JP5899671B2 - Method for producing ultraviolet curable ink jet composition - Google Patents

Description

The present invention relates to a method for producing an ultraviolet curable inkjet composition.

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, in the ink jet method, a composition that cures when irradiated with ultraviolet rays (ultraviolet curable ink jet composition) has been used in order to make the abrasion resistance, water resistance, solvent resistance, etc. particularly excellent. (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 characteristics such as glossiness inherent to the metal. In addition, the composition is inferior in 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 for producing 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 in providing the manufacturing method of .

Such an object is achieved by the present invention described below.
Method for producing a UV curable ink jet composition of the present invention is a manufacturing method of an ultraviolet curable ink composition to be ejected by an inkjet method,
It has a mixing step of mixing a metal powder surface-treated with a silane compound with a polymerizable compound and an adsorption / desorption component that can be adsorbed / desorbed on the metal powder .
Thereby, the ultraviolet curable inkjet composition which can be used suitably for manufacture of the recorded matter provided with the pattern (printing part) excellent in storage stability, glossiness, and abrasion resistance can be provided.

In the method for producing an ultraviolet curable inkjet composition of the present invention, it is preferable to use a fatty acid and / or an aliphatic amine as the adsorption / desorption component.
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 do.

In the manufacturing method of the ultraviolet curable inkjet composition of this invention, it is preferable that the said metal powder is surface-treated with the fluorine-type silane compound.
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 do.

In the method for producing an ultraviolet curable inkjet composition of the present invention, the fluorine-based silane compound 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 further improved, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable ink jet composition are further improved. can do.

In the method for producing the ultraviolet curable inkjet composition of the present invention, the fluorine-based silane compound preferably has a perfluoroalkyl structure.
As a result, the storage stability of the ultraviolet curable ink jet composition is further improved, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable ink jet composition are further improved. can do.

In the method for producing an ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder is a powder whose surface is mainly composed of Al and is surface-treated with the silane compound.
Al originally exhibits a particularly excellent gloss feeling among various metal materials, but when a powder composed of Al is applied to the ultraviolet curable inkjet composition, the ultraviolet curable inkjet composition is used. The present inventor has found that the storage stability is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation occur particularly remarkably. On the other hand, in the present invention, the occurrence of the above-described problems can be reliably prevented even when a powder whose surface is composed of Al is used. That is, the effect of the present invention is particularly remarkable when the metal powder according to the present invention is a powder whose surface is mainly composed of Al and is surface-treated with a silane compound.

In the method for producing an ultraviolet curable inkjet composition of the present invention, the metal powder is preferably in the form of a scale.
Thereby, the glossiness, abrasion resistance, etc. of the recorded matter manufactured using the ultraviolet curable ink jet composition can be made particularly excellent.
In the method for producing the ultraviolet curable inkjet composition of the present invention, it is preferable that the average particle size of the metal powder is 500 nm or more and 2.0 μm or less.
Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable ink jet composition can be further improved. In addition, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved.

In the production method of the ultraviolet ray curable ink jet composition of the present invention, the polymerizable compound is preferably one containing phenoxyethyl acrylate.
As a result, the storage stability and ejection stability of the UV curable inkjet composition are excellent, and the reactivity of the UV curable inkjet composition after ejection by the inkjet method is particularly excellent, and the production of recorded matter In particular, the rub resistance of the formed pattern can be made particularly excellent.

In the method for producing the ultraviolet curable ink jet composition of the present invention, the polymerizable compound includes 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate in addition to the phenoxyethyl acrylate. It is preferable to include at least one selected from the group consisting of acrylate and 4-hydroxybutyl acrylate.
As a result, the storage stability and ejection stability of the UV curable inkjet composition are excellent, and the reactivity of the UV curable inkjet composition after ejection by the inkjet method is particularly excellent, and the production of recorded matter In particular, the rub resistance of the formed pattern can be made particularly excellent.

In the method for producing an ultraviolet curable inkjet composition of the present invention, the polymerizable compound preferably contains dimethylol tricyclodecane diacrylate and / or amino 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 .

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 ink jet composition of the present invention is ejected by an ink jet method, and is composed of a polymerizable compound, a metal powder by a silane compound, and an adsorption / desorption component capable of being adsorbed / desorbed (adsorption and desorption) on the metal powder. Is included.

