JP2012193262A - Powder, ultraviolet light-curing type inkjet composition, method for producing recorded matter, and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide recorded matter including a pattern (printed part) excellent in glossy feeling and scuff resistance, a method of production, capable of producing such recorded matter in a good efficiency, an ultraviolet light-curing type inkjet composition capable of suitably being used for producing such recorded matter, and also powder used for producing such ultraviolet light-curing type inkjet composition.SOLUTION: This ultraviolet light-curing type inkjet composition ejected by an inkjet method is characterized by including a polymerizable compound and scale-formed powder, wherein the powder includes an Al layer constituted with Al and a ferromagnetic layer having ferromagnetism.

Description

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

Conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.
However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion.
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. There is.

JP 2009-57548 A

  An object of the present invention is to provide a recorded matter provided with a pattern (printing portion) excellent in glossiness and abrasion resistance, to provide a production method capable of efficiently producing the recorded matter, It is providing the ultraviolet curable inkjet composition which can be used suitably for manufacture of a thing, and providing the powder used for manufacture of the said ultraviolet curable inkjet composition.

Such an object is achieved by the present invention described below.
The powder of the present invention is a powder used for producing an ultraviolet curable ink jet composition discharged by an ink jet method,
Scaly,
An Al layer composed of Al and a ferromagnetic layer having ferromagnetism are provided.
Thereby, the powder for ultraviolet curable inkjet compositions which can be used suitably for manufacture of the recorded matter provided with the pattern (printing part) excellent in glossiness and abrasion resistance can be provided.

The powder of the present invention preferably includes the Al layer on both sides of the ferromagnetic layer.
Thereby, the glossiness and high-class feeling of the pattern (printing part) formed using an ultraviolet curable inkjet composition can be made especially excellent.
In the powder of the present invention, the ferromagnetic layer is preferably composed of an Fe—Si—Al alloy.
Thereby, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more reliably and suitably arranged, and the pattern (printing) formed using the ultraviolet curable ink-jet composition. Part) can be more reliably improved in glossiness. Further, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion. Moreover, even if the powder has an Al layer provided only on one surface side of the ferromagnetic layer, the glossiness and luxury of the pattern (printed portion) formed using the ultraviolet curable ink jet composition. Can be made particularly excellent. In addition, when the powder is provided with an Al layer only on one surface side of the ferromagnetic layer, the storage stability and ejection stability of the ultraviolet curable inkjet composition may be particularly excellent. And the productivity of recorded matter can be made particularly excellent.

In the powder of the present invention, the Fe—Si—Al alloy contains Fe as a main component, 8.2 mass% to 11.2 mass% Si, and 4.0 mass% to 7.0 mass%. It is preferable that Al is included.
Thereby, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more surely and suitably arranged, and the pattern (printing) formed using the ultraviolet-curable ink jet composition. Part) can be more reliably improved in glossiness. Moreover, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion. Moreover, even if the powder has an Al layer provided only on one surface side of the ferromagnetic layer, the glossiness and luxury of the pattern (printed portion) formed using the ultraviolet curable ink jet composition. Can be further improved. Further, when the powder is provided with an Al layer only on one surface side of the ferromagnetic layer, the storage stability and ejection stability of the ultraviolet curable inkjet composition may be further improved. In addition, the productivity of recorded matter can be further improved.

In the powder of the present invention, the Fe—Si—Al alloy preferably has a total content of components other than Fe, Si and Al of 2.0% by mass or less.
Thereby, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more surely and suitably arranged, and the pattern (printing) formed using the ultraviolet-curable ink jet composition. Part) can be more reliably improved in glossiness. Moreover, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion. Moreover, even if the powder has an Al layer provided only on one surface side of the ferromagnetic layer, the glossiness and luxury of the pattern (printed portion) formed using the ultraviolet curable ink jet composition. Can be further improved. Further, when the powder is provided with an Al layer only on one surface side of the ferromagnetic layer, the storage stability and ejection stability of the ultraviolet curable inkjet composition may be further improved. In addition, the productivity of recorded matter can be further improved.

In the powder of the present invention, the average particle size is preferably 500 nm or more and 2.0 μm or less.
Thereby, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more surely and suitably arranged, and the pattern (printing) formed using the ultraviolet-curable ink jet composition. Part) can be more reliably improved in glossiness. Moreover, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion.

In the powder of the present invention, the average thickness of the Al layer is preferably 5 nm or more and 250 nm or less.
This makes it possible to more effectively express the glossiness inherent in Al in the pattern (printing part) formed using the UV curable ink jet composition while ensuring the function of the ferromagnetic layer. Can be made.

