JP2017165969A - Ultraviolet-curable inkjet composition and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV-curable inkjet composition having excellent storage stability and suitably used for forming a pattern (printed part) excellent in glossiness and rubbing resistance, and to provide a recorded matter having a pattern formed by using the above UV-curable inkjet composition and having excellent glossiness and rubbing resistance.SOLUTION: The UV-curable inkjet composition is to be discharged in an inkjet system and comprises a polymerizable compound, a metal powder, and a dispersant. The composition contains: as the metal powder, a powder surface-treated with a fluorine-based silane compound and/or a fluorine-based phosphoric acid compound as a surface treatment agent; and as the dispersant, a basic dispersant having a polymer structure.SELECTED DRAWING: None

Description

  The present invention relates to an ultraviolet curable ink jet composition and a recorded matter.

Conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.
However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion. In addition, the foil stamping printing has a problem that it is difficult to cope with multi-product production because it has low on-demand property, and gradation-like metallic printing cannot be performed.

On the other hand, as a recording method on a recording medium using a composition containing a pigment or a dye, a recording method using an inkjet method is used. The ink jet method is excellent in that it can be suitably applied to formation of a fine pattern and recording on a curved surface portion. In recent years, compositions that cure when irradiated with ultraviolet rays (ultraviolet curable inkjet compositions) have been used in the ink jet method in order to achieve particularly excellent abrasion resistance, water resistance, solvent resistance, and the like. (For example, refer to Patent Document 1).
However, in the ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. In addition, the composition has poor stability (storage stability), and causes problems such as a decrease in ejection stability due to an increase in viscosity due to gelation.

JP 2009-57548 A

  An object of the present invention is to provide an ultraviolet curable inkjet composition that can be suitably used for forming a pattern (printed portion) having excellent storage stability, glossiness, and abrasion resistance, It is an object of the present invention to provide a recorded matter having a pattern excellent in glossiness and abrasion resistance formed using an ultraviolet curable ink jet composition.

Such an object is achieved by the present invention described below.
The ultraviolet curable inkjet composition of the present invention is an ultraviolet curable inkjet composition discharged by an inkjet method,
A polymerizable compound, a metal powder, and a dispersant;
The metal powder includes a surface treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound as a surface treatment agent,
The dispersant includes a basic one having a polymer structure.
Thereby, it is possible to provide an ultraviolet curable inkjet composition that can be suitably used for the production of a recorded product having a pattern (printing portion) having excellent storage stability, glossiness, and abrasion resistance. .

In the ultraviolet curable ink jet composition of the present invention, the metal powder is a powder whose surface is mainly composed of Al and is surface-treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound. Is preferred.
Al originally exhibits a particularly excellent gloss feeling among various metal materials. However, when a powder composed of Al is applied to an ultraviolet curable inkjet composition, it is used for an ultraviolet curable inkjet. The inventor has found that the storage stability of the composition is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation are particularly prominent. On the other hand, in this invention, even if it is a case where the surface uses the powder comprised by Al, generation | occurrence | production of the above problems can be prevented reliably. That is, the metal powder constituting the ultraviolet curable ink-jet composition is a powder whose surface is mainly composed of Al and is surface-treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound. The effect of the present invention is particularly remarkable.
In the ultraviolet curable inkjet composition of the present invention, the metal powder preferably has a scaly shape.
Thereby, the glossiness, abrasion resistance, etc. of the recorded matter manufactured using the ultraviolet curable inkjet composition can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder includes a surface treated with the fluorine-based silane compound having a chemical structure represented by the following formula (1).
R ¹ SiX ¹ _a R ² _(3-a) (1)
(In Formula (1), R ¹ represents a hydrocarbon group in which part or all of the hydrogen atoms are substituted with fluorine atoms, X ¹ represents a hydrolyzable group, an ether group, a chloro group, or a hydroxyl group; ² represents an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 3 inclusive.)
As a result, the storage stability of the ultraviolet curable ink jet composition is particularly excellent, and the glossiness and abrasion resistance of the printed part of the recorded matter produced using the ultraviolet curable ink jet composition are particularly excellent. Can be.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder includes a surface treated with the fluorophosphate compound having a chemical structure represented by the following formula (2).
POR _n (OH) _3-n (2)
(In the formula (2), R _{is, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, and n is 1 or more and 3 or less. M is an integer of 2 to 18, and l is an integer of 1 to 18.)
As a result, the storage stability of the ultraviolet curable ink jet composition is particularly excellent, and the glossiness and abrasion resistance of the printed part of the recorded matter produced using the ultraviolet curable ink jet composition are particularly excellent. Can be.

In the ultraviolet curable inkjet composition of the present invention, the surface treatment agent preferably has a perfluoroalkyl structure.
As a result, the storage stability of the UV curable ink jet composition is further improved, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the UV curable ink jet composition are further improved. Can be.

In the ultraviolet curable inkjet composition of the present invention, the average particle size of the metal powder is preferably 500 nm or more and 3.0 μm or less.
Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the polymerizable compound contains phenoxyethyl acrylate.
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, as the polymerizable compound, in addition to the phenoxyethyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, It is preferable that it contains at least one selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate and 4-hydroxybutyl acrylate.
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

In the ultraviolet curable ink jet composition of the present invention, as the polymerizable compound, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, It is preferable to include at least one selected from the group consisting of acryloylmorpholine, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. .
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the abrasion resistance of the formed pattern can be further improved.

In the ultraviolet curable inkjet composition of the present invention, the ultraviolet curable inkjet composition preferably further includes a substance A having a partial structure represented by the following formula (5).

  Thereby, the storage stability and curability of the ultraviolet curable ink jet composition can be made particularly excellent. In addition, in the recorded matter produced using the ultraviolet curable ink jet composition, the glossiness and luxury feeling inherent in the metal material constituting the metal powder is more effectively exhibited, and the gloss of the printed part The feeling and abrasion resistance can be made particularly excellent, and the durability of the recorded matter can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, when the content of the substance A is X _A [% by mass] and the content of the metal powder is X _M [% by mass], 0.01 ≦ X _A / It is preferable to satisfy the relationship of X _M ≦ 0.8.
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the glossiness and resistance of the printed part formed using the ultraviolet curable inkjet composition can be improved. The rubbing property can be further improved.

The recorded matter of the present invention is produced by applying the ultraviolet curable inkjet composition of the present invention onto a recording medium and then irradiating with ultraviolet rays.
Thereby, it is possible to provide a recorded matter having a pattern (printing portion) excellent in glossiness and abrasion resistance.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<< UV-curable inkjet composition >>
First, the ultraviolet curable inkjet composition of the present invention will be described.
The ultraviolet curable inkjet composition of the present invention is ejected by an inkjet method and contains a polymerizable compound that is polymerized by irradiation with ultraviolet rays.

By the way, conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.
However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion. In addition, foil stamp printing has a problem that gradation-like metallic printing cannot be performed.

On the other hand, as a recording method on a recording medium using a composition containing a pigment or a dye, a recording method using an inkjet method is used. The ink jet method is excellent in that it can be suitably applied to formation of a fine pattern and recording on a curved surface portion. In recent years, compositions that cure when irradiated with ultraviolet rays (ultraviolet curable inkjet compositions) have been used in the ink jet method in order to achieve particularly excellent abrasion resistance, water resistance, solvent resistance, and the like. ing.
However, in the ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. In addition, the composition has poor stability (storage stability), and causes problems such as a decrease in ejection stability due to an increase in viscosity due to gelation.

