JP2012188486A - Ultraviolet ray-curing type ink-jet composition, method for producing ultraviolet ray-curing type ink-jet composition and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet ray-curing type ink-jet composition capable of being suitably used for forming patterns excellent in storage stability and excellent in gloss feeling and abrasion resistance, to provide a production method by which the ultraviolet ray-curing type ink-jet composition can efficiently be produced, and to provide a record having a pattern formed using the ultraviolet ray-curing type ink-jet composition and excellent in gloss feeling and abrasion resistance.SOLUTION: The ultraviolet ray-curing type ink-jet composition that is discharged by an ink-jet method is characterized by containing a polymerizable compound and scary powder comprising an Fe-Si-Al alloy. The Fe-Si-Al alloy preferably comprises Fe as a main component, Si in an amount of 8.2-11.2 wt.% and Al in an amount of 4.0-7.0 wt.%.

Description

  The present invention relates to an ultraviolet curable inkjet composition, a method for producing an ultraviolet curable inkjet composition, and a recorded product.

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, compositions that cure when irradiated with ultraviolet rays (ultraviolet curable inkjet compositions) have been used in the ink jet method in order to achieve particularly excellent abrasion resistance, water resistance, solvent resistance, and the like. (For example, refer to Patent Document 1).
However, in the ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. In addition, the composition is inferior in stability and causes problems such as a decrease in ejection stability due to an increase in viscosity due to gelation.

JP 2009-57548 A

  An object of the present invention is to provide an ultraviolet curable inkjet composition that can be suitably used for forming a pattern (printed portion) having excellent storage stability, glossiness, and abrasion resistance, and the ultraviolet curing. A production method capable of efficiently producing a composition for a type inkjet, and a recorded matter having a pattern excellent in glossiness and abrasion resistance formed using the ultraviolet curable inkjet composition Is to provide.

Such an object is achieved by the present invention described below.
The ultraviolet curable inkjet composition of the present invention is an ultraviolet curable inkjet composition discharged by an inkjet method,
A polymerizable compound;
And a scaly powder composed of an Fe-Si-Al alloy.
Thereby, the ultraviolet curable inkjet composition which can be used suitably for formation of the pattern (printing part) excellent in glossiness and abrasion resistance can be provided.

In the ultraviolet curable inkjet composition of the present invention, the Fe—Si—Al alloy contains Fe as a main component, 8.2 wt% to 11.2 wt% Si, and 4.0 wt% to 7.0 wt%. % Of Al is preferably contained.
Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

In the ultraviolet curable inkjet composition of the present invention, the Fe—Si—Al alloy preferably has a sum of the content ratios of components other than Fe, Si and Al of 2.0 wt% or less.
Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

In the ultraviolet curable inkjet composition of the present invention, the powder is preferably obtained by scalyzing a powder produced by a water atomization method.
Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

In the ultraviolet curable inkjet composition of the present invention, the average particle size of the 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 inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that phenoxyethyl acrylate is included as the polymerizable compound.
As a result, the storage stability of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like.

In the ultraviolet curable inkjet composition of the present invention, as the polymerizable compound, in addition to the phenoxyethyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, And it is preferable that at least 1 sort (s) selected from the group which consists of 4-hydroxybutyl acrylate is included.
As a result, the storage stability of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that dimethylol tricyclodecane diacrylate and / or amino acrylate is included as the polymerizable compound.
As a result, the storage stability of the ultraviolet curable inkjet composition can be further improved, and the scratch resistance of the pattern to be formed can be further improved.

The method for producing an ultraviolet curable inkjet composition of the present invention is a method for producing an ultraviolet curable inkjet composition discharged by an inkjet method,
A powder production process for producing a powder composed of an Fe-Si-Al alloy by a water atomization method;
Agitation step of agitating the powder together with beads and scaling the powder;
And a mixing step of mixing the scaled powder with a polymerizable compound.
Thus, there is provided a method for producing an ultraviolet curable inkjet composition capable of efficiently producing an ultraviolet curable inkjet composition that can be suitably used for forming a pattern having excellent gloss and abrasion resistance. be able to.