In the powder of the present invention, the powder is formed by a vapor deposition method to form a laminated body in which a layer made of a ferromagnetic material and a layer made of Al are laminated, and then the laminated body is pulverized. It is preferable that it was obtained by.
This makes it possible to more effectively express the glossiness inherent in Al in the pattern (printing part) formed using the UV curable ink jet composition while ensuring the function of the ferromagnetic layer. Can be made. Moreover, the dispersion | variation in the characteristic between each particle | grain can be suppressed.

The ultraviolet curable inkjet composition of the present invention is an ultraviolet curable inkjet composition discharged by an inkjet method,
Including a polymerizable compound and a scaly powder,
The powder includes a powder comprising an Al layer made of Al and a ferromagnetic layer having ferromagnetism.
Thereby, the ultraviolet curable inkjet composition which can be used suitably for manufacture of the recorded matter provided with the pattern (printing part) excellent in glossiness and abrasion resistance can be provided.

In the ultraviolet curable inkjet composition of the present invention, the ultraviolet curable inkjet composition preferably contains phenoxyethyl acrylate as the polymerizable compound.
Thereby, while making the storage 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 the recorded matter is particularly excellent. In addition, the rub resistance of the formed pattern can be made particularly excellent. Further, the powder can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, the ultraviolet curable inkjet composition includes, as the polymerizable compound, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate in addition to the phenoxyethyl acrylate. It is preferable that it contains at least one selected from the group consisting of acrylate, tripropylene glycol diacrylate, and 4-hydroxybutyl acrylate.
As a result, the storage stability of the ultraviolet curable inkjet composition is excellent, the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is further improved, and the productivity of recorded matter is further improved. In addition, the rub resistance of the formed pattern can be further improved. In addition, the powder can be arranged more suitably, and the gloss and high quality of the recorded matter can be further improved.

In the ultraviolet curable inkjet composition of the present invention, the ultraviolet curable inkjet composition preferably contains dimethylol tricyclodecane diacrylate and / or amino acrylate as the polymerizable compound.
As a result, the storage stability of the ultraviolet curable ink jet composition can be further improved, and the scratch resistance of the formed pattern can be further improved. Further, the powder can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

A method for producing a recorded material according to the present invention is a method for producing an ultraviolet curable inkjet composition containing a powder comprising an Al layer composed of Al having a scale shape and a ferromagnetic layer having ferromagnetism, and a polymerizable compound, and an inkjet method. A composition applying step to be applied to the recording medium by:
An alignment step of arranging the powder constituting the ultraviolet curable inkjet composition applied to the recording medium by magnetic force;
And a polymerization step of polymerizing the polymerizable compound by irradiating with ultraviolet rays.
Thereby, the manufacturing method which can manufacture efficiently the recorded matter provided with the pattern (printing part) excellent in glossiness and abrasion resistance can be provided.

In the method for producing a recorded matter of the present invention, in the arranging step, it is preferable to apply a magnetic force so that the powder is arranged on the outer surface side of the ultraviolet curable inkjet composition applied to the recording medium. .
Thereby, it is possible to further improve the gloss and luxury of the recorded matter finally obtained.
The recorded matter of the present invention is manufactured using the method of the present invention.
Thereby, the recorded matter provided with the pattern (printing part) excellent in glossiness and abrasion resistance can be provided.

It is a perspective view which shows the droplet discharge apparatus used for manufacture of a recorded matter.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<Powder>
First, the powder of the present invention (powder for ultraviolet curable ink jet composition) will be described.
The powder of the present invention is used for the production of an ultraviolet curable ink jet composition ejected by an ink jet method, and has a scaly shape, an Al layer composed of Al, a ferromagnetic layer having ferromagnetism, and Is provided.

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, 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. There is.

  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, in the present invention, the powder for the ultraviolet curable ink jet composition is provided with an Al layer composed of Al and composed of Al and a ferromagnetic layer having ferromagnetism. Thereby, by applying a magnetic force to the ultraviolet curable ink jet composition applied to the recording medium, the powder constituting the ultraviolet curable ink jet composition can be arranged. A recorded matter having a pattern (printing portion) excellent in rubbing property can be efficiently produced. This can prevent a decrease in glossiness due to diffused reflection of light by arranging the powder, and prevent the formation of unintentional protrusions due to curing in a state where the powder stands up. It is thought that it is because it can do.

  As described above, the powder has a scaly shape. When the powder has a scale shape, the powder constituting the ultraviolet curable inkjet composition can be suitably arranged (oriented) on the recording medium. On the other hand, when the powder has a shape other than the scale shape, the powder will diffusely reflect the incident light on the recording medium, and the glossiness of the recorded material shall be sufficiently excellent. I can't.

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.

