JP2013147543A - Ultraviolet ray-curing inkjet composition and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet ray-curing inkjet composition which is excellent in curability, and can be suitably used for forming a pattern (a printing portion) excellent in glossy sense and high-class feeling.SOLUTION: An ultraviolet ray-curing inkjet composition discharged by an inkjet system includes: a metallic powder composed of a metal material at least in the vicinity of the surface thereof; a polymerizable compound to be polymerized on irradiation of ultraviolet rays, and a compound A expressed by formula (1), where a relation of 0.001≤X/X≤0.060 is satisfied, when the content of the polymerizable compound is X(mass%) and the content of the compound A is set as X(mass%). In the formula (1), Rand Rare each independently a hydrogen atom, a halogen atom or a 1-6C hydrocarbon group.

Description

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

Conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.
However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion.
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, the ultraviolet curable ink jet composition has the following problems when it is attempted to apply metal powder instead of pigments and dyes. That is, when applying metal powder, in order to express the glossiness and high-class feeling inherent in the metal material, the particle size of the metal powder should be relatively large, with sufficient reflectivity. It is necessary to use a material having a high reflectivity to reflect light, to make the thickness of the metal powder relatively thick, and to arrange the metal powder near the surface of the printing part. When constituted, there was a problem that ultraviolet rays having sufficient strength did not reach the polymerizable compound constituting the ultraviolet ray curable ink jet composition and did not sufficiently cure. In UV curable inkjet compositions containing pigments or dyes, in order to accelerate the polymerization reaction, polymerization of benzoin, benzyl ketal, α-hydroxyacetophenone, titanocene, trichloromethyltriazine, bisimidazole, alkylamine, etc. is initiated. An agent may be used, but it is difficult to solve the above problems even if such a polymerization initiator is used in an ultraviolet curable ink jet composition containing a metal powder. In addition, it is conceivable to improve the curability by extremely increasing the content of the polymerization initiator. In such a case, the printed portion formed using the ultraviolet curable ink jet composition is provided. Problems such as yellow discoloration occur, making it difficult to express the glossiness and high-class feeling inherent in metal materials.

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 (printing portion) having excellent curability, glossiness, and luxury, Another object of the present invention is to provide a recorded matter having a pattern excellent in glossiness and high-quality feeling formed using a composition for a type inkjet.

これにより、硬化性に優れ、光沢感、高級感に優れたパターン（印刷部）の形成に好適に用いることのできる紫外線硬化型インクジェット用組成物を提供することができる。 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,
Including at least a surface of the metal powder composed of a metal material, a polymerizable compound that is polymerized by irradiation with ultraviolet rays, and a compound A represented by the following formula (1):
When the content of the polymerizable compound is X ₀ [% by mass] and the content of the compound A is X ₁ [% by mass], the relationship of 0.001 ≦ X ₁ / X ₀ ≦ 0.060 is satisfied. It is characterized by that.

Thereby, the composition for ultraviolet curable inkjets which can be used suitably for formation of the pattern (printing part) which was excellent in sclerosis | hardenability, and was excellent in the glossiness and the high-class feeling can be provided.

In the ultraviolet curable inkjet composition of the present invention, the metal powder preferably has a scaly shape.
Thereby, the glossiness of a pattern (printing part) formed using an ultraviolet curable inkjet composition and a high-class feeling can be made especially excellent.
In the ultraviolet curable inkjet composition of the present invention, the metal powder is preferably composed of Al at least near the surface.
Thereby, the glossiness of a pattern (printing part) formed using an ultraviolet curable inkjet composition and a high-class feeling can be made especially excellent.

In the ultraviolet curable inkjet composition of the present invention, the metal powder is preferably composed of a ferromagnetic material.
As a result, the metal powder can be easily and reliably disposed near the outer surface of the printing part, and more effectively prevent the color tone of the printing part from being adversely affected by the cured product of the polymerizable compound. In addition, the gloss and luxury of the printed part can be made particularly excellent.

