together with the above hydroxyl group-containing (meth)acrylate, an amine-modified (meth)acrylate may be used in combination as a second radical polymerizable component. As the amine-modified (meth)acrylate, for example, various radical-polymerizable compounds having a structure in which a monomer or oligomer of (meth)acrylate is modified with an amino group can be used.

[0034] Among them, as the amine-modified (meth)acrylate, an amine-modified acrylate having an acrylic group as a functional group is preferable in order to enhance the reactivity with the hydroxyl group-containing (meth)acrylate and to increase the curing start rate and the curing rate of the primer ink. Specific examples of the amine-modified (meth)acrylate include, but are not limited to, CN371, CN373, CN383, CN386, etc. manufactured by Sartomer Co., Ltd., all of which are amine-modified acrylates, and CN371 is particularly preferable.

[0035] One or more of these amine-modified (meth)acrylates can be used. As the radically polymerizable component, various third radically polymerizable components capable of radical polymerization such as 2-phenoxyethyl acrylate, dipentaerythritol hexaacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, etc. can also be used in combination.

[0036] One or more of these third radically polymerizable components can be used. Ratio R of the hydroxyl group-containing (meth)acrylate OHA is preferably 8% by mass or more, particularly preferably 18% by mass or more, in the total amount of the radically polymerizable components. Ratio R of the hydroxyl group-containing (meth)acrylate OHA If it is less than this range, the effect of enhancing the adhesion of the primer layer to the surface of the glass substrate may not be sufficiently obtained by the reaction with the amino group-containing silane coupling agent described above.

[0037] On the other hand, by setting the ratio R of the hydroxyl group-containing (meth)acrylate OHA within the above range, the reactivity with the amino group-containing silane coupling agent can be enhanced, and the adhesion of the primer layer to the surface of the glass substrate can be further enhanced. Note that the upper limit of the ratio R of the hydroxyl group-containing (meth)acrylate OHA is not particularly limited, and the total amount of the radically polymerizable components, that is, 100% by mass in the total amount of the radically polymerizable components may be the hydroxyl group-containing (meth)acrylate.

[0038] However, when using the second and third radically polymerizable components such as amine-modified (meth)acrylate in combination, the proportion R of the hydroxyl group-containing (meth)acrylate OHA is preferably 99% by mass or less in the total amount of the radically polymerizable components. The proportion R of the amine-modified (meth)acrylate as the second radically polymerizable component NMA is preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and preferably 3% by mass or less, particularly preferably 2.5% by mass or less in the total amount of the radically polymerizable components.

[0039] The amine-modified (meth)acrylate also functions as a sensitizer for the primer ink, and particularly improves the resistance of the primer layer after curing to warm water and the like, and enhances the adhesion of the primer layer to the surface of the glass substrate. However, when the proportion R of the amine-modified (meth)acrylate NMA is less than the above range, such an effect cannot be sufficiently obtained, and thus the effect of improving the adhesion of the primer layer to the surface of the glass substrate may not be sufficiently obtained.

[0040] On the other hand, when the proportion R of the amine-modified (meth)acrylate NMA exceeds the above range, relatively, the proportion of the hydroxyl group-containing (meth)acrylate is insufficient, and conversely, the adhesion of the primer layer to the surface of the glass substrate may decrease. In contrast, if the proportion R of the amine-modified (meth)acrylate NMA is within the above range, the adhesion of the primer layer to the surface of the glass substrate can be further improved.

[0041] Also, the proportion of the third radically polymerizable component such as 2-phenoxyethyl acrylate is the remaining amount of the hydroxyl group-containing (meth)acrylate and the amine-modified (meth)acrylate. That is, when a hydroxyl group-containing (meth)acrylate and an amine-modified (meth)acrylate are each blended at the above-described predetermined ratio, the ratio of the third radically polymerizable component may be set so that the total amount of the radically polymerizable components becomes 100% by mass.

[0042] Further, when the total ratio of the hydroxyl group-containing (meth)acrylate and the amine-modified (meth)acrylate is 100% by mass of the total amount of the radically polymerizable components, the third radically polymerizable component may be omitted. (Colorant) The primer ink can be colored in any light color tone such as white, milky white, and light yellow in order to improve the reproducibility of the color tone of the colored layer, and it is particularly preferable to color it white in terms of color tone reproducibility.

[0043] As the colorant for coloring the primer ink white, various white pigments, dyes, etc. can be used. Particularly, considering improving the Weather resistance etc., a white pigment is preferable. Examples of the white pigment include at least one white metal oxide selected from the group consisting of titanium oxide, zinc oxide, and antimony oxide. Particularly, titanium oxide having excellent coloring power, hiding power, and weather resistance is preferable.

[0044] The white pigment may be surface-treated in order to improve its dispersion stability in the primer ink. Further, the white pigment may be used in the production of the primer ink in the state of a liquid pigment dispersion in which it is dispersed in an arbitrary dispersion medium. A dispersant or the like may be added to the pigment dispersion in order to disperse the white pigment well.

[0045] As the dispersant, various dispersants such as polymer-based dispersants and surfactants can all be used. As the dispersion medium, any organic solvent or various radically polymerizable components can all be used. Particularly, it is preferable to use at least one of the above-described third radically polymerizable components.

[0046] When a radically polymerizable component is used as the dispersion medium, the ratio R of the hydroxyl group-containing (meth)acrylate described above OHA The ratio of the radically polymerizable component, such as, etc., shall be represented by a value obtained in consideration of the radically polymerizable component as the dispersion medium. The ratio of the colorant such as the white pigment can be arbitrarily set according to the type of the colorant and the color tone of the primer layer.

[0047] In addition, if the glass substrate itself that is the basis of the glass product is colored in any light color tone such as white, milky white, light yellow, etc., even if the primer ink is colorless and transparent, the reproducibility of the color tone of the colored layer can be ensured. In that case, the colorant of the primer ink can also be omitted. (Photo radical polymerization initiator) For example, when the active energy ray to be irradiated is light such as ultraviolet ray, in order to impart photocurability as the active energy ray curability to the primer ink, it is preferable that the primer ink contains a photo radical polymerization initiator in addition to the above components.

[0048] As the photo radical polymerization initiator, various compounds that can generate radicals by irradiation with light of any wavelength and cause the radically polymerizable component to undergo a radical polymerization reaction can all be used. Specific examples of the photo radical polymerization initiator include, but are not limited to, for example, the following various compounds.

[0049] Benzophenone, hydroxybenzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone (Michler's ketone), 4,4′-bisdimethylaminobenzophenone (Michler's ketone), 4-methoxy-4′-dimethylaminobenzophenone, benzophenone compounds represented by the general formula (1) in JP-A-2008-280427, etc., benzophenones or salts thereof.

[0050] Thioxanthones or salts thereof, such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-diethylthioxanthone, 4-isopropylthioxanthone, isopropoxy chlorothioxanthone, and thioxanthone compounds represented by the general formula (2) in JP-A-2008-280427.