As described above, the powder according to the present invention includes an Al layer composed of Al and a ferromagnetic layer having ferromagnetism.
The Al layer mainly affects the glossiness of the pattern (printed portion) formed using the ultraviolet curable ink jet composition.
The Al layer may be provided on at least one side of the ferromagnetic layer, but is preferably provided on both sides of the ferromagnetic layer. Thereby, the glossiness and high-class feeling of the pattern (printing part) formed using an ultraviolet curable inkjet composition can be made especially excellent.

  The average thickness of the Al layer is preferably 5 nm or more and 250 nm or less, and more preferably 10 nm or more and 150 nm or less. When the average thickness of the Al layer is within the above range, in the pattern (printing portion) formed using the ultraviolet curable ink jet composition, the function of the ferromagnetic layer is surely exhibited, and Al is originally The glossiness etc. which it has can be expressed more effectively.

The Al layer only needs to be mainly composed of Al. For example, the Al layer may contain other components other than Al as long as the characteristics inherent to metallic aluminum are not impaired. In this case, the content of components other than Al in the Al layer is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 0.5% by mass or less.
The ferromagnetic layer is preferably composed of a material containing Fe. Since the material containing Fe generally shows high ferromagnetism, the powder can be more suitably arranged in the finally obtained recorded matter.

  In particular, the ferromagnetic layer is preferably composed of an Fe—Si—Al alloy. Thereby, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more reliably and suitably arranged, and the pattern (printing) formed using the ultraviolet curable ink-jet composition. Part) can be more reliably improved in glossiness. Further, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion. Moreover, even if the powder has an Al layer provided only on one surface side of the ferromagnetic layer, the glossiness and luxury of the pattern (printed portion) formed using the ultraviolet curable ink jet composition. Can be made particularly excellent. In addition, when the powder is provided with an Al layer only on one surface side of the ferromagnetic layer, the storage stability and ejection stability of the ultraviolet curable inkjet composition may be particularly excellent. And the productivity of recorded matter can be made particularly excellent.

  When the ferromagnetic layer is composed of an Fe-Si-Al alloy, the Fe-Si-Al alloy has Fe as a main component, 8.2 mass% to 11.2 mass% Si, and It is preferable to contain 4.0 mass% or more and 7.0 mass% or less of Al. Thereby, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more surely and suitably arranged, and the pattern (printing) formed using the ultraviolet-curable ink jet composition. Part) can be more reliably improved in glossiness. Moreover, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion. Moreover, even if the powder has an Al layer provided only on one surface side of the ferromagnetic layer, the glossiness and luxury of the pattern (printed portion) formed using the ultraviolet curable ink jet composition. Can be further improved. Further, when the powder is provided with an Al layer only on one surface side of the ferromagnetic layer, the storage stability and ejection stability of the ultraviolet curable inkjet composition may be further improved. In addition, the productivity of recorded matter can be further improved.

  As described above, in the Fe—Si—Al alloy, Fe is preferably the main component (having the largest content in the constituent elements of the alloy), but the Fe content in the Fe—Si—Al alloy is preferable. The content is preferably 80.0 mass% or more and 87.8 mass% or less, more preferably 81.3 mass% or more and 86.8 mass% or less, and 82.5 mass% or more and 85.8 mass% or less. More preferably, it is at most mass%. 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% by mass or more and 11.2% by mass or less, but 8.7% by mass or more and 10.7% by mass. % Or less, more preferably 9.2% by mass or more and 10.2% by mass 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% by mass or more and 7.0% by mass or less, but 4.5% by mass or more and 6.5% by mass. % Or less is more preferable, and 5.0 mass% or more and 6.0 mass% or less is further more preferable. 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 mass% or less. It is preferable that it is 1.0% by mass or less, more preferably 0.6% by mass or less. Thereby, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more surely and suitably arranged, and the pattern (printing) formed using the ultraviolet-curable ink jet composition. Part) can be more reliably improved in glossiness. Moreover, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion. Moreover, even if the powder has an Al layer provided only on one surface side of the ferromagnetic layer, the glossiness and luxury of the pattern (printed portion) formed using the ultraviolet curable ink jet composition. Can be further improved. Further, when the powder is provided with an Al layer only on one surface side of the ferromagnetic layer, the storage stability and ejection stability of the ultraviolet curable inkjet composition may be further improved. In addition, the productivity of recorded matter can be further improved.

The powder may be such that the ferromagnetic layer and the Al layer are in contact with each other, and at least one intermediate layer may be provided therebetween.
The average particle size of the 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, in the pattern (printing part) formed using the ultraviolet curable ink-jet composition, the powder can be more surely and suitably arranged, and the pattern (printing) formed using the ultraviolet-curable ink jet composition. Part) can be more reliably improved in glossiness. Moreover, even when the thickness of the powder (Al layer) is relatively thin, it is possible to more reliably prevent the color tone of the ferromagnetic layer from adversely affecting the appearance of the printed portion. 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.

