JP6056933B2 - Ultraviolet curable ink jet composition and method for producing recorded matter - Google Patents

Description

The present invention relates to an ultraviolet curable ink jet composition and a method for producing 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, 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

It is an object of the present invention two or more properties to provide both excellent UV-curable ink jet composition, also to provide a method of manufacturing a recorded matter using the ultraviolet ray curable ink composition .

Such an object is achieved by the present invention described below.
UV curable ink jet composition of the present invention is a UV-curable ink jet composition ejected by an inkjet method,
Containing a polymerizable compound and a metal powder;
The metal powder includes those subjected to surface treatment with two or more different compounds,
In addition to 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. It is characterized by including at least 1 sort .
Thereby, it is possible to provide an ultraviolet curable ink jet composition excellent in both of two or more characteristics.
In particular, 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, and the recorded product productivity Can be made particularly excellent, and the formed pattern can be made particularly excellent in abrasion resistance and the like.
In addition, while making the storage stability and ejection stability of the ultraviolet curable inkjet composition excellent, the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent, and the productivity of recorded matter Can be made particularly excellent, and the formed pattern can be made particularly excellent in abrasion resistance and the like.
The ultraviolet curable inkjet composition of the present invention is an ultraviolet curable inkjet composition discharged by an inkjet method,
Containing a polymerizable compound and a metal powder;
The metal powder includes those subjected to surface treatment with two or more different compounds,
The polymerizable compound contains dimethylol tricyclodecane diacrylate and / or amino acrylate.
Thereby, it is possible to provide an ultraviolet curable ink jet composition excellent in both of two or more characteristics.
In particular, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the scratch resistance of the formed pattern can be further improved.

In the ultraviolet curable inkjet composition of the present invention, the metal powder has a surface treatment with a short-chain compound having an alkyl group which may have a substituent having 2 to 4 carbon atoms, and 8 or more carbon atoms. The surface treatment with a long-chain compound having an alkyl group which may have 20 or less substituents is preferably performed.
Accordingly, it is possible to provide an ultraviolet curable inkjet composition that can be suitably used for forming a pattern (printing portion) having excellent storage stability, droplet ejection stability, glossiness, and abrasion resistance. it can.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder is subjected to a surface treatment with the short chain compound after being subjected to a surface treatment with the long chain compound.
As a result, the density of the film formed on the surface of the metal particles by the surface treatment with the short chain compound and the long chain compound is made particularly high, and the storage stability and ejection stability of the UV curable ink jet composition are particularly excellent. In addition, the glossiness and abrasion resistance of the pattern (printed portion) formed using the ultraviolet curable inkjet composition can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, the surface treatment is preferably performed using a material selected from the group consisting of a silane coupling agent, a phosphate ester, and a carboxylic acid.
As a result, the storage stability of the ultraviolet curable inkjet composition can be made particularly excellent, and the glossiness and abrasion resistance of the printed part formed using the ultraviolet curable inkjet composition are particularly excellent. Can be.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder has been subjected to a surface treatment with two or more different fluorine-based compounds.
Since it is difficult for a fluorine-based compound to form a dense film compared to a non-fluorine-based compound, the metal surface is easily exposed, but a film defect can be filled by combining a short-chain compound. Conversely, non-fluorinated compounds tend to form dense films, but have higher surface energy than fluorine-based compounds, and for low surface tension monomers, metal powders are preferably arranged near the outer surface of the print area. (Leafing) is difficult, and glossiness is not easily produced. Therefore, a dense and glossy surface treatment can be performed by combining fluorine compounds.

In the ultraviolet curable inkjet composition of the present invention, the metal powder is preferably subjected to a surface treatment with a fluorine compound and a surface treatment with a non-fluorine compound.
As a result, the density of the film formed on the surface of the metal particles by the surface treatment with the fluorine compound and the non-fluorine compound is made particularly high, and the storage stability and the ejection stability of the UV curable inkjet composition are made particularly excellent. On the other hand, the glossiness and abrasion resistance of the pattern (printed portion) formed using the ultraviolet curable ink jet composition can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, the fluorine 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 ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder is obtained by surface-treating at least a powder mainly composed of aluminum with two or more different compounds.
Aluminum originally exhibits particularly excellent glossiness among various metal materials, but when an attempt is made to apply a powder composed of aluminum to an 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 this invention, even if it is a case where the powder whose surface is comprised with aluminum is used, generation | occurrence | production of the above problems can be prevented reliably. That is, the metal powder composing the ultraviolet curable ink jet composition according to the present invention is one in which at least the surface of the powder composed mainly of aluminum is surface-treated with two or more different compounds. The effect is particularly remarkable.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder has a scaly shape.
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 ultraviolet curable inkjet composition of the present invention, the average particle size of the metal powder is preferably 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.