  Therefore, the inventor has intensively studied for the purpose of solving the above problems, and as a result, has reached the present invention. That is, the ultraviolet curable inkjet composition of the present invention includes a polymerizable compound and a surface treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound as a surface treatment agent as a metal powder, Including a dispersant having a basic polymer structure. As a result, the chemical stability and dispersion stability of the metal powder in the UV curable ink jet composition are excellent, and the storage stability of the UV curable ink jet composition and the long-term ejection stability are excellent. In addition, in the recorded matter manufactured using the ultraviolet curable ink jet composition, the metal powder can be suitably arranged in the vicinity of the outer surface of the printing portion, and the metal material constituting the metal powder Can fully exhibit the properties such as glossiness inherent in the. Further, even when a polymerizable compound having a low surface tension is used as a constituent material of an ultraviolet curable ink jet composition, a metal powder is reliably produced in a recorded matter produced using the ultraviolet curable ink jet composition. Can be suitably arranged (leafing) in the vicinity of the outer surface of the printing part, and the properties such as glossiness inherent in the metal material constituting the metal powder can be sufficiently exhibited. Therefore, the selection range of the polymerizable compound is widened, and the characteristics of the ultraviolet curable inkjet composition and the ultraviolet curable inkjet composition are manufactured without sacrificing the glossiness of the metal material. It is possible to easily adjust the characteristics of the recorded matter (for example, the viscosity, storage stability, ejection stability, and rubbing resistance of the recorded matter).

<Metal powder>
As described above, the ultraviolet curable inkjet composition of the present invention includes a metal powder that has been surface-treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound as a surface treatment agent.
(Mother particles)
First, mother particles (particles subjected to surface treatment with a surface treatment agent) constituting metal particles will be described.
The mother particles constituting the metal powder need only have at least a region including the vicinity of the surface made of a metal material. For example, the whole may be made of a metal material or a non-metal material. And a base made of a metal material covering the base.

  Further, as the metal material constituting the mother particle, a single metal, various alloys, or the like can be used. However, the mother particle is preferably composed mainly of Al at least near the surface. Al originally exhibits a particularly excellent gloss feeling among various metal materials. However, when a powder composed of Al is applied to an ultraviolet curable inkjet composition, it is used for an ultraviolet curable inkjet. The inventor has found that the storage stability of the composition is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation are particularly prominent. On the other hand, in this invention, even if it is a case where the surface uses the powder comprised by Al, generation | occurrence | production of the above problems can be prevented reliably. That is, the metal powder constituting the ultraviolet curable ink jet composition is a powder whose surface is mainly composed of Al and is surface-treated with a surface treatment agent (fluorine silane compound and / or fluorine phosphate compound). Therefore, the effect of the present invention is particularly remarkable.

Further, the mother particles may be produced by any method, but when they are made of Al, a film made of Al is formed by a vapor deposition method, and then It is preferably obtained by pulverizing the membrane. Thereby, the glossiness etc. which Al originally has in the pattern (printing part) formed using the ultraviolet curable inkjet composition of this invention can be expressed more effectively. Moreover, the dispersion | variation in the characteristic between each particle | grain can be suppressed. Moreover, even if it is a comparatively thin metal powder, it can manufacture suitably by using the said method.
When producing mother particles using such a method, for example, the mother particles can be suitably produced by forming a film made of Al (film formation) on a substrate. As the substrate, for example, a plastic film such as polyethylene terephthalate can be used. Further, the substrate may have a release agent layer on the film forming surface.

Moreover, it is preferable that the said grinding | pulverization is performed by providing an ultrasonic vibration to the said film | membrane in a liquid. This makes it possible to easily and surely obtain mother particles having the above-described particle diameter, and to suppress the variation in size, shape, and characteristics among the particles.
When the pulverization is performed by the above method, the liquid includes alcohols such as methanol, ethanol, propanol, and butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, and cymene. Hydrocarbon compounds such as durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , Diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, triplicate Ether compounds such as pyrene glycol dimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane, propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone , N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dimethyl sulfoxide, cyclohexanone, acetonitrile and the like can be preferably used. By using such a liquid, the productivity of the mother particles and metal powder is made particularly excellent while preventing unintentional oxidation of the mother particles, and the size, shape, and characteristics between each particle Can be made particularly small.

(Surface treatment agent)
As described above, the metal powder according to the present invention is surface-treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound as a surface treatment agent.
First, among the surface treatment agents, the fluorine-based silane compound will be described in detail.
As the fluorine-based silane compound, a silane compound having at least one fluorine atom in the molecule can be used.

In particular, the fluorinated silane compound as the surface treatment agent preferably has a chemical structure represented by the following formula (1).
R ¹ SiX ¹ _a R ² _(3-a) (1)
(In Formula (1), R ¹ represents a hydrocarbon group in which part or all of the hydrogen atoms are substituted with fluorine atoms, X ¹ represents a hydrolyzable group, an ether group, a chloro group, or a hydroxyl group; ² represents an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 3 inclusive.)
As a result, the storage stability of the ultraviolet curable ink jet composition is particularly excellent, and the glossiness and abrasion resistance of the printed part of the recorded matter produced using the ultraviolet curable ink jet composition are particularly excellent. Can be.

Examples of R ¹ in the formula (1) include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. in which a part or all of hydrogen atoms are substituted with fluorine atoms, and are further included in the molecular structure. At least a part of hydrogen atoms (hydrogen atoms not substituted with fluorine atoms) may be substituted with an amino group, a carboxyl group, a hydroxyl group, a thiol group, etc., and -O-, -S in the carbon chain A hetero atom such as-, -NH-, -N =, or an aromatic ring such as benzene may be sandwiched. Specific examples of R ¹ include, for example, a phenyl group, a benzyl group, a phenethyl group, a hydroxyphenyl group, a chlorophenyl group, an aminophenyl group, a naphthyl group, an anthrenyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, Pyrenyl group, thienyl group, pyrrolyl group, cyclohexyl group, cyclohexenyl group, cyclopentyl group, cyclopentenyl group, pyridinyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Butyl group, tert-butyl group, octadecyl group, n-octyl group, chloromethyl group, methoxyethyl group, hydroxyethyl group, aminoethyl group, cyano group, mercaptopropyl group, vinyl group, allyl group, acryloxyethyl group, Methacryloxyethyl group, glycidoxypropyl Group, acetoxy group and the like.