  The powder may be manufactured by any method, but a vapor-phase film-forming method is used to form a laminate in which a layer composed of a ferromagnetic material and a layer composed of Al are laminated. Then, it is preferable to be obtained by pulverizing the laminate. This makes it possible to more effectively express the glossiness inherent in Al in the pattern (printing part) formed using the UV curable ink jet composition while ensuring the function of the ferromagnetic layer. Can be made. Moreover, the dispersion | variation in the characteristic between each particle | grain can be suppressed. Moreover, even if it is a comparatively thin powder, it can manufacture suitably by using the said method.

When producing a powder using such a method, for example, it is possible to suitably produce a powder by sequentially forming a film on a substrate so as to correspond to the layer structure of the powder to be produced. it can. 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 laminated body in a liquid. As a result, it is possible to easily and reliably obtain a powder having the above-mentioned particle size without destroying the laminated structure as described above, and to generate variations in size, shape, and characteristics among the particles. Can be suppressed.

  When the pulverization is performed by the above method, the liquid includes alcohols such as methanol, ethanol, propanol, and butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, and cymene. , Durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene and other hydrocarbon compounds, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether , 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane and the like ether compounds Furthermore, polar compounds such as propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dimethyl sulfoxide, cyclohexanone, and acetonitrile are preferably used. be able to. By using such a liquid, while preventing unintentional oxidation or the like of the Al layer, the productivity of the powder is made particularly excellent, and the variation in size, shape, and characteristics among the particles is particularly significant. It can be small.

<< UV curable inkjet composition >>
Next, the ultraviolet curable inkjet composition of the present invention will be described.
The ultraviolet curable ink jet composition of the present invention is ejected by an ink jet method, and contains a polymerizable compound and the above-described powder. Thereby, the ultraviolet curable inkjet composition which can be used suitably for manufacture of the recorded matter provided with the pattern (printing part) excellent in glossiness and abrasion resistance can be provided.

<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. In addition, since the polymerizable compound is cured, the powder arranged (orientated) as described above can be fixed, so that the glossiness of the recorded matter can be stably improved.

  The polymerizable compound is in a liquid state, and preferably functions as a dispersion medium for dispersing the 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. Thereby, while making the storage 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 the recorded matter is particularly excellent. In addition, the rub resistance of the formed pattern can be made particularly excellent. Further, the powder can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter 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 of the ultraviolet curable inkjet composition is excellent, the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is further improved, and the productivity of recorded matter is further improved. In addition, the rub resistance of the formed pattern can be further improved. In addition, the powder can be arranged more suitably, and the gloss and high quality of the recorded matter can be further improved.

  Moreover, it is preferable that an ultraviolet curable inkjet composition contains dimethylol tricyclodecane diacrylate and / or aminoacrylate as a polymeric compound. As a result, the storage stability of the ultraviolet curable ink jet composition can be further improved, and the scratch resistance of the formed pattern can be further improved. Further, the powder can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

  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 according to the present embodiment may include components other than those described above (other components). Such components include, for example, photopolymerization initiators, slip agents (leveling agents), dispersants, polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), colorants, fixing agents, anti-blocking agents. Examples include glazes, preservatives, antioxidants, chelating agents, thickeners, and sensitizers (sensitizing dyes).

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

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

  Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine. , Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl Oxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. 1 type or 2 types or more selected from these can be used in combination.

The content of the photopolymerization initiator in the ultraviolet curable inkjet composition is preferably 0.5% by mass or more and 10% by mass or less. When the content of the photopolymerization initiator is within the above range, the ultraviolet curing rate is sufficiently high, and the photopolymerization initiator is hardly dissolved or colored due to the photopolymerization initiator.
When the ultraviolet curable inkjet composition contains a slip agent, the surface of the recorded matter becomes smooth due to the leveling action, and the abrasion resistance is improved.

Although it does not specifically limit as a slip agent, For example, silicone type surfactants, such as polyester modified silicone and polyether modified silicone, can be used, It is preferable to use polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane. .
When the ultraviolet curable inkjet composition contains a dispersant, the dispersibility of the powder can be improved, and the storage stability and ejection stability of the ultraviolet curable inkjet composition should be particularly excellent. Can do. 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.
Further, the ultraviolet curable inkjet composition of the present invention may be any material that has a scaly shape and contains a powder comprising an Al layer composed of Al and a ferromagnetic layer having ferromagnetism. It may also contain a powder having the following structure.