Method of manufacturing a recorded matter of the present invention, the ultraviolet ray curable ink composition of the present invention was applied onto the medium, then, and then irradiating ultraviolet rays.
Thereby, it is possible to provide a recorded matter having a pattern (printing portion) excellent in glossiness, abrasion resistance and the like.

Hereinafter, preferred embodiments of the present invention will be described in detail.
《Metal powder》
First, the metal powder (powder for ultraviolet curable ink jet composition) of the present invention will be described.
The metal powder of the present invention is used for the production of an ultraviolet curable ink jet composition ejected by an ink jet method, and is subjected to two or more different surface treatments.

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.
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. Yes.
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 metal powder of the present invention has been subjected to two or more different surface treatments. Thereby, the metal powder used for manufacture of the ultraviolet curable inkjet composition which was excellent in the 2 or more types of characteristic can be provided. In particular, the composition described in detail below provides excellent chemical stability and dispersion stability of the metal powder in the ultraviolet curable inkjet composition, and the storage stability of the ultraviolet curable inkjet composition. In addition, it is possible to make the ejection stability over a long period of time excellent, and in the recorded matter produced using the ultraviolet curable ink jet composition, the glossiness inherent in the metal material constituting the metal powder, etc. The above characteristics can be fully exhibited. Such an excellent effect is more prominently exhibited when the ultraviolet curable inkjet composition contains a plurality of different polymerizable compounds. Further, the excellent effects as described above are obtained by applying two or more kinds of surface treatments with different metal powders, and when the surface treatment is not performed or only one kind is obtained. It cannot be obtained when the surface treatment is applied.

<Mother particles>
First, mother particles (particles subjected to surface treatment) 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, 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 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 effect of the present invention is particularly remarkably exhibited when the metal powder according to the present invention is surface-treated with at least two kinds of compounds different from the powder whose surface is mainly composed of Al.

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 containing the metal powder 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. It is preferable to use one containing two or more selected from the group consisting of such liquids. As a result, the productivity of the mother particles and metal powder is made particularly excellent while preventing unintentional oxidation of the mother particles, and the variation in size, shape, and characteristics among the particles is particularly small. It can be.

<Surface treatment>
As described above, the metal powder according to the present invention has been subjected to two or more different surface treatments.
Although the kind of surface treatment with respect to a mother particle is not specifically limited, For example, the process using the material selected from the group which consists of a silane coupling agent, phosphate ester, and carboxylic acid is mentioned. By performing such a surface treatment, the storage stability of the ultraviolet curable inkjet composition can be made particularly excellent, and the glossiness of the printed part formed using the ultraviolet curable inkjet composition, The rubbing resistance can be made particularly excellent.