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, 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 contain a polymerizable compound and are cured when irradiated with ultraviolet rays (ultraviolet curable ink jet compositions) in order to make the ink jet method particularly excellent in abrasion resistance, water resistance, solvent resistance, etc. Is used.

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 characteristics such as glossiness inherent to the metal. In addition, the composition is inferior in 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, a metal powder by a silane compound, and an adsorption / desorption component that can be adsorbed / desorbed on the metal powder.

  As described above, the metal powder contained together with the polymerizable compound is surface-treated with the silane compound, and further contains an adsorbing / desorbing component that can be adsorbed / desorbed on the metal powder. Excellent chemical stability and dispersion stability of metal powder, storage stability of UV curable ink jet composition, long-term ejection stability, curability (curing reaction progress rate, printing part formed The recorded material produced using the UV curable ink jet composition has the glossiness and high quality inherent to the metal material constituting the metal powder. It is possible to effectively exert the gloss of the printed part and the abrasion resistance, and the durability of the recorded matter can be improved.

<Metal powder>
The metal powder contained in the ultraviolet curable inkjet composition of the present invention is obtained by surface-treating at least the mother particles having a surface made of a metal material with a silane compound.
(Mother particles)
First, mother particles (particles subjected to surface treatment with a silane compound) constituting metal particles will be described.
The mother particles constituting the metal powder need only have at least a region including the surface made of a metal material, for example, the whole may be made of a metal material, or a non-metal material. You may have the comprised base part and the film comprised with the metal material which coat | covers the said base part.

  Further, as the metal material constituting the mother particle, a single metal, various alloys, or the like can be used, but it is preferable that the mother particle has at least a surface mainly composed of Al. Al originally exhibits a particularly excellent gloss feeling among various metal materials, but when a powder composed of Al is applied to the ultraviolet curable inkjet composition, the ultraviolet curable inkjet composition is used. The present inventor has found that the storage stability is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation occur particularly remarkably. On the other hand, in the present invention, the occurrence of the above-described problems can be reliably prevented even when a powder whose surface is composed of Al is used. That is, the effect of the present invention is particularly remarkable when the metal powder according to the present invention is a powder whose surface is mainly composed of Al and is surface-treated with a silane compound.

  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. , Durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene and other hydrocarbon compounds, 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.

(Silane compound)
As described above, the metal powder according to the present invention is surface-treated with a silane compound.
As the silane compound, a compound having a structure in which a hydrogen atom and / or a hydrocarbon group (including those in which part or all of the hydrogen atoms are substituted with other atoms or atomic groups) is directly bonded to a silicon atom is used. be able to.

More specifically, examples of the silane compound include silicon hydride (Si _n H _{2n + 2} (where n is an integer of 1 or more)), H _a SiR _(4-a) (where R Can be a hydrocarbon group which may have a substituent, a is an integer of 1 or more and 4 or less, etc., but as a silane compound having at least one fluorine atom in the molecule The fluorine-based silane compound is preferably used. 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 do.

In particular, the fluorinated silane compound 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 further improved, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable ink jet composition are further improved. can do.

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) triethoxy Silane, 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-iodopropyltrimethoxylane, 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′-tri Ethoxysilylpropylurea, S-N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane, phenethyl Dimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltrimethoxy Silane, 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) propylsuccinic anhydride, N- [5 (Trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethylammonium chloride, phenyl vinyl Diethoxysilane, 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-tributylammonium Bro Id, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyltriethoxysilane, vinyltrimethoxy Silane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenylmethylchlorosilane, vinyltriphenoxysilane, vinyltris t-butoxysilane, adamantylethyltrichlorosilane, allylphenyltrichlorosilane, (aminoethylaminomethyl) phenethyltrimethoxy Silane, 3-aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, benzyltrichlorosilane, benzyldimethylchlorosilane, benzylmethyldichlorosilane, phenethyldiisopropylchlorosilane, phenethyltrichlorosilane, phenethyldimethylchlorosilane, phenethylmethyldisilane Chlorosilane, 5- (bicycloheptenyl) trichlorosilane, 5- (bicycloheptenyl) triethoxysilane, 2- (bicycloheptyl) dimethylchlorosilane, 2- (bicycloheptyl) trichlorosilane, 1,4-bis (trimethoxysilyl) Ethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, 3-pheno Shi propyl trichlorosilane, t- butyl phenyl chlorosilane, t- butyl phenyl silane, t- butyl phenyl dichlorosilane, p-(t-butyl) phenethyl dimethylchlorosilane, p-(t-butyl) phenethyl trichlorosilane, 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-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3- Some or all of the hydrogen atoms of silane compounds such as cyanopropyldimethylethoxysilane, 3-cyanopropylmethyldichlorosilane, and 3-cyanopropyltrichlorosilane In may be mentioned compounds having a structure resulting from substitution.