<Method for producing recorded matter>
Next, the manufacturing method of the recorded matter of the present invention will be described.
FIG. 1 is a perspective view showing a droplet discharge device used for manufacturing a recorded matter.
A method for producing a recorded material according to the present invention is a method for producing an ultraviolet curable inkjet composition containing a powder comprising an Al layer composed of Al having a scale shape and a ferromagnetic layer having ferromagnetism, and a polymerizable compound, and an inkjet method. The composition applying step (1a) applied to the recording medium by the above, the arranging step (1b) for arranging the powder constituting the ultraviolet curable ink jet composition applied to the recording medium by magnetic force, and ultraviolet irradiation A polymerization step (1c) for polymerizing the polymerizable compound. Thereby, the manufacturing method which can manufacture efficiently the recorded matter provided with the pattern (printing part) excellent in glossiness and abrasion resistance can be provided.

<Composition application process>
First, the ultraviolet curable inkjet composition 2 as described above is applied to the recording medium 11 by an inkjet method (1a).
As an ink jet method (droplet discharge method), for example, a piezo method or a method of discharging ink by bubbles generated by heating the ink can be used. From the viewpoint of the difficulty of alteration 2 and the like, the piezo method is preferable.

In the following description, it is assumed that the ultraviolet curable inkjet composition is discharged using a droplet discharge apparatus as shown in FIG.
As shown in FIG. 1, a droplet discharge device 100 used in this step includes a tank 101 that holds an ultraviolet curable inkjet composition 2, a tube 110, and an ultraviolet curable inkjet composition from the tank 101 via the tube 110. 2 and a discharge scanning unit 102 to which 2 is supplied. The ejection scanning unit 102 includes a droplet ejection unit 103 in which a plurality of droplet ejection heads (inkjet heads) are mounted on a carriage, and a first position control device 104 (moving unit) that controls the position of the droplet ejection unit 103. A stage 106 that holds the recording medium (base material) 11, a second position control device 108 (moving means) that controls the position of the stage 106, and a control means 112. The tank 101 and the plurality of droplet discharge heads in the droplet discharge means 103 are connected by a tube 110, and the ultraviolet curable inkjet composition 2 is compressed by compressed air from the tank 101 to each of the plurality of droplet discharge heads. Supplied.

  The first position control device 104 moves the droplet discharge means 103 along the X-axis direction and the Z-axis direction orthogonal to the X-axis direction in response to a signal from the control means 112. Further, the first position control device 104 also has a function of rotating the droplet discharge means 103 around an axis parallel to the Z axis. In the present embodiment, the Z-axis direction is a direction parallel to the vertical direction (that is, the direction of gravitational acceleration). The second position controller 108 moves the stage 106 along the Y-axis direction orthogonal to both the X-axis direction and the Z-axis direction in response to a signal from the control unit 112. Further, the second position control device 108 also has a function of rotating the stage 106 around an axis parallel to the Z axis.

The stage 106 has a plane parallel to both the X-axis direction and the Y-axis direction. The stage 106 is configured so that the recording medium 11 to which the ultraviolet curable inkjet composition 2 is to be applied can be fixed or held on the plane.
As described above, the droplet discharge means 103 is moved in the X-axis direction by the first position control device 104. On the other hand, the stage 106 is moved in the Y-axis direction by the second position control device 108. That is, the first position control device 104 and the second position control device 108 change the relative position of the droplet discharge head with respect to the stage 106 (the recording medium 11 held on the stage 106 and the droplet discharge means 103 are relative to each other). To go to).
The control means 112 is configured to receive ejection data representing a relative position at which the ultraviolet curable inkjet composition 2 is to be ejected from an external information processing apparatus.

The ultraviolet curable inkjet composition 2 is applied to the recording medium 11 using the droplet discharge device 100 as described above. By using the apparatus as described above, the ultraviolet curable inkjet composition 2 can be efficiently and selectively applied to a desired portion of the recording medium 11. In the configuration shown in the figure, the droplet discharge device 100 has only one set of the tank 101, the tube 110, and the like corresponding to one type of the ultraviolet curable inkjet composition 2, but these members are You may have only the part of multiple types of ultraviolet curable inkjet composition 2. FIG. In the production of recorded matter, a plurality of droplet discharge devices 100 corresponding to a plurality of types of ultraviolet curable inkjet compositions 2 may be used.
In the present invention, the droplet discharge head may use a piezo element or an electrostatic actuator as a drive element. The droplet discharge head may be configured to use an electrothermal conversion element as a drive element and to discharge the ultraviolet curable ink jet composition using thermal expansion of a material by the electrothermal conversion element.

<Sequence process>
Next, the powder which comprises the ultraviolet curable inkjet composition 2 provided to the recording medium 11 by a magnetic force is arranged (1b).
In this step, for example, the powder can be arranged using a magnet. As the magnet, a permanent magnet or an electromagnet may be used.
When the ferromagnetic layer of the powder is composed of a magnet (magnetized material), the powder is arranged using a member composed of a non-magnetized ferromagnetic material (for example, iron). May be.