[0051] Anthraquinones such as ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, and chloroanthraquinone. Acetophenones such as acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxyphenylacetophenone, 4'-dimethylaminoacetophenone, and dimethylhydroxyacetophenone.

[0052] Imidazoles such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, and 2,4,5-triaryl imidazole dimer. Imidazoles such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triaryl imidazole dimer, etc.

[0053] Benzyl dimethyl ketal, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenyl-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 9,10-phenanthrenequinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n-butyl ether and other benzoins.

[0054] Acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane. Bisacylphosphine oxides, bisphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and other phosphine oxides.

[0055] 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}2-methylpropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methyl benzoylformate, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trihalomethyltriazine, benzyl, methyl benzoyl, methyl benzoylformate, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone and the like.

[0056] One or more of these photo radical polymerization initiators can be used. The ratio of the photo radical polymerization initiator can be arbitrarily set. However, considering imparting good photocurability to the primer ink, the ratio of the photo radical polymerization initiator is preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and preferably 10% by mass or less, particularly preferably 5% by mass or less, based on the total amount of the primer ink.

[0057] When two or more photo radical polymerization initiators are used in combination, the total ratio may be within the above range. (Sensitizer) An optional sensitizer may be added to the photocurable primer ink as needed. The sensitizer becomes excited by irradiation with ultraviolet rays or the like and interacts with the photo radical polymerization initiator to assist in the generation of radicals in the photo radical polymerization initiator.

[0058] In particular, when an LED is used as the light source, since its wavelength range is narrow, it is preferable to add a sensitizer to widen the wavelength range in which the primer ink has sensitivity and improve the sensitivity, that is, to sensitize. Examples of the sensitizer include thioxanthones such as 2,4 - diethylthioxanthone, 1 - chloro - 4 - propoxythioxanthone, and a mixture of 2 - isopropylthioxanthone and 4 - isopropylthioxanthone or salts thereof, eutectic mixtures of benzophenone and 2,3 - and 4 - methylbenzophenone, methyl - 2 - benzophenone, benzophenone, 4 - benzoyl - 4′ - methylphenyl sulfide, 4 - methylbenzophenone, 4 - phenylbenzophenone and other benzophenones or salts thereof, 2 - ethylanthraquinone, 4,4′ - bisdiethylaminobenzophenone (Michler's ketone), etc.

[0059] In addition, examples of other sensitizers include benzoate compounds such as ethyl-4-(dimethylamino)benzoate and 2-ethyl-4-(dimethylaminobenzoate), naphthalene benzoxazolyl derivatives, thiophene benzoxazolyl derivatives, stilbene benzoxazolyl derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives, stilbene derivatives, styryl derivatives of benzene and biphenyl, bis(benzazol-2-yl) derivatives, carbostyryl, naphthalimide, derivatives of dibenzothiophene-5,5'-dioxide, pyrene derivatives, pyridotriazole, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethanolamine, diethanolamine, triethanolamine, and the like.

[0060] As the sensitizer, one or more compounds having an absorption wavelength range suitable for sensitization can be used from among the various sensitizers described above, according to the wavelength range of light from the light source and the absorption wavelength range of the photoinitiator for radical polymerization. The ratio of the sensitizer can be arbitrarily set. However, considering the good manifestation of the sensitization effect by the sensitizer, the ratio of the sensitizer is preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, of the total amount of the primer ink, and preferably 5% by mass or less, particularly preferably 3% by mass or less.

[0061] When two or more sensitizers are used in combination, the total ratio may be within the above range. (Radical polymerization inhibitor) The primer ink may be blended with a radical polymerization inhibitor as necessary. The radical polymerization inhibitor can prevent the radical polymerizable component from undergoing a radical polymerization reaction and gelling the primer ink during storage of the primer ink or storage in a package.

[0062] As the radical polymerization inhibitor, any of various compounds having such a function can be used. Examples of radical polymerization inhibitors include nitrosoamine compounds, hydroquinones, catechols, hindered amines, phenols, phenothiazines, quinones of condensed aromatic rings, and the like.

[0063] Examples of nitrosoamine compounds include ammonium salts of N-nitrosophenylhydroxylamine (ammonium-N-nitrosophenylhydroxylamine), aluminum salts of N-nitrosophenylhydroxylamine (aluminum-N-nitrosophenylhydroxylamine), and the like. Examples of hydroquinones include hydroquinone, hydroquinone monomethyl ether, 1-o-2,3,5-trimethylol hydroquinone, 2-tert-butyl hydroquinone, and the like.

[0064] Examples of catechols include catechol, 4-methylcatechol, 4-tert-butylcatechol, and the like. Examples of hindered amines include any hindered amines having a polymerization inhibitory effect, and the like. Examples of phenols include phenol, butylhydroxytoluene, butylhydroxyanisole, pyrogallol, alkyl gallate, hindered phenols, and the like.

[0065] Examples of phenothiazines include phenothiazine, and the like. Furthermore, examples of quinones of condensed aromatic rings include naphthoquinone, and the like. One or more of these radical polymerization inhibitors can be used. The proportion of the radical polymerization inhibitor is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, of the total amount of the primer ink, and preferably 3% by mass or less, particularly preferably 0.5% by mass or less.

[0066] (Other) Various additives may be further added to the primer ink. Examples of the additive include a surface conditioner for adjusting the wettability, adhesion, etc. of the primer ink to the surface of the glass substrate. Specific examples of the surface conditioner include, but are not limited to, BYK (registered trademark) 307, 310, 320, 330, 333, 342, 377, UV3510, etc. manufactured by BYK Chemie Japan Co., Ltd., all of which are silicone-based, and UV3510 is particularly preferred.

[0067] The proportion of the surface conditioner is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, based on the total amount of the primer ink, and preferably 3% by mass or less, particularly preferably 0.5% by mass or less. In addition, it is also conceivable to mix an arbitrary organic solvent into the primer ink to dissolve or disperse the above-mentioned respective components. However, since the primer ink containing an organic solvent takes a long time to dry, the productivity of glass products may decrease.

[0068] On the other hand, since all of the above-mentioned radically polymerizable components are liquid at the printing environment temperature before curing, it is possible to omit the organic solvent. Therefore, the primer ink preferably does not contain any organic solvent, or does not contain any other organic solvent when the organic solvent is contained as a dispersion medium in the pigment dispersion, and is a solvent-free type.

[0069] The primer ink can be prepared by mixing the above-mentioned respective components at predetermined ratios and stirring them. Note that the primer ink is not limited to being photocurable, and may be a primer ink having curability with respect to any active energy rays such as electron beams. 〈(B) Colored Ink〉 As described above, the colored ink contains 2-(2-vinyloxyethoxy)ethyl (meth)acrylate as a radically polymerizable component.

[0070] (Radically Polymerizable Component) As the radical polymerizable component 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl acrylate (hereinafter may be abbreviated as "VEEA"), and / or 2-(2-vinyloxyethoxy)ethyl methacrylate (hereinafter may be abbreviated as "VEEM") can be mentioned.