(Silane coupling agent)
As the silane coupling agent, for example, a silane compound having a silyl group and a hydrocarbon group can be used. Specific examples of such compounds include dimethyldimethoxysilane, diethyldiethoxysilane, 1-propenylmethyldichlorosilane, propyldimethylchlorosilane, propylmethyldichlorosilane, propyltrichlorosilane, propyltriethoxysilane, propyltrimethoxysilane, styryl. Ethyltrimethoxysilane, tetradecyltrichlorosilane, 3-thiocyanatepropyltriethoxysilane, p-tolyldimethylchlorosilane, p-tolylmethyldichlorosilane, p-tolyltrichlorosilane, p-tolyltrimethoxysilane, p-tolyltriethoxysilane , Di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane, di-n-butyldi-n-butyroxysilane, di-sec-butyldi sec-Butyloxysilane, Di-t-butyldi-t-Butyloxysilane, Octadecyltrichlorosilane, Octadecylmethyldiethoxysilane, Octadecyltriethoxysilane, Octadecyltrimethoxysilane, Octadecyldimethylchlorosilane, Octadecylmethyldichlorosilane, Octadecylmethoxydichlorosilane, 7- Octenyldimethylchlorosilane, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane, octylmethyldichlorosilane, octyldimethylchlorosilane, octyltrichlorosilane, 10-undecenyldimethylchlorosilane, undecyltrichlorosilane, vinyldimethylchlorosilane, Methyloctadecyldimethoxysilane, methyldodecyldiethoxysilane, methylocta Sildimethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triacontyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n- Propoxysilane, Methylisopropoxysilane, Methyl-n-Butyloxysilane, Methyltri-sec-Butyloxysilane, Methyltri-t-Butyloxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltri-n-propoxysilane, Ethylisopropoxysilane, Ethyl- n-Butyloxysilane, Ethyltri-sec-Butyloxysilane, Ethyltri-t-Butyloxysilane, n-Propyltrimethoxysilane, Iso Butyltrimethoxysilane, 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, dibenzyldiethoxysilane , Phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, benzylmethyldimethoxy Silane, benzyldimethylmethoxysilane, benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, benzyltriethoxysilane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, 3-acetoxypropyltrimethoxysilane 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, amyltriethoxysilane, benzoxacilepin dimethyl ester, 5- (bicycloheptenyl) triethoxysilane, bis (2 Hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane, 2-chloromethyltriethoxysilane, chloro Methylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxy Silane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltrimethyl Xysilane, cyanomethylphenethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyclohexenyltrichlorosilane, 2- (3-Cyclohexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyldimethylchlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane, cyclohexyldimethylchlorosilane, cyclohexylethyldimethoxysilane, cyclohexyl Methyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, Looctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltrichlorosilane, cyclopentyltrimethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitrophenylamino) propyl Triethoxysilane, (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) triethoxysilane, 2-hydro Cis-4- (3-triethoxypropoxy) diphenyl ketone, 3- (p-methoxyphenyl) propylmethyldichlorosilane, 3- (p-methoxyphenyl) propyltrichlorosilane, p- (methylphenethyl) methyldichlorosilane, p -(Methylphenethyl) trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 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-isocyanate Propyltriethoxysilane, (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′-triethoxysilyl Propylurea, S-N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane, phenethyldimethoxysilane, Phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltrimethoxysilane, N -(Triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane, (S)- N-triethoxysilylpropyl-O-ment 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-trimethylammonium 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-tributylammonium bromide, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxy Silylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinyl Phenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenylmethylchlorosilane, vinyltriphenoxysilane, vinyltris-t-butoxysilane Adamantylethyltrichlorosilane, allylphenyltrichlorosilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, benzyltrichlorosilane, benzyldimethylchlorosilane, benzyl Methyldichlorosilane, phenethyldiisopropylchlorosilane, phenethyltrichlorosilane, phenethyldimethylchlorosilane, phenethylmethyldichlorosilane, 5- (bicycloheptenyl) trichlorosilane, 5- (bicycloheptenyl) triethoxysilane, 2- (bicycloheptyl) dimethylchlorosilane 2- (bicycloheptyl) trichlorosilane, 1,4-bis (to Methoxysilylethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, 3-phenoxypropyltrichlorosilane, t-butylphenylchlorosilane, t-butylphenylmethoxysilane, t-butylphenyldichlorosilane, p- (t- Butyl) phenethyldimethylchlorosilane, p- (t-butyl) phenethyltrichlorosilane, 1,3- (chlorodimethylsilylmethyl) heptacosane, ((chloromethyl) phenylethyl) dimethylchlorosilane, ((chloromethyl) phenylethyl) methyldi Chlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl) phenylethyl) trimethoxysilane, chlorophenyltrichlorosilane, 2-cyanoethyltri Chlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldiethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropyldimethylethoxysilane, 3-cyanopropylmethyldichlorosilane, Examples include 3-cyanopropyltrichlorosilane.

(Phosphate ester)
As phosphate ester, what has a chemical structure obtained, for example by dehydration condensation of phosphoric acid and alcohol can be used. Specific examples of such a compound include lauryl phosphate, lauryl-2 phosphate, steareth-2 phosphate, 2- (perfluorohexyl) ethylphosphonic acid, and the like.
(carboxylic acid)
As the carboxylic acid, a compound (fatty acid) having a hydrocarbon group and a carboxyl group can be used. Specific examples of such compounds include decanoic acid, tetradecanoic acid, octadecanoic acid, cis-9-octadecenoic acid and the like.