In the method for producing an ultraviolet curable inkjet composition of the present invention, it is preferable that the scabling step is performed in the presence of phenoxyethyl acrylate.
Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable ink jet composition can be made particularly excellent. In addition, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be made particularly excellent.
The recorded matter of the present invention is produced by applying the ultraviolet curable ink jet composition of the present invention onto a recording medium and then irradiating with ultraviolet rays.
Thereby, it is possible to provide a recorded matter having a pattern (printing portion) excellent in glossiness and abrasion resistance.

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

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

  On the other hand, as a recording method on a recording medium using a composition containing a pigment or a dye, a recording method using an inkjet method is used. The ink jet method is excellent in that it can be suitably applied to formation of a fine pattern and recording on a curved surface portion. In recent years, compositions that cure when irradiated with ultraviolet rays (ultraviolet curable inkjet compositions) have been used in the ink jet method in order to achieve particularly excellent abrasion resistance, water resistance, solvent resistance, and the like. ing.

However, in the ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. In addition, the composition is inferior in 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 ink jet composition of the present invention includes a scaly powder composed of an Fe—Si—Al alloy as a metal powder together with a polymerizable compound.

  As described above, by including a scaly powder composed of an Fe—Si—Al alloy as a metal powder together with a polymerizable compound, the ultraviolet curable ink jet is enjoyed by the benefit of curing when irradiated with ultraviolet rays. Occurrence of problems that occur when a general metal powder is included in the composition for use can be reliably prevented. That is, it can be suitably used for the production of a recorded matter having a pattern (printing portion) excellent in storage stability of the ultraviolet curable ink jet composition and having excellent glossiness, abrasion resistance and the like.

<Powder (metal powder)>
As described above, the ultraviolet curable ink jet composition of the present invention includes a scaly powder composed of a Fe—Si—Al alloy as a powder (metal powder).
The Fe—Si—Al alloy constituting the metal powder may be any alloy as long as it has a composition containing Fe, Si, and Al, Fe as a main component, and 8.2 wt% or more and 11.2 wt% or less of Si, and It is preferable to contain 4.0 wt% or more and 7.0 wt% or less of Al. Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

  As described above, in the Fe-Si-Al alloy, Fe may be a main component (having the largest content in the constituent elements of the alloy), but the Fe content in the Fe-Si-Al alloy The rate is preferably 80.0 wt% or more and 87.8 wt% or less, more preferably 81.3 wt% or more and 86.8 wt% or less, and 82.5 wt% or more and 85.8 wt% or less. Further preferred. Thereby, the effects as described above can be exhibited more remarkably.

As described above, the Si content in the Fe-Si-Al alloy is preferably 8.2 wt% or more and 11.2 wt% or less, but is 8.7 wt% or more and 10.7 wt% or less. More preferably, it is 9.2 wt% or more and 10.2 wt% or less. Thereby, the effects as described above can be exhibited more remarkably.
As described above, the Al content in the Fe—Si—Al alloy is preferably 4.0 wt% or more and 7.0 wt% or less, but is 4.5 wt% or more and 6.5 wt% or less. Is more preferably 5.0 wt% or more and 6.0 wt% or less. Thereby, the effects as described above can be exhibited more remarkably.

  The Fe—Si—Al alloy may contain components other than Fe, Si, and Al, but the sum of the contents of components other than Fe, Si, and Al is 2.0 wt% or less. It is more preferable that it is 1.0 wt% or less, and it is more preferable that it is 0.6 wt% or less. Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

  The metal powder may be produced by any method, for example, a pulverization method for pulverizing a coarse powder obtained by pulverizing an ingot or the like to a desired particle size, vapor phase formation such as vapor deposition, and the like. A method of peeling and crushing a metal film formed on the film by a membrane method or the like (particularly a method of peeling and crushing in a liquid and dispersing in the liquid), a method of chemical granulation method, etc. However, in the present invention, the metal powder is preferably obtained by scaling a product produced by a water atomization method.