[0071] Also, as the radical polymerizable component, together with the above 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, an N-group-containing radical polymerizable component containing an N group in the molecule may be used in combination as the second radical polymerizable component. Examples of the N-group-containing radical polymerizable component include at least one selected from the group consisting of urethane (meth)acrylate, amine-modified (meth)acrylate, and acrylamide compounds.

[0072] Since the N group in these N-group-containing radical polymerizable components forms a hydrogen bond with the hydroxyl group of the hydroxyl group-containing (meth)acrylate in the primer ink, the adhesion of the colored layer to the primer layer can be enhanced. In particular, urethane (meth)acrylate can impart flexibility to the colored layer, making the colored layer less likely to crack and further enhancing the adhesion of the colored layer to the primer layer.

[0073] As urethane (meth)acrylate, for example, a reaction product of an isocyanate having an isophorone diisocyanate structure in the molecule, a polyol containing a caprolactone-based polyol, and a hydroxyl group-containing (meth)acrylate can be used. Urethane (meth)acrylate preferably has a weight average molecular weight Mw of 1000 or more and 10000 or less.

[0074] In the case of urethane (meth)acrylate having a weight average molecular weight Mw less than this range, the film strength of the colored layer after the curing reaction may decrease, and the abrasion resistance of characters, patterns, etc. by the colored layer may decrease. On the other hand, in the case of urethane (meth)acrylate having a weight average molecular weight Mw exceeding the above range, the viscosity of the colored ink becomes too high, the ejection stability from the nozzles of the inkjet printer decreases, and nozzle clogging or the like may easily occur.

[0075] On the contrary, by using urethane (meth)acrylate having a weight average molecular weight Mw within the above range, while suppressing an increase in the viscosity of the colored ink and a decrease in ejection stability, the abrasion resistance of characters, patterns, etc. formed by the colored layer can be further improved. In order to synthesize urethane (meth)acrylate having a weight average molecular weight within the above range, the types and ratios of isocyanate, polyol, and hydroxyl group-containing (meth)acrylate may be adjusted.

[0076] Further, urethane (meth)acrylate preferably has two or more functional groups, that is, two or more acrylic groups in the molecule, in order to introduce a three-dimensional network structure into the colored layer which is a cured product of the colored ink and form a stronger pattern layer. Although bifunctional urethane (meth)acrylate can form a three-dimensional network structure, its curing rate is lower than that of trifunctional urethane (meth)acrylate, so the crosslinking density is insufficient, the film strength of the colored layer decreases, and the abrasion resistance of characters, patterns, etc. formed by the colored layer may not be sufficiently ensured.

[0077] On the other hand, tetrafunctional or higher urethane (meth)acrylate has a high curing rate, but the viscosity of the colored ink becomes too high, the ejection stability from the nozzles of the inkjet printer decreases, and nozzle clogging or the like may easily occur. On the contrary, trifunctional urethane (meth)acrylate has a high curing rate and a lower viscosity than tetrafunctional or higher urethane (meth)acrylate, so while suppressing an increase in the viscosity of the colored ink and a decrease in ejection stability, the abrasion resistance of characters, patterns, etc. formed by the colored layer can be further improved.

[0078] Therefore, urethane (meth)acrylate is particularly preferably trifunctional. The bifunctional urethane (meth)acrylate can be synthesized using isophorone diisocyanate as the isocyanate. In addition, the trifunctional or higher-functional urethane (meth)acrylate can be synthesized using a modified product having three or more, that is, three or more isocyanate groups, such as an isocyanurate-modified product of isophorone diisocyanate.

[0079] As the polyol, a caprolactone-based polyol is used. As the caprolactone-based polyol, various caprolactone-based polyols having an arbitrary molecular weight and preferably having two functional groups, that is, two hydroxyl groups, and using caprolactone as a starting material can be used. In addition, another polyol may be used in combination with the caprolactone-based polyol.

[0080] As the other polyol, one or more of, for example, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc. can be used. Furthermore, as the hydroxyl group-containing (meth)acrylate, one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, caprolactone-modified 2-hydroxyethyl methacrylate can be used.

[0081] Specific examples of the urethane (meth)acrylate include, but are not limited to, for example, a reaction product (trifunctional) of an isocyanurate form of isophorone diisocyanate, a bifunctional caprolactone-based polyol, and 2-hydroxyethyl acrylate, which has an arbitrary weight average molecular weight Mw within the above-described range. One or more of these urethane (meth)acrylates can be used.

[0082] As the amine-modified (meth)acrylate, the same amine-modified (meth)acrylate as that used in the primer ink can be used. That is, as the amine-modified (meth)acrylate, various radically polymerizable compounds having a structure in which, for example, a monomer or oligomer of (meth)acrylate is modified with an amino group can be used.

[0083] Among them, an amine-modified acrylate having an acrylic group as a functional group is preferable in order to enhance the reactivity with 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and to increase the curing start rate and curing rate of the colored ink. Specific examples of the amine-modified (meth)acrylate include, but are not limited to, CN371, CN373, CN383, CN386, etc. manufactured by Sartomer Co., Ltd., all of which are amine-modified acrylates, and CN371 is particularly preferable.

[0084] Specific examples of the acrylamide compound include, but are not limited to, for example, the following various compounds. Acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-sec-butylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, N-(2-hydroxyethyl)acrylamide, N,N-diethylacrylamide, N-[3-(dimethylamino)propyl]acrylamide, dimethylaminoethyl acrylate benzyl chloride quaternary salt, 4-acryloylmorpholine, N-isopropylacrylamide, dimethylaminopropyl acrylamide methyl chloride quaternary salt, 1-acryloylpyrrolidine, N-methylolacrylamide, N-(methoxyethyl)acrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide, diacetoneacrylamide.

[0085] One or more of these acrylamides can be used. As the N-group-containing radically polymerizable component, as described above, urethane (meth)acrylate capable of imparting flexibility to the colored layer is used, and it is preferable to use in combination at least one selected from the group consisting of amine-modified (meth)acrylate and acrylamide compounds. Also, as the radically polymerizable component, various third radically polymerizable components capable of radical polymerization such as 2-phenoxyethyl acrylate, dipentaerythritol hexaacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, etc. can be used in combination.

[0086] One or more of these third radically polymerizable components can be used. The ratio R of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate VEE is preferably 8% by mass or more, particularly preferably 12% by mass or more, and preferably 70% by mass or less, particularly preferably 60% by mass or less, based on the total amount of the radically polymerizable components. The ratio R of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate VEE If it is less than this range, the colored ink may not be solidified promptly.

[0087] And there may be cases where the colored ink mixes with the primer ink and the color changes, or it bleeds and the boundary becomes unclear, and it cannot be sufficiently suppressed. Also, as a result of the colored ink sinking to the interface between the primer precursor layer and the glass substrate and inhibiting the function of the amino group-containing silane coupling agent, the adhesion of the primer layer to the surface of the glass substrate may decrease.