  Moreover, you may use the fluorine-type compound which contains at least 1 fluorine atom in a molecule | numerator for the surface treatment of a metal particle. By using such a fluorine-based compound, the chemical stability and dispersion stability of the metal powder in the ultraviolet curable inkjet composition are sufficiently improved, and the storage stability and longness of the ultraviolet curable inkjet composition are improved. The discharge stability over a period can be made sufficiently excellent, and in a recorded matter produced using an ultraviolet curable inkjet composition, metal powder can be suitably arranged in the vicinity of the outer surface of the printing part. Thus, it is possible to more effectively exhibit the properties such as glossiness inherent in the metal material constituting the metal powder. Further, since the metal powder is surface-treated with a fluorine compound, the ultraviolet curable inkjet composition can be used even when a polymerizable compound having a low surface tension is used as a constituent material of the ultraviolet curable inkjet composition. In the recorded matter produced using the product, the metal powder can be reliably arranged (leafing) in the vicinity of the outer surface of the printing part, and the glossiness inherent in the metal material constituting the metal powder, etc. The above characteristics can be fully 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 scratch resistance of the recorded matter of the ultraviolet curable inkjet composition).

  When the metal powder is subjected to a surface treatment with a fluorine compound, the fluorine 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 addition, the fluorine-based compound that can be used for the surface treatment may be any compound that contains at least one fluorine atom in the molecule. Examples include acid esters and compounds having a structure in which at least some of the hydrogen atoms of the carboxylic acid are substituted with fluorine atoms (fluorine silane compounds, fluorine phosphates, fluorine-substituted fatty acids, etc.). By using these compounds, the effects as described above are more remarkably exhibited.

In particular, 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 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.

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) have a structure in which some or all of the hydrogen atoms of the compound exemplified as the silane compound having a silyl group and a hydrocarbon group are substituted with fluorine atoms. A compound can be mentioned.

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.

Further, the fluorine-based phosphate ester preferably has a chemical structure represented by the following formula (4).
POR _n (OH) _3-n (4)
(In the formula (4), 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 O— or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, n is an integer of 1 to 3, m is an integer of 4 to 20, Is an integer from 4 to 20.)

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 formula (4), m is preferably an integer of 4 or more and 16 or less. Thereby, the effects as described above are more remarkably exhibited.
In formula (4), l is preferably an integer of 4 or more and 16 or less. Thereby, the effects as described above are more remarkably exhibited.

  Surface treatment with a short-chain compound having an alkyl group that may have a substituent having 2 to 4 carbon atoms, and an alkyl group that may have a substituent having 8 to 20 carbon atoms The surface treatment with a long chain compound is preferable. As a result, it is suitable for the production of an ultraviolet curable ink jet composition that can be suitably used for forming a pattern (printing part) having excellent storage stability, droplet ejection stability, glossiness, and abrasion resistance. A metal powder that can be used can be provided.

Moreover, the carbon number of the alkyl group which may have a substituent that the long-chain compound has may be 8 or more and 20 or less, but is preferably 4 or more and 16 or less. Thereby, the effects as described above are more remarkably exhibited.
In addition, when the alkyl group of the short chain compound and / or the alkyl group of the long chain compound has a substituent, examples of the substituent include a halogeno group such as a fluoro group, a chloro group, and a bromo group, a hydroxyl group, and the like. Is mentioned.

  Moreover, the metal powder may have been subjected to surface treatment with two or more different fluorine compounds. Since it is difficult for a fluorine-based compound to form a dense film compared to a non-fluorine-based compound, the metal surface is easily exposed, but a film defect can be filled by combining a short-chain compound. Conversely, non-fluorinated compounds tend to form dense films, but have higher surface energy than fluorine-based compounds, and for low surface tension monomers, metal powders are preferably arranged near the outer surface of the print area. (Leafing) is difficult, and glossiness is not easily produced. Therefore, a dense and glossy surface treatment can be performed by combining fluorine compounds.

  The metal powder may be subjected to a surface treatment with a fluorine compound and a surface treatment with a non-fluorine compound. As a result, the density of the film formed on the surface of the metal particles by the surface treatment with the fluorine compound and the non-fluorine compound is made particularly high, and the storage stability and the ejection stability of the UV curable inkjet composition are made particularly excellent. On the other hand, the glossiness and abrasion resistance of the pattern (printed portion) formed using the ultraviolet curable ink jet composition can be made particularly excellent.