The direction of the magnetic force applied to the powder in this step may be constant or may change over time (for example, an alternating magnetic field).
Further, the direction of the magnetic force (direction of the magnetic force lines) applied to the powder in this step may be any direction, but is preferably substantially parallel to the normal direction of the recording medium 11. Specifically, the angle formed between the direction of the magnetic force acting on the powder in this step (the direction of the line of magnetic force) and the normal direction of the portion to which the ultraviolet curable inkjet composition 2 of the recording medium 11 is applied is 10 °. It is preferably below, more preferably 5 ° or below. As a result, the main surface of the scaly powder constituting the ultraviolet curable inkjet composition 2 can be more reliably arranged so as to be substantially parallel to the surface of the recording medium 11, and the finally obtained recording The glossiness of the object can be made particularly excellent.
In this step, it is preferable to apply a magnetic force so that the powder is arranged on the outer surface side of the ultraviolet curable inkjet composition 2 applied to the recording medium 11. Thereby, it is possible to further improve the gloss and luxury of the recorded matter finally obtained.

In the following description, a case where a magnetic field is applied to powder using a magnetic field generator (for example, a permanent magnet or an electromagnet) will be mainly described.
The maximum intensity (absolute value) of a magnetic field generated by a magnetic field generator (for example, a permanent magnet or an electromagnet) that applies a magnetic field to the ultraviolet curable inkjet composition 2 applied to the recording medium 11 is not particularly limited. It is preferably 1 to 10000 Gs, more preferably 1000 to 5000 Gs. This makes it possible to arrange the powder more suitably while making the productivity of the recorded matter particularly excellent, and the glossiness of the finally obtained recorded matter can be made particularly excellent.

  The distance (shortest distance) between the magnetic field generator and the surface of the recording medium 11 to which the ultraviolet curable inkjet composition 2 is applied is not particularly limited, but is preferably 1 cm or more and 100 cm or less, for example. More preferably, it is 50 cm or less. This makes it possible to arrange the powder more suitably while making the productivity of the recorded matter particularly excellent, and the glossiness of the finally obtained recorded matter can be made particularly excellent.

  The orientation of the powder by magnetic force may be performed after the ultraviolet curable inkjet composition 2 is applied to the recording medium 11, but the liquid of the ultraviolet curable inkjet composition 2 discharged from the droplet discharge device 100 is used. It may be performed before the droplets land on the surface of the recording medium 11. Thereby, since the orientation of the powder in the droplets can be controlled, the arrangement of the droplets after landing on the recording medium 11 can be made more suitable.

<Polymerization process>
Thereafter, the polymerizable compound constituting the ultraviolet curable inkjet composition 2 applied to the recording medium 11 is cured by irradiating ultraviolet rays (1c). Thereby, a recorded matter is obtained.
In the present invention, before the polymerizable compound is cured, the powder constituting the ultraviolet curable inkjet composition 2 is in a state of being arranged by a magnetic force. Therefore, in this step, the powder is arranged in a predetermined direction. In this state, the polymerizable compound is cured, and the powder is fixed in this direction. And although the powder which comprises the ultraviolet curable inkjet composition 2 has an Al layer comprised with Al, Al originally has the outstanding glossiness (metallic luster). Therefore, by arranging such powders, irregular reflection of light is prevented, and as a result, the recorded matter has an excellent gloss.

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.
In addition, you may perform this process, making a magnetic force act. Thereby, the ultraviolet curable inkjet composition 2 can be cured without disturbing the arrangement state of the powder arranged in the arrangement step, and the gloss of the recorded matter is made particularly excellent. it can.

《Recordings》
Next, the recorded matter of the present invention will be described.
The recorded matter of the present invention is manufactured using the method as described above. Such a recorded matter has a pattern (printing portion) excellent in glossiness and abrasion resistance.
As described above, the ultraviolet curable inkjet composition according to the present invention contains a polymerizable compound and has excellent adhesion to a recording medium. As described above, since the ultraviolet curable inkjet composition according to 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 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 film made of polyethylene terephthalate having a smooth surface (surface roughness Ra of 0.02 μm or less) was prepared.

Next, silicone oil was applied to the entire one surface of the film.
Next, a first Al layer made of Al, a ferromagnetic layer made of Fe-Si-Al alloy, and a second made of Al are formed on the surface side coated with silicone oil by vapor deposition. Al layers were sequentially formed to obtain a laminate. Each of the first Al layer and the second Al layer had an average thickness of 20 nm. The average thickness of the ferromagnetic layer was 20 nm. The ferromagnetic layer had a composition of Fe: 84.9% by mass, Si: 9.9% by mass, and Al: 5.2% by mass.