[0088] On the other hand, when the ratio R of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate VEE exceeds the above range, the proportion of the N-group-containing radically polymerizable component is relatively insufficient, and the adhesion of the colored layer to the primer layer may decrease. In contrast, the ratio R of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate VEEIf it is within the above range, the curing rate of the colored ink can be increased without reducing the adhesion of the colored layer to the primer layer.

[0089] Therefore, the colored ink for forming the colored precursor layer printed on the primer precursor layer is solidified as quickly as possible during the curing reaction of both precursor layers, so that the colored ink does not mix with the primer ink and the color changes, or bleed and the boundary becomes unclear. In addition, it is possible to prevent the colored ink from sinking to the interface between the primer precursor layer and the glass substrate, and suppress the decrease in the adhesion of the primer layer to the surface of the glass substrate.

[0090] The total ratio R of the N-group-containing radically polymerizable component as the second radically polymerizable component TNR is preferably 80% by mass or less, particularly 75% by mass or less in the total amount of the radically polymerizable components. The total ratio R of the N-group-containing radically polymerizable component TNR If it exceeds this range, the proportion of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate is relatively insufficient, and the colored ink may not be solidified quickly.

[0091] And in some cases, it may not be possible to sufficiently suppress the colored ink from mixing with the primer ink and changing the color, bleeding and the boundary becoming unclear. In addition, as a result of the colored ink sinking to the interface between the primer precursor layer and the glass substrate and inhibiting the action of the amino group-containing silane coupling agent, the adhesion of the primer layer to the surface of the glass substrate may decrease.

[0092] The total ratio R of the N-group-containing radically polymerizable component TNR The lower limit of is not particularly limited, and the colored ink does not contain an N-group-containing radically polymerizable component, that is, the total ratio R of the N-group-containing radically polymerizable component TNR may be 0% by mass. However, in order to satisfactorily realize the effect of increasing the adhesion of the colored layer to the primer layer, the total ratio R of the N-group-containing radical polymerizable components is TNR is preferably 7% by mass or more, particularly preferably 20% by mass or more, of the total amount of the radically polymerizable components.

[0093] The total R of the N-group-containing radically polymerizable components TNR When two or more of the above-mentioned three types are used in combination as the N-group-containing radically polymerizable component, the ratio of the total is literally the ratio of the total, and when only one type is used alone, it is the ratio of only that one type. In addition, when a urethane (meth)acrylate is used in combination with at least one of the other two types as the N-group-containing radical polymerizable component, the ratio R of the urethane (meth)acrylate is UAA is preferably 1 mass % or more, particularly preferably 2 mass % or more, and is preferably 85 mass % or less, particularly preferably 70 mass % or less, of the total amount of the N-group-containing radically polymerizable components.

[0094] Ratio of urethane (meth)acrylate UAA By setting the content within this range, the effect of adding the urethane (meth)acrylate to the colored layer, which imparts flexibility to the colored layer and makes it less likely to crack, and which also enhances the adhesion of the colored layer to the primer layer, can be further improved. In addition, the proportion R of urethane (meth)acrylate, which generally tends to have a higher viscosity than the other two types of N-group-containing radical polymerizable components, UAA By setting the content of the color ink in the above range, an increase in the viscosity of the color ink can be suppressed, and the ejection properties of the color ink from the nozzles can be improved.

[0095] Furthermore, the proportion of the third radically polymerizable component such as 2-phenoxyethyl acrylate is the remainder of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and the N-group-containing radically polymerizable component. That is, when 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and the N-group-containing radically polymerizable component are each blended at the above-specified ratio, the ratio of the third radically polymerizable component may be set so that the total amount of the radically polymerizable components becomes 100% by mass.

[0096] Further, when the total ratio of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and the N-group-containing radically polymerizable component is 100% by mass of the total amount of the radically polymerizable components, the third radically polymerizable component may be omitted. (Colorant) As the colorant, various pigments, dyes, etc. of each color corresponding to the color tone of the colored ink can be used.

[0097] In particular, considering improving the Weather resistance etc. of the pattern layer, various inorganic pigments and / or organic pigments are preferable. Among these, examples of the inorganic pigment include metal compounds such as iron oxide, or various carbon blacks of neutral, acidic, basic, etc. manufactured by known methods such as the contact method, the furnace method, and the thermal method.

[0098] Examples of the organic pigment include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, or chelate azo pigments, etc.), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, or quinophthalone pigments, etc.), dye chelates (for example, basic dye type chelates, acidic dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc.

[0099] Specific examples of the pigment include the following various pigments. (Yellow Pigment) C.I. Pigment Yellow 1, 2, 3, 12, 13, 14, 14C, 16, 17, 20, 24, 73, 74, 75, 83, 86, 93, 94, 95, 97, 98, 109, 110, 114, 117, 120, 125, 128, 129, 130, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213, 214 (Magenta pigment) C.I. Pigment Red 5, 7, 9, 12, 48(Ca), 48(Mn), 49, 52, 53, 57(Ca), 57:1, 97, 112, 122, 123, 149, 168, 177, 178, 179, 184, 202, 206, 207, 209, 242, 254, 255 (Cyan pigment) C.I. Pigment Blue 1, 2, 3, 15, 15:1, 15:3, 15:4, 15:6, 15:34, 16, 22, 60 (Black pigment) C.I. Pigment Black 7 (Orange pigment) C.I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 74 (Green pigment) C.I. Pigment Green 7, 36 (Violet pigment) C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50 One or more pigments can be used according to the color tone of the colored ink.

[0100] For example, when expressing black with carbon black, a cyan pigment may be added to make it look more blue - black. The pigments may be surface - treated to improve their dispersion stability in the colored ink. Also, the pigments may be used in the production of colored inks in the form of a liquid pigment dispersion in which they are dispersed in an arbitrary dispersion medium.

[0101] Dispersants or the like may be added to the pigment dispersion to disperse the pigments well. As the dispersant, various dispersants such as polymer dispersants and surfactants can all be used. As the dispersion medium, any organic solvent or various radical polymerizable components can all be used. In particular, it is preferable to use at least one of the above-described third radical polymerizable components.

[0102] When using a radical polymerizable component as the dispersion medium, the ratios R VEE , R TNR , R UAA etc. shall be represented by values obtained in consideration of the radical polymerizable component as the dispersion medium. The ratio of the colorant such as the pigment can be arbitrarily set according to the type of the colorant, the color tone of the colored ink, etc.

[0103] (Photo radical polymerization initiator) As described above, when making the primer ink photocurable, in order to simultaneously cause a curing reaction of the primer precursor layer made of the primer ink and the colored precursor layer made of the colored ink, it is sufficient to impart photocurability to the colored ink as well. Therefore, it is preferable to blend a photo radical polymerization initiator in the colored ink in addition to the above components.

[0104] Specific examples of the photo radical polymerization initiator include various photo radical polymerization initiators exemplified in the primer ink. Among them, it is preferable to select and use any photo radical polymerization initiator having sensitivity to light in the same wavelength range as the photo radical polymerization initiator of the primer ink, particularly the same photo radical polymerization initiator used in the primer ink.