The fluorine-based silane compound preferably has a perfluoroalkyl structure (C _n F _{2n + 1} ). As a result, the storage stability of the ultraviolet curable ink jet composition is further improved, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable ink jet composition are further improved. can do.
The fluorine-based silane compound having a perfluoroalkyl structure _{(C n F 2n + 1)} , for example, those represented by the following formula (2).
_{C n F 2n + 1 (CH} 2) m SiX 1 a R 2 (3-a) (2)
(In Formula (2), 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 (3).

_{C p F 2p + 1 O (} C p F 2p O) r (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 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.

  The silane 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 treated with the silane compound. Also good. Thereby, the modification | change by the chemical bond by a silane compound can be more reliably performed to the mother particle surface, and the effect by this invention as mentioned above 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 inkjet 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, and the metal constituting the metal powder The glossiness etc. inherent to the material can be exerted more effectively on the resulting recorded matter, and the glossiness and luxury feeling of the formed pattern (printed part) should be particularly excellent. In addition, it is possible to make the printed material particularly excellent in abrasion resistance. In addition, when the metal powder is not subjected to the surface treatment with the silane compound as described above, or the ultraviolet curable inkjet composition does not include the adsorption / desorption component described in detail later, the metal powder has a scaly shape. However, in the present invention, even when the metal powder has a scaly shape, the tendency that the storage stability and ejection stability of the ultraviolet curable ink jet composition are low has been remarkable. The occurrence of such a problem can be reliably prevented. 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 2.0 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 ink jet composition can be further improved. In addition, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved.

<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 inkjet 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 an ultraviolet curable inkjet composition with respect to various recording media (base materials) can be made excellent by containing a polymeric compound. That is, by including the polymerizable compound, the ultraviolet curable ink jet 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, various oligomers (including dimers, trimers, etc.) can be used, but ultraviolet curable inkjet compositions are polymerized. The active 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, phenyl glycidyl ether acrylate, phenoxydiethylene glycol acrylate, EO modified phenol acrylate, phenoxyethyl acrylate, EO modified phenol acrylate, EO modified cresol acrylate, methoxy polyethylene 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, acrylic acid 2- (2-vinyloxy ethoxy) ethyl 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 UV curable inkjet composition are excellent, and the reactivity of the UV curable inkjet composition after ejection by the inkjet method is particularly excellent, and the production of recorded matter In particular, the rub resistance of the formed pattern can be made particularly excellent.

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

  The ultraviolet curable inkjet composition preferably contains dimethylol tricyclodecane diacrylate and / or amino acrylate as the polymerizable compound. 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 inkjet 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 inkjet composition can be made excellent, and the abrasion resistance of the pattern to be formed 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.

<Adsorption / desorption component>
The ultraviolet curable ink-jet composition of the present invention contains an adsorption / desorption component that can be adsorbed / desorbed on the metal powder, in addition to the metal powder (metal powder surface-treated with a silane compound) and a polymerizable compound as described above. By including such an adsorption / desorption component together with a metal powder surface-treated with a silane compound, the dispersion stability of the metal powder in the ultraviolet curable inkjet composition is improved, and the ultraviolet curable inkjet composition Storage stability can be improved. Moreover, the pattern (printing part) excellent in the glossiness of the pattern (printing part) formed using an ultraviolet curable inkjet composition can be made excellent. In addition, by including an adsorbing / desorbing component that can be adsorbed / desorbed in the metal powder, the adsorbing / desorbing component is desorbed from the metal powder even when a frictional force acts on the printed part formed using the UV curable inkjet composition. It is possible to suitably prevent the metal powder from peeling off from the recording medium due to frictional force. That is, it is possible to improve the abrasion resistance of the printed part.