  In the water atomization method, a metal melted at high temperature is atomized into water, so the particles produced by the water atomization method have an oxide film on the surface, and have high chemical stability. The reactivity with is low. And such a property will be hold | maintained even after scaling up using a bead. As a result, it is possible to further improve the gloss and luxury of the recorded matter produced using the ultraviolet curable ink jet composition. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

  As described above, the metal powder constituting the ultraviolet curable ink jet composition of the present invention has a scaly shape. Since the metal powder has a scaly shape, on the recording medium to which the ultraviolet curable ink jet composition is applied by the ink jet method, the metal powder is arranged so that the main surface of the metal powder follows the surface shape of the recording medium. Powder can be placed. As a result, in combination with the fact that the metal powder is composed of an Fe—Si—Al alloy, the glossiness etc. inherent to the Fe—Si—Al alloy constituting the metal powder can be obtained in the recorded matter obtained. Can also be fully exerted. On the other hand, when the metal powder has a shape other than scaly, the metal powder will diffusely reflect the incident light on the recording medium, and the glossiness of the recorded matter is sufficiently excellent. Can not do it.

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 inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved. In the present invention, the average particle diameter refers to the average particle diameter based on the number, and the average of the diameters of perfect circles having the same area as the area S ₁ when observed from the direction in which the projected area is maximized. Refers to the value.

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

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

  Examples of the monomer as the polymerizable compound include isobornyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, phenoxyethyl acrylate, isooctyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, Benzyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate, tetrahydrofurfuryl acrylate , Ethyl carbitol acrylate, 2,2,2-trifluoroethyl acrylate, 2, , 2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, EO modified nonylphenol acrylate, 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 of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like.

  In addition to the phenoxyethyl acrylate, the ultraviolet curable inkjet composition includes 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and 4 as a polymerizable compound. It is preferable that it contains at least one selected from the group consisting of -hydroxybutyl acrylate. As a result, the storage stability of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like.

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

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

  When the ultraviolet curable ink jet composition contains a dispersant, the metal powder can have excellent dispersibility, and the ultraviolet curable ink jet composition has particularly excellent storage stability and ejection stability. It can be. 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, and more preferably 3 mPa · s or more and 15 mPa · s or less. Thereby, the droplet discharge by an inkjet method can be performed suitably.

<< Method for Producing UV-Curable Inkjet Composition >>
Next, the manufacturing method of the ultraviolet curable inkjet composition of this invention is demonstrated.
The method for producing the ultraviolet curable ink jet composition of the present embodiment includes a powder production step (1a) for producing a metal powder composed of an Fe—Si—Al alloy by a water atomizing method, and stirring the powder together with beads. A scale-up step (1b) for scaling the metal powder, a bead removal step (1c) for removing the beads used for scaling the metal powder, a classification step (1d) for classifying the metal powder, In addition, by using such a method having a mixing step (1e) in which the powder is mixed with a polymerizable compound, an ultraviolet curable type which can be suitably used for forming a pattern having excellent gloss and abrasion resistance. An ink jet composition can be produced efficiently.

<Powder manufacturing process>
In the production method of the present embodiment, first, metal powder composed of an Fe—Si—Al alloy is produced by a water atomization method (1a).
The metal powder may be produced by any method, but by being produced by the water atomization method, the discoloration or aggregation of the metal powder in the ultraviolet curable ink jet composition is more effective. Can be prevented.