[0105] One or more of these photo radical polymerization initiators can be used. The ratio of the photo radical polymerization initiator can be arbitrarily set. However, considering imparting good photocurability to the colored ink, the proportion of the photoinitiator is preferably 3% by mass or more, particularly preferably 5% by mass or more, of the total amount of the colored ink, and preferably 12% by mass or less, particularly preferably 10% by mass or less.

[0106] When two or more photoinitiators are used in combination, the total proportion thereof may be within the above range. (Sensitizer) A sensitizer may be blended in the colored ink in the same manner as in the primer ink. Specific examples of the sensitizer include various sensitizers exemplified for the primer ink.

[0107] Among them, it is preferable to select and use any sensitizer having an absorption wavelength range similar to that of the sensitizer for the primer ink, particularly the same sensitizer used for the primer ink. One or more of these sensitizers can be used. The proportion of the sensitizer can be arbitrarily set. However, considering expressing the sensitizing effect by the sensitizer well, the proportion of the sensitizer is preferably 0.1% by mass or more, particularly preferably 1% by mass or more, of the total amount of the colored ink, and preferably 10% by mass or less, particularly preferably 5% by mass or less.

[0108] When two or more sensitizers are used in combination, the total proportion thereof may be within the above range. (Radical polymerization inhibitor) A radical polymerization inhibitor may also be blended in the colored ink. Specific examples of the radical polymerization inhibitor include various radical polymerization inhibitors exemplified for the primer ink, and among them, it is preferable to select and use the same radical polymerization inhibitor used for the primer ink.

[0109] One or more of these radical polymerization inhibitors can be used. The proportion of the radical polymerization inhibitor is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, of the total amount of the colored ink, and preferably 3% by mass or less, particularly preferably 0.5% by mass or less. (Others) Various additives may be further blended into the colored ink.

[0110] Examples of the additives include surface modifiers for adjusting the wettability, adhesion, etc. of the colored ink to the primer precursor layer or the primer layer. As specific examples of the surface modifier, one or more arbitrary surface modifiers similar to those used in the primer ink can be used. The proportion of the surface modifier is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, of the total amount of the colored ink, and preferably 3% by mass or less, particularly preferably 0.5% by mass or less.

[0111] Although it is also conceivable to blend an arbitrary organic solvent into the colored ink, the colored ink containing an organic solvent may take a long time to dry, which may reduce the productivity of glass products. On the other hand, since all of the above-mentioned radically polymerizable components are liquid at the printing environment temperature before curing, it is possible to omit the organic solvent. Therefore, it is preferable that the colored ink is a solvent-free type that does not contain any organic solvent or does not contain any other organic solvent when the organic solvent is contained as a dispersion medium in the pigment dispersion.

[0112] The colored ink can be prepared by blending each of the above components at a predetermined ratio and stirring. Note that the colored ink is not necessarily limited to photocurability, and may be a colored ink having curability with respect to any active energy ray such as an electron beam. The ink set of the present invention can be preferably used for on-demand thermal or piezo inkjet printers in particular.

[0113] "Glass Product and Its Manufacturing Method" The glass product of the present invention is formed by sequentially laminating a primer layer made of primer ink and a colored layer made of colored ink among the above-described ink sets of the present invention on the surface of a glass substrate such as a glass bottle. Moreover, the manufacturing method of the glass product of the present invention is as follows. A step of printing a primer ink on the surface of a glass substrate by an inkjet printing method to form a primer precursor layer. A step of printing a colored ink on the formed primer precursor layer by an inkjet printing method to form a colored precursor layer, and A step of irradiating both precursor layers with active energy rays to cause a curing reaction of the primer ink and the colored ink that form the both precursor layers, thereby forming a primer layer and the colored layer. It includes the above steps.

[0114] According to the present invention, by the functions of the primer ink and the colored ink constituting the ink set of the present invention described above, characters and patterns having high adhesion and excellent color reproducibility and fineness can be directly printed on the surface of the glass substrate. In the inkjet printing method, the primer ink and the colored inks of each color are used in a single on-demand type inkjet printer sequentially. Specifically, first, a primer precursor layer is formed using the primer ink, and then a colored precursor layer is printed so as to overlap using the colored ink.

[0115] Moreover, as the colored ink, three colors of cyan (C), magenta (M), and yellow (Y), four colors obtained by adding black (K) to the above three colors, or more than two colors of colored ink can be used. Then, by ejecting such multi-color colored inks simultaneously or sequentially from a plurality of nozzles of an on-demand type inkjet printer, an arbitrary colored precursor layer from full color to monochrome can be printed on the primer precursor layer.

[0116] Next, a primer precursor layer and a coloring precursor layer sequentially laminated on the surface of a glass substrate are subjected to a curing reaction by irradiation with active energy rays (ultraviolet rays) from an active energy ray source such as a UV lamp, whereby a glass product can be manufactured. The active energy ray source can be incorporated, for example, into the head of an inkjet printer or prepared separately from the inkjet printer.

[0117] However, in order to suppress changes in the color tone of the colored ink and bleeding and unclear boundaries, it is preferable to arrange the active energy ray source so that the active energy rays can be quickly irradiated after printing the coloring precursor layer to cure both precursor layers by a curing reaction.

Example

[0118] The present invention will be further described below based on examples and comparative examples, but the configuration of the present invention is not limited to these examples. 〈White pigment dispersion〉 The following components were blended at the ratios shown in Table 1, stirred, and then dispersed using a bead mill to prepare a white pigment dispersion.

[0119] White pigment: Titanium oxide [rutile type, CR-50 manufactured by Ishihara Sangyo Co., Ltd.] Dispersant: SOLSPERSE (registered trademark) 32000 manufactured by Lubrizol Dispersion medium: 2-phenoxyethyl acrylate which does not contain a hydroxyl group in the molecule and is a third radically polymerizable component [SR339NS manufactured by Sartomer Co., Ltd.]

[0120]

Table 1

[0121] 〈Primer ink (I)〉 As the amino group-containing silane coupling agent, N-phenyl-3-aminopropyltrimethoxysilane [KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.], which is an amino group-containing silane coupling agent having a phenyl group in the molecule, was used. In addition, as the hydroxyl group-containing (meth)acrylate among the radically polymerizable components, 4-hydroxybutyl acrylate (4HBA) was used, and an amine-modified acrylate [CN371 manufactured by Sartomer] was used in combination as the second radically polymerizable component.

[0122] These components and the following respective components were blended at the ratios shown in Table 2 and stirred until completely dissolved. Then, the previously prepared white pigment dispersion was added at the ratio shown in Table 2 and further stirred. After that, it was filtered using a 5-μm membrane filter to prepare a white primer ink. Photo radical polymerization initiator: 2,4,6-trimethylbenzoyldiphenylphosphine oxide [SpeedCure (registered trademark) TPO manufactured by Lambson Japan Co., Ltd.] Sensitizer: 2-isopropylthioxanthone [SpeedCure 2-ITX manufactured by Lambson Japan Co., Ltd.] Radical polymerization inhibitor: Aluminum salt of N-nitrosophenylhydroxylamine [Q-1301 manufactured by Fujifilm Wako Pure Chemical Corporation] Surface conditioner: Silicone-based [BYK UV3510 manufactured by BYK-Chemie Japan Co., Ltd.]