  The adsorption / desorption component may be any as long as it can be adsorbed / desorbed on metal powder (metal powder surface-treated with a silane compound), such as fatty acid, alkylsulfonic acid, aliphatic alcohol, aliphatic amine. Etc., but fatty acids and / or aliphatic amines are preferred. 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 do.

  As the fatty acid, a compound having a hydrocarbon group and a carboxyl group (carboxylic acid) can be used. Specific examples of such compounds include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid Octadecanoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, cis, cis-9,12-octadecadienoic acid, 9,12,15-octadecanetrienoic acid, 6,9,12-octadecatrienoic acid, Nonadecanoic acid, eicosanoic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, 5,8,11-eicosatetraenoic acid, docosanoic acid, tetracosanoic acid, cis-15-tetracosanoic acid, hexacosane An acid, octacosanoic acid, triacontanoic acid, etc. can be mentioned. In addition, perfluorooctanoic acid and the like can be given as fatty acids in which a hydrogen group is substituted with a fluorine group.

  As the fatty amine, a compound having a hydrocarbon group and an amino group can be used. Specific examples of such compounds include butylamine, pentynoic acid, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, pentadecylamine, hexadecylamine, 9-hexadecenylamine, Examples include heptadecylamine, octadecylamine, cis-9-octadecenylamine, 11-octadecenylamine, and nonadecylamine.

  In the ultraviolet curable ink jet composition, the adsorption / desorption component is adsorbed and desorbed from the surface of the metal particles. For example, the above ultraviolet curable ink jet composition can be removed with a commercially available desktop ultrasonic cleaner. This can be confirmed by applying ultrasonic waves. In the case of adsorption and desorption, the polymerization reaction is immediately started by contact between the metal particles, the polymerizable compound and the polymerization initiator, and the occurrence of the gelation phenomenon can be visually confirmed.

<Other ingredients>
The ultraviolet curable inkjet composition of the present invention may contain components other than those described above (other components). Such components include, for example, photopolymerization initiators, slip agents (leveling agents), dispersants, polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), colorants, fixing agents, anti-blocking agents. Examples include glazes, preservatives, antioxidants, chelating agents, thickeners, and sensitizers (sensitizing dyes).

  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, diethyl Oxanthone, 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 inkjet 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. .

  When the ultraviolet curable inkjet composition contains a dispersant, the dispersibility of the metal powder can be improved, and the storage stability and ejection stability of the ultraviolet curable inkjet composition are particularly excellent. be able to. The dispersant is not particularly limited, and examples thereof include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, and sulfur-containing polymers. , Fluorine-containing polymers, epoxy resins and the like.

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, 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 inkjet 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 inkjet composition of the present invention is excellent in adhesion to a recording medium, the recording medium may be any type, and either absorbing or non-absorbing may be used. Well, for example, natural fibers / synthetic fibers such as paper (plain paper, ink jet dedicated paper, etc.), plastic materials, metals, ceramics, wood, shells, cotton, polyester, wool, etc., 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 or a method of discharging ink by bubbles generated by heating the ink can be used. The piezo method is preferred from the standpoint of difficulty in handling.
The discharge of the ultraviolet curable inkjet composition by the inkjet method can be performed using a known droplet discharge device.

The ultraviolet curable inkjet composition discharged by the inkjet 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 (ultraviolet curable inkjet composition) (Example 1)
First, a polyethylene terephthalate film (Made by Mitsubishi Plastics, Diafoil G440E) having a smooth surface 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 tetraethylene 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 are used as (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane (CF ₃ (CF ₃ ( CF ₂ ) ₇ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ) in a 1% by mass tetraethylene glycol diethyl ether solution and stirred for 10 seconds, thereby surface treatment with a silane compound (fluorinated silane compound) To obtain a metal powder.
The metal powder thus obtained had an average particle size of 0.8 μm and an average thickness of 35 nm.