<Scaling process>
The metal powder obtained as described above usually has a substantially spherical shape. When an ultraviolet curable inkjet composition containing a substantially spherical metal powder is used, incident light is irregularly reflected on the recording medium in a recorded matter produced using the ultraviolet curable inkjet composition. Therefore, the glossiness of the recorded material cannot be made sufficiently excellent.
Therefore, in the present embodiment, the metal powder obtained as described above is scaled (deformed).

Although this process may be performed by any method, it can be suitably performed by using a planetary ball mill. Thereby, the metal powder of the suitable shape (scale shape) as mentioned above can be obtained efficiently.
When this step is performed with a planetary ball mill, beads made of zirconia, alumina, chrome steel or the like can be used, but beads made of zirconia are preferably used. Thereby, the metal powder having a suitable shape (scale-like shape) as described above can be obtained more efficiently while more reliably preventing the metal powder from being modified. Moreover, it can suppress that the powder which is not a desired shape is formed, and the classification process after this process can be abbreviate | omitted or simplified.

  When this step is performed with a planetary ball mill, the size (diameter) of the beads is preferably 1 mm or more and 10 mm or less, and more preferably 3 mm or more and 7 mm or less. Thereby, the metal powder of the suitable shape (scale shape) as mentioned above can be obtained still more efficiently. Moreover, it can suppress that the powder which is not a desired shape is formed, and the classification process after this process can be abbreviate | omitted or simplified.

In this step, the treatment may be performed a plurality of times. For example, a first process using beads having a relatively large particle diameter and a second process using beads having a smaller particle diameter than the beads used in the first process may be performed.
In particular, this step is preferably performed in the presence of phenoxyethyl acrylate. Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable ink jet composition can be made particularly excellent. In addition, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be made particularly excellent.

<Bead removal process>
Next, the beads used for sizing the metal powder are removed. As a result, it is possible to prevent adverse effects caused by the inclusion of the beads in the finally obtained ultraviolet curable inkjet composition, and the glossiness of the recorded matter produced using the ultraviolet curable inkjet composition. (Aesthetic appearance) can be reliably improved.
The removal of the beads can be suitably performed by a method such as filtration and centrifugation.

<Classification process>
In the present embodiment, after the metal powder is scaled, the metal powder is classified. This makes it possible to sharpen the particle size distribution of the metal powder in the finally obtained ultraviolet curable inkjet composition, and to give glossiness to the recorded matter produced using the ultraviolet curable inkjet composition. (Aesthetic appearance) can be reliably improved.
<Mixing process>
Thereafter, the scaled metal powder is mixed with a polymerizable compound. Thereby, the ultraviolet curable ink jet composition as described above is obtained.

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

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

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

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

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

Next, specific examples of the present invention will be described.
[1] Production of inkjet composition (ultraviolet curable inkjet composition) (Example 1)
First, a metal powder having a spherical shape and an average particle diameter of 9.2 μm was manufactured by a water atomization method using a molten Fe—Si—Al alloy (powder manufacturing process). The manufactured metal powder had a composition of Fe: 84.9 wt%, Si: 9.9 wt%, and Al: 5.2 wt%.

Next, the substantially spherical metal powder obtained as described above was deformed (scaled) into a scaly shape by a planetary ball mill using zirconia beads (diameter: 5 mm) (scaling step). This step was performed in phenoxyethyl acrylate.
Next, the mixture obtained in the scaly process is introduced into an ultrasonic disperser, finely processed, and then filtered through a 5 μm membrane filter to remove zirconia beads and coarse particles of metal powder. Was cut to obtain a dispersion having an average particle diameter D50 of 0.8 μm.

  Next, the scaled metal powder was separated, and then phenoxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, Irgacure 819 as a photopolymerization initiator ( Ciba Japan Co., Ltd.), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, UV-3500 (manufactured by Big Chemie) as a leveling agent, and An ink jet composition (ultraviolet curable ink jet composition) was obtained by mixing with p-methoxyphenol as a polymerization inhibitor.