In the ultraviolet curable ink jet composition of the present invention, the metal powder preferably has an average particle size of 500 nm to 2.0 μm.
As a result, the gloss of the pattern (printed portion) formed using the ultraviolet curable ink jet composition while sufficiently improving the storage stability and droplet discharge stability of the ultraviolet curable ink jet composition. The feeling and luxury can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the polymerizable compound contains phenoxyethyl acrylate.
As a result, the storage stability of the ultraviolet curable inkjet composition and the ejection stability of the droplets are excellent, and the reactivity (curability) of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly high. It is possible to improve the productivity of the recorded matter, and to make the formed pattern particularly excellent in abrasion resistance. Further, the metal powder can be suitably arranged on the outer surface side of the printed matter, 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, 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 inkjet composition and the ejection stability of the droplets are improved, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is further improved. Further, the productivity of the recorded matter can be further improved, and the scratch resistance of the formed pattern can be further improved. Further, the metal powder can be suitably arranged on the outer surface side of the printed matter, and the glossiness and high-quality feeling of the recorded matter can be further improved.

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the polymerizable compound contains dimethylol tricyclodecane diacrylate and / or amino acrylate.
As a result, the storage stability of the ultraviolet curable ink jet composition and the ejection stability of the droplets can be further improved, and the abrasion resistance of the formed pattern can be further improved. Further, the metal powder can be suitably arranged on the outer surface side of the printed matter, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

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

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.
<< UV-curable inkjet composition >>
First, the ultraviolet curable inkjet composition of the present invention will be described.
The ultraviolet ray curable ink composition of the present invention is ejected by an ink jet method and contains a metal powder and a polymerizable compound.

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, the ultraviolet curable ink jet composition has the following problems when it is attempted to apply metal powder instead of pigments and dyes. That is, when applying metal powder, in order to express the glossiness and high-class feeling inherent in the metal material, the particle size of the metal powder should be relatively large, with sufficient reflectivity. It is necessary to use a material having a high reflectivity to reflect light, to make the thickness of the metal powder relatively thick, and to arrange the metal powder near the surface of the printing part. When constituted, there was a problem that ultraviolet rays having sufficient strength did not reach the polymerizable compound constituting the ultraviolet ray curable ink jet composition and did not sufficiently cure. In UV curable inkjet compositions containing pigments or dyes, in order to accelerate the polymerization reaction, polymerization of benzoin, benzyl ketal, α-hydroxyacetophenone, titanocene, trichloromethyltriazine, bisimidazole, alkylamine, etc. is initiated. An agent may be used, but it is difficult to solve the above problems even if such a polymerization initiator is used in an ultraviolet curable ink jet composition containing a metal powder. In addition, it is conceivable to improve the curability by extremely increasing the content of the polymerization initiator. In such a case, the printed portion formed using the ultraviolet curable ink jet composition is provided. Problems such as yellow discoloration occur, making it difficult to express the glossiness and high-class feeling inherent in metal materials.
Therefore, the inventor has intensively studied for the purpose of solving the above problems, and as a result, has reached the present invention. That is, the ultraviolet curable inkjet composition of the present invention contains a predetermined amount of the compound A represented by the following formula (1) together with the metal powder and the polymerizable compound.

  Thus, by including a predetermined amount of Compound A together with the metal powder and the polymerizable compound, the recording medium can effectively exhibit the glossiness and high-class feeling inherent in the metal material constituting the metal powder. The curability of the polymerizable compound that constitutes the ultraviolet ray curable ink jet composition imparted to can be made excellent.

<Metal powder>
As described above, the ultraviolet curable ink jet composition of the present invention includes a metal powder at least near the surface made of a metal material.
In the present invention, by including such a metal powder, it is possible to form a printing portion that exhibits glossiness and high-class feeling peculiar to a metal material.
The metal powder only needs to have at least the vicinity of the surface made of a metal material. For example, the metal powder may be made entirely of a metal material, or the surface of a base made of a non-metal material may be made of metal. The thing of the structure formed by coat | covering the layer comprised with the material may be sufficient.