Specific examples of the fluorine-based silane compound represented by the formula (1) include dimethyldimethoxysilane, diethyldiethoxysilane, 1-propenylmethyldichlorosilane, propyldimethylchlorosilane, propylmethyldichlorosilane, propyltrichlorosilane, and propyltriethoxy. Silane, propyltrimethoxysilane, styrylethyltrimethoxysilane, tetradecyltrichlorosilane, 3-thiocyanatepropyltriethoxysilane, p-tolyldimethylchlorosilane, p-tolylmethyldichlorosilane, p-tolyltrichlorosilane, p-tolyltrimethoxy Silane, p-tolyltriethoxysilane, di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane, di-n-butyldi-n-butyroxysilane Di-sec-butyldi-sec-butyroxysilane, di-t-butyldi-t-butyroxysilane, octadecyltrichlorosilane, octadecylmethyldiethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyldimethylchlorosilane, octadecylmethyldichlorosilane, octadecyl Methoxydichlorosilane, 7-octenyldimethylchlorosilane, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane, octylmethyldichlorosilane, octyldimethylchlorosilane, octyltrichlorosilane, 10-undecenyldimethylchlorosilane, undecyltri Chlorosilane, vinyldimethylchlorosilane, methyloctadecyldimethoxysilane, methyldodecyldiethoxy Silane, methyloctadecyldimethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triaconyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri -N-propoxysilane, methyl isopropoxy silane, methyl-n-butoxy silane, methyl tri-sec-butoxy silane, methyl tri-t-butoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tri-n-propoxy silane, ethyl isopropoxy silane , Ethyl-n-butyroxysilane, ethyltri-sec-butyroxysilane, ethyltri-t-butyroxysilane, n-propylto Limethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-propyltriethoxysilane, Isobutyltriethoxysilane, n-hexyltriethoxysilane, hexadecyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltriethoxysilane, 2- [2- (trichlorosilyl) ethyl] Pyridine, 4- [2- (trichlorosilyl) ethyl] pyridine, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,3- (trichlorosilylmethyl) heptacosane, dibenzyldimethoxysilane, Benzyldiethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, Benzylmethyldimethoxysilane, benzyldimethylmethoxysilane, benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, benzyltriethoxysilane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, 3-acetoxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane Allyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, amyltriethoxysilane, benzoxacilepin dimethyl ester, 5- (bicycloheptenyl) trie Xysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane, 2-chloro Methyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, -Cyanoethyltrimethoxysilane, cyanomethylphenethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyclo Hexenyltrichlorosilane, 2- (3-cyclohexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyldimethylchlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane, cyclohexyldimethylchlorosilane, cyclohexylethyl Dimethoxysilane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyl Limethoxysilane, cyclooctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltrichlorosilane, cyclopentyltrimethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitro Phenylamino) propyltriethoxysilane, (dimethylchlorosilyl) methyl-7,7-dimethylnorpinane, (cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, N, N- Diethyl-3-aminopropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (furfuryloxymethyl) trieth Sisilane, 2-hydroxy-4- (3-triethoxypropoxy) diphenyl ketone, 3- (p-methoxyphenyl) propylmethyldichlorosilane, 3- (p-methoxyphenyl) propyltrichlorosilane, p- (methylphenethyl) methyl Dichlorosilane, p- (methylphenethyl) trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltri Methoxysilane, 1,2,3,4,7,7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7,7, -hexachloro-6-triethoxysilyl- 2-norbornene, 3-iodopropyltrimethoxyra , 3-isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-methacryloxypropyltrimethoxysilane, methyl {2- (3-trimethoxysilylpropylamino) ethylamino} -3-propionate, 7-octenyltrimethoxysilane, RN-α-phenethyl-N′- Triethoxysilylpropylurea, S-N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane, phenet Tildimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltri Methoxysilane, N- (triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane, (S) -N-triethoxysilylpropyl-O-menth carbamate, 3- (triethoxysilylpropyl) -p-nitrobenzamide, 3- (triethoxysilyl) propyl succinic anhydride,
N- [5- (trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethyl Ammonium chloride, phenylvinyldiethoxysilane, 3-thiocyanatopropyltriethoxysilane, N- {3- (triethoxysilyl) propyl} phthalamic acid, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2 -(Trimethoxysilyl) ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N-trimethoxysilylpropyl-N, N , N-Tributylammo Umbromide, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyltriethoxysilane, vinyltri Methoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenylmethylchlorosilane, vinyltriphenoxysilane, vinyltris -T-butoxysilane, adamantylethyltrichlorosilane, allylphenyltrichlorosilane, (aminoethylaminomethyl) phenethyl Limethoxysilane, 3-aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, benzyltrichlorosilane, benzyldimethylchlorosilane, benzylmethyldichlorosilane, phenethyldiisopropylchlorosilane, phenethyltrichlorosilane, phenethyldimethylchlorosilane, phenethyl Methyldichlorosilane, 5- (bicycloheptenyl) trichlorosilane, 5- (bicycloheptenyl) triethoxysilane, 2- (bicycloheptyl) dimethylchlorosilane, 2- (bicycloheptyl) trichlorosilane, 1,4-bis (tri Methoxysilylethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, -Phenoxypropyltrichlorosilane, t-butylphenylchlorosilane, t-butylphenylmethoxysilane, t-butylphenyldichlorosilane, p- (t-butyl) phenethyldimethylchlorosilane, p- (t-butyl) phenethyltrichlorosilane, 1, 3- (chlorodimethylsilylmethyl) heptacosane, ((chloromethyl) phenylethyl) dimethylchlorosilane, ((chloromethyl) phenylethyl) methyldichlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl) phenyl Ethyl) trimethoxysilane, chlorophenyltrichlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldiethoxysilane, 3-cyanopro Some or all of the hydrogen atoms of silane compounds such as rumethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropyldimethylethoxysilane, 3-cyanopropylmethyldichlorosilane, and 3-cyanopropyltrichlorosilane are fluorine. Mention may be made of compounds having a structure substituted with atoms.

The fluorine-based silane compound (surface treatment agent) preferably has a perfluoroalkyl structure (C _n F _{2n + 1} ). As a result, the storage stability of the UV curable ink jet composition is further improved, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the UV curable ink jet composition are further improved. Can be.

The fluorine-based silane compound having a perfluoroalkyl structure _{(C n F 2n + 1)} , for example, those represented by the following formula (3).
_{C n F 2n + 1 (CH} 2) m SiX 1 a R 2 (3-a) (3)
(In Formula (3), X ¹ represents a hydrolyzable group, an ether group, a chloro group or a hydroxyl group, R ² represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 14) M is an integer of 2 to 6, and a is an integer of 1 to 3.

Specific examples of the compound having such a structure include CF ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF _3. (CF ₂ ) ₅ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ —CH _{2 CH 2 -Si (OCH 3) 3} , CF 3 (CF 2) 11 -CH 2 CH 2 -Si (OC 2 H 5) 3, CF 3 (CF 2) 3 -CH 2 CH 2 -Si (CH 3) _{(OCH 3) 2, CF 3} (CF 2) 7 -CH 2 CH 2 -Si (CH 3) (OCH 3) 2, CF 3 (CF 2) 8 -CH 2 CH 2 -Si (CH 3) (OC _{2 H 5) 2, CF 3} (CF 2) _{8 -CH 2 CH 2 -Si (C} 2 H 5) (OC 2 H 5) 2 and the like.

Further, as the fluorine-based silane compound may be used those having a perfluoroalkyl ether structure _{(C n F 2n + 1 O} ) in place of the above-mentioned perfluoroalkyl structure _{(C n F 2n + 1)} .
The fluorine-based silane compound having a perfluoroalkyl ether structure _{(C n F 2n + 1 O} ), for example, those represented by the following formula (4).

_{C p F 2p + 1 O (} C p F 2p O) r (CH 2) m SiX 1 a R 2 (3-a) (4)
(In Formula (4), X ¹ represents a hydrolyzable group, an ether group, a chloro group, or a hydroxyl group, R ² represents an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 4 inclusive. Yes, r is an integer from 1 to 10, m is an integer from 2 to 6, and a is an integer from 1 to 3.

Specific examples of the compound having such a structure include CF ₃ O (CF ₂ O) ₆ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ , CF ₃ O (C ₃ F ₆ O) ₄ —CH. ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ O (C ₃ F ₆ O) ₂ (CF ₂ O) ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ O (C ₃ F ₆ O _{) 8 -CH 2 CH 2 -Si (} OCH 3) 3, CF 3 O (C 4 F 9 O) 5 -CH 2 CH 2 -Si (OCH 3) 3, CF 3 O (C 4 F 9 O) 5 _{-CH 2 CH 2 -Si (CH 3} ) (OC 2 H 5) 2, CF 3 O (C 3 F 6 O) 4 -CH 2 CH 2 -Si (C 2 H 5) (OCH 3) 2 and the like Can be mentioned.