(Examples 2 to 10)
The same as in Example 1 except that the composition shown in Table 1 was obtained by changing the type and ratio of the raw materials used for the preparation of the inkjet composition (ultraviolet curable inkjet composition). Thus, an inkjet composition (ultraviolet curable inkjet composition) was produced.

(Comparative Example 1)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1 except that Ag powder was used in place of the Fe—Si—Al alloy powder as the metal powder.
(Comparative Example 2)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1 except that Al powder was used as the metal powder instead of the Fe-Si-Al alloy powder.

(Comparative Example 3)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1 except that a spherical powder that had not been scaled was used as the metal powder.
(Comparative Example 4)
Scale-like metal powder obtained in the same manner as in Example 1, 1,2-hexanediol, trimethylolpropane, Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.), triethanolamine, and glycerin A polyflow 401 (manufactured by Nissin Chemical Industry Co., Ltd.) and ion-exchanged water were mixed to produce an inkjet composition. That is, the inkjet composition of this comparative example does not contain a polymerizable compound that cures when irradiated with ultraviolet rays.

The composition of the ink jet composition for each of the above Examples and Comparative Examples is summarized in Table 1. In the table, phenoxyethyl acrylate is “PEA”, 2- (2-hydroxyethoxy) ethyl acrylate is “VEEA”, tripropylene glycol diacrylate is “TPGDA”, dipropylene glycol diacrylate is “DPGDA”, N -Vinylcaprolactam "VC", benzyl methacrylate "BM", dimethylol tricyclodecane diacrylate "DMTCDDA", amino acrylate "AA", urethane acrylate "UA", Irgacure 819 (manufactured by Ciba Japan) "Ic819", Speedcure TPO (manufactured by ACETO) is "scTPO", Speedcure DETX (manufactured by Lambson) is "scDETX", and UV-3500 (manufactured by BYK Chemie) is "UV3500" p-methoxyphenol is "pMP", 4-hydroxybutyl acrylate is "HBA", 1,2-hexanediol is "1,2HD", trimethylolpropane is "TMP", Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) ) Is indicated by “S465”, triethanolamine is indicated by “TEA”, glycerin is indicated by “GL”, and polyflow 401 (manufactured by Nissin Chemical Industry Co., Ltd.) is indicated by “PF401”. In addition, each of the arbitrary 10 metal particles contained in each inkjet composition is observed, and the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan) and 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 thereof is The results are shown in Table 1. In addition, the viscosity at 20 ° C. of the inkjet composition (ultraviolet curable inkjet composition) of each of the above examples measured using a vibration viscometer in accordance with JIS Z8809 is 3 mPa · s. The value was within the range of 15 mPa · s or less.

[2] Droplet discharge stability evaluation (discharge stability evaluation)
Using the ink jet compositions of the respective Examples and Comparative Examples, evaluations by the following tests were performed.
First, a droplet discharge device installed in a chamber (thermal chamber) and the ink jet compositions of the above examples and comparative examples were prepared, and the driving waveform of the piezoelectric element was optimized at 25 ° C. and 55%. Under the RH environment, for each color ink, 20000 (2000,000) droplets were continuously discharged from each nozzle of the droplet discharge head. Thereafter, the operation of the droplet discharge device was stopped, and the droplet discharge device was left in an environment of 25 ° C. and 55% RH for 120 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 0.09 μm.
B: The average value of the shift amount d is 0.09 μm or more and less than 0.15 μm.
C: The average value of the shift amount d is 0.15 μm or more and less than 0.18 μm.
D: The average value of the shift amounts d is 0.18 μm or more and less than 0.22 μm.
E: The average value of the shift amounts d is 0.22 μm or more.