  The metal powder may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably has a scaly shape. Thereby, on the recording medium to which the ultraviolet curable ink jet composition is applied, the metal powder can be arranged so that the main surface of the metal powder follows the surface shape of the recording medium, thereby constituting the metal powder. The glossiness inherent in the metal material can be more effectively exhibited in the obtained recorded matter, and the glossiness and luxury feeling of the pattern (printed portion) to be formed are particularly excellent. be able to. Further, in the configuration not including Compound A, which will be described in detail later, when the metal powder has a scaly shape, the tendency of insufficient curing of the polymerizable compound has been particularly remarkable. Then, even if the metal powder has a scaly shape, the occurrence of such a problem can be reliably prevented. That is, when the shape of the metal powder is scaly, the effect of the present invention is more remarkably exhibited.

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

  As the metal material constituting the metal powder, a single metal, various alloys, or the like can be used, but the metal powder is preferably composed of Al at least near the surface. Since Al exhibits particularly excellent glossiness and luxury among various metal materials, a pattern (printing portion) formed using an ultraviolet curable ink-jet composition by including such a metal powder. ) Can be made particularly excellent in glossiness and luxury.

The metal powder is preferably composed of a ferromagnetic material. Accordingly, the metal powder can be easily and reliably disposed near the outer surface of the printing portion by a method described in detail later, and the color tone of the printing portion is adversely affected by the cured product of the polymerizable compound. This can be more effectively prevented, and the gloss and luxury of the printed part can be made particularly excellent. In particular, when an ultraviolet curable inkjet composition that does not contain compound A, which will be described in detail later, is used, the polymerization / curing of the polymerizable compound proceeds sufficiently when the metal powder is placed near the surface of the printing part. However, in the present invention, even when the metal powder is arranged near the surface of the printing part (when it is unevenly distributed), the polymerization / curing of the polymerizable compound can be sufficiently advanced. it can. That is, by adopting such a configuration, the effects of the present invention can be exhibited more remarkably.
Examples of the metal powder that satisfies the above conditions include those having a structure in which a base made of a ferromagnetic material is covered with a coating made of Al.

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

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

  Examples of the monomer as the polymerizable compound include isobornyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, phenoxyethyl acrylate, isooctyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, Benzyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate, tetrahydrofurfuryl acrylate , Ethyl carbitol acrylate, 2,2,2-trifluoroethyl acrylate, 2, , 2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, EO modified nonylphenol acrylate, 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 inkjet composition and the ejection stability of the droplets are excellent, and the reactivity (curability) of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly high. It is possible to improve the productivity of the recorded matter, and to make the formed pattern particularly excellent in abrasion resistance. Further, the metal powder can be suitably arranged on the outer surface side of the printed matter, 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 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 inkjet composition and the ejection stability of the droplets are improved, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is further improved. Further, the productivity of the recorded matter can be further improved, and the scratch resistance of the formed pattern can be further improved. Further, the metal powder can be suitably arranged on the outer surface side of the printed matter, and the glossiness and high-quality feeling of the recorded matter can be further improved.

  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 ink jet composition and the ejection stability of the droplets can be further improved, and the abrasion resistance of the formed pattern can be further improved. Further, the metal powder can be suitably arranged on the outer surface side of the printed matter, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

  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.