[0123]

Table 2

[0124] Ratio R of 4HBA in the total amount of the radically polymerizable components to which SR339NS in the white pigment dispersion was added OHA was 85.8% by mass, and the ratio R of CN371 NMA was 1.8% by mass. 〈Primer Ink (II)〉 As the hydroxyl group-containing (meth)acrylate, a white primer ink was prepared in the same manner as the primer ink (I), except that 2-hydroxypropyl acrylate (2HPA) was blended in the same amount instead of 4HBA.

[0125] Ratio R of 2HPA in the total amount of radical polymerizable components, with SR339NS added to the white pigment dispersion OHA was 85.8% by mass, and the ratio R of CN371 NMA was 1.8% by mass. 〈Primer Ink (III)〉 As the hydroxyl group-containing (meth)acrylate, a white primer ink was prepared in the same manner as the primer ink (I), except that 2-phenoxyethyl acrylate [SR339 manufactured by Sartomer Co., Ltd.], which is a third radical polymerizable component and does not contain a hydroxyl group in the molecule, was blended in the same amount instead of 4HBA.

[0126] Ratio R of 4HBA in the total amount of radical polymerizable components, with SR339NS added to the white pigment dispersion OHA was 0% by mass, and the ratio R of CN371 NMA was 1.8% by mass. 〈Primer Ink (IV) to (VI)〉 A white primer ink was prepared in the same manner as the primer ink (I), except that 4HBA and SR339 were blended at the ratios shown in Table 3.

[0127] Ratio R of 4HBA in the total amount of radical polymerizable components, with SR339NS added to the white pigment dispersion OHA was as shown in Table 3, and the ratio R of CN371 NMA was 1.8% by mass.

[0128]

Table 3

[0129] 〈Primer Ink (VII)〉 As a silane coupling agent, instead of KBM-573, a white primer ink was prepared in the same manner as primer ink (I), except that 3-aminopropyltrimethoxysilane [KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.], which is an amino group-containing silane coupling agent having no phenyl group in the molecule, was blended in the same amount.

[0130] Ratio R of 4HBA in the total amount of radically polymerizable components, with SR339NS added to the white pigment dispersion OHA was 85.8% by mass, and the ratio R of CN371 NMA was 1.8% by mass. 〈Primer Ink (VIII)〉 As a silane coupling agent, instead of KBM-573, a white primer ink was prepared in the same manner as primer ink (I), except that 3-glycidoxypropyltriethoxysilane [KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.], which is an epoxy-based silane coupling agent, was blended in the same amount.

[0131] Ratio R of 4HBA in the total amount of radically polymerizable components, with SR339NS added to the white pigment dispersion OHA was 85.8% by mass, and the ratio R of CN371 NMA was 1.8% by mass. 〈Primer Ink (IX)〉 A white primer ink was prepared in the same manner as primer ink (I), except that SR339, which is a third radically polymerizable component, was blended in the same amount instead of the silane coupling agent.

[0132] Ratio R of 4HBA in the total amount of radically polymerizable components, with SR339NS added to the white pigment dispersion OHA was 85.0% by mass, and the ratio R of CN371 NMA was 1.8% by mass. 〈Primer Ink (X)〉 A colorless and transparent primer ink was prepared in the same manner as primer ink (I), except that no white pigment dispersion was blended and the amount of 4HBA was 93.4% by mass.

[0133] Ratio R of 4HBA in the total amount of radically polymerizable components OHA was 98.4% by mass, and the ratio R of CN371 NMA was 1.6% by mass. 〈Primer Ink (XI)〉 A white primer ink was prepared in the same manner as primer ink (I), except that CN371, which is the second radically polymerizable component, was not blended and the amount of the silane coupling agent was 2.3% by mass.

[0134] Ratio R of 4HBA in the total amount of radically polymerizable components, to which SR339NS was added in the white pigment dispersion OHA was 87.4% by mass, and the ratio R of CN371 NMA was 0% by mass. 〈Black Pigment Dispersion〉 The following components were blended at the ratios shown in Table 4, stirred, and then dispersed using a bead mill to prepare a black pigment dispersion.

[0135] Black pigment: C.I. Pigment Black 7 [Carbon Black MA-7 manufactured by Mitsubishi Chemical Corporation] Dispersant: Solsperse 32000 manufactured by Lubrizol Corporation Dispersion medium: 2-Phenoxyethyl acrylate which does not contain a hydroxyl group in the molecule and is the third radically polymerizable component [SR339NS manufactured by Sartomer Company]

[0136]

Table 4

[0137] 〈Colored Ink (1)〉 As 2-(2-Vinyloxyethoxy)ethyl (meth)acrylate among the radically polymerizable components, 2-(2-Vinyloxyethoxy)ethyl acrylate (VEEA) [VEEA-AI manufactured by Nippon Shokubai Co., Ltd.] was used. Further, as the second radically polymerizable component, the following three types of N-group-containing radically polymerizable components were used in combination.

[0138] Urethane (meth) acrylate: Reaction product of an isocyanurate of isophorone diisocyanate, a bifunctional caprolactone polyol, and 2-hydroxyethyl acrylate [weight average molecular weight Mw: 2000, trifunctional, may be abbreviated as "UAA" hereinafter.] Amine-modified acrylate: CN371 manufactured by Sartomer Diethylacrylamide (DEAA) These components and the following respective components were blended at the ratios shown in Table 5 and stirred until completely dissolved. Then, the previously prepared black pigment dispersion was added at the ratio shown in Table 5 and further stirred. After that, it was filtered using a 5-μm membrane filter to prepare a black (K) colored ink.

[0139] Photo radical polymerization initiator: 2,4,6-trimethylbenzoyl diphenylphosphine oxide [SpeedCure (registered trademark) TPO manufactured by Lambson Japan Co., Ltd.] Sensitizer: 2-isopropylthioxanthone [SpeedCure 2-ITX manufactured by Lambson Japan Co., Ltd.] Radical polymerization inhibitor: Aluminum salt of N-nitrosophenylhydroxylamine [Q-1301 manufactured by Fujifilm Wako Pure Chemical Corporation] Surface conditioner: Silicone-based [BYK UV3510 manufactured by BYK-Chemie Japan Co., Ltd.]

[0140] [Table 5]

[0141] Ratio R of VEEA in the total amount of radical polymerizable components, with SR339NS added in the black pigment dispersion VEE was 47.8% by mass, and the total ratio R of N-group-containing radical polymerizable components TNR was 38.8% by mass, and the ratio R of UAA in the total amount of N-group-containing radical polymerizable components UAA was 21.2% by mass. 〈Yellow pigment dispersion〉 The following components were blended at the ratios shown in Table 6, stirred, and then dispersed using a bead mill to prepare a yellow pigment dispersion.