  Next, phenoxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 4-hydroxybutyl acrylate, octadecanoic acid as an adsorption / desorption component, light Irgacure 819 (manufactured by Ciba Japan) as a polymerization initiator, Speedcure TPO (manufactured by Lambson) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, UV-3500 as a leveling agent ( The ink-jet composition (ultraviolet curable ink-jet composition) was obtained by mixing with hydroquinone monomethyl ether as a polymerization inhibitor.

(Examples 2 to 10)
The composition of the metal particles (the composition of the mother particles and the type of silane compound used for the surface treatment) is shown in Table 1, and the type and ratio of the raw materials used for the preparation of the ink jet composition (ultraviolet curable ink jet composition) An ink jet composition (ultraviolet curable ink jet composition) was produced in the same manner as in Example 1 except that the composition shown in Table 1 was changed.

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

(Comparative Example 3)
Instead of (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane (CF ₃ (CF ₂ ) ₇ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ) as a silane compound Inkjet composition as in Example 1 except that CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —O— (CH ₂ ) ₁₁ —SH was used to obtain a metal powder by surface treatment. (Ultraviolet curable inkjet composition) was produced.

(Comparative Example 4)
In the preparation of the ink jet composition (ultraviolet curable ink jet composition), the examples described above were used except that the composition shown in Table 1 was obtained by changing the ratio of each component without using the adsorption / desorption component. In the same manner as in Example 1, an inkjet composition (ultraviolet curable inkjet composition) was produced.

(Comparative Example 5)
In the preparation of the ink jet composition (ultraviolet ray curable ink jet composition), the comparative example was used except that the composition shown in Table 1 was obtained by changing the ratio of each component without using the adsorption / desorption component. In the same manner as in Example 1, an inkjet composition (ultraviolet curable inkjet composition) was produced.

Table 1 summarizes the composition of the ink jet composition for each of the above Examples and Comparative Examples. In the table, CF ₃ (CF ₂ ) ₇ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ 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 —CH ₂ CH ₂ —SiCl ₃ is “S4”, CH ₃ (CH ₂ ) ₁₇ O—Si ( OC ₂ H _{5) 3} to _{"S5", NH 2 CH 2 CH 2 NH} (CH 2) 3 O-Si (OCH 3) 3 to _{"S6", NH 2 (CH 2) 3} O-Si (OCH 3) ₃ is “S7”, CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —O— (CH ₂ ) ₁₁ —SH is “S8”, CH ₃ (CH ₂ ) ₁₆ —COOH is “A1”, CH ₃ ( CH ₂₎ a ₁₂ -COOH _{"A2", CH 3 (CH 2) 8} -COO H is “A3”, CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ —COOH is “A4”, CH ₃ (CH ₂ ) ₁₇ —NH ₂ is “A5”, CH ₃ (CH ₂ ) ₇ the -NH ₂ "A6", phenoxyethyl ethyl acrylate "PEA", acrylic acid 2- (2-hydroxyethoxy) ethyl "VEEA", tripropylene glycol diacrylate "TPGDA", dipropylene glycol diacrylate "DPGDA ”, N-vinylcaprolactam“ VC ”, benzyl methacrylate“ BM ”, dimethylol tricyclodecane diacrylate“ DMTCDDA ”, amino acrylate“ AA ”, urethane acrylate“ UA ”, Irgacure 819 (Ciba Japan) "Ic819", Speedcure TP (Manufactured by ACETO) "scTPO", Speedcure DETX (manufactured by Lambson) "scDETX", UV-3500 (manufactured by Big Chemie) "UV3500", hydroquinone monomethyl ether "MEHQ", 4-hydroxybutyl acrylate " HBA ". 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 It was shown together with 1. Moreover, in the table | surface, the composition of the constituent material of the mother particle about Example 9, 10 showed the content rate of each element by weight ratio. In addition, the viscosity at 20 ° C. of the inkjet compositions (ultraviolet curable inkjet compositions) of the respective examples measured using a vibration viscometer according to JIS Z8809 is 3 mPa · s or more and 15 mPa. -It was a value within the range of s or less. In addition, the mother particles in the above Examples and Comparative Examples each had a content of components other than the constituent materials shown in the table of 0.5% by mass or less.