Next, a fluorine-type phosphoric acid compound is demonstrated in detail among surface treating agents.
As the fluorine-based phosphate compound, a phosphate ester having at least one fluorine atom in the molecule can be used.
In particular, the fluorine-based phosphoric acid compound preferably has a chemical structure represented by the following formula (2).

POR _n (OH) _3-n (2)
(In the formula (2), R _{is, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, and n is 1 or more and 3 or less. M is an integer of 2 to 18, and l is an integer of 1 to 18.)

As a result, the storage stability of the ultraviolet curable ink jet composition is particularly excellent, and the glossiness and abrasion resistance of the printed part of the recorded matter produced using the ultraviolet curable ink jet composition are particularly excellent. Can be.
In formula (2), m is preferably an integer of 3 to 14, but more preferably an integer of 4 to 12. Thereby, the effects as described above are more remarkably exhibited.
In formula (2), l is preferably an integer of 1 to 14, but more preferably an integer of 1 to 10. Thereby, the effects as described above are more remarkably exhibited.

Further, fluorine-based phosphate compound (surface treatment agent) is preferably one having a perfluoroalkyl structure _{(C n F 2n + 1)} . As a result, the storage stability of the UV curable ink jet composition is further improved, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the UV curable ink jet composition are further improved. Can be.

  The surface treatment agent (fluorine-based silane compound, fluorine-based phosphate compound) as described above may be processed directly on the mother particles, but after the acid or base is treated on the mother particles, The mother particles are preferably treated with a surface treatment agent (fluorine silane compound, fluorine phosphate compound). As a result, the surface of the mother particle can be more reliably modified by chemical bonding with a surface treatment agent (fluorine silane compound and / or fluorine phosphate compound), and the effects of the present invention as described above can be achieved. It can be exhibited more effectively. Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, hyposulfite, nitrous acid, hyponitrous acid, phosphorous acid, and the following. Protic acids such as phosphorous acid can be used. Of these, hydrochloric acid, phosphoric acid, and acetic acid are preferable. On the other hand, as the base, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide or the like can be used. Of these, sodium hydroxide and potassium hydroxide are preferred.

  The metal powder may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably has a scaly shape. Thereby, on the recording medium to which the ultraviolet curable ink jet composition is applied, the metal powder can be arranged so that the main surface of the metal powder follows the surface shape of the recording medium, thereby constituting the metal powder. The glossiness inherent in the metal material can be more effectively exhibited in the obtained recorded matter, and the glossiness and luxury feeling of the pattern (printed portion) to be formed are particularly excellent. In addition, the rub resistance of the recorded matter can be made particularly excellent. In addition, in the configuration in which the surface treatment with the fluorine-based silane compound and / or the fluorine-based phosphate compound as described above is not performed, the metal powder has a scaly shape, so that the ultraviolet curable inkjet composition can be stored. Although the tendency that the stability and the discharge stability are low has been particularly remarkable, in the present invention, even if the metal powder has a scaly shape, the occurrence of such a problem is surely prevented. be able to. That is, when the shape of the metal powder is scaly, the effect of the present invention is more remarkably exhibited.

In the present invention, the scale shape is an area when the area when observed from a predetermined angle (when viewed in plan) is observed from an angle orthogonal to the observation direction, such as a flat plate shape or a curved plate shape. In particular, the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximum (when viewed in plan) and the direction orthogonal to the observation direction are observed. The ratio (S ₁ / S ₀ ) with respect to the area S ₀ [μm ² ] when observed from the direction in which the area of the area becomes maximum is preferably 2 or more, more preferably 5 or more, and still more preferably 8 or more. It is. As this value, for example, it is possible to observe an arbitrary 10 particles and adopt an average value of values calculated for these particles.

The average particle size of the metal powder is preferably 500 nm or more and 3.0 μm or less, and more preferably 800 nm or more and 1.8 μm or less. Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.
The content of the metal powder in the ultraviolet curable inkjet composition is preferably 0.5% by mass or more and 10.0% by mass or less, and more preferably 1.0% by mass or more and 5.0% by mass or less. More preferred.

<Dispersant>
In addition to the metal powder as described above, the ultraviolet curable inkjet composition of the present invention includes a basic dispersant having a polymer structure (hereinafter also referred to as “basic polymer dispersant”). It is a waste.
Accordingly, the ultraviolet curable inkjet composition can be suitably used for the production of a recorded matter having a pattern (printing portion) having excellent storage stability, glossiness, and abrasion resistance. Can do. Such an excellent effect is obtained by including the metal powder (surface-treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound as a surface treatment agent) and a basic polymer dispersant as described above. In the case where only one of the metal powder and the basic polymer dispersant as described above is contained, the above excellent effects cannot be obtained.
In the present invention, the basic polymer dispersant is not particularly limited as long as it shows basicity and has a polymer structure.

The polymer structure constituting the basic polymer dispersant is not particularly limited. For example, an acrylic polymer structure (including a copolymer), a methacrylic polymer structure (including a copolymer), and polyurethane. Examples thereof include a polymer structure, a hydroxyl group-containing carboxylic acid ester structure, a polyether polymer structure, and a silicone polymer structure.
The amine value of the basic polymer dispersant is not particularly limited, but is preferably 3 mgKOH / g or more and 80 mgKOH / g or less, more preferably 10 mgKOH / g or more and 70 mgKOH / g or less.

  Specific examples of the basic polymer dispersant that can be used in the present invention include DISPERBYK-116 (manufactured by Big Chemie), DISPERBYK-182 (manufactured by Big Chemie), DISPERBYK-183 (manufactured by Big Chemie), DISPERBYK-184 ( Bicchemy), DISPERBYK-2155 (Bicchemy), DISPERBYK-2164 (Bicchemy), DISPERBYK-108 (Bicchemy), DISPERBYK-112 (Bicchemy), DISPERBYK-198 (Bicchemy), DISPERBYK-2150 (manufactured by Big Chemie), PAA-1112 (manufactured by Nittobo), and the like.

  The content of the basic polymer dispersant in the ultraviolet curable inkjet composition is preferably 0.01% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 2.0% by mass or less. It is more preferable that As a result, the storage stability, ejection stability, and curability of the ultraviolet curable inkjet composition can be further improved, and the gloss of the recorded matter produced using the ultraviolet curable inkjet composition can be improved. The feeling, abrasion resistance, etc. can be further improved. The ultraviolet curable ink jet composition may contain two or more compounds as a basic polymer dispersant. In this case, it is preferable that the total content of these compounds is a value within the above range.

<Polymerizable compound>
The polymerizable compound is a component that is polymerized and cured by irradiation with ultraviolet rays. By including such a component, it is possible to improve the abrasion resistance, water resistance, solvent resistance, and the like of the recorded matter produced using the ultraviolet curable ink jet composition.
The polymerizable compound is in a liquid state and preferably functions as a dispersion medium for dispersing the metal powder in the ultraviolet curable ink jet composition. As a result, it is not necessary to use a dispersion medium that is removed (evaporated) separately in the production process of the recorded material, and it is not necessary to provide a process for removing the dispersion medium in the production of the recorded material. The property can be made particularly excellent. Moreover, since it is not necessary to use what is generally used as an organic solvent as a dispersion medium, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented. Moreover, the adhesiveness of the printing part formed using the ultraviolet curable inkjet composition with respect to various recording media (base materials) can be made excellent by including a polymeric compound. That is, by including the polymerizable compound, the ultraviolet curable inkjet composition has excellent media compatibility.

  The polymerizable compound may be any component that can be polymerized by irradiation with ultraviolet rays. For example, various monomers and various oligomers (including dimers and trimers) can be used. The polymerizable compound preferably contains at least a monomer component. Since the monomer is generally a component having a low viscosity as compared with the oligomer component or the like, it is advantageous for making the ejection stability of the ultraviolet curable inkjet composition particularly excellent.