The surface treatment on the mother particles can be performed using the above-described compound (surface treatment agent), but the surface treatment is performed on the mother particles a plurality of times using a plurality of types of compounds (surface treatment agents) sequentially. The surface treatment may be performed on the mother particles using a mixture of a plurality of types of compounds (surface treatment agents).
In particular, when the metal powder is subjected to a surface treatment with a short chain compound and a long chain compound, the metal powder is subjected to a surface treatment with a short chain compound after being subjected to a surface treatment with the long chain compound. It is preferable. As a result, the density of the film formed on the surface of the metal particles by the surface treatment with the short chain compound and the long chain compound is made particularly high, and the storage stability and ejection stability of the UV curable ink jet composition are particularly excellent. In addition, the glossiness and abrasion resistance of the pattern (printed portion) formed using the ultraviolet curable inkjet composition can be made particularly excellent.

  Further, when the ultraviolet curable inkjet composition contains phenoxyethyl acrylate and 2- (2-hydroxyethoxy) ethyl acrylate as the polymerizable compound, the metal powder contains 2- (perfluorohexyl) ethylphosphonic acid and It is preferable that the surface treatment is performed with (3,3,3-trifluoropropyl) trimethoxysilane. As a result, the phosphoric acid ester of a long-chain fluorine compound having a high adsorption rate can be subjected to leafing by surface-treating most of the metal powder, and the short-chain fluorine-based compound silane compound having the next highest bonding strength The effect of improving the storage stability can be obtained by forming a dense film by surrounding the film defects on the surface of the metal powder.

  In addition, the compound (surface treatment agent) as described above may be directly treated on the mother particles, but after the mother particles are treated with an acid or a base, the surface of the mother particles is treated. It is preferable to perform treatment with a treating agent. Thereby, the modification | change by the chemical bond by a surface treating agent can be more reliably performed to the base 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. Moreover, in the structure which has not performed the surface treatment as mentioned above, when the metal powder has a scaly shape, there is a tendency that the storage stability and ejection stability of the ultraviolet curable ink jet composition are low. Although particularly prominent, in the present invention, even when the metal powder has a scaly shape, 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.

<< UV curable inkjet composition >>
Next, 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 includes a polymerizable compound and the metal powder as described above (a metal powder subjected to two or more different surface treatments). It is a waste. Thereby, it is possible to provide an ultraviolet curable ink jet composition excellent in both of two or more characteristics. In particular, by including the metal powder as described above, the chemical stability and dispersion stability of the metal powder in the ultraviolet curable inkjet composition are improved, and the storage stability and longness of the ultraviolet curable inkjet composition are improved. In addition to having excellent ejection stability over a period of time, characteristics such as glossiness inherent in the metal material constituting the metal powder in the recorded matter produced using the ultraviolet curable ink jet composition Can be fully exhibited.

<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.

<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 wt% or more and 10 wt% 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, abrasion resistance and the like.
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 diethylene glycol diethyl ether, and ultrasonic vibration was applied. As a result, scaly Al particles (particles to be mother particles) were obtained.

Next, Al particles obtained as described above are immediately separated by filtration, and the Al particles are added to diethylene glycol diethyl ether so that the solid content concentration is 5 wt%. did. Thereafter, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane as a fluorine-based silane compound (long chain compound) is added to the liquid (dispersion) so as to have a content of 3 wt%. The mixture was added and stirred for 4 hours at 40 ° C. for surface treatment. Thereafter, Al particles treated with a fluorine-based silane compound (short chain compound) were separated by filtration, and the Al particles were added to diethylene glycol diethyl ether so that the solid content concentration was 5 wt%. Thereafter, (3,3,3-trifluoropropyl) trimethoxysilane as a fluorine-based silane compound (short-chain compound) was added to this liquid (dispersion) so as to have a content of 3 wt%, and 40 ° C. The surface treatment was carried out by stirring for 4 hours. As a result, a dispersion was obtained in which Al particles (metal powder) surface-treated with a short chain compound (fluorine silane compound) and a long chain compound (fluorine silane compound) were dispersed in diethylene glycol diethyl ether.
The metal powder thus obtained had an average particle size of 0.8 μm and an average thickness of 30 nm.