<Compound A>
The ultraviolet curable inkjet composition of the present invention contains a predetermined amount of the compound A represented by the above formula (1) in addition to the metal powder and the polymerizable compound as described above.
By containing a predetermined amount of such compound A, ultraviolet rays irradiated to the polymerizable compound due to the presence of the metal powder while sufficiently exhibiting the glossiness and high-class feeling inherent in the metal material constituting the metal powder. Even when the amount is relatively small, the polymerization reaction of the polymerizable compound can be sufficiently advanced, and the curability (reactivity) of the ultraviolet curable inkjet composition as a whole is sufficiently excellent It can be.
In the ultraviolet curable inkjet composition according to the present invention, the content of the polymerizable compound in the ultraviolet curable inkjet composition is X ₀ [mass%], and the content of the compound A is X ₁ [mass%]. When satisfied, the relationship of 0.001 ≦ X ₁ / X ₀ ≦ 0.060 is satisfied. By including the compound A at such a content rate, the above-described effects are reliably exhibited. On the other hand, when the value of X ₁ / X ₀ is less than the lower limit value, the effect of including the compound A is not sufficiently exhibited. On the other hand, when the value of X ₁ / X ₀ exceeds the upper limit, the ejection stability of the ultraviolet curable ink jet composition by the ink jet method is remarkably lowered.

As described above, the ultraviolet curable ink jet composition of the present invention satisfies the relationship of 0.001 ≦ X ₁ / X ₀ ≦ 0.060, and in particular, 0.005 ≦ X ₁ / X. _It is preferable that the relationship of ₀ ≦ 0.040 is satisfied, and it is more preferable that the relationship of 0.006 ≦ X ₁ / X ₀ ≦ 0.030 is satisfied. Thereby, the effects of the present invention as described above are more remarkably exhibited.

R ¹ and R ^{2 in} formula (1) may be independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, but a hydrogen atom, a fluorine atom, a chlorine atom or a carbon number It is preferably a couple of hydrocarbon groups. Thereby, the effects of the present invention as described above are more remarkably exhibited.
The content of Compound A in the ultraviolet curable inkjet composition is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass or less. More preferred. Thereby, the effects of the present invention as described above are more remarkably exhibited.

<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).

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 recorded matter>
Next, an example of a method for producing a recorded material according to the present invention, in particular, a metal powder made of a ferromagnetic material (preferably a metal powder made by coating a base made of a ferromagnetic material with a coating made of Al. An example of a method for producing a recorded product using an ultraviolet curable ink jet composition containing) will be described.

FIG. 1 is a perspective view showing a droplet discharge device used for manufacturing a recorded matter.
The method for producing a recorded matter of the present embodiment includes a composition applying step (1a) for applying the ultraviolet curable ink composition according to the present invention as described above to a recording medium by an ink jet method, and applying a magnetic force to the recording medium. It has the arrangement | sequence process (1b) which arranges the metal powder which comprises the provided ultraviolet curable inkjet composition, and the superposition | polymerization process (1c) which superposes | polymerizes a polymeric compound by irradiating an ultraviolet-ray. Thereby, the manufacturing method which can manufacture efficiently the recorded matter provided with the pattern (printing part) excellent in glossiness and a high-class feeling 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 in which ink is discharged by bubbles generated by heating the ink can be used. The piezo method is preferable from the viewpoint of the difficulty of alteration of the product 2.

In the following description, it is assumed that the ultraviolet curable inkjet composition is discharged using a droplet discharge device 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 ink composition 2, a tube 110, and an ultraviolet curable ink jet from the tank 101 via the tube 110. And a discharge scanning unit 102 to which the composition 2 is supplied. The ejection scanning unit 102 includes a droplet ejection unit 103 having a plurality of droplet ejection heads (inkjet heads) mounted on a carriage, and a first position control device (moving unit) 104 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 (moving means) 108 that controls the position of the stage 106, and a control means 112. The tank 101 and a 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 air from the tank 101 to each of the plurality of droplet discharge heads. Supplied by

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 ink jet 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 kind of the ultraviolet curable ink-jet composition 2, but these members are used. In addition, it may have as many as two or more kinds of ultraviolet ray curable ink jet compositions 2. 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. In addition, 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 the thermal expansion of the material by the electrothermal conversion element.