  Examples of the monomer as the polymerizable compound include isobornyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, phenoxyethyl acrylate, isooctyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, Benzyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate, tetrahydrofurfuryl acrylate , Ethyl carbitol acrylate, 2,2,2-trifluoroethyl acrylate, 2, , 2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, EO-modified nonylphenol acrylate, phenylglycidyl ether acrylate, phenoxydiethylene glycol acrylate, EO-modified phenol acrylate, phenoxyethyl acrylate, EO-modified phenol acrylate, EO-modified cresol acrylate, methoxypolyethylene glycol acrylate, dipropylene glycol acrylate, dicyclopentenyl acrylate, dicyclo Tertenyloxyethyl acrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, 1.9-nonanediol diacrylate, 1,4- Butanediol diacrylate, bisphenol A EO modified diacrylate, 1.6-hexanediol diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 300 diacrylate, neopentyl glycol hydroxypiparate diacrylate, 2-ethyl-2-butyl- Propanediol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol diacrylate 1.9-nonanediol diacrylate, 1.6-hexanediol diacrylate, bisphenol A EO modified diacrylate, bisphenol A EO modified diacrylate, bisphenol A EO modified diacrylate, PO modified bisphenol A diacrylate, EO modified water Bisphenol A diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane EO-modified triacrylate, glycerin PO-added triacrylate, trisacryloyloxyethyl phosphate, penta Erythritol tetraacrylate, PO-modified trimethylolpropane triacrylate, P Modified trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, 1-adamantylmethyl acrylate 1-adamantyl acrylate, 2-acryloyloxyethyl phthalate, isobornyl acrylate, 3-acryloyloxypropyl acrylate, acryloyl morpholine, lipoxy SP series, dicyclopentanyl acrylate, 2-hydroxy 3-phenoxypropyl acrylate, w -Carboxyacryloyloxyethyl phthalate, dimethylol dicyclopentane diacrylate, diacrylated iso Arureto / triacrylated mixture, neopentyl glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta / hexaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane PO-modified triacrylate, diethylene glycol diethyl ether, and the like. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane tri Preferred are acrylate, trimethylolpropane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate.

  In particular, the ultraviolet curable ink jet composition preferably contains phenoxyethyl acrylate as the polymerizable compound. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

  In addition to phenoxyethyl acrylate, the ultraviolet curable ink jet composition is composed of 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy as a polymerizable compound. It is preferable that it contains at least one selected from the group consisting of 3-phenoxypropyl acrylate and 4-hydroxybutyl acrylate. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

  In addition, the ultraviolet curable ink jet composition includes, as the polymerizable compound, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acryloyl. It is preferable to include at least one selected from the group consisting of morpholine, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the abrasion resistance of the formed pattern can be further improved.

  Moreover, the ultraviolet curable ink jet composition may contain an oligomer in addition to the monomer as the polymerizable compound. In particular, those containing polyfunctional oligomers are preferred. As a result, the storage stability of the ultraviolet curable ink-jet composition can be made excellent, and the abrasion resistance of the formed pattern can be made particularly excellent. In the present invention, among polymerizable compounds, those having a repeating structure in the molecular skeleton and having a molecular weight of 600 or more are called oligomers. As the oligomer, a urethane oligomer whose repeating structure is urethane, an epoxy oligomer whose repeating structure is epoxy, and the like are preferably used.

  The content of the polymerizable compound in the ultraviolet curable inkjet composition is preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass or less. As a result, the storage stability, ejection stability, and curability of the ultraviolet curable inkjet composition can be further improved, and the gloss of the recorded matter produced using the ultraviolet curable inkjet composition can be improved. The feeling, abrasion resistance, etc. can be further improved. The ultraviolet curable inkjet composition may contain two or more compounds as the polymerizable compound. In this case, it is preferable that the total content of these compounds is a value within the above range.

<Substance A>
Moreover, it is preferable that the ultraviolet curable inkjet composition of this invention contains the substance A which has a partial structure shown by following formula (5).

  The ultraviolet curable ink jet composition contains the substance A having such a chemical structure together with the metal particles subjected to the surface treatment as described above and the basic polymer dispersant, thereby forming the ultraviolet curable ink jet composition. The storage stability and curability of the product can be made particularly excellent. In addition, in the recorded matter produced using the ultraviolet curable ink jet composition, the glossiness and luxury feeling inherent in the metal material constituting the metal powder is more effectively exhibited, and the gloss of the printed part The feeling and abrasion resistance can be made particularly excellent, and the durability of the recorded matter can be made particularly excellent.

In the formula (5), R ¹ may be a hydrogen atom, a hydrocarbon group or an alkoxyl group (a chain or alicyclic hydrocarbon group bonded to an oxygen atom), particularly a hydrogen atom, methyl It is preferably a group or an octyloxy group. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the glossiness and resistance of the printed part formed using the ultraviolet curable inkjet composition can be improved. The rubbing property can be further improved.

In Formula (5), R ^{2 to} R ⁵ may be independently a hydrogen atom or a hydrocarbon group, but are preferably an alkyl group having 1 to 3 carbon atoms, and is a methyl group. Is more preferable. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the glossiness and resistance of the printed part formed using the ultraviolet curable inkjet composition can be improved. The rubbing property can be further improved.

The content of the substance A in the ultraviolet curable inkjet composition is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass or less. More preferred. As a result, the storage stability, ejection stability, and curability of the ultraviolet curable inkjet composition can be further improved, and the gloss of the recorded matter produced using the ultraviolet curable inkjet composition can be improved. The feeling, abrasion resistance, etc. can be further improved. The ultraviolet curable inkjet composition may contain two or more compounds as the substance A. In this case, it is preferable that the total content of these compounds is a value within the above range.
When the content of the substance A is X _A [mass%] and the content of the metal powder is X _M [mass%], it is preferable that the relationship of 0.01 ≦ X _A / X _M ≦ 0.8 is satisfied. More preferably, the relationship 0.05 ≦ X _A / X _M ≦ 0.4 is satisfied. By satisfying such a relationship, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the ultraviolet curable inkjet composition is formed. The glossiness and abrasion resistance of the printed part can be further improved.

<Other ingredients>
The ultraviolet curable inkjet composition of the present invention may contain components other than those described above (other components). Examples of such components include photopolymerization initiators, slip agents (leveling agents), dispersants other than basic polymer dispersants, polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants). , Colorants, fixing agents, antifungal agents, antiseptics, antioxidants, chelating agents, thickeners, sensitizers (sensitizing dyes) and the like.

  The photopolymerization initiator is not particularly limited as long as it generates active species such as radicals and cations by ultraviolet irradiation and initiates the polymerization reaction of the polymerizable compound. As the photopolymerization initiator, a radical photopolymerization initiator or a cationic photopolymerization initiator can be used, but it is preferable to use a radical photopolymerization initiator. When using a photopolymerization initiator, the photopolymerization initiator preferably has an absorption peak in the ultraviolet region.

Examples of the photo radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples thereof include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Among these, at least one selected from an acylphosphine oxide compound and a thioxanthone compound is preferable from the viewpoint of solubility in a polymerizable compound and curability, and it is more preferable to use an acylphosphine oxide compound and a thioxanthone compound in combination.

Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine. , Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthio Xanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. 1 type or 2 types or more selected from these can be used in combination.
The content of the photopolymerization initiator in the ultraviolet curable inkjet composition is preferably 0.5% by mass or more and 10% by mass or less. When the content of the photopolymerization initiator is within the above range, the ultraviolet curing rate is sufficiently high, and the photopolymerization initiator is hardly dissolved or colored due to the photopolymerization initiator.