  Next, the metal powder was phenoxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, Irgacure 819 (manufactured by Ciba Japan) as a photopolymerization initiator, Speedcure TPO (manufactured by Lambson) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, UV-3500 (manufactured by BYK Chemie) as a leveling agent, and p-- as a polymerization inhibitor By mixing with methoxyphenol, an inkjet composition (ultraviolet curable inkjet composition) was obtained.

(Examples 2 to 10)
Table 1 shows the composition of the metal particles (the composition of the mother particles and the type of surface treatment agent used for the surface treatment), and the types and ratios of the raw materials used for the preparation of the ink jet composition (ultraviolet curable ink jet composition). The inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1 except that the composition shown in Table 1 was changed by changing the above.

(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 had not been surface-treated were used as the metal powder.
(Comparative Example 2)
An 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 a gas atomization method was used as the metal powder. ) Was manufactured.

(Comparative Example 3)
Surface treatment of (3,3,3-trifluoropropyl) trimethoxysilane as a fluorine-based silane compound (short chain compound) has been performed, and (Heptadecafluoro-) as a fluorine-based silane compound (long chain compound) The inkjet composition (ultraviolet curable type) was used in the same manner as in Example 1 except that Al particles that were not subjected to surface treatment of (1,1,2,2-tetrahydrodecyl) triethoxysilane were used as the metal powder. An inkjet composition) was produced.

(Comparative Example 4)
Surface treatment of (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane as a fluorine-based silane compound (long-chain compound) has been performed, and as a fluorine-based silane compound (short-chain compound) An inkjet composition (ultraviolet curable type) was used in the same manner as in Example 1 except that Al particles that were not subjected to surface treatment of (3,3,3-trifluoropropyl) trimethoxysilane were used as the metal powder. An 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, (3,3,3-trifluoropropyl) trimethoxysilane (fluorine-based silane compound (short chain compound)) is referred to as “ST1”, (heptadecafluoro-1,1,2,2-tetrahydrodecyl). ) Triethoxysilane (fluorine silane compound (long chain compound)) “ST2”, stearic acid (non-fluorine carboxylic acid (long chain compound)) “ST3”, tetradecanoic acid (non-fluorine carboxylic acid (long chain compound)) Compound)) is “ST4”, lauryl phosphate (non-fluorine phosphate ester (long chain compound)) is “ST5” 2- (perfluorohexyl) ethylphosphonic acid (fluorine phosphate ester (long chain compound)) ) “ST6”, steareth-2-phosphate (non-fluorine phosphate ester (long chain compound)) “ST7”, butyltrimethoxysilane (non-fluorine sila) Compound (short-chain compound)) “ST8”, phenoxyethyl acrylate “PEA”, 2- (2-hydroxyethoxy) ethyl acrylate “VEEA”, tripropylene glycol diacrylate “TPGDA”, dipropylene glycol di Acrylate as “DPGDA”, N-vinylcaprolactam as “VC”, benzyl methacrylate as “BM”, dimethylol tricyclodecane diacrylate as “DMTCDDA”, amino acrylate as “AA”, urethane acrylate as “UA”, Irgacure 819 (Ciba Japan) is “ic819”, Speedcure TPO (ACETO) is “scTPO”, Speedcure DETX (Lambson) is “scDETX”, UV-3500 (Bicchemi) The company Ltd.) "UV3500", hydroquinone monomethyl ether "MEHQ" showed 4-hydroxybutyl acrylate in "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 1 and Table 2 are also shown. Moreover, in the table | surface, the composition of the constituent material of the mother particle about Example 9 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.

[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, for each color ink, 2 million droplets (2000000 droplets) were continuously discharged from each nozzle of the droplet discharge head. Thereafter, the operation of the liquid droplet ejection device was stopped, and the liquid droplet ejection device was left in an environment of 25 ° C. and 55% RH for 480 hours with each ink 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 aiming position of the center position of each landed droplet for the 3000000 droplets ejected from the designated nozzle near the center of the droplet ejection head after being left for 120 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 30 days in an environment of 45 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 10%.
B: Increase rate of viscosity is 10% or more and less than 15%.
C: Increase rate of viscosity is 15% 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.

[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 is performed at an ink amount of wet 10 g / m ^2. Immediately after printing, an LED-UV lamp; Foseon's RX firefly (gap 6 mm, peak wavelength 365 nm, 1000 mW / cm ² ) is used to irradiate ultraviolet rays. 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: Cured with an 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.

