JP2012206363A - Method of producing recorded matter, and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recorded matter having a pattern (a printed part) excellent in glossy sense, and abrasion resistance, and a method of producing the recorded matter capable of efficiently producing the recorded matter.SOLUTION: The method of producing a recorded matter using an ultraviolet-curable type composition for inkjet containing metal particles and a polymerizable compound includes a composition-applying process for applying the ultraviolet-curable type composition for inkjet to a record medium by an inkjet system, and a polymerization process for polymerizing the polymerizable compound by irradiating the same with ultraviolet rays to form a printed layer wherein a thickness of the printed layer is not grater than 1/200times the average value of maximum lengths of the metal particles.

Description

  The present invention relates to 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. Also,
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 inkjet method is excellent in that it can be suitably applied to the formation of fine patterns and recording on curved surfaces, can be printed only on specific parts on demand, and can be printed with gradation. Yes. In recent years, in order to make the ink jet method particularly excellent in abrasion resistance, water resistance, solvent resistance, etc.
A composition that cures when irradiated with ultraviolet rays (ultraviolet curable inkjet composition) is used (for example, see Patent Document 1).
However, in an ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, the metal is inherently present, particularly by curing before the metal particles are oriented / leafed. There is a problem that the glossiness and other properties cannot be fully exhibited.

JP 2009-57548 A

An object of the present invention is to provide a recorded matter provided with a pattern (printing layer) excellent in glossiness and abrasion resistance, and to provide a production method capable of efficiently producing the recorded matter. is there.

Such an object is achieved by the present invention described below.
The method for producing a recorded matter of the present invention is a method for producing a recorded matter, wherein a recorded matter is produced using an ultraviolet curable ink composition containing metal particles and a polymerizable compound,
A composition application step of applying the ultraviolet curable inkjet composition to a recording medium by an inkjet method;
A polymerization step of polymerizing the polymerizable compound by irradiating with ultraviolet rays to form a printed layer, and
The thickness of the print layer is 1/200 ^1/2 or less of the average value of the maximum length of the metal particles.
Thereby, the manufacturing method which can manufacture efficiently the recorded matter provided with the pattern (printing layer) excellent in glossiness and abrasion resistance can be provided.

In the recorded matter manufacturing method of the present invention, it is preferable that the metal particles have a scaly shape.
Thereby, the glossiness of the formed printing layer can be made more excellent.
In the recorded matter manufacturing method of the present invention, the metal particles preferably include aluminum.
Thereby, the formed printing layer has a particularly excellent metallic gloss.

In the method for producing a recorded matter of the present invention, the ultraviolet curable ink jet composition preferably contains 10% by mass or more of a solvent.
Thereby, the pattern (printing layer) excellent in glossiness and abrasion resistance can be formed more easily.
In the method for producing a recorded matter of the present invention, it is preferable that the recording medium has an ink receiving layer on a surface to which the ultraviolet curable ink jet composition is applied.
Thereby, the pattern (printing layer) excellent in glossiness and abrasion resistance can be formed more easily.

In the method for producing a recorded matter of the present invention, it is preferable that the ultraviolet ray curable inkjet composition contains phenoxyethyl acrylate as the polymerizable compound.
As a result, the storage stability of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like. Further, the metal particles can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

In the method for producing a recorded matter 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. , Tripropylene glycol diacrylate, and at least one selected from the group consisting of 4-hydroxybutyl acrylate are preferable.

As a result, the storage stability of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like. Further, the metal particles can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

In the method for producing a recorded matter of the present invention, the ultraviolet curable inkjet composition preferably contains dimethylol tricyclodecanediacrylate and / or aminoacrylate as the polymerizable compound.
As a result, the storage stability of the ultraviolet curable inkjet composition can be further improved, and the scratch resistance of the pattern to be formed can be further improved. Further, the metal particles can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.
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 layer) 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.
<Method for producing recorded matter>
First, the manufacturing method of the recorded matter of this invention is demonstrated.
FIG. 1 is a perspective view showing a droplet discharge device used for manufacturing a recorded matter.
The method for producing a recorded product of the present invention includes a composition applying step (1) of applying an ultraviolet curable inkjet composition containing metal particles and a polymerizable compound to a recording medium by an inkjet method.
a) and a polymerization step (1b) in which the polymerizable compound is polymerized by irradiation with ultraviolet rays to obtain a printed layer.

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 inkjet method is excellent in that it can be suitably applied to the formation of fine patterns and recording on curved surfaces, can be printed only on specific parts on demand, and can be printed with gradation. Yes. In recent years, in order to make the ink jet method particularly excellent in abrasion resistance, water resistance, solvent resistance, etc.
Compositions that cure when irradiated with ultraviolet rays (ultraviolet curable ink jet compositions) are used.
However, in an ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, the metal is inherently cured by being cured before the metal particles are oriented / leafed. There is a problem that the properties such as glossiness cannot be fully exhibited.

On the other hand, the present invention is characterized in that the thickness of the printed layer to be formed is 1/200 ^1/2 or less of the average value of the maximum length of the metal particles. With such a feature, the metal particles can be arranged in the printed layer, and a reduction in glossiness due to irregular reflection of light can be prevented. In addition, it is possible to prevent unintentional protrusions from being formed by curing the metal particles in a standing state. As a result, a recorded matter having a pattern (printing portion) excellent in glossiness and abrasion resistance can be efficiently produced.

<Composition application process>
First, an ultraviolet curable inkjet composition 2 containing metal particles and a polymerizable compound,
It 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 controls a position of the droplet ejection unit 103 and a droplet ejection unit 103 having a plurality of droplet ejection heads (inkjet heads) mounted on the carriage.
A position control device 104 (moving means), 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 the control means 1
12. 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 responds to a signal from the control means 112 in accordance with the droplet discharge means 103.
Are moved along the X-axis direction and the Z-axis direction orthogonal to the X-axis direction. 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. In addition, the second
The 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 color of the tank 101, the tube 110, and the like for holding the ultraviolet curable ink jet composition 2, but these members are provided with a plurality of types. You may have only the part for the composition 2 for ultraviolet curable inkjets. 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.
The ultraviolet curable ink jet composition will be described in detail later.

<Polymerization process>
Thereafter, by irradiating with ultraviolet rays, the polymerizable compound constituting the ultraviolet curable inkjet composition 2 applied to the recording medium 11 is cured to obtain a printed layer (1b). Thereby, a recorded matter is obtained.
In the present invention, the thickness of the printing layer to be formed is 1/200 of the average value of the maximum length of the metal particles.
^In order to make it ^1/2 or less, before the polymerizable compound is cured, the metal particles constituting the ultraviolet curable inkjet composition 2 are arranged. In this step, the polymerizable compound is cured with the metal particles arranged in a predetermined direction, and the metal particles are fixed in the direction. The metal particles constituting the ultraviolet curable ink jet composition 2 are at least the surface of which is made of a metal material, and the metal material generally has an excellent gloss (metal luster). is there. Therefore, by arranging such metal particles, irregular reflection of light is prevented, and as a result, the recorded matter has an excellent gloss.

The thickness of the formed printing layer is 1/200 ^1/2 or less of the average value of the maximum length of the metal particles. Specifically, the average thickness is 140 nm or more and 1700 nm or less. Preferably, it is 200 nm or more and 1200 nm or less. When the average thickness of the printing layer is in such a range, the printing layer has excellent gloss and particularly excellent abrasion resistance.
When the print layer is composed of a plurality of layers, it is only necessary that the outermost layer on the viewing side satisfies the above relationship.

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, from the viewpoint of small size, long life, high efficiency, and low cost, an ultraviolet light emitting diode (UV-L
ED) and ultraviolet laser diodes (UV-LD) are preferred.
In addition, you may perform this process, making a magnetic force act. This makes it possible to cure the ultraviolet curable inkjet composition 2 without disturbing the arrangement state of the powder arranged in the arrangement step, and to make the gloss of the recorded matter particularly surely excellent. Can do.

<< UV-curable inkjet composition >>
Hereinafter, the ultraviolet curable inkjet composition used in the present invention will be described in detail.
<Metal particles>
As described above, the ultraviolet curable ink jet composition contains metal particles (metal powder). In this specification, the metal particle means a particle having at least a surface made of a metal material.

Although it does not specifically limit as a metal material which comprises a metal particle, It is preferable to use aluminum. Thereby, the powder can be more suitably arranged in the finally obtained recorded matter. In addition, aluminum generally has a particularly excellent metallic luster. Therefore, when the metal particles are composed of aluminum, the gloss and high quality of the recorded matter can be made particularly excellent.
The metal particles may have any shape such as a circular shape, an elliptical shape, a needle shape, and a scale shape, but a scale shape is preferable. Thereby, the metal particle which comprises an ultraviolet curable inkjet composition can be arranged more suitably on a recording medium, and the glossiness of the formed printing layer can be made more excellent.

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

The scale-like metal particles may be produced by any method, but can be obtained by forming a film composed of metal by a vapor deposition method and then crushing the film. It is preferable that Thereby, the glossiness etc. which a metal originally has in the pattern (printing layer) formed using an ultraviolet curable inkjet composition can be expressed more effectively. Moreover, the dispersion | variation in the characteristic between each metal particle can be suppressed.

When producing metal particles using such a method, for example, metal particles can be suitably produced by forming a film made of metal (film formation) on a substrate. As the substrate, for example, a plastic film such as polyethylene terephthalate can be used. Further, the substrate may have a release agent layer on the film forming surface.
Moreover, it is preferable that the said grinding | pulverization is performed by providing an ultrasonic vibration to the said film | membrane in a liquid. Thereby, the first particles having the above-described particle diameter can be obtained easily and reliably, and the occurrence of 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 Propylene carbonate, γ- butyrolactone,
Polar compounds such as N-methyl-2-pyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dimethyl sulfoxide, cyclohexanone and acetonitrile can be preferably used. By using such a liquid, while preventing unintentional oxidation of the metal particles, the productivity of the metal particles is particularly excellent,
Variations in size, shape, and characteristics among the metal particles can be made particularly small.

When the metal particles are scaly, the average thickness of the metal particles 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 metal particles is a value within the above range, the storage layer of the ultraviolet curable inkjet composition and the discharge stability of the droplets are particularly excellent, and the metal originally has in the printed layer. The glossiness and the like can be expressed more effectively.

The average particle size of the metal particles is preferably 500 nm or more and 2.0 μm or less, and 800 n
m or more and 1.8 μm or less is more preferable. Thereby, in the pattern (printing layer) formed using the ultraviolet curable ink-jet composition, the first particles can be more reliably arranged appropriately, and formed using the ultraviolet curable ink-jet composition. The glossiness of the pattern (printing portion) can be further improved with certainty. In the present invention, the average particle diameter refers to the average particle diameter based on the number, and the average of the diameters of perfect circles having the same area as the area S ₁ when observed from the direction in which the projected area is maximized. Refers to the value.

<Polymerizable compound>
The ultraviolet curable ink jet composition includes a polymerizable compound that 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. Moreover, since the metal particles arranged (orientated) as described above can be fixed by curing the polymerizable compound, 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 ink jet composition. As a result,
It is not necessary to use a dispersion medium that is removed (evaporated) in the production process of recorded matter, and it is not necessary to provide a process for removing the dispersion medium in the production of recorded matter. It can be. 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.

As the polymerizable compound, any component that can be polymerized by irradiation with ultraviolet rays can be used. For example, various monomers, various oligomers (including dimers, trimers, etc.) can be used.
The ultraviolet curable ink jet composition preferably contains at least a monomer component as a polymerizable compound. 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, 2,2,2-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, phenylglycidyl ether acrylate, phenoxydiethylene glycol acrylate EO-modified phenol acrylate,
Phenoxyethyl acrylate, EO-modified phenol acrylate, EO-modified cresol acrylate, methoxypolyethylene glycol acrylate, dipropylene glycol acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl 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 hydrogenated bisphenol A diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane EO modified triacrylate, glycerin PO-added triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, PO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate,
Examples include trimethylolpropane triacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane tri Preferred are acrylate, trimethylolpropane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate.

In particular, the ultraviolet curable ink jet composition preferably contains phenoxyethyl acrylate as the polymerizable compound. As a result, the storage stability of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like. Further, the metal particles 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 as a polymerizable compound. −
It is preferable that it contains at least one selected from the group consisting of hydroxybutyl acrylate. As a result, the storage stability of the ultraviolet curable ink jet composition is excellent, while the reactivity of the ultraviolet curable ink jet composition after ejection by the ink jet method is particularly excellent, and the productivity of recorded matter is improved. In addition to being particularly excellent, it is possible to make the formed pattern particularly excellent in abrasion resistance and the like. Further, the metal particles can be arranged more suitably, and the glossiness and high-quality feeling of the recorded matter can be made particularly excellent.

Moreover, it is preferable that the ultraviolet curable inkjet composition contains dimethylol tricyclodecane diacrylate and / or amino acrylate as the polymerizable compound.
As a result, the storage stability of the ultraviolet curable inkjet composition can be further improved, and the scratch resistance of the pattern to be formed can be further improved. Further, the metal particles 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 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, the compound has a repeating structure in the skeleton of the molecule and has a molecular weight of 600.
The above is called an oligomer. 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 contain components other than those described above (other components). Such components include, for example, photopolymerization initiators, slip agents (leveling agents), dispersants, polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), colorants, fixing agents, anti-blocking agents. Examples include glazes, preservatives, antioxidants, chelating agents, thickeners, and sensitizers (sensitizing dyes).

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

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

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

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 UV curing rate is sufficiently high, and the photopolymerization initiator is not dissolved and there is almost no color derived from the photopolymerization initiator.
When the ultraviolet curable ink jet composition contains a slip agent, the surface of the recorded matter becomes smooth due to the leveling action, and the abrasion resistance is improved.

Although it does not specifically limit as a slip agent, For example, silicone type surfactants, such as polyester modified silicone and polyether modified silicone, can be used, It is preferable to use polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane. .
When the ultraviolet curable ink jet composition contains a dispersant, the metal particles 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,
For example, polyoxyalkylene polyalkylene polyamine, vinyl polymer and copolymer, acrylic polymer and copolymer, polyester, polyamide, polyimide, polyurethane, amino polymer, silicon-containing polymer, sulfur-containing polymer, fluorine-containing polymer, epoxy resin, etc. It is done.

Moreover, the ultraviolet curable inkjet composition used in the present invention may contain a solvent, and particularly preferably contains 10% by mass or more. As a result, the ultraviolet curable ink jet composition can be made highly penetrable into the recording medium, and the thickness of the printing layer can be made easier in the above-described range.
Examples of such solvents include polar glycol ethers such as diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, tripropylene glycol dimethyl ether, and diethylene glycol diethyl ether, various organic solvents such as acetate and diols, water, and carbon tetrachloride. Various inorganic solvents such as can be used.
The viscosity at room temperature (20 ° C.) of the ultraviolet curable inkjet composition used in the present invention is 2
It is preferably 0 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.

《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 layer) excellent in glossiness and abrasion resistance.
As described above, the ultraviolet curable inkjet composition according to the present invention contains a polymerizable compound and has excellent adhesion to a recording medium. As described above, since the ultraviolet curable ink jet composition 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, paper (plain paper, ink jet dedicated paper, etc.), plastic material, metal, ceramics, wood, shells, etc. can be used.

Further, as the recorded material, it is preferable to use a recording material having an ink receiving layer on the surface to which the ultraviolet curable ink jet composition is applied. Since such a recorded matter has a high absorbability of the ultraviolet curable ink jet composition, the thickness of the printed layer can be easily made suitable, and a printed layer excellent in glossiness and abrasion resistance can be obtained. It can be formed more easily.
The ink receiving layer refers to a layer that absorbs only liquid components such as solvents and monomers and leaves metal particles in the vicinity of the surface.

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 matter of the present invention include a console lid,
Display items such as switch bases, center clusters, interior panels, emblems, center consoles, meter nameplates, and other vehicle interior parts, various electronic device operation parts (key switches), decorative parts, indicators, logos, etc. Etc.
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) (Preparation Example 1)
First, a polyethylene terephthalate film having a smooth surface (surface roughness Ra is 0.0
2 μm or less) was prepared. Next, silicone oil was applied to the entire one surface of the film. Next, a film made of Al was sequentially formed on the side coated with silicone oil by vapor deposition. Next, a film made of polyethylene terephthalate on which an Al film is formed (
Substrate) was placed in a liquid composed of diethylene glycol diethyl ether and subjected to ultrasonic vibration. Thereby, the scale-like metal particle comprised with Al was obtained. The average particle size of the metal particles was 800 nm. Moreover, the average thickness of the metal particles was 40 nm. The average value of the maximum length of the metal particles was 900 nm.

Thereafter, the obtained metal particles were mixed with phenoxyethyl acrylate, acrylic acid 2- (2-
Hydroxyethoxy) ethyl, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 4-hydroxybutyl acrylate, Irgacure 819 (manufactured by Ciba Japan) as a photopolymerization initiator, Speedcu as a photopolymerization initiator
re TPO (manufactured by ACETO), Speedcure DETX as photopolymerization initiator
(Manufactured by Lambson), UV-3500 (manufactured by Big Chemie) as a leveling agent,
And the inkjet composition (ultraviolet curable inkjet composition) was obtained by mixing with p-methoxyphenol as a polymerization inhibitor.

(Preparation Examples 2 to 12)
Except for the composition shown in Table 1 by changing the type and ratio of raw materials used for the preparation of the ink jet composition (ultraviolet curable ink jet composition) and the production conditions of the metal particles. In the same manner as in Preparation Example 1, an inkjet composition (ultraviolet curable inkjet composition) was produced.

(Preparation Example 13)
First, using a molten Fe-Si-Al alloy, the water atomization method makes a spherical shape,
A powder having an average particle size of 9.2 μm was produced (powder production process). The produced powder is Fe: 8
The composition had a composition of 4.9% by mass, Si: 9.9% by mass, and Al: 5.2% by mass.
Next, the substantially spherical powder obtained as described above was added to zirconia beads (diameter: 5 mm).
) Was deformed (scaled) into a scale shape (scaled step). This step was performed in phenoxyethyl acrylate.

Next, the mixture obtained in the scaly process is introduced into an ultrasonic disperser, finely processed, and then filtered through a 5 μm membrane filter to remove zirconia beads and remove coarse particles of powder. Cut to obtain a dispersion having an average particle diameter D50 of 0.8 μm.
Next, the scaled powder was separated, and then phenoxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, and Irgacure 819 (
Ciba Japan), Speedcure TPO (ACETO) as a photopolymerization initiator
SPEEDCURE DETX (manufactured by Lambson) as a photopolymerization initiator,
An ink jet composition (ultraviolet curable ink jet composition) was obtained by mixing with UV-3500 (manufactured by Big Chemie) as a leveling agent and p-methoxyphenol as a polymerization inhibitor.

Table 1 shows the composition of the ink jet composition for each of the above preparation examples. In the table, phenoxyethyl acrylate is “PEA”, acrylic acid 2- (2-hydroxyethoxy) ethyl is “VEEA”, and tripropylene glycol diacrylate is “TPA”.
GDA ", dipropylene glycol diacrylate" DPGDA ", 4-hydroxybutyl acrylate" HBA ", N-vinylcaprolactam" VC ", benzyl methacrylate" BM ", dimethylol tricyclodecane diacrylate" DMTCDDA "
”, Amino acrylate“ AA ”, urethane acrylate“ UA ”, Irgacur
e 819 (Ciba Japan Co., Ltd.) is changed to “ic819”, Speedcure TPO (A
CETO) is "scTPO", Speedcure DETX (Lambson) is "scDETX", UV-3500 (Bic Chemie) is "UV3500", p-
Methoxyphenol was indicated as “pMP”, triethylene glycol diethyl ether as a solvent as “TEDE”, butyl diglycol as “BDG”, and diethylene glycol diethyl ether as “DDE”. In addition, each of the arbitrary 10 metal particles contained in each inkjet composition is observed, and the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan) and The ratio (S ₁ / S) 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.
₀ ) was determined, and the average value of these was also shown in Table 1. Also, using a vibrating viscometer,
The viscosities at 20 ° C. of the ink jet compositions (ultraviolet curable ink jet compositions) of the respective preparation examples measured in accordance with JIS Z8809 are all values in the range of 3 mPa · s to 15 mPa · s. Met.

[2] Droplet discharge stability evaluation (discharge stability evaluation)
Using the ink jet composition of each of the preparation examples, evaluation by the following tests was performed.
First, a droplet discharge device installed in a chamber (thermal chamber) and the ink jet composition of the above-described preparation example were prepared, and the driving waveform of the piezoelectric element was optimized at 25 ° C.
20% from each nozzle of the droplet discharge head for each color ink in an environment of 55% RH.
Continuous discharge of 00000 droplets (2000000 droplets) was performed. Thereafter, the operation of the droplet discharge device is stopped, and each ink is filled in the flow path of the droplet discharge device at 25 ° C. and 55% RH.
In the environment of 120 hours.

Thereafter, from each nozzle of the droplet discharge head, 30000 in an environment of 25 ° C. and 55% RH.
00 droplets (3 million droplets) were continuously discharged. After leaving for 120 hours,
For the 3000000 droplets ejected from the specified nozzle near the center of the droplet ejection head, the average value of the deviation amounts d from the center aiming position of the center position of each landed droplet is obtained, and the following five steps Evaluation was performed according to the criteria of It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amounts d is less than 0.9 μm.
B: The average value of the shift amount d is 0.9 μm or more and less than 1.5 μm.
C: The average value of the shift amount d is 1.5 μm or more and less than 2.4 μm.
D: The average value of the shift amounts d is 2.4 μm or more and less than 3.0 μm.
E: The average value of the shift amount d is 3.0 μm or more.

[3] Storage stability evaluation of ink jet composition (long-term stability evaluation)
About the composition for inkjet of each said preparation example, after leaving it to stand in a 40 degreeC environment for 20 days, it observed visually and evaluated according to the following five 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 preparation examples, it was introduced into an Epson inkjet printer; PM800C, and a base material manufactured by Mitsubishi Plastics, Diafoil G440E (
Using a thickness of 38 μm), solid printing was performed at an ink amount of 9 g / m ² , and after printing,
LED-UV lamp immediately; RX firefly made by Foseon (gap 6mm
1000 mW / cm ² ) was irradiated with ultraviolet rays to confirm whether or not the inkjet composition was cured, 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. The following A
Whether or not the irradiation dose falls within the range of ~ E can be calculated according to how many seconds the lamp has been 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.
These results are shown in Table 2.

[5] Manufacture of recorded matter (Example 1)
Inkjet composition prepared in Preparation Example 1 (UV curable inkjet composition)
Was used to produce an interior panel as a recorded material as follows.
First, the inkjet composition immediately after production was put into an inkjet apparatus.

Polyethylene terephthalate (Diafoil G440E 3 manufactured by Mitsubishi Plastics, Inc.)
The ink-jet composition was discharged in a predetermined pattern (composition application step).
Thereafter, ultraviolet rays having a spectrum having a maximum value at wavelengths of 365 nm, 380 nm, and 395 nm are irradiated, irradiation intensity of 180 mW / cm ² is irradiated for 20 seconds, the inkjet composition on the recording medium is cured, and a printed layer is formed. A record was obtained.
Ten recorded items were produced using the method as described above.

(Examples 2 to 13)
While using what is shown in Table 3 as an inkjet composition, the thickness of a printing layer is shown in Table 3.
A recorded matter was produced in the same manner as in Example 1 except for the above.
(Comparative Examples 1-4)
While using what is shown in Table 3 as an inkjet composition, the thickness of a printing layer is shown in Table 3.
A recorded matter was produced in the same manner as in Example 1 except for the 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 forming portion of each recorded matter produced in each of the above Examples and Comparative Examples, a glossiness meter (
Using MINOLTA MULTI GLOSS 268), the glossiness at a turning angle of 60 ° was measured and evaluated according to the following criteria.
A: Glossiness is 300 or more.
B: Glossiness is 200 or more and less than 300.
C: Glossiness is 100 or more and less than 200.
D: Glossiness is less than 100.

[6.3] Scratch resistance 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 [5.2] above, the glossiness (turning angle 60 °) of the recorded material after the abrasion resistance test was also measured, and the glossiness before and after the abrasion resistance test was measured. The reduction rate was determined and evaluated according to the following criteria.
A: The reduction rate of glossiness is less than 10%.
B: The reduction rate of glossiness is 10% or more and less than 20%.
C: The reduction rate of glossiness is 20% or more and less than 30%.
D: The reduction rate of the glossiness is 30% or more, or the metal particles fall off and the base can be seen.
These results are shown in Table 3.

As is apparent from Table 3, the recorded matter of the present invention had excellent gloss and appearance, and was excellent in the abrasion resistance of the printed layer. On the other hand, in the comparative example, a satisfactory result was not obtained.

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)

A method for producing a recorded matter, comprising producing a recorded matter using an ultraviolet curable inkjet composition comprising metal particles and a polymerizable compound,
A composition application step of applying the ultraviolet curable inkjet composition to a recording medium by an inkjet method;
A polymerization step of polymerizing the polymerizable compound by irradiating with ultraviolet rays to form a printed layer, and
The method for producing a recorded matter, wherein the thickness of the printed layer is 1/200 ^1/2 or less of an average value of the maximum length of the metal particles.   The method for producing a recorded matter according to claim 1, wherein the metal particles have a scaly shape.   The method for manufacturing a recorded matter according to claim 1, wherein the metal particles include aluminum. The method for producing a recorded matter according to any one of claims 1 to 3, wherein the ultraviolet curable inkjet composition contains 10% by mass or more of a solvent. The method for producing a recorded matter according to any one of claims 1 to 4, wherein the recording medium has an ink receiving layer on a surface to which the ultraviolet curable ink jet composition is applied. The method for producing a recorded matter according to any one of claims 1 to 5, wherein the ultraviolet curable ink jet 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 the polymerizable compound.
The method for producing a recorded matter according to claim 6, comprising at least one selected from the group consisting of 4-hydroxybutyl acrylate. The method for producing a recorded matter according to any one of claims 1 to 7, wherein the ultraviolet curable ink jet composition contains dimethylol tricyclodecane diacrylate and / or amino acrylate as the polymerizable compound. A recorded matter produced using the method according to any one of claims 1 to 8.

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