Next, the polyethylene terephthalate film (base material) on which the laminate was formed was placed in a liquid composed of diethylene glycol diethyl ether, and ultrasonic vibration was applied. Thus, a scaly powder composed of the first Al layer, the ferromagnetic layer, and the second Al layer was obtained. The average particle size of the powder was 0.8 μm.
Next, the powder is separated from the above liquid, and then phenoxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, 4-hydroxybutyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, photopolymerization start Irgacure 819 (manufactured by Ciba Japan) as a photoinitiator, Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, UV-3500 (manufactured by BYK Chemie) as a leveling agent Manufactured) and p-methoxyphenol as a polymerization inhibitor was mixed to obtain an ink jet composition (ultraviolet curable ink jet composition).

(Examples 2 to 11)
Example 1 except that the composition of the powder used for the preparation of the inkjet composition (ultraviolet curable inkjet composition) and the type and ratio of the raw materials were changed so that the composition shown in Table 1 was obtained. In the same manner, an inkjet composition (ultraviolet curable inkjet composition) was produced.

(Comparative Example 1)
An ink jet composition (ultraviolet curable ink jet composition) was produced in the same manner as in Example 1 except that powder composed of Ag and not having a laminated structure was used.
(Comparative Example 2)
An ink jet composition (ultraviolet curable ink jet composition) was produced in the same manner as in Example 1 except that powder composed of Al and having no laminated structure was used.

(Comparative Example 3)
A powder composed of an Fe—Si—Al alloy (having a composition of Fe: 84.9% by mass, Si: 9.9% by mass, Al: 5.2% by mass) and having no laminated structure An ink jet composition (ultraviolet curable ink jet composition) was produced in the same manner as in Example 1 except that it was used.
(Comparative Example 4)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Comparative Example 2 except that a spherical Al powder produced using a gas atomization method was used as the powder.

(Comparative Example 5)
Scale-like 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 Inkjet composition was manufactured by mixing Polyflow 401 (manufactured by Nissin Chemical Industry Co., Ltd.) and ion-exchanged water. That is, the inkjet composition of this comparative example does not contain a polymerizable compound that is cured by irradiation with ultraviolet rays.

Table 1 summarizes the composition of the ink jet composition for each of the above Examples and Comparative Examples. 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, the observation is performed on each of the 10 arbitrary metal particles contained in each inkjet composition, and the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan), The ratio (S ₁ / S ₀ ) to the area S ₀ [μm ² ] when observed from the direction in which the area when observed is the maximum among the directions orthogonal to the observation direction is determined, and the average value of these is expressed as It was shown together with 1. In Comparative Example 1, the conditions for the layer made of Ag are shown in the column of the ferromagnetic layer. 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. Moreover, in each layer of the powder which comprises the inkjet composition of each said Example and a comparative example, all content other than the component shown in Table 1 was 0.1 mass% 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 inkjet compositions of the examples and comparative examples were prepared, and the driving waveform of the piezoelectric element was optimized, and the environment at 25 ° C. and 55% RH. Below, 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.

  Thereafter, 4 million droplets (4000000 droplets) were continuously discharged from each nozzle of the droplet discharge head in an environment of 25 ° C. and 55% RH. For the 4000000 droplets ejected from the designated nozzle near the center of the droplet ejection head after being left for 120 hours, the average deviation amount d from the center aiming position of the center position of each landed droplet Values were obtained and evaluated according to the following five-step criteria. It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amount d is less than 0.10 μm.
B: The average value of the shift amounts d is 0.10 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 0.27 μm.
D: The average value of the shift amounts d is 0.27 μm or more and less than 0.33 μm.
E: The average value of the shift amounts d is 0.33 μm or more.

[3] Storage stability evaluation of inkjet composition (long-term stability evaluation)
About the inkjet composition of each said Example and comparative example, after leaving it to stand in 35 degreeC environment for 14 days, visual observation was performed and it evaluated according to the following 5 steps | paragraphs of criteria.
A: Aggregation / sedimentation of the powder is not recognized at all.
B: Almost no aggregation or sedimentation of powder is observed.
C: Slight aggregation / sedimentation of powder is observed.
D: Agglomeration and sedimentation of powder are clearly recognized.
E: Agglomeration / sedimentation of powder is noticeable.

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

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

[5] Manufacture of Recorded Items For each example, an interior panel as a recorded product was manufactured as follows using the inkjet composition (ultraviolet curable inkjet composition) immediately after manufacture, respectively.
First, the ink jet composition immediately after production was put into an ink jet apparatus.

Thereafter, an ink jet composition was ejected in a predetermined pattern onto a recording medium having a curved surface portion formed using polycarbonate (manufactured by Asahi Glass Co., Ltd., Carboglass polish 2 mm thick) (composition applying step).
After that, a permanent magnet (magnetic flux density: 2000 Gs) having the same surface shape as the surface of the recording medium (surface to which the ink jet composition is applied) is installed on the surface of the recording medium (surface to which the ink jet composition is applied). Then, the powder contained in the ink jet composition applied on the recording medium was arranged so that the direction of the magnetic force line was parallel to the normal direction of the recording medium (arrangement step). At this time, the distance between the surface of the permanent magnet and the surface of the recording medium was set to 10 cm.