<Sequence process>
Next, the metal powder constituting the ultraviolet curable inkjet composition 2 applied to the recording medium 11 by magnetic force is applied to the outer surface side of the ultraviolet curable inkjet composition 2 applied on the recording medium 11. Arrange (1b).
In this step, for example, the metal powder can be arranged using a magnet. As the magnet, a permanent magnet or an electromagnet may be used.
Further, when the metal powder is composed of a magnet material (magnetized material), the metal powder is arranged using a member composed of a non-magnetized ferromagnetic material (for example, iron). Also good.

The direction of the magnetic force applied to the metal 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 applied to the metal powder in this step (the direction of the magnetic force line) may be any direction, but is preferably substantially parallel to the normal direction of the recording medium 11. Specifically, the angle formed by the direction of the magnetic force acting on the metal 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, The angle is preferably 10 ° or less, and more preferably 5 ° or less. Thereby, the metal powder which comprises the ultraviolet curable inkjet composition 2 can be arranged more suitably, and the glossiness of the recorded matter finally obtained can be made especially excellent.

In the following description, a case where a magnetic field is applied to metal 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 metal powders 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, for example, 1 cm to 100 cm. More preferably, it is 50 cm or less. This makes it possible to arrange the metal powders 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 metal powder by magnetic force may be performed after the ultraviolet curable inkjet composition 2 is applied to the recording medium 11, but the ultraviolet curable inkjet composition discharged from the droplet discharge device 100 is used. It may be performed before the second droplet reaches the surface of the recording medium 11. Thereby, the orientation of the metal powder in the droplet can be controlled, and as a result, the arrangement of the metal powder after landing of the droplet 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.
Since the ultraviolet curable inkjet composition 2 applied to the recording medium 11 contains a predetermined amount of the compound A, the polymerization reaction of the polymerizable compound proceeds promptly in this step. As a result, in the obtained recorded matter, the occurrence of problems due to insufficient effects is reliably prevented.

In particular, in this embodiment, before the polymerizable compound is cured, the metal powder constituting the ultraviolet curable ink-jet composition 2 is arranged by magnetic force. In the state of being arranged in the direction, the polymerizable compound is cured, and the powder is fixed in the direction. As a result, the recorded matter has an excellent gloss feeling.
The wavelength of the ultraviolet rays irradiated in this step is preferably 350 nm or more and 450 nm or less.
The irradiation intensity of the ultraviolet irradiation in this step is preferably 10 mW / cm ² or more 2000 mW / cm ² or less.
The irradiation energy of ultraviolet rays in this step is preferably 5 mJ / cm ² or more 1000 mJ / cm ² or less.

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 metal powders arranged in the arrangement step, and the gloss of the recorded matter is particularly excellent. be able to.

《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 luxury.

  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 according to the present invention has excellent adhesion to a recording medium, the recording medium may be anything, and either absorbable or nonabsorbable is used. For example, natural fibers / synthetic fibers such as paper (plain paper, inkjet exclusive paper, etc.), plastic materials, metals, ceramics, wood, shells, cotton, polyester, wool, etc., non-woven fabrics, etc. can be used.

The recorded matter of the present invention may be used for any purpose, and may be applied to, for example, a decorative article or other items. Specific examples of the recorded material of the present invention include console interiors for vehicles such as console lids, switch bases, center clusters, interior panels, emblems, center consoles, meter nameplates, operation parts (key switches) of various electronic devices, decorations. Display items such as decorative parts, indicators, logos, etc. that exhibit properties.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.

Next, specific examples of the present invention will be described.
[1] Production of inkjet composition (UV-curable inkjet composition) (Example 1)
First, a film made of polyethylene terephthalate having a smooth surface (surface roughness Ra of 0.1 μm or less) was prepared.
Next, silicone oil was applied to the entire one surface of the film.

Next, a first Al layer composed of Al, a ferromagnetic layer composed of a Ni-Fe alloy, and a second Al layer composed of Al are formed on the side coated with silicone oil by vapor deposition. Were sequentially formed to obtain a laminate. Each of the first Al layer and the second Al layer had an average thickness of 4 nm. The average thickness of the ferromagnetic layer was 5 nm. The ferromagnetic layer had a composition of Ni: 50.4% by mass and Fe: 49.6% 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. As a result, a scaly metal powder composed of the first Al layer, the ferromagnetic layer, and the second Al layer was obtained. The average particle size of the metal powder was 0.8 μm.