  Further, the ultraviolet curable ink jet composition is treated with ultrasonic waves for 10 minutes with a tabletop ultrasonic cleaner (100 W 28 kHz: W-113 (manufactured by Honda Electronics Co., Ltd.)), and the presence or absence of the gelation phenomenon is visually confirmed. Thus, in the ultraviolet curable inkjet compositions of the above Examples and Comparative Examples 1 to 3, it was confirmed that the adsorption / desorption component was adsorbed and desorbed on the surface of the metal particles. In 4, 5, such adsorption / desorption was not observed.

[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 allowed to stand in an environment of 25 ° C. and 55% RH for 360 hours in a state where the flow path of the droplet discharge device was filled.

  After that, 3 million droplets (3 million 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 3000000 droplets discharged from the designated nozzle near the center of the droplet discharge head after being left for 180 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 amounts d is less than 0.9 μm.
B: The average value of the shift amount d is 0.9 μm or more and less than 1.5 μm.
C: The average value of the shift amount d is 1.5 μm or more and less than 1.8 μm.
D: The average value of the shift amount d is 1.8 μm or more and less than 2.2 μm.
E: The average value of the shift amounts d is 2.2 μm or more.

[3] 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: The rate of increase in viscosity is 10% or more and less than 20%.
D: Increase rate of viscosity is 20% or more and less than 25%.
E: The rate of increase in viscosity is 25% or more, or generation of foreign matter is observed.
F: Viscosity cannot be measured due to gelation.

[4] Curability About the inkjet composition of each of the above Examples and Comparative Examples, it was introduced into an Epson inkjet printer; PM800C, and Mitsubishi Plastics, Diafoil G440E (thickness 38 μm) was used as the 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 by the ultraviolet irradiation amount of 1000 mJ / cm < ² > or more. Or it does not cure at all.

[5] 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.

[6] Evaluation of recorded matter The following evaluation was performed on each recorded matter obtained as described above.
[6.1] 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.

[6.2] 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 310 or more.
B: Glossiness is 210 or more and less than 310.
C: Glossiness is 110 or more and less than 210.
D: Glossiness is less than 110.

[6.3] 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 Love 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 [6.2] 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 26%.
E: Gloss reduction rate is 26% or more, or the surface of the recording medium is exposed due to metal particles falling off.

  These results are shown in Table 2. 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 apparent from Table 2, 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.

Claims (11)

A method for producing an ultraviolet curable inkjet composition ejected by an inkjet method,
A method for producing an ultraviolet curable ink jet composition, comprising: mixing a metal powder surface-treated with a silane compound with a polymerizable compound and an adsorption / desorption component capable of being adsorbed / desorbed on the metal powder.   The method for producing an ultraviolet curable ink jet composition according to claim 1, wherein a fatty acid and / or an aliphatic amine is used as the adsorption / desorption component.   The method for producing an ultraviolet curable ink jet composition according to claim 1 or 2, wherein the metal powder is surface-treated with a fluorine-based silane compound. The method for producing an ultraviolet curable inkjet composition according to claim 3, wherein the fluorine-based silane compound 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.)   The method for producing an ultraviolet curable inkjet composition according to claim 3 or 4, wherein the fluorine-based silane compound has a perfluoroalkyl structure.   The method for producing an ultraviolet curable ink jet composition according to any one of claims 1 to 5, wherein the metal powder is a powder whose surface is mainly composed of Al and is surface-treated with the silane compound. .   The method for producing an ultraviolet curable inkjet composition according to any one of claims 1 to 6, wherein the metal powder has a scaly shape.   The method for producing an ultraviolet curable inkjet composition according to any one of claims 1 to 7, wherein an average particle size of the metal powder is 500 nm or more and 2.0 µm or less.   The method for producing an ultraviolet curable inkjet composition according to any one of claims 1 to 8, wherein the polymerizable compound contains phenoxyethyl acrylate.   The polymerizable compound is selected from the group consisting of 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and 4-hydroxybutyl acrylate in addition to the phenoxyethyl acrylate. The method for producing an ultraviolet curable inkjet composition according to claim 9, comprising at least one selected from the group consisting of: 11. The method for producing an ultraviolet curable inkjet composition according to claim 1, wherein the polymerizable compound contains dimethylol tricyclodecane diacrylate and / or amino acrylate .