[3] Storage stability evaluation of ink jet composition (long-term stability evaluation)
The ink jet compositions of the above Examples and Comparative Examples were allowed to stand for 30 days in an environment of 40 ° C., then visually observed and evaluated according to the following five-stage criteria.
A: No aggregation or sedimentation of the metal powder is observed.
B: Almost no aggregation or sedimentation of the metal powder is observed.
C: Slight aggregation / sedimentation of metal powder is observed.
D: Aggregation / sedimentation of metal powder is clearly observed.
E: Aggregation / sedimentation of metal powder is remarkably observed.

[4] Curability About the ink jet compositions of the respective Examples and Comparative Examples, the ink jet printer manufactured by Epson; introduced into PM800C, and Diafoil G440E (thickness 38 μm) manufactured by Mitsubishi Plastics Co., Ltd. was used as a base material. Then, solid printing was performed at an ink amount of 9 g / m ^2. Immediately after printing, an LED-UV lamp; Foseon's RX firefly (gap 6 mm 1000 mW / cm ² ) was used to irradiate ultraviolet rays for inkjet use. 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 matter An interior panel as a recorded matter was produced in the following manner for each of the Examples and Comparative Examples using the ink jet composition immediately after production.
First, the inkjet composition immediately after production was put into an inkjet apparatus.
Thereafter, an inkjet composition was discharged 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).

After that, 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 20 seconds, the ink jet composition on the substrate was cured, and the interior as a recorded matter I got a panel.
Using the method as described above, 10 interior panels (recorded materials) 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 materials) were produced in the same manner as described above, except that the molded compositions 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 300 or more.
B: Glossiness is 200 or more and less than 300.
C: Glossiness is 100 or more and less than 200.
D: Glossiness is less than 100.

[6.3] Scratch resistance For the recorded materials according to the respective examples and comparative examples, a rub resistance test was performed according to JIS K5701 using a Southerland Love Tester after 48 hours had passed since the production of the recorded materials. 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 10%.
B: The reduction rate of glossiness is 10% or more and less than 20%.
C: The reduction rate of glossiness is 20% or more and less than 30%.
D: The reduction rate of glossiness is 30% or more.

  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)

An ultraviolet curable ink jet composition discharged by an ink jet method,
A polymerizable compound;
An ultraviolet curable ink jet composition comprising: a scaly powder composed of an Fe-Si-Al alloy.   2. The Fe—Si—Al alloy containing Fe as a main component and containing 8.2 wt% or more and 11.2 wt% or less of Si and 4.0 wt% or more and 7.0 wt% or less of Al. UV curable ink jet composition.   3. The ultraviolet curable ink jet composition according to claim 1, wherein the Fe—Si—Al alloy has a total content of components other than Fe, Si, and Al of 2.0 wt% or less.   The ultraviolet curable inkjet composition according to any one of claims 1 to 3, wherein the powder is obtained by scaling a powder produced by a water atomization method.   The ultraviolet curable ink jet composition according to claim 1, wherein the powder has an average particle size of 500 nm to 2.0 μm.   The ultraviolet curable ink jet composition according to any one of claims 1 to 5, comprising phenoxyethyl acrylate as the polymerizable compound.   In addition to the 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 The composition for ultraviolet curable inkjets of Claim 6 containing at least 1 sort (s) which is made.   The ultraviolet curable ink jet composition according to any one of claims 1 to 7, comprising dimethylol tricyclodecane diacrylate and / or amino acrylate as the polymerizable compound. A method for producing an ultraviolet curable inkjet composition ejected by an inkjet method,
A powder production process for producing a powder composed of an Fe-Si-Al alloy by a water atomization method;
Agitation step of agitating the powder together with beads and scaling the powder;
A method for producing an ultraviolet curable ink jet composition, comprising a mixing step of mixing the scaled powder with a polymerizable compound.   The method for producing an ultraviolet curable ink jet composition according to claim 9, wherein the scaly step is performed in the presence of phenoxyethyl acrylate.   A recorded matter produced by applying the ultraviolet ray curable ink jet composition according to claim 1 onto a recording medium and then irradiating with ultraviolet rays.