  Next, the metal powder is separated from the above liquid, and then phenoxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 4-hydroxybutyl acrylate, By mixing with compound A represented by (2), UV-3500 (produced by Big Chemie) as a leveling agent, and p-methoxyphenol as a polymerization inhibitor, an ink jet composition (a composition for ultraviolet curable ink jet) Product).

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

(Comparative Example 1)
Except that the composition as shown in Table 1 was used by changing the kind and ratio of the raw materials used for the preparation of the ink jet composition (ultraviolet curable ink jet composition) without using the compound A. In the same manner as in Example 1, an inkjet composition (ultraviolet curable inkjet composition) was produced.

(Examples 2 and 3)
The ink jet composition was the same as in Example 1, except that the composition shown in Table 1 was obtained by changing the ratio of the raw materials used for the preparation of the ink jet composition (ultraviolet curable ink jet composition). A product (ultraviolet curable ink jet composition) was produced.

(Comparative Examples 4 and 5)
Except that the composition as shown in Table 1 was used by changing the kind and ratio of the raw materials used for the preparation of the ink jet composition (ultraviolet curable ink jet composition) without using the compound A. In the same manner as in Example 1, an inkjet composition (ultraviolet curable inkjet composition) was produced.

(Comparative Example 6)
An ink jet composition (ultraviolet curable ink jet composition) was produced in the same manner as in Comparative Example 1 except that a metal powder composed of Ag was used.
(Comparative Example 7)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Comparative Example 1 except that a spherical Al powder produced using a gas atomization method was used as the metal powder.

(Comparative Example 8)
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 Then, an ink jet 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, the compound A represented by the above formula (2) is (2), the compound A represented by the following formula (3) is (3), the compound A represented by the following formula (4) is (4), The compound A represented by the following formula (5) is (5), the compound A represented by the following formula (6) is (6), the compound A represented by the following formula (7) is (7), and the following formula (8) (8), compound A represented by the following formula (9) is (9), phenoxyethyl acrylate is “PEA”, acrylic acid 2- (2-hydroxyethoxy) ethyl is “VEEA”, tri Propylene glycol diacrylate is "TPGDA", dipropylene glycol diacrylate is "DPGDA", N-vinylcaprolactam is "VC", benzyl methacrylate is "BM", dimethylol tricyclodecane diacrylate is "DM" CDDA ", amino acrylate" AA ", urethane acrylate" UA ", UV-3500 (manufactured by Big Chemie)" UV3500 ", p-methoxyphenol" pMP ", 4-hydroxybutyl acrylate" HBA ", 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 was converted to “BDMB”, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholine-4 -Il-phenyl) -butan-1-one is "DMMB", 1,2-hexanediol is "1,2HD", trimethylolpropane is "TMP", Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) “S465”, triethanolamine “TEA”, glycerin “GL”, polyflow 401 (manufactured by Nissin Chemical Industry Co., Ltd.) “ F401 shown in ". Moreover, in Table 1, the weight ratio of each component was shown about the alloy composition among the compositions of metal powder. 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 addition, the viscosity at 20 ° C. of the ink-jet compositions (ultraviolet-curing ink-jet compositions) of the above-described examples measured according to JIS Z8809 using a vibration viscometer is 3 mPa · s or more. The value was within a range of 15 mPa · s or less. Moreover, in each layer of the metal powder constituting the ink jet compositions of the respective Examples and Comparative Examples, the content other than the components shown in Table 1 was 0.1% by 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 72 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 0.17 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 a comparative example, after leaving it for 14 days in 30 degreeC environment, the inkjet composition of each said Example measured based on JISZ8809 using a vibration-type viscometer The viscosity of the product at 20 ° C. was measured, the rate of increase in viscosity immediately after production was determined, and evaluated according to the following criteria.

A: Increase rate of viscosity is less than 5%.
B: Increase rate of viscosity is 5% or more and less than 10%.
C: The rate of increase in viscosity is 10% or more and less than 20%.
D: Increase rate of viscosity is 20% or more and less than 30%.
E: Increase rate of viscosity is 30% or more.

[4] Curability About the inkjet composition of each of the above Examples and Comparative Examples, it was introduced into an Epson inkjet printer; PM800C, and Mitsubishi Plastics, Diafoil G440E (thickness 38 μm) was used as the recording medium. Solid printing was performed at an ink amount of 9 g / m ^2. Immediately after printing, an LED-UV lamp; Foseon RX RXrefly (gap 6 mm, peak wavelength 395 nm, 1000 mW / cm ² ) was used to irradiate ultraviolet rays. Whether the composition was cured or not was evaluated and evaluated according to the following five-step criteria. Whether or not it was cured was determined by using FT-IR (product name “MAGNA-IR 860 Nicolet”, manufactured by Thermo Fisher Scientific Co., Ltd.), a vinyl group in each radiation curable ink composition before and after irradiation with actinic radiation. It was judged by the peak (810 cm ⁻¹ ) of the absorption spectrum. Specifically, first, using the peak height _{A 0} before irradiation of 810 cm ^-1, seek, and peak height _{A t} of 810 cm ^-1 after irradiation from the IR spectrum, the following formula (X) curing The rate was calculated.

Curing rate (%) = 100 × (1−A _t / A ₀ ) (X)
Accordingly, when the radiation curable ink composition had a curing rate of 90% or more, it was determined as “cured”.
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 For each example, an interior panel as a recorded matter was manufactured as follows using the ink jet composition (ultraviolet curable ink jet composition) immediately after the production.
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). In addition, the direction of the magnetic lines of force was made parallel to the normal direction of the recording medium (arrangement process). 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 ink jet composition of the present invention was excellent in curability and also excellent in droplet ejection stability and storage stability. In addition, the recorded matter of the present invention had excellent glossiness and luxury, 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.
Further, when the recorded matter was produced using the ink-jet compositions of the examples and comparative examples in the same manner as described above except that no magnet was used, it was recognized that there was a tendency similar to the above. While excellent results were obtained, satisfactory results were not obtained in the comparative examples.

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

Claims (9)

An ultraviolet curable ink jet composition discharged by an ink jet method,
Including at least a surface of the metal powder composed of a metal material, a polymerizable compound that is polymerized by irradiation with ultraviolet rays, and a compound A represented by the following formula (1):
When the content of the polymerizable compound is X ₀ [% by mass] and the content of the compound A is X ₁ [% by mass], the relationship of 0.001 ≦ X ₁ / X ₀ ≦ 0.060 is satisfied. An ultraviolet curable inkjet composition characterized by the above.

  The composition for ultraviolet curable ink jet according to claim 1, wherein the metal powder has a scaly shape.   The ultraviolet curable ink jet composition according to claim 1, wherein the metal powder is composed of Al at least near the surface.   The ultraviolet curable inkjet composition according to any one of claims 1 to 3, wherein the metal powder is composed of a ferromagnetic material.   The ultraviolet curable inkjet composition according to any one of claims 1 to 4, wherein the metal powder has an average particle size of 500 nm or more and 2.0 µm or less.   The ultraviolet curable inkjet composition according to any one of claims 1 to 5, wherein the polymerizable compound contains phenoxyethyl acrylate.   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 ink jets according to any one of claims 1 to 6, comprising at least one selected from the group consisting of:   The ultraviolet curable inkjet composition according to claim 1, wherein the polymerizable compound includes dimethylol tricyclodecane diacrylate and / or amino acrylate.   A recorded matter produced by applying the ultraviolet curable ink jet composition according to any one of claims 1 to 8 onto a recording medium and then irradiating with ultraviolet rays.

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