JP2013227453A - Ultra-violet curing type inkjet composition and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultra-violet curing type inkjet composition usable suitably for forming a pattern (a printing portion) excellent in storage stability, and excellent in glossiness feeling and friction resistance, and to provide recorded matter having the pattern excellent in the glossiness feeling and the friction resistance formed by using the ultra-violet curing type inkjet composition.SOLUTION: An ultra-violet curing type inkjet composition includes a polymerizable compound, metal powder, and a dispersant, the metal powder includes one surface-treated with an alkyl phosphate, and the dispersant includes one having basic polymer structure.

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. In addition, the foil stamping printing has a problem that it is difficult to cope with multi-product production because it has low on-demand property, and gradation-like metallic printing cannot be performed.

On the other hand, as a recording method on a recording medium using a composition containing a pigment or a dye, a recording method using an inkjet method is used. The ink jet method is excellent in that it can be suitably applied to formation of a fine pattern and recording on a curved surface portion. In recent years, compositions that cure when irradiated with ultraviolet rays (ultraviolet curable inkjet compositions) have been used in the ink jet method in order to achieve particularly excellent abrasion resistance, water resistance, solvent resistance, and the like. (For example, refer to Patent Document 1).
However, in the ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. In addition, the composition has poor stability (storage stability), and causes problems such as a decrease in ejection stability due to an increase in viscosity due to gelation.

JP 2009-57548 A

  An object of the present invention is to provide an ultraviolet curable inkjet composition that can be suitably used for forming a pattern (printed portion) having excellent storage stability, glossiness, and abrasion resistance, It is an object of the present invention to provide a recorded matter having a pattern excellent in glossiness and abrasion resistance formed using an ultraviolet curable ink jet composition.

Such an object is achieved by the present invention described below.
The ultraviolet curable inkjet composition of the present invention is ejected by an inkjet method,
A polymerizable compound, a metal powder, and a dispersant;
The metal powder includes a surface treated with an alkyl phosphate ester,
The dispersant includes a basic one having a polymer structure.
Thereby, it is possible to provide an ultraviolet curable inkjet composition that can be suitably used for the production of a recorded product having a pattern (printing portion) having excellent storage stability, glossiness, and abrasion resistance. .

In the ultraviolet curable inkjet composition of the present invention, it is preferable that the metal powder is obtained by subjecting at least a surface mainly composed of Al to a surface treatment with a phosphoric acid alkyl ester.
Al originally exhibits a particularly excellent gloss feeling among various metal materials. However, when a powder composed of Al is applied to an ultraviolet curable inkjet composition, it is used for an ultraviolet curable inkjet. The inventor has found that the storage stability of the composition is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation are particularly prominent. On the other hand, in this invention, even if it is a case where the surface uses the powder comprised by Al, generation | occurrence | production of the above problems can be prevented reliably. That is, the effect of the present invention is particularly remarkable when the metal powder constituting the ultraviolet curable ink jet composition is a powder whose surface is mainly composed of Al and is surface-treated with an alkyl phosphate ester. Demonstrated.

In the ultraviolet curable inkjet composition of the present invention, the metal powder preferably has a scaly shape.
Thereby, the glossiness, abrasion resistance, etc. of the recorded matter manufactured using the ultraviolet curable inkjet composition can be made particularly excellent.
In the ultraviolet curable ink jet composition of the present invention, the alkyl phosphate is preferably composed of only C, H, P, and O as constituent elements.
Thereby, the dispersibility of the metal powder in the dispersion medium becomes particularly excellent, and the dispersed state of the metal powder can be maintained without using a dispersant.

The ultraviolet curable inkjet composition of the present invention preferably includes the metal powder that has been surface-treated with the alkyl phosphate ester having a chemical structure represented by the following formula (1).
POR _n (OH) _3-n (1)
(In the formula (1), R _{is, CH 3 (CH 2) m} -, CH 3 (CH 2) m (CH 2 O) l -, CH 3 (CH 2) m (CH 2 CH 2 O) l - Or CH ₃ (CH ₂ ) _m O—, n is an integer of 1 to 3, m is an integer of 2 to 18, and l is an integer of 1 to 18.
As a result, the storage stability of the ultraviolet curable ink jet composition is particularly excellent, and the glossiness and abrasion resistance of the printed part of the recorded matter produced using the ultraviolet curable ink jet composition are particularly excellent. Can be.

In the ultraviolet curable inkjet composition of the present invention, the average particle size of the metal powder is preferably 500 nm or more and 3.0 μm or less.
Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.

The ultraviolet curable inkjet composition of the present invention preferably contains phenoxyethyl acrylate as the polymerizable compound.
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

In addition to the phenoxyethyl acrylate, the ultraviolet curable inkjet composition of the present invention includes 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, It is preferable that it contains at least one selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate and 4-hydroxybutyl acrylate.
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

The ultraviolet curable ink jet composition of the present invention includes, as the polymerizable compound, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, It preferably contains at least one selected from the group consisting of acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate.
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the abrasion resistance of the formed pattern can be further improved.