[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 are irradiated, irradiation intensity of 180 mW / cm ² is irradiated for 20 seconds, the ink jet composition on the substrate is 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, as a base material, what was shape | molded using polyethylene terephthalate (Diafoil G440E 38micrometer thickness made from a Mitsubishi resin company), low density polyethylene (TuX (L-LDPE) HC-E # 80 by Mitsui Chemicals Tosero Co., Ltd.) ), 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 320 or more.
B: Glossiness is 220 or more and less than 320.
C: Glossiness is 120 or more and less than 220.
D: Glossiness is less than 120.

[6.3] Scratch resistance With respect to the recorded matter according to each of the above examples and comparative examples, when 36 hours have passed since the manufacture of the recorded matter, a rust resistance test was performed according to JIS K5701 using a Southerland Love Tester. In the same manner as described in [6.2] above, the glossiness (turning angle 60 °) was also measured for the recorded matter after the abrasion resistance test, and the glossiness before and after the abrasion resistance test was measured. The reduction rate was determined and evaluated according to the following criteria.

A: The reduction rate of glossiness is less than 6%.
B: The reduction rate of glossiness is 6% or more and less than 14%.
C: The reduction rate of glossiness is 14% or more and less than 24%.
D: The reduction rate of glossiness is 24% or more and less than 28%.
E: Gloss reduction rate is 28% 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 3, “M1” is a recorded matter manufactured using a polycarbonate substrate, “M2” is a recorded material manufactured 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 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.
In particular, the ultraviolet curable inkjet composition contains phenoxyethyl acrylate and 2- (2-hydroxyethoxy) ethyl acrylate as the polymerizable compound, and the metal powder contains (3,3,3-trimethyl). In the example (Example 3) in which the treatment with (fluoropropyl) trimethoxysilane and the treatment with 2- (perfluorohexyl) ethylphosphonic acid were performed in combination, the storage stability and glossiness were particularly excellent. . On the other hand, in the comparative example, a satisfactory result was not obtained.

Claims (12)

An ultraviolet curable inkjet composition discharged by an inkjet method,
Containing a polymerizable compound and a metal powder;
As the metal powder, it saw including those surface treatment with two or more different compounds is performed,
In addition to 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. An ultraviolet curable inkjet composition comprising at least one selected from the group consisting of: An ultraviolet curable inkjet composition discharged by an inkjet method,
Containing a polymerizable compound and a metal powder;
As the metal powder, it saw including those surface treatment with two or more different compounds is performed,
An ultraviolet curable inkjet composition comprising dimethylol tricyclodecane diacrylate and / or amino acrylate as the polymerizable compound . The metal powder may have a surface treatment with a short-chain compound having an alkyl group which may have a substituent having 2 to 4 carbon atoms and a substituent having 8 to 20 carbon atoms. The ultraviolet curable inkjet composition according to claim 1 or 2 , which has been subjected to a surface treatment with a long-chain compound having a good alkyl group. The ultraviolet curable inkjet composition according to claim 3 , wherein the metal powder is subjected to a surface treatment with the long chain compound and then a surface treatment with the short chain compound. The ultraviolet curable inkjet composition according to any one of claims 1 to 4 , wherein the surface treatment is performed using a material selected from the group consisting of a silane coupling agent, a phosphate ester, and a carboxylic acid . . The ultraviolet curable inkjet composition according to any one of claims 1 to 5 , wherein the metal powder is subjected to a surface treatment with two or more different fluorine compounds. The metal powder, fluorine-based surface treatment with the compounds, the ultraviolet ray curable ink composition according to any one of claims 1 in which the surface-treated by a fluorine-free compound 6. The ultraviolet curable ink jet composition according to claim 1, wherein the fluorine-based compound has a perfluoroalkyl structure. It said metal powder is powder at least the surface is mainly composed of aluminum, claims 1 in which surface-treated with two or more different compounds to the ultraviolet ray curable ink composition according to any one of 8. The metal powder, ultraviolet ray curable ink composition according to any one of claims 1 in which forms a scaly 9. The ultraviolet curable inkjet composition according to any one of claims 1 to 10 , wherein an average particle size of the metal powder is 500 nm or more and 2.0 µm or less. Claims 1 and applied on the medium with ultraviolet curable ink jet composition as claimed in any one of 11, then, the production method of the recorded material and then irradiating ultraviolet rays.