When the ultraviolet curable ink jet composition contains a slip agent, the surface of the recorded matter becomes smooth due to the leveling action, and the abrasion resistance is improved.
Although it does not specifically limit as a slip agent, For example, silicone type surfactants, such as polyester modified silicone and polyether modified silicone, can be used, It is preferable to use polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane. .

  The ultraviolet curable inkjet composition of the present invention may contain a polymerization inhibitor, but even when it contains a polymerization inhibitor, the polymerization inhibitor in the ultraviolet curable inkjet composition. The content of is preferably 0.6% by mass or less, and more preferably 0.2% by mass or less. Accordingly, since the content of the polymerizable compound in the ultraviolet curable inkjet composition can be relatively increased, the abrasion resistance of the printed portion formed using the ultraviolet curable inkjet composition can be increased. The property and the like can be made particularly excellent. In the present invention, even when the content of the polymerization inhibitor is relatively low, the storage stability and ejection stability of the ultraviolet curable ink jet composition may be sufficiently excellent. it can.

Moreover, it is preferable that the ultraviolet curable inkjet composition of the present invention does not contain an organic solvent that is removed (evaporated) in the manufacturing process of the recorded matter. Thereby, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented effectively.
The viscosity at room temperature (20 ° C.) of the ultraviolet curable inkjet composition of the present invention is preferably 20 mPa · s or less, and more preferably 3 mPa · s or more and 15 mPa · s or less. Thereby, the droplet discharge by an inkjet method can be performed suitably.

《Recordings》
Next, the recorded matter of the present invention will be described.
The recorded matter of the present invention is produced by applying the ultraviolet curable ink jet composition as described above onto a recording medium and then irradiating with ultraviolet rays. Such a recorded matter has a pattern (printing portion) excellent in glossiness and abrasion resistance.

  As described above, the ultraviolet curable inkjet composition according to the present invention contains a polymerizable compound and has excellent adhesion to a recording medium. As described above, since the ultraviolet curable ink jet composition of the present invention is excellent in adhesion to a recording medium, the recording medium may be any one, using either absorbing or non-absorbing. For example, paper (plain paper, ink jet dedicated paper, etc.), plastic materials, metals, ceramics, wood, shells, cotton, polyester, wool and other natural fibers / synthetic fibers, non-woven fabrics, etc. can be used.

  The recorded matter of the present invention may be used for any purpose, and may be applied to, for example, a decorative article or other items. Specific examples of the recorded material of the present invention include console interiors for vehicles such as console lids, switch bases, center clusters, interior panels, emblems, center consoles, meter nameplates, operation parts (key switches) of various electronic devices, decorations. Display items such as decorative parts, indicators, logos, etc. that exhibit properties.

As a droplet discharge method (inkjet method), a piezo method, a method of discharging ink by bubbles generated by heating ink, or the like can be used. The piezo method is preferable from the viewpoint of difficulty in alteration.
The ultraviolet curable ink jet composition can be discharged by an ink jet method using a known droplet discharge device.

The ultraviolet ray curable ink jet composition discharged by the ink jet method is cured by irradiation with ultraviolet rays.
As the ultraviolet light source, for example, a mercury lamp, a metal halide lamp, an ultraviolet light emitting diode (UV-LED), an ultraviolet laser diode (UV-LD), or the like can be used. Among these, ultraviolet light emitting diodes (UV-LED) and ultraviolet laser diodes (UV-LD) are preferable from the viewpoints of small size, long life, high efficiency, and low cost.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.

Next, specific examples of the present invention will be described.
[1] Production of inkjet composition (UV-curable inkjet composition) (Example 1)
First, a film made of polyethylene terephthalate having a smooth surface (surface roughness Ra of 0.02 μm or less) was prepared.

Next, silicone oil was applied to the entire one surface of the film.
Next, a film made of Al was formed on the side coated with silicone oil by vapor deposition.
Next, a polyethylene terephthalate film (base material) on which an Al film was formed was placed in a liquid composed of diethylene glycol diethyl ether, and ultrasonic vibration was applied. As a result, scaly Al particles (particles to be mother particles) were obtained.

Next, the Al particles obtained as described above were placed in a 1% by mass propanol solution of CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O—PO (OH) ₂ as a fluorine-based phosphate compound. The mixture was stirred and stirred for 10 seconds to perform surface treatment with a fluorine-based phosphoric acid compound to obtain a metal powder.
The average particle diameter of the metal powder thus obtained was 0.8 μm, and the average thickness was 60 nm.

  Next, the metal powder was mixed with DISPERBYK-183 (manufactured by Big Chemie) as a basic dispersant having a polymer structure (basic polymer dispersant), phenoxyethyl acrylate, and Irgacure 819 as a photopolymerization initiator (Ciba. Japan)), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, and a substance A having a chemical structure represented by the following formula (6) And an ink jet composition (ultraviolet curable ink jet composition) was obtained.

(Examples 2 to 11)
The composition of the metal particles (the composition of the mother particles and the type of compound (fluorine compound) used for the surface treatment) is as shown in Tables 1 and 2, and the inkjet composition (ultraviolet curable inkjet composition) was prepared. Inkjet composition (ultraviolet curable inkjet composition) in the same manner as in Example 1 except that the composition shown in Tables 1 and 2 was changed by changing the type and ratio of raw materials used in ) Was manufactured.

(Comparative Example 1)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1 except that Al particles that were not subjected to surface treatment were used as the metal powder.
(Comparative Example 2)
The inkjet composition (ultraviolet curable inkjet composition) was used in the same manner as in Comparative Example 1 except that a spherical Al powder (non-surface-treated) manufactured using the gas atomization method was used as the metal powder. Product).

(Comparative Example 3)
Instead of CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O—PO (OH) _{2 as} the fluorine-based phosphate compound, NH ₃ — (CH ₂ ) ₃ that is neither a fluorine-based silane compound nor a fluorine-based phosphate compound. An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1 except that surface treatment was performed using —Si (OCH ₃ ) ₃ to obtain a metal powder.

(Comparative Example 4)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1, except that the basic polymer dispersant was not used and the content of each component was as shown in Table 2.
(Comparative Example 5)
Instead of the basic polymer dispersant, an ink jet composition (as in Example 1 above) was used except that Emanon 4110 (manufactured by Kao Corporation) as a dispersant having a polymer structure but not basic was used. UV-curable inkjet composition) was produced.
(Comparative Example 6)
An inkjet composition (in the same manner as in Example 1 except that Nonion P-208 (manufactured by NOF Corporation) as a dispersant having no polymer structure was used instead of the basic polymer dispersant. UV-curable inkjet composition) was produced.