[0142] Yellow pigment: C.I. Pigment Yellow 155 [Inkjet Yellow 4GC manufactured by Clariant] Dispersant: Solsperse 32000 manufactured by Lubrizol Dispersion medium: 2-Phenoxyethyl acrylate that does not contain a hydroxyl group in the molecule and is a third radically polymerizable component [SR339NS manufactured by Sartomer]

[0143]

Table 6

[0144] 〈Magenta Pigment Dispersion〉 The following components were blended at the ratios shown in Table 7, stirred, and then dispersed using a bead mill to prepare a magenta pigment dispersion. Magenta pigment: C.I. Pigment Red 202 [Cinquasia Magenta L4530 manufactured by BASF] Dispersant: Solsperse 32000 manufactured by Lubrizol Dispersion medium: 2-Phenoxyethyl acrylate that does not contain a hydroxyl group in the molecule and is a third radically polymerizable component [SR339NS manufactured by Sartomer]

[0145]

Table 7

[0146] 〈Cyan Pigment Dispersion〉 The following components were blended at the ratios shown in Table 8, stirred, and then dispersed using a bead mill to prepare a cyan pigment dispersion. Cyan pigment: C.I. Pigment Blue 15:4 [Heliogen Blue D7110F manufactured by BASF] Dispersant: Solsperse 32000 manufactured by Lubrizol Dispersion medium: 2-phenoxyethyl acrylate (SR339NS manufactured by Sartomer Co., Ltd.) which does not contain a hydroxyl group in the molecule and is the third radically polymerizable component

[0147]

Table 8

[0148] 〈Colored ink (2)〉 A yellow (Y) colored ink was prepared in the same manner as the colored ink (1), except that the previously prepared yellow pigment dispersion was blended in the same amount instead of the black pigment dispersion. Ratio R of VEEA in the total amount of radically polymerizable components, with SR339NS added to the yellow pigment dispersion VEE was 47.8% by mass, and the total ratio R TNR of N-group-containing radically polymerizable components was 38.8% by mass, and the ratio R UAA of UAA in the total amount of N-group-containing radically polymerizable components was 21.2% by mass.

[0149] 〈Colored ink (3)〉 A magenta (M) colored ink was prepared in the same manner as the colored ink (1), except that the previously prepared magenta pigment dispersion was blended in the same amount instead of the black pigment dispersion. Ratio R of VEEA in the total amount of radically polymerizable components, with SR339NS added to the magenta pigment dispersion VEE was 47.8% by mass, and the total ratio R TNR of N-group-containing radically polymerizable components was 38.8% by mass, and the ratio R UAA of UAA in the total amount of N-group-containing radically polymerizable components was 21.2% by mass.

[0150] 〈Colored ink (4)〉 A cyan (C) colored ink was prepared in the same manner as the colored ink (1), except that the previously prepared cyan pigment dispersion was blended in the same amount instead of the black pigment dispersion. Ratio R of VEEA in the total amount of radically polymerizable components, with SR339NS added to the cyan pigment dispersion VEEwas 47.8% by mass, and the total proportion R of the N-group-containing radically polymerizable components TNR was 38.8% by mass, and the proportion R of UAA in the total amount of the N-group-containing radically polymerizable components UAA was 21.2% by mass.

[0151] 〈Colored Inks (5) to (9)〉 A black (K) colored ink was prepared in the same manner as the colored ink (1), except that VEEA, UAA, CN371, DEAA, and SR339 as the third radically polymerizable component were blended at the ratios shown in Table 9. The proportion R of VEEA in the total amount of the radically polymerizable components, to which SR339NS in the black pigment dispersion was added VEE , and the total proportion R of the N-group-containing radically polymerizable components TNR were as shown in Table 9, and the proportion R of UAA in the total amount of the N-group-containing radically polymerizable components UAA was 21.2% by mass.

[0152]

Table 9

[0153] 〈Colored Inks (10) to (14)〉 A black (K) colored ink was prepared in the same manner as the colored ink (1), except that VEEA, UAA, CN371, DEAA, and dipentaerythritol hexaacrylate (DPHANS) as the third radically polymerizable component, 2-(2-ethoxyethoxy)ethyl acrylate [SR256 manufactured by Sartomer] were blended at the ratios shown in Table 10.

[0154] The proportion R of VEEA in the total amount of the radically polymerizable components, to which SR339NS in the black pigment dispersion was added VEE , the total proportion R of the N-group-containing radically polymerizable components TNR , and the proportion R of UAA in the total amount of the N-group-containing radically polymerizable components UAA were as shown in Table 10.

[0155]

Table 10

[0156] 〈Colored Inks (15) to (18)〉 A black (K) colored ink was prepared in the same manner as the colored ink (1), except that UAA, CN371, and DEAA were blended at the ratios shown in Table 11. Ratio R of VEEA in the total amount of radically polymerizable components, with SR339NS added to the black pigment dispersion VEE was 47.8% by mass, and the total ratio R of N-group-containing radically polymerizable components TNR was 38.8% by mass, and the ratio R of UAA in the total amount of N-group-containing radically polymerizable components UAA was as shown in Table 11.

[0157]

Table 11

[0158] 〈Preparation of Glass Product Samples〉 A primer ink was printed on the surface of a glass substrate using an inkjet printer to form a primer precursor layer, and then a colored ink was printed on the formed primer precursor layer using an inkjet printer to form a colored precursor layer. Next, the laminated precursor layers were irradiated with ultraviolet rays as active energy rays to cause a curing reaction of the primer ink and the colored ink forming the two precursor layers, thereby forming a primer layer and a colored layer, and obtaining a sample of a glass product.

[0159] 〈Warm Water Resistance Test〉 The prepared glass product samples were immersed in warm water at 70°C for 30 minutes, and then a cross-cut test described in Japanese Industrial Standard JIS K5600-5-6 :1999 “General Test Methods for Paints - Part 5: Mechanical Properties of Paint Films - Section 6: Adhesion (Cross-Cut Method)” was performed. Then, based on the classification of the test results specified in the same standard, the warm water resistance was evaluated according to the following criteria.

[0160] ◎: The classification was 0 to 1. The hot water resistance was extremely good. ○○: The classification was 2. The hot water resistance was good. ○: The classification was 3. The hot water resistance was somewhat good. △: The classification was 4. The hot water resistance was normal. ×: The classification was 5. The hot water resistance was poor.

[0161] 〈Color density reproducibility test〉 The optical density OD value of the sample of the fabricated glass product was measured. Separately, the optical density of the colored ink alone printed directly on the substrate and cured, that is, the original optical density OD0 of the colored ink, was measured, and the reduction rate of the optical density of the sample with respect to the optical density OD0 was determined, and the reproducibility of the color density was evaluated according to the following criteria.

[0162] ○: The reduction rate was less than 3%. The reproducibility of the color density was good. △: The reduction rate was 3% or more and less than 10%. The reproducibility of the color density was normal. ×: The reduction rate was 10% or more. The reproducibility of the color density was poor. 〈Dischargeability test of colored ink〉 During the production of the sample of the glass product described above, the state of the printed pre-coloring layer was observed, and the dischargeability of the colored ink from the nozzles of the inkjet printer was evaluated.

[0163] ○: A pre-coloring layer without omission due to non-discharging nozzles was formed. The dischargeability was good. △: There were some non-discharging nozzles, and omissions were observed in the pre-coloring layer. The dischargeability was normal. ×: Discharge did not occur from all nozzles, and the pre-coloring layer could not be formed. The dischargeability was poor. 〈Examples 1 to 8, Comparative Examples 1 to 3〉 Samples of the glass product described above were fabricated and evaluated by combining the primer ink shown in Tables 12 and 13 with the colored ink (1).

[0164] In Examples 1 to 6, 8, and Comparative Examples 1 to 3, a colorless and transparent glass substrate was used as the glass substrate, and in Example 7, a white glass substrate was used. The results are shown in Tables 12 and 13.

[0165]

Table 12

[0166]

Table 13

[0167] From the results of Examples 1 to 8 and Comparative Examples 1 to 3 in Tables 12 and 13, it was found that by using a primer ink containing an amino group-containing silane coupling and a hydroxyl group-containing (meth)acrylate, a primer layer with good hot water resistance (adhesion) can be formed on the surface of the glass substrate. However, from the results of Examples 1, 2, and 6, considering further improving such an effect, as the hydroxyl group-containing (meth)acrylate, 4HBA with a long crosslinked chain is preferably used, and as the amino group-containing silane coupling agent, N-phenyl-3-aminopropyltrimethoxysilane having a phenyl group in the molecule is preferably used.

[0168] Also, from the results of Examples 1, 3 to 5, considering further improving the above effect, the ratio R OHA of the hydroxyl group-containing (meth)acrylate is preferably 8% by mass or more, particularly preferably 18% by mass or more, and preferably 99% by mass or less in the total amount of the radically polymerizable components. Also, from the results of Examples 1 and 8, as the radically polymerizable component, it is preferable to use an amine-modified (meth)acrylate in combination with the hydroxyl group-containing (meth)acrylate, and the ratio R NMA is preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and preferably 3% by mass or less, particularly preferably 2.5% by mass or less in the total amount of the radically polymerizable components.

[0169] Furthermore, from the results of Examples 1 and 7, in the case of a colorless and transparent glass substrate, it is preferable that the primer ink be white. However, from the results of Examples 1 and 7, when the glass substrate is white, it was found that the same effect can be obtained by omitting the blending of the white pigment and making the primer ink colorless and transparent. <Examples 9 to 24, Comparative Example 4> Samples of glass products were prepared and evaluated in the same manner as in Example 1, except that the primer ink (I) was combined with the colored inks (2) to (18) shown in Tables 14 to 17.

[0170] The results are shown in Tables 14 to 17 together with the results of Example 1.

[0171] [Table 14]

[0172] [Table 15]

[0173] [Table 16]

[0174] [Table 17]

[0175] From the results of Examples 1, 12 to 24, and Comparative Example 4 in Tables 14 to 17, it was found that by using a colored ink containing 2-(2-vinyloxyethoxy)ethyl (meth)acrylate as a radical polymerizable component, a colored layer with good reproducibility of color density can be formed on the primer layer. Also, from the results of Examples 1, 9 to 11, it was found that such an effect can be obtained not only with black (K) colored ink but also with colored inks of various colors such as yellow (Y), magenta (M), and cyan (C).

[0176] From the results of Examples 1, 12 to 15, considering further improving the above effects, the ratio R of 2-(2-vinyloxyethoxy)ethyl (meth)acrylate VEE was found to preferably be 8% by mass or more, particularly preferably 12% by mass or more, and preferably 70% by mass or less, particularly preferably 60% by mass or less, based on the total amount of the radically polymerizable components. From the results of Examples 1 and 20, it was found that the colored ink can form a colored layer with particularly good hot water resistance (adhesion) on the primer layer by using an N-group-containing radically polymerizable component in combination.

[0177] From the results of Examples 1, 16 to 19, considering forming a colored layer with good reproducibility of color density while further improving the above effects, in such a combined system, the total ratio R of the N-group-containing radically polymerizable components TNR was found to preferably be 7% by mass or more, particularly preferably 20% by mass or more, and preferably 80% by mass or less, particularly preferably 75% by mass or less, based on the total amount of the radically polymerizable components.

[0178] Furthermore, from the results of Examples 1, 21 to 24, considering further improving the above effects while suppressing an increase in the viscosity of the colored ink and improving the ejection property from the nozzle, the ratio R of urethane (meth)acrylate UAA was found to preferably be 1% by mass or more, particularly preferably 2% by mass or more, and preferably 85% by mass or less, particularly preferably 70% by mass or less, based on the total amount of the N-group-containing radically polymerizable components.

Claims

1. (A) A primer ink containing an amino group-containing silane coupling agent and a hydroxyl group-containing (meth)acrylate as a radically polymerizable component, having active energy ray curability, and (B) At least one colored ink containing 2-(2-vinyloxyethoxy)ethyl (meth)acrylate as a radically polymerizable component, having active energy ray curability, comprising: The primer ink further contains an amine-modified (meth)acrylate as the radically polymerizable component, and is an ink set.

2. The ink set according to claim 1, wherein the amino group-containing silane coupling agent contained in the primer ink is N-phenyl-3-aminopropyltrimethoxysilane.

3. The ink set according to claim 1 or 2, wherein the hydroxyl group-containing (meth)acrylate contained in the primer ink is at least one selected from the group consisting of 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.

4. The ink set according to any one of claims 1 to 3, wherein the colored ink further contains an N-group-containing radically polymerizable component containing an N group in the molecule as the radically polymerizable component.

5. The ink set according to claim 4, wherein the N-group-containing radically polymerizable component is at least one selected from the group consisting of urethane (meth)acrylate, amine-modified (meth)acrylate, and acrylamide compounds.

6. The ink set according to claim 5, wherein the N-group-containing radically polymerizable component is used in combination with at least one selected from the group consisting of the urethane (meth)acrylate, the amine-modified (meth)acrylate, and the acrylamide compounds.

7. A glass product in which a primer layer composed of the primer ink and a colored layer composed of the colored ink among the ink sets according to any one of claims 1 to 6 are sequentially laminated on the surface of a glass substrate.

8. A method for manufacturing the glass product according to claim 7, comprising: A step of printing the primer ink on the surface of the glass substrate by an inkjet printing method to form an uncured precursor layer of the primer layer. A step of printing the colored ink on the formed precursor layer by an inkjet printing method to form an uncured precursor layer of the colored layer, and a step of irradiating the both precursor layers with active energy rays to cause a curing reaction of the primer ink and the colored ink that form the both precursor layers, thereby forming the primer layer and the colored layer, A method for manufacturing a glass product including these steps.

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