これにより、紫外線硬化型インクジェット用組成物の保存安定性、硬化性を特に優れたものとすることができる。また、紫外線硬化型インクジェット用組成物を用いて製造される記録物においては、金属粉末を構成する金属材料が本来有している光沢感・高級感をより効果的に発揮させ、印刷部の光沢感、耐擦性を特に優れたものとし、記録物の耐久性を特に優れたものとすることができる。 The ultraviolet curable inkjet composition of the present invention preferably further contains a substance A having a partial structure represented by the following formula (5).

Thereby, the storage stability and curability of the ultraviolet curable ink jet composition can be made particularly excellent. In addition, in the recorded matter produced using the ultraviolet curable ink jet composition, the glossiness and luxury feeling inherent in the metal material constituting the metal powder is more effectively exhibited, and the gloss of the printed part The feeling and abrasion resistance can be made particularly excellent, and the durability of the recorded matter can be made particularly excellent.

In the ultraviolet curable inkjet composition of the present invention, when the content of the substance A is X _A [% by mass] and the content of the metal powder is X _M [% by mass], 0.01 ≦ X _A / It is preferable to satisfy the relationship of X _M ≦ 0.8.
As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the glossiness and resistance of the printed part formed using the ultraviolet curable inkjet composition can be improved. The rubbing property can be further improved.
The recorded matter of the present invention is produced by applying the ultraviolet curable ink jet composition of the present invention onto a recording medium and then irradiating with ultraviolet rays.
Thereby, it is possible to provide a recorded matter having a pattern (printing portion) excellent in glossiness and abrasion resistance.

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

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

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

However, in the ultraviolet curable ink jet composition, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. In addition, the composition has poor stability (storage stability), and causes problems such as a decrease in ejection stability due to an increase in viscosity due to gelation.
Therefore, the inventor has intensively studied for the purpose of solving the above problems, and as a result, has reached the present invention. That is, the ultraviolet curable inkjet composition of the present invention includes a polymerizable compound and a surface treated with an alkyl phosphate as a metal powder, and further includes a basic dispersant having a polymer structure. It is a waste. As a result, the chemical stability and dispersion stability of the metal powder in the UV curable ink jet composition are excellent, and the storage stability of the UV curable ink jet composition and the long-term ejection stability are excellent. In addition, in the recorded matter manufactured using the ultraviolet curable ink jet composition, the metal powder can be suitably arranged in the vicinity of the outer surface of the printing portion, and the metal material constituting the metal powder Can fully exhibit the properties such as glossiness inherent in the. Further, even when a polymerizable compound having a low surface tension is used as a constituent material of an ultraviolet curable ink jet composition, a metal powder is reliably produced in a recorded matter produced using the ultraviolet curable ink jet composition. Can be suitably arranged (leafing) in the vicinity of the outer surface of the printing part, and the properties such as glossiness inherent in the metal material constituting the metal powder can be sufficiently exhibited. Therefore, the selection range of the polymerizable compound is widened, and the characteristics of the ultraviolet curable inkjet composition and the ultraviolet curable inkjet composition are manufactured without sacrificing the glossiness of the metal material. It is possible to easily adjust the characteristics of the recorded matter (for example, the viscosity, storage stability, ejection stability, and rubbing resistance of the recorded matter).

<Metal powder>
As described above, the ultraviolet curable inkjet composition of the present invention includes a metal powder that has been surface-treated with an alkyl phosphate ester.
(Mother particles)
First, mother particles constituting the metal particles (particles subjected to surface treatment with an alkyl phosphate ester) will be described.
The mother particles constituting the metal powder need only have at least a region including the vicinity of the surface made of a metal material. For example, the whole may be made of a metal material or a non-metal material. And a base made of a metal material covering the base.

  Further, as the metal material constituting the mother particle, a single metal, various alloys, or the like can be used. However, the mother particle is preferably composed mainly of Al at least near the surface. Al originally exhibits a particularly excellent gloss feeling among various metal materials. However, when a powder composed of Al is applied to an ultraviolet curable inkjet composition, it is used for an ultraviolet curable inkjet. The inventor has found that the storage stability of the composition is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation are particularly prominent. On the other hand, in this invention, even if it is a case where the surface uses the powder comprised by Al, generation | occurrence | production of the above problems can be prevented reliably. That is, the effect of the present invention is particularly remarkable when the metal powder constituting the ultraviolet curable ink jet composition is a powder whose surface is mainly composed of Al and is surface-treated with an alkyl phosphate ester. Demonstrated.

  Further, the mother particles may be produced by any method, but when they are made of Al, a film made of Al is formed by a vapor deposition method, and then It is preferably obtained by pulverizing the membrane. Thereby, the glossiness etc. which Al originally has in the pattern (printing part) formed using the ultraviolet curable inkjet composition of this invention can be expressed more effectively. Moreover, the dispersion | variation in the characteristic between each particle | grain can be suppressed. Moreover, even if it is a comparatively thin metal powder, it can manufacture suitably by using the said method.