After that, with the permanent magnet installed, the ultraviolet ray of the spectrum having the maximum value at wavelengths of 365 nm, 380 nm, and 395 nm is irradiated, and the irradiation intensity of 180 mW / cm ² is irradiated for 20 seconds to cure the ink jet composition on the recording medium. To obtain an interior panel as a record.
Ten interior panels (recorded matter) were manufactured using the method as described above.

Also, a recording medium formed using polyethylene terephthalate (Diafoil G440E 38 μm thickness manufactured by Mitsubishi Plastics), low-density polyethylene (T.U.X (L-LDPE) HC-E # 80 manufactured by Mitsui Chemicals, Inc.) ), 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 molded ones were used.
For each comparative example, an interior panel (recorded material) was produced using the ink jet composition immediately after production in the same manner as described above.

[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 210 or more and less than 320.
C: Glossiness is 100 or more and less than 210.
D: Glossiness is less than 100.

[6.3] Scratch resistance With respect to the recorded matter according to each of the above examples and comparative examples, when 72 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.

  These results are shown in Table 2. In Table 2, “M1” is a recorded matter manufactured using a recording medium made of polycarbonate, “M2” is a recorded matter manufactured using a recording medium made of polyethylene terephthalate, and a recording medium made of low-density polyethylene “M3” is a recorded matter manufactured using a biaxially oriented polypropylene recording medium, and “M4” is a recorded matter manufactured using a recording medium made of hard vinyl chloride. 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.

  DESCRIPTION OF SYMBOLS 11 ... Recording medium (base material) 2 ... Ultraviolet curable inkjet composition 100 ... Droplet discharge apparatus 101 ... Tank 102 ... Discharge scanning part 103 ... Droplet discharge means 104 ... 1st position control apparatus (moving means) 106 ... Stage 108 ... Second position control device (moving means) 110 ... Tube 112 ... Control means

Claims (15)

A powder used for producing an ultraviolet curable ink jet composition discharged by an ink jet method,
Scaly,
A powder comprising an Al layer composed of Al and a ferromagnetic layer having ferromagnetism.   The powder according to claim 1, comprising the Al layer on both sides of the ferromagnetic layer.   The powder according to claim 1 or 2, wherein the ferromagnetic layer is composed of an Fe-Si-Al alloy.   The Fe-Si-Al alloy contains Fe as a main component and contains 8.2 mass% or more and 11.2 mass% or less of Si, and 4.0 mass% or more and 7.0 mass% or less of Al. Item 4. The powder according to Item 3.   The powder according to claim 3 or 4, wherein the Fe-Si-Al alloy has a total content of components other than Fe, Si, and Al of 2.0 mass% or less.   The powder according to any one of claims 1 to 5, having an average particle size of 500 nm or more and 2.0 µm or less.   The powder according to any one of claims 1 to 6, wherein an average thickness of the Al layer is 5 nm or more and 250 nm or less.   The powder was obtained by forming a laminated body in which a layer composed of a ferromagnetic material and a layer composed of Al were laminated by a vapor deposition method, and then pulverizing the laminated body. The powder according to any one of claims 1 to 7. An ultraviolet curable inkjet composition discharged by an inkjet method,
Including a polymerizable compound and a scaly powder,
An ultraviolet curable inkjet composition comprising the powder comprising an Al layer composed of Al and a ferromagnetic layer having ferromagnetism.   The ultraviolet curable inkjet composition according to claim 9, wherein the ultraviolet curable inkjet composition contains phenoxyethyl acrylate as the polymerizable compound.   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 the polymerizable compound. The ultraviolet curable inkjet composition according to claim 10, comprising at least one selected from the group consisting of -hydroxybutyl acrylate.   The ultraviolet curable inkjet composition according to any one of claims 9 to 11, wherein the ultraviolet curable inkjet composition contains dimethylol tricyclodecane diacrylate and / or amino acrylate as the polymerizable compound. Composition applying step for applying an ultraviolet curable inkjet composition containing a powder having a scale-like Al layer composed of Al and a ferromagnetic layer having ferromagnetism, and a polymerizable compound to a recording medium by an inkjet method When,
An alignment step of arranging the powder constituting the ultraviolet curable inkjet composition applied to the recording medium by magnetic force;
And a polymerization step of polymerizing the polymerizable compound by irradiating with ultraviolet rays.   The method for producing a recorded matter according to claim 13, wherein in the arranging step, a magnetic force is applied so that the powder is arranged on the outer surface side of the ultraviolet curable ink jet composition applied to the recording medium.   A recorded matter produced by using the method according to claim 13 or 14.

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