Tables 1 and 2 collectively show the composition of the ink jet composition for each of the above Examples and Comparative Examples. In the table, CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O—PO (OH) ₂ is “S1”, CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ Is “S2”, CF ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ is “S3”, CF ₃ (CF ₂ ) ₇ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ is “S4”, CF _{3 (CF 2) 5 (CH 2} ) 2 O-PO a _{(OH) (OC 2 H 5} ) _{"S5", CF 3 (CF 2) 5} -CH 2 CH 2 -Si (OCH 3) 3 to "S6" , NH ₃ — (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ is “S′1”, DISPERBYK-183 (BIC Chemie, amine value: 17 mgKOH / g) is “D1”, DISPERBYK-182 (BIC Chemie) , Amine value: 13 mg KOH / g) D2 ", DISPERBYK-184 (Bic Chemie, amine value: 15 mgKOH / g) is" D3 ", DISPERBYK-116 (Bicchemy, amine value: 65 mgKOH / g) is" D4 ", DISPERBYK-2155 (Bicchemy) , Amine value: 48 mg KOH / g) “D5”, DISPERBYK-2164 (manufactured by BYK Chemie, amine value: 14 mg KOH / g) “D6”, PAA-1112 (manufactured by Nittobo) “D7”, Emanon 4110 ( "D'1" for Kao Corporation, "D'2" for Nonion P-208 (manufactured by NOF Corporation), "PEA" for phenoxyethyl acrylate, "TPGDA" for tripropylene glycol diacrylate, dipropylene Glycol diacrylate is “DPGDA”, 2-hydro Xyl-3-phenoxypropyl acrylate "HPPA", N-vinylcaprolactam "VC", dimethyloltricyclodecane diacrylate "DMTCDDA", dimethylol dicyclopentane diacrylate "DMDCPTA", dicyclopentenyl acrylate " DCPTeA ”, dicyclopentanyl acrylate“ DCPTaA ”, isobornyl acrylate“ IBA ”, acryloylmorpholine“ AM ”, tetrahydrofurfuryl acrylate“ THFA ”, ethyl carbitol acrylate“ ECA ”, methoxytriethylene Glycol acrylate “MTEGA”, cyclohexyl acrylate “CHA”, isobutyl acrylate “IBA”, t-butyl acrylate “TBA”, benzyl acrylate Relate is “BA”, 2- (2-hydroxyethoxy) ethyl acrylate is “VEEA”, 4-hydroxybutyl acrylate is “HBA”, benzyl methacrylate is “BM”, urethane acrylate is “UA”, and the above formula (6 ) Is represented by “A1”, the compound represented by formula (7) (substance A) is represented by “A2”, and the compound represented by formula (8) is represented by “substance A”. A3 ”, substance A represented by the following formula (9) is“ A4 ”, Irgacure 819 (Ciba Japan) is“ ic819 ”, Speedcure TPO (ACETO) is“ scTPO ”, Speedcure DETX (Lambson) "ScDETX", UV-3500 (manufactured by Big Chemie) "UV3500", hydroquinone monomethyl ether " It is shown in EHQ ". Moreover, about Example 9, the composition of the constituent material of a mother particle showed the content rate of each element with the weight ratio about Example 9. In addition, the observation is performed on each of the 10 arbitrary metal particles contained in each inkjet composition, and the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan), The ratio (S ₁ / S ₀ ) to the area S ₀ [μm ² ] when observed from the direction in which the area when observed is the maximum among the directions orthogonal to the observation direction is determined, and the average value of these is expressed as 1 and Table 2 are also shown. In addition, the viscosity at 20 ° C. of the ink-jet compositions (ultraviolet-curing ink-jet compositions) of the above-described examples measured according to JIS Z8809 using a vibration viscometer is 3 mPa · s or more. The value was within a range of 15 mPa · s or less. D1 to D7 are all basic and have a polymer structure (basic polymer dispersant).

[2] Droplet discharge stability evaluation (discharge stability evaluation)
Using the inkjet compositions of the respective Examples and Comparative Examples, the evaluation by the following tests was performed.
First, a droplet discharge device installed in a chamber (thermal chamber) and the ink-jet compositions of the above examples and comparative examples are prepared, and the driving waveform of the piezo element is optimized, at 25 ° C. and 55% RH. Under the environment, about 2 million droplets (2000000 droplets) were continuously discharged from each nozzle of the droplet discharge head for each inkjet composition. Thereafter, the operation of the droplet discharge device was stopped, and the droplet discharge device was left in an environment of 25 ° C. and 55% RH for 240 hours in a state where each ink jet composition was filled in the flow path.

  Thereafter, 4 million droplets (4000000 droplets) were continuously discharged from each nozzle of the droplet discharge head in an environment of 25 ° C. and 55% RH. The average deviation amount d from the center target position of the center position of each landed droplet for the 4000000 droplets discharged from the designated nozzle near the center of the droplet discharge head after being left for 150 hours. Values were obtained and evaluated according to the following five-step criteria. It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amount d is less than 0.07 μm.
B: The average value of the shift amount d is 0.07 μm or more and less than 0.14 μm.
C: The average value of the shift amount d is 0.14 μm or more and less than 0.17 μm.
D: The average value of the shift amount d is 0.17 μm or more and less than 0.21 μm.
E: The average value of the shift amounts d is 0.21 μm or more.

[3] Frequency characteristics of inkjet composition In the state where a droplet discharge device installed in a chamber (thermal chamber) and the inkjet compositions of the respective examples and comparative examples are prepared and the drive waveform of the piezoelectric element is optimized In an environment of 25 ° C. and 55% RH, each ink jet composition was subjected to droplet discharge while changing the frequency (frequency) of the piezo element from all nozzles of the droplet discharge head. The droplet discharge time at each frequency was 10 minutes. The frequency range that can be actually used was evaluated according to the following four-stage criteria, with the number of undischarged nozzles being less than 1% of the total number of nozzles at the time point after 10 minutes of discharge as the highest frequency that can be actually used. It can be said that the larger this value, the better the frequency characteristics.
A: 15 kHz or more.
B: 10 kHz or more and less than 15 kHz.
C: 5 kHz or more and less than 10 kHz.
D: Less than 5 kHz.

[4] Storage stability evaluation of inkjet composition (long-term stability evaluation)
About the inkjet composition of each said Example and a comparative example, after leaving for 40 days in an environment of 40 degreeC, the inkjet composition of each said Example measured based on JISZ8809 using a vibration-type viscometer. The viscosity of the product at 20 ° C. was measured, the rate of increase in viscosity immediately after production was determined, and evaluated according to the following criteria.

A: Increase rate of viscosity is less than 5%.
B: Increase rate of viscosity is 5% or more and less than 10%.
C: Increase rate of viscosity is 10% or more and less than 18%.
D: Increase rate of viscosity is 18% or more and less than 23%.
E: The rate of increase in viscosity is 23% or more, or generation of foreign matter is observed.

[5] Curability About the ink jet compositions of the respective Examples and Comparative Examples, the ink jet printer manufactured by Epson; introduced into PM800C, and using Diafoil G440E (thickness 38 μm) manufactured by Mitsubishi Resin Co., Ltd. as a recording medium, Solid printing was performed at an ink amount of 9 g / m ^2. Immediately after printing, the LED-UV lamp; Foseon's RX firefly (gap 6 mm, peak wavelength 365 nm, 1000 mW / cm ² ) was used to irradiate ultraviolet rays, and inkjet Whether the composition was cured or not was evaluated and evaluated according to the following five-step criteria. Whether it was cured or not was determined by rubbing the surface with a cotton swab and whether or not the uncured ink composition adhered. In addition, whether it corresponds to the irradiation amount of the following AE can be calculated by how many seconds the lamp is irradiated.

A: Cured with an ultraviolet irradiation dose of less than 100 mJ / cm ² .
B: It hardened | cured with the ultraviolet irradiation amount of 100 mJ / cm < ² > or more and less than 200 mJ / cm < ² >.
C: Cured with an ultraviolet irradiation amount of 200 mJ / cm ² or more and less than 500 mJ / cm ² .
D: It hardened | cured with the ultraviolet irradiation amount of 500 mJ / cm < ² > or more and less than 1000 mJ / cm < ² >.
E: It hardens | cures with the ultraviolet irradiation amount of 1000 mJ / cm < ² > or more. Or it does not cure at all.

[6] Manufacture of Recorded Items Using the inkjet compositions of the examples and comparative examples, interior panels as recorded products were manufactured as follows.
First, the inkjet composition was put into an inkjet apparatus.
Thereafter, the inkjet composition was ejected in a predetermined pattern onto a base material (recording medium) having a curved surface portion formed using polycarbonate (manufactured by Asahi Glass Co., Ltd., Carboglass polish 2 mm thick).

Thereafter, ultraviolet rays having a spectrum having maximum values at wavelengths of 365 nm, 380 nm, and 395 nm were irradiated, irradiation intensity of 180 mW / cm ² was irradiated for 15 seconds, the ink jet composition on the substrate was cured, and an interior panel as a recorded matter Got.
Using the method as described above, ten interior panels (recorded matter) were produced using the ink-jet compositions of the examples and comparative examples.

  Moreover, what was shape | molded using polyethylene terephthalate (Diafoil G440E 38micrometer thickness made from Mitsubishi Plastics) as a base material, low density polyethylene (TuX (L-LDPE) HC-E # 80 made from Mitsui Chemicals, Inc. cello). ), Biaxially stretched polypropylene (OP U-1 # 60 made by Mitsui Chemical Tosero Co., Ltd.), hard vinyl chloride (Sunday sheet (transparent) 0.5 mm thickness made by Acrysandy Co.) Ten interior panels (recorded matter) were produced in the same manner as described above except that the ones molded using the same were used, using the inkjet compositions of the examples and comparative examples.

[7] Evaluation of recorded matter Each recorded matter obtained as described above was evaluated as follows.
[7.1] Appearance evaluation of recorded matter Each recorded matter produced in each of the above examples and comparative examples was visually observed and evaluated according to the following seven criteria.

A: It has a glossy feeling rich in luxury and has an extremely excellent appearance.
B: It has a glossy feeling full of luxury and has a very excellent appearance.
C: It has a glossiness with a high-class feeling and has an excellent appearance.
D: Glossy with a high-class feeling and a good appearance.
E: Inferior gloss and appearance is slightly poor.
F: Inferior glossiness and poor appearance.
G: Inferior glossiness and extremely poor appearance.

[7.2] Glossiness About the pattern formation part of each recorded matter manufactured in each of the above Examples and Comparative Examples, the glossiness at a turning angle of 60 ° was measured using a glossmeter (MINOLTA MULTI GLOSS 268). Evaluation was made according to the following criteria.
A: Glossiness is 400 or more.
B: Glossiness is 300 or more and less than 400.
C: Glossiness is 200 or more and less than 300.
D: Glossiness is less than 200.

[7.3] Abrasion resistance With respect to the recorded matter according to each of the above examples and comparative examples, when 48 hours have elapsed since the production of the recorded matter, a Southerland Lab Tester was used and polyethylene terephthalate was used as a phase paper according to JIS K5701. A rub resistance test using a film made by Mitsubishi Plastics (Diafoil G440E) was performed, and the recorded material after the rub resistance test was also glossy by the same method as described in [7.2] above. The degree of reduction in gloss before and after the abrasion resistance test was determined and evaluated according to the following criteria.

A: The reduction rate of glossiness is less than 5%.
B: The reduction rate of glossiness is 5% or more and less than 13%.
C: The reduction rate of glossiness is 13% or more and less than 23%.
D: The reduction rate of glossiness is 23% or more and less than 27%.
E: Gloss reduction rate is 27% or more, or the surface of the recording medium is exposed due to metal particles falling off.

  These results are shown in Table 3. In Table 2, “M1” represents a recorded material produced using a polycarbonate substrate, “M2” represents a recorded material produced using a polyethylene terephthalate substrate, and a low density polyethylene substrate. “M3” is a recorded matter manufactured using a biaxially oriented polypropylene base material, and “M4” is a recorded matter manufactured using a biaxially oriented polypropylene base material. Indicated by “M5”.

  As is clear from Table 3, the ultraviolet curable inkjet composition of the present invention was excellent in droplet ejection stability, storage stability, and curability. Further, the recorded matter of the present invention had excellent gloss and appearance, and was excellent in the abrasion resistance of the pattern forming portion. On the other hand, in the comparative example, a satisfactory result was not obtained.

Such an object is achieved by the present invention described below.
The ultraviolet curable inkjet composition of the present invention is an ultraviolet curable inkjet composition discharged by an inkjet method,
A polymerizable compound, a metal powder, and a dispersant;
The content of the polymerizable compound is 70% by mass or more and 99% by mass or less,
The metal powder includes a surface treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound as a surface treatment agent,
The dispersant includes a basic one having a polymer structure.
Thereby, it is possible to provide an ultraviolet curable inkjet composition that can be suitably used for the production of a recorded product having a pattern (printing portion) having excellent storage stability, glossiness, and abrasion resistance. .

Claims (13)

An ultraviolet curable ink jet composition discharged by an ink jet method,
A polymerizable compound, a metal powder, and a dispersant;
The metal powder includes a surface treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound as a surface treatment agent,
An ultraviolet curable ink jet composition comprising a basic dispersant having a polymer structure as the dispersant.   2. The ultraviolet curable ink jet composition according to claim 1, wherein the metal powder is a powder whose surface is mainly composed of Al and is surface-treated with a fluorine-based silane compound and / or a fluorine-based phosphate compound. .   The ultraviolet curable ink jet composition according to claim 1, wherein the metal powder has a scaly shape. The ultraviolet curable inkjet composition according to any one of claims 1 to 3, wherein the metal powder includes a surface treated with the fluorine-based silane compound having a chemical structure represented by the following formula (1).
R ¹ SiX ¹ _a R ² _(3-a) (1)
(In Formula (1), R ¹ represents a hydrocarbon group in which part or all of the hydrogen atoms are substituted with fluorine atoms, X ¹ represents a hydrolyzable group, an ether group, a chloro group, or a hydroxyl group; ² represents an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 3 inclusive.) The ultraviolet curable ink jet composition according to any one of claims 1 to 4, wherein the metal powder includes a surface treated with the fluorine-based phosphoric acid compound having a chemical structure represented by the following formula (2). .
POR _n (OH) _3-n (2)
(In the formula (2), R _{is, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, and n is 1 or more and 3 or less. M is an integer of 2 to 18, and l is an integer of 1 to 18.)   6. The ultraviolet curable ink jet composition according to claim 1, wherein the surface treatment agent has a perfluoroalkyl structure.   The ultraviolet curable ink jet composition according to claim 1, wherein the metal powder has an average particle size of 500 nm to 3.0 μm.   The ultraviolet curable ink jet composition according to any one of claims 1 to 7, wherein the polymerizable compound contains phenoxyethyl acrylate.   As the polymerizable compound, in addition to the phenoxyethyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy 3-phenoxypropyl acrylate, and 4 The ultraviolet curable inkjet composition according to claim 8, comprising at least one selected from the group consisting of -hydroxybutyl acrylate.   Examples of the polymerizable compound include dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, isobutyl. The ultraviolet curable ink jet according to any one of claims 1 to 9, comprising at least one selected from the group consisting of acrylate, t-butyl acrylate, benzyl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. Composition. The ultraviolet curable inkjet composition according to any one of claims 1 to 10, wherein the ultraviolet curable inkjet composition further comprises a substance A having a partial structure represented by the following formula (5).

Claims satisfying a relationship of 0.01 ≦ X _A / X _M ≦ 0.8, where X _A [mass%] is the content of the substance A and X _M [mass%] is the metal powder. Item 12. The ultraviolet curable inkjet composition according to any one of Items 1 to 11.   A recorded matter produced by applying the ultraviolet curable inkjet composition according to any one of claims 1 to 12 onto a recording medium and then irradiating with ultraviolet rays.