When producing mother particles using such a method, for example, the mother particles can be suitably produced by forming a film made of Al (film formation) on a substrate. As the substrate, for example, a plastic film such as polyethylene terephthalate can be used. Further, the substrate may have a release agent layer on the film forming surface.
Moreover, it is preferable that the said grinding | pulverization is performed by providing an ultrasonic vibration to the said film | membrane in a liquid. This makes it possible to easily and surely obtain mother particles having the above-described particle diameter, and to suppress the variation in size, shape, and characteristics among the particles.

  When the pulverization is performed by the above method, the liquid includes alcohols such as methanol, ethanol, propanol, and butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, and cymene. , 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 , Diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, triplicate Ether compounds such as pyrene glycol dimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane, propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone , N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dimethyl sulfoxide, cyclohexanone, acetonitrile and the like can be preferably used. By using such a liquid, the productivity of the mother particles and metal powder is made particularly excellent while preventing unintentional oxidation of the mother particles, and the size, shape, and characteristics between each particle Can be made particularly small.

(Alkyl phosphate ester)
As described above, the metal powder according to the present invention is surface-treated with a phosphoric acid alkyl ester.
The phosphoric acid alkyl ester has a structure in which at least a part of OH groups of phosphoric acid is esterified with a functional group containing an alkyl group (C _n H _{2n + 1} — (where n is an integer of 1 or more)). It is.
It is preferable that the phosphoric acid alkyl ester contains only C, H, P, and O as constituent elements. Thereby, the dispersibility of the metal powder in the dispersion medium becomes particularly excellent, and the dispersed state of the metal powder can be maintained without using a dispersant.

In particular, the phosphoric acid alkyl ester preferably has a chemical structure represented by the following formula (1).
POR _n (OH) _3-n (1)
(In the formula (1), R _{is, CH 3 (CH 2) m} -, CH 3 (CH 2) m (CH 2 O) l -, CH 3 (CH 2) m (CH 2 CH 2 O) l - Or CH ₃ (CH ₂ ) _m O—, n is an integer of 1 to 3, m is an integer of 2 to 18, and l is an integer of 1 to 18.

As a result, the storage stability of the ultraviolet curable ink jet composition is particularly excellent, and the glossiness and abrasion resistance of the printed part of the recorded matter produced using the ultraviolet curable ink jet composition are particularly excellent. Can be.
In formula (1), m is preferably an integer of 3 or more and 14 or less, more preferably an integer of 4 or more and 12 or less. Thereby, the effects as described above are more remarkably exhibited.
In formula (1), l is preferably an integer of 1 or more and 14 or less, more preferably an integer of 1 or more and 10 or less. Thereby, the effects as described above are more remarkably exhibited.

Preferable specific examples of the alkyl phosphate ester include, for example, C ₁₄ H ₂₉ (O) P (OCH ₂ CH ₃ ) ₂ , C ₁₆ H ₃₃ (O) P (OCH ₂ CH ₃ ) ₂ , C ₁₈ H ₃₇ ( _{O) P (OH) 2,} C 18 H 37 (O) P (OH) (OCH 2 CH 3), C 12 H 25 (O) P (OCH 2 CH 3) 2, C 12 H 25 (O) P _{(OCH 2 CH 3)} 2 and the like.
The alkyl phosphate ester as described above may be processed directly on the mother particles, but after the mother particles are treated with an acid or base, the mother particles are treated with an alkyl phosphate ester. It is preferable to carry out the treatment. Thereby, the modification | change by the chemical coupling | bonding by phosphoric acid alkylester can be more reliably performed on the mother particle surface, and the effect by this invention as mentioned above can be exhibited more effectively. In addition, even when an oxide film is formed on the surface of the particles to be the mother particles before the surface treatment with the phosphoric acid alkyl ester, the oxide film can be reliably removed. Since the surface treatment with the phosphoric acid alkyl ester can be performed in the removed state, the glossiness of the produced metal powder can be made particularly excellent. Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, hyposulfite, nitrous acid, hyponitrous acid, phosphorous acid, and the following. Protic acids such as phosphorous acid can be used. Of these, hydrochloric acid, phosphoric acid, and acetic acid are preferable. On the other hand, as the base, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide or the like can be used. Of these, sodium hydroxide and potassium hydroxide are preferred.

  The metal powder may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably has a scaly shape. Thereby, on the recording medium to which the ultraviolet curable 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. In addition, the rub resistance of the recorded matter can be made particularly excellent. Moreover, in the structure which has not performed the surface treatment by the phosphoric acid alkyl ester as mentioned above, when the metal powder has a scaly shape, the storage stability and ejection stability of the ultraviolet curable ink jet composition are low. However, in the present invention, even when the metal powder has a scaly shape, the occurrence of such a problem can be reliably prevented. That is, when the shape of the metal powder is scaly, the effect of the present invention is more remarkably exhibited.

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

The average particle size of the metal powder is preferably 500 nm or more and 3.0 μm or less, and more preferably 800 nm or more and 1.8 μm or less. Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable inkjet composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable ink jet composition can be further improved.
The content of the metal powder in the ultraviolet curable inkjet composition is preferably 0.5% by mass or more and 10.0% by mass or less, and more preferably 1.0% by mass or more and 5.0% by mass or less. More preferred.

<Dispersant>
In addition to the metal powder as described above, the ultraviolet curable inkjet composition of the present invention includes a basic dispersant having a polymer structure (hereinafter also referred to as “basic polymer dispersant”). It is a waste.
Accordingly, the ultraviolet curable inkjet composition can be suitably used for the production of a recorded matter having a pattern (printing portion) having excellent storage stability, glossiness, and abrasion resistance. Can do. Such an excellent effect is obtained by including a metal powder (surface-treated with an alkyl phosphate ester) as described above and a basic polymer dispersant, and the metal powder as described above. When only one of the basic polymer dispersants is contained, the excellent effects as described above cannot be obtained.

In the present invention, the basic polymer dispersant is not particularly limited as long as it shows basicity and has a polymer structure.
The polymer structure constituting the basic polymer dispersant is not particularly limited. For example, an acrylic polymer structure (including a copolymer), a methacrylic polymer structure (including a copolymer), and polyurethane. Examples thereof include a polymer structure, a hydroxyl group-containing carboxylic acid ester structure, a polyether polymer structure, and a silicone polymer structure.

The amine value of the basic polymer dispersant is not particularly limited, but is preferably 3 mgKOH / g or more and 80 mgKOH / g or less, more preferably 10 mgKOH / g or more and 70 mgKOH / g or less.
Specific examples of the basic polymer dispersant that can be used in the present invention include DISPERBYK-116 (manufactured by Big Chemie), DISPERBYK-182 (manufactured by Big Chemie), DISPERBYK-183 (manufactured by Big Chemie), DISPERBYK-184 ( Bicchemy), DISPERBYK-2155 (Bicchemy), DISPERBYK-2164 (Bicchemy), DISPERBYK-108 (Bicchemy), DISPERBYK-112 (Bicchemy), DISPERBYK-198 (Bicchemy), DISPERBYK-2150 (manufactured by Big Chemie), PAA-1112 (manufactured by Nittobo), and the like.

  The content of the basic polymer dispersant in the ultraviolet curable inkjet composition is preferably 0.01% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 2.0% by mass or less. It is more preferable that As a result, the storage stability, ejection stability, and curability of the ultraviolet curable inkjet composition can be further improved, and the gloss of the recorded matter produced using the ultraviolet curable inkjet composition can be improved. The feeling, abrasion resistance, etc. can be further improved. The ultraviolet curable ink jet composition may contain two or more compounds as a basic polymer dispersant. In this case, it is preferable that the total content of these compounds is a value within the above range.

<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, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, phenylglycidyl ether acrylate, phenoxy Diethylene glycol 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-propane Diol diacrylate, tripropylene glycol diacrylate, Traethylene 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 di Acrylate, neopentyl glycol hydroxypivalate diacrylate, 2-ethyl-2-butyl-propanediol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol 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, tris (Acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, 1-adamantylmethyl acrylate, 1-adamantyl acrylate, 2- Acryloyloxyethyl phthalate, isobornyl acrylate, 3-actyl Leuoxypropyl acrylate, acryloylmorpholine, lipoxy SP series, dicyclopentanyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, w-carboxyacryloyloxyethyl phthalate, dimethylol dicyclopentane diacrylate, diacrylated isosialate / tri Examples include acrylated mixtures, neopentyl glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta / hexaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane PO-modified triacrylate, diethylene glycol diethyl ether, and the like. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol Propane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate are preferred.

  In particular, the ultraviolet curable ink jet composition preferably contains phenoxyethyl acrylate as the polymerizable compound. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

  In addition to phenoxyethyl acrylate, the ultraviolet curable ink jet composition is composed of 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy as a polymerizable compound. It is preferable that it contains at least one selected from the group consisting of 3-phenoxypropyl acrylate and 4-hydroxybutyl acrylate. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition are excellent, and the reactivity of the ultraviolet curable inkjet composition after ejection by the inkjet method is particularly excellent. The productivity of the pattern can be made particularly excellent, and the rub resistance of the formed pattern can be made particularly excellent.

  In addition, the ultraviolet curable ink jet composition includes, as the polymerizable compound, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acryloyl. It is preferable to include at least one selected from the group consisting of morpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the abrasion resistance of the formed pattern can be further improved.

  Moreover, the ultraviolet curable 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.

  The content of the polymerizable compound in the ultraviolet curable inkjet composition is preferably 70% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass or less. As a result, the storage stability, ejection stability, and curability of the ultraviolet curable inkjet composition can be further improved, and the gloss of the recorded matter produced using the ultraviolet curable inkjet composition can be improved. The feeling, abrasion resistance, etc. can be further improved. The ultraviolet curable inkjet composition may contain two or more compounds as the polymerizable compound. In this case, it is preferable that the total content of these compounds is a value within the above range.

<Substance A>
Moreover, it is preferable that the ultraviolet curable inkjet composition of this invention contains the substance A which has the partial structure shown by following formula (5).

  The ultraviolet curable ink jet composition contains the substance A having such a chemical structure together with the metal particles subjected to the surface treatment as described above and the basic polymer dispersant, thereby forming the ultraviolet curable ink jet composition. The storage stability and curability of the product can be made particularly excellent. In addition, in the recorded matter produced using the ultraviolet curable ink jet composition, the glossiness and luxury feeling inherent in the metal material constituting the metal powder is more effectively exhibited, and the gloss of the printed part The feeling and abrasion resistance can be made particularly excellent, and the durability of the recorded matter can be made particularly excellent.

In the formula (5), R ¹ may be a hydrogen atom, a hydrocarbon group or an alkoxyl group (a chain or alicyclic hydrocarbon group bonded to an oxygen atom), particularly a hydrogen atom, methyl It is preferably a group or an octyloxy group. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the glossiness and resistance of the printed part formed using the ultraviolet curable inkjet composition can be improved. The rubbing property can be further improved.

In Formula (5), R ^{2 to} R ⁵ may be independently a hydrogen atom or a hydrocarbon group, but are preferably an alkyl group having 1 to 3 carbon atoms, and is a methyl group. Is more preferable. As a result, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the glossiness and resistance of the printed part formed using the ultraviolet curable inkjet composition can be improved. The rubbing property can be further improved.

  The content of the substance A in the ultraviolet curable ink jet composition is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass or less. . As a result, the storage stability, ejection stability, and curability of the ultraviolet curable inkjet composition can be further improved, and the gloss of the recorded matter produced using the ultraviolet curable inkjet composition can be improved. The feeling, abrasion resistance, etc. can be further improved. The ultraviolet curable inkjet composition may contain two or more compounds as the substance A. In this case, it is preferable that the total content of these compounds is a value within the above range.

When the content of the substance A is X _A [mass%] and the content of the metal powder is X _M [mass%], it is preferable that the relationship of 0.01 ≦ X _A / X _M ≦ 0.8 is satisfied. More preferably, the relationship 0.05 ≦ X _A / X _M ≦ 0.4 is satisfied. By satisfying such a relationship, the storage stability and ejection stability of the ultraviolet curable inkjet composition can be further improved, and the ultraviolet curable inkjet composition is formed. The glossiness and abrasion resistance of the printed part can be further improved.

<Other ingredients>
The ultraviolet curable inkjet composition of the present invention may contain components other than those described above (other components). Examples of such components include photopolymerization initiators, slip agents (leveling agents), dispersants other than basic polymer dispersants, polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants). , Colorants, fixing agents, antifungal agents, antiseptics, antioxidants, chelating agents, thickeners, sensitizers (sensitizing dyes) and the like.

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

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

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

The content of the photopolymerization initiator in the ultraviolet curable inkjet composition is preferably 0.5% by mass or more and 10% by mass or less. When the content of the photopolymerization initiator is within the above range, the ultraviolet curing rate is sufficiently high, and the photopolymerization initiator is hardly dissolved or colored due to the photopolymerization initiator.
When the ultraviolet curable 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. .

  The ultraviolet curable inkjet composition of the present invention may contain a polymerization inhibitor, but even when it contains a polymerization inhibitor, the polymerization inhibitor in the ultraviolet curable inkjet composition. The content of is preferably 0.6% by mass or less, and more preferably 0.2% by mass or less. Accordingly, since the content of the polymerizable compound in the ultraviolet curable inkjet composition can be relatively increased, the abrasion resistance of the printed portion formed using the ultraviolet curable inkjet composition can be increased. The property and the like can be made particularly excellent. In the present invention, even when the content of the polymerization inhibitor is relatively low, the storage stability and ejection stability of the ultraviolet curable ink jet composition may be sufficiently excellent. it can.

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.

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

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

  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 lids, switch bases, center clusters, interior panels, emblems, center consoles, meter nameplates and other vehicle interior parts, operation parts (key switches) of various electronic devices, indoors Examples include advertisements, gift boxes for confectionery, cosmetic boxes, tarpaulins and other outdoor advertisements, decorative parts that exhibit decorative properties, indicators, logos and other display objects.

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

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

Next, specific examples of the present invention will be described.
[1] Production of inkjet composition (UV-curable inkjet composition) (Example 1)
First, a film made of polyethylene terephthalate having a smooth surface (surface roughness Ra of 0.02 μm or less) was prepared.

Next, silicone oil was applied to the entire one surface of the film.
Next, a film made of Al was formed on the side coated with silicone oil by vapor deposition.
Next, a polyethylene terephthalate film (base material) on which an Al film was formed was placed in a liquid composed of diethylene glycol diethyl ether, and ultrasonic vibration was applied. As a result, a dispersion (dispersion) of scaly Al particles (particles to be mother particles) was obtained. The content of Al particles in the dispersion was 3.7% by mass.

Next, C ₁₂ H ₂₅ (O) P (OH) (OCH ₂ CH ₃ ) as an alkyl phosphate is added to the dispersion containing Al particles obtained as described above, and the liquid temperature : Surface treatment reaction was carried out at 55 ° C. while applying ultrasonic vibration for 3 hours. After completion of the reaction, the surface-treated Al particles (metal powder) are spun down in a centrifuge (6000 rpm × 30 minutes), the supernatant is discarded, and then diethylene glycol diethyl ether is added. Furthermore, by applying ultrasonic vibration, the metal powder was redispersed to obtain a dispersion liquid (redispersion liquid) having a metal powder content of 3.7% by mass. This re-dispersed liquid was concentrated with an evaporator to obtain a paste-like dispersion liquid (dispersion medium: diethylene glycol diethyl ether) having a metal powder content of 10% by mass. The average particle diameter of the metal powder thus obtained was 0.8 μm, and the average thickness was 60 nm.

  Next, DISPERBYK-183 (manufactured by Big Chemie) as a dispersant having a polymer structure (basic polymer dispersant), phenoxyethyl acrylate, and photopolymerization are started. Irgacure 819 (manufactured by Ciba Japan) as an agent, Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, and the following formula (6) By mixing with a substance A having a chemical structure, an inkjet composition (ultraviolet curable inkjet composition) was obtained.

(Examples 2 to 11)
The composition of the metal particles (the composition of the mother particles and the type of compound (phosphoric acid alkyl ester) used for the surface treatment) is as shown in Tables 1 and 2, and the inkjet composition (ultraviolet curable inkjet composition) An ink jet composition (ultraviolet curable ink jet composition) in the same manner as in Example 1 except that the composition shown in Tables 1 and 2 was changed by changing the type and ratio of raw materials used for the preparation. Product).

(Comparative Example 1)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1 except that Al particles that were not subjected to surface treatment were used as the metal powder.
(Comparative Example 2)
The inkjet composition (ultraviolet curable inkjet composition) was used in the same manner as in Comparative Example 1 except that a spherical Al powder (non-surface-treated) manufactured using the gas atomization method was used as the metal powder. Product).

(Comparative Example 3)
Instead of C ₁₂ H ₂₅ (O) P (OCH ₂ CH ₃ ) ₂ as a phosphoric acid alkyl ester, surface treatment was performed using H ₃ PO ₄ that is not a phosphoric acid alkyl ester, and a metal powder was obtained. In the same manner as in Example 1, an inkjet composition (ultraviolet curable inkjet composition) was produced.

(Comparative Example 4)
An inkjet composition (ultraviolet curable inkjet composition) was produced in the same manner as in Example 1, except that the basic polymer dispersant was not used and the content of each component was as shown in Table 2.
(Comparative Example 5)
Instead of the basic polymer dispersant, an ink jet composition (as in Example 1 above) was used except that Emanon 4110 (manufactured by Kao Corporation) as a dispersant having a polymer structure but not basic was used. UV-curable inkjet composition) was produced.
(Comparative Example 6)
An inkjet composition (in the same manner as in Example 1 except that Nonion P-208 (manufactured by NOF Corporation) as a dispersant having no polymer structure was used instead of the basic polymer dispersant. UV-curable inkjet composition) was produced.

Tables 1 and 2 collectively show the composition of the ink jet composition for each of the above Examples and Comparative Examples. In the table, C ₁₂ H ₂₅ (O) P (OH) (OCH ₂ CH ₃ ) is “S1”, (C ₁₄ H ₂₉ ) ₃ (O) P is “S2”, and (C ₁₆ H ₃₃ ) _2. (O) P (OH) is “S3”, C ₁₈ H ₃₇ (O) P (OH) (OCH ₂ CH ₃ ) is “S4”, (C ₁₈ H ₃₇ ) ₂ (O) P (C ₁₆ H ₃₃ ) Is “S5”, C ₁₄ H ₂₉ (O) P (OH) (OCH ₂ CH ₂ CH ₂ CH ₃ ) is “S6”, H ₃ PO ₄ is “S′1”, DISPERBYK-183 (manufactured by BYK Chemie) , Amine value: 17 mgKOH / g) “D1”, DISPERBYK-182 (manufactured by Big Chemie, amine value: 13 mgKOH / g) “D2”, DISPERBYK-184 (manufactured by Big Chemie, amine value: 15 mgKOH / g) “ D3 ", DISP RBYK-116 (by Big Chemie, amine value: 65 mgKOH / g) is “D4”, DISPERBYK-2155 (by Big Chemie, amine value: 48 mgKOH / g) is “D5”, DISPERBYK-2164 (by Big Chemie, amine value) : 14 mgKOH / g) “D6”, PAA-1112 (manufactured by Nittobo Co., Ltd.) “D7”, Emanon 4110 (manufactured by Kao Corporation) “D′ 1”, Nonion P-208 (manufactured by NOF Corporation) "D'2", phenoxyethyl acrylate "PEA", tripropylene glycol diacrylate "TPGDA", dipropylene glycol diacrylate "DPGDA", 2-hydroxy 3-phenoxypropyl acrylate "HPPA", N- Vinyl caprolactam "VC", dimethylol Cyclodecane diacrylate is "DMTCDDA", dimethylol dicyclopentane diacrylate is "DMDCPTA", dicyclopentenyl acrylate is "DCPTeA", dicyclopentanyl acrylate is "DCPTaA", isobornyl acrylate is "IBA", acryloyl Morpholine “AM”, tetrahydrofurfuryl acrylate “THFA”, ethyl carbitol acrylate “ECA”, methoxytriethylene glycol acrylate “MTEGA”, 2- (2-hydroxyethoxy) ethyl acrylate “VEEA”, 4-Hydroxybutyl acrylate is “HBA”, benzyl methacrylate is “BM”, urethane acrylate is “UA”, the compound represented by the above formula (6) (substance A) is “A1”, The compound (substance A) represented by the formula (7) is “A2”, the compound (substance A) represented by the following formula (8) is “A3”, and the substance A represented by the following formula (9) is “ A4 ", Irgacure 819 (Ciba Japan)" ic819 ", Speedcure TPO (ACETO)" scTPO ", Speedcure DETX (Lambson)" scDETX ", UV-3500 (Bicchemy) “UV3500” and hydroquinone monomethyl ether are indicated by “MEHQ”. Moreover, about Example 9, the composition of the constituent material of a mother particle showed the content rate of each element with the weight ratio about Example 9. In addition, the observation is performed on each of the 10 arbitrary metal particles contained in each inkjet composition, and the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan), The ratio (S ₁ / S ₀ ) to the area S ₀ [μm ² ] when observed from the direction in which the area when observed is the maximum among the directions orthogonal to the observation direction is determined, and the average value of these is expressed as 1 and Table 2 are also shown. In addition, the viscosity at 20 ° C. of the inkjet compositions (ultraviolet curable inkjet compositions) of each of the above 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. D1 to D7 are all basic and have a polymer structure (basic polymer dispersant).

[2] Droplet discharge stability evaluation (discharge stability evaluation)
Using the inkjet compositions of the respective Examples and Comparative Examples, the evaluation by the following tests was performed.
First, a droplet discharge device installed in a chamber (thermal chamber) and the ink-jet compositions of the above examples and comparative examples are prepared, and the driving waveform of the piezo element is optimized, at 25 ° C. and 55% RH. Under the environment, about 2 million droplets (2000000 droplets) were continuously discharged from each nozzle of the droplet discharge head for each inkjet composition. 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 240 hours in a state where each ink jet composition was filled in the flow path.

  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. The average deviation amount d from the center target position of the center position of each landed droplet for the 4000000 droplets discharged from the designated nozzle near the center of the droplet discharge head after being left for 150 hours. Values were obtained and evaluated according to the following five-step criteria. It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amounts d is less than 0.17 μm.
B: The average value of the shift amounts d is 0.17 μm or more and less than 0.24 μm.
C: The average value of the shift amount d is 0.24 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 0.31 μm.
E: The average value of the shift amounts d is 0.31 μm or more.

[3] Frequency characteristics of inkjet composition In the state in which the droplet ejection device installed in the chamber (thermal chamber) and the inkjet compositions of the respective examples and comparative examples are prepared and the drive waveform of the piezoelectric element is optimized, In an environment of 25 ° C. and 55% RH, each ink jet composition was subjected to droplet discharge while changing the frequency (frequency) of the piezo element from all nozzles of the droplet discharge head. The droplet discharge time at each frequency was 10 minutes. The frequency range that can be actually used was evaluated according to the following four-stage criteria, with the number of undischarged nozzles being less than 1% of the total number of nozzles at the time point after 10 minutes of discharge as the highest frequency that can be actually used. It can be said that the larger this value, the better the frequency characteristics.
A: 12 kHz or more.
B: 7 kHz or more and less than 12 kHz.
C: 3 kHz or more and less than 7 kHz.
D: Less than 3 kHz.

[4] Storage stability evaluation of inkjet composition (long-term stability evaluation)
About the inkjet composition of each said Example and a comparative example, after leaving for 40 days in an environment of 40 degreeC, the inkjet composition of each said Example measured based on JISZ8809 using a vibration-type viscometer. The viscosity of the product at 20 ° C. was measured, the rate of increase in viscosity immediately after production was determined, and evaluated according to the following criteria.

A: Increase rate of viscosity is less than 10%.
B: Increase rate of viscosity is 10% or more and less than 15%.
C: Increase rate of viscosity is 15% or more and less than 20%.
D: Increase rate of viscosity is 20% or more and less than 25%.
E: The rate of increase in viscosity is 25% or more, or generation of foreign matter is observed.

[5] Curability About the ink jet compositions of the respective Examples and Comparative Examples, the ink jet printer manufactured by Epson; introduced into PM800C, and using Diafoil G440E (thickness 38 μm) manufactured by Mitsubishi Resin Co., Ltd. as a recording medium, Solid printing was performed at an ink amount of 9 g / m ^2. Immediately after printing, the LED-UV lamp; Foseon's RX firefly (gap 6 mm, peak wavelength 365 nm, 1000 mW / cm ² ) was used to irradiate ultraviolet rays, and inkjet Whether the composition was cured or not was evaluated and evaluated according to the following five-step criteria. Whether it was cured or not was determined by rubbing the surface with a cotton swab and whether or not the uncured ink composition adhered. In addition, whether it corresponds to the irradiation amount of the following AE can be calculated by how many seconds the lamp is irradiated.

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

[6] Manufacture of Recorded Items Using the inkjet compositions of the examples and comparative examples, interior panels as recorded products were manufactured as follows.
First, the inkjet composition was put into an inkjet apparatus.
Thereafter, the inkjet composition was discharged in a predetermined pattern onto a base material (recording medium) having a curved surface portion formed using polycarbonate (Asahi Glass Co., Ltd., Carboglass polish 2 mm thickness).

Thereafter, ultraviolet rays having a spectrum having maximum values at wavelengths of 365 nm, 380 nm, and 395 nm are irradiated at an irradiation intensity of 180 mW / cm ² for 15 seconds to cure the ink jet composition on the substrate, thereby obtaining an interior panel as a recorded matter. It was.
Using the method as described above, ten interior panels (recorded matter) were produced using the ink-jet compositions of the examples and comparative examples.

  Moreover, what was shape | molded using polyethylene terephthalate (Diafoil G440E 38micrometer thickness made from Mitsubishi Plastics) as a base material, low density polyethylene (TuX (L-LDPE) HC-E # 80 made from Mitsui Chemicals, Inc. cello). ), Biaxially stretched polypropylene (OP U-1 # 60 made by Mitsui Chemical Tosero Co., Ltd.), hard vinyl chloride (Sunday sheet (transparent) 0.5 mm thickness made by Acrysandy Co.) Ten interior panels (recorded matter) were produced in the same manner as described above except that the ones molded using the same were used, using the inkjet compositions of the examples and comparative examples.

[7] Evaluation of recorded matter Each recorded matter obtained as described above was evaluated as follows.
[7.1] 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.

[7.2] 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 400 or more.
B: Glossiness is 300 or more and less than 400.
C: Glossiness is 200 or more and less than 300.
D: Glossiness is less than 200.

[7.3] Abrasion resistance With respect to the recorded matter according to each of the above examples and comparative examples, when 48 hours have elapsed since the production of the recorded matter, a Southerland Lab Tester was used and polyethylene terephthalate was used as a phase paper according to JIS K5701. A rub resistance test using a film made by Mitsubishi Plastics (Diafoil G440E) was performed, and the recorded material after the rub resistance test was also glossy by the same method as described in [7.2] above. The degree of reduction in gloss before and after the abrasion resistance test was determined and evaluated according to the following criteria.

A: The reduction rate of glossiness is less than 10%.
B: The reduction rate of glossiness is 10% or more and less than 20%.
C: The reduction rate of glossiness is 20% or more and less than 30%.
D: The reduction rate of glossiness is 30% or more and less than 40%.
E: Gloss reduction rate is 40% or more, or the surface of the recording medium is exposed due to metal particles falling off.

  These results are shown in Table 3. In Table 3, “M1” is a recorded matter manufactured using a polycarbonate substrate, “M2” is a recorded material manufactured using a polyethylene terephthalate substrate, and a low density polyethylene substrate. “M3” is a recorded matter manufactured using a biaxially oriented polypropylene base material, and “M4” is a recorded matter manufactured using a biaxially oriented polypropylene base material. Indicated by “M5”.

  As is clear from Table 3, the ultraviolet curable inkjet composition of the present invention was excellent in droplet ejection stability, storage stability, and curability. Further, the recorded matter of the present invention had excellent gloss and appearance, and was excellent in the abrasion resistance of the pattern forming portion. On the other hand, in the comparative example, a satisfactory result was not obtained.

Claims (12)

An ultraviolet curable ink jet composition discharged by an ink jet method,
A polymerizable compound, a metal powder, and a dispersant;
The metal powder includes a surface treated with an alkyl phosphate ester,
An ultraviolet curable ink jet composition comprising a basic dispersant having a polymer structure as the dispersant.   2. The ultraviolet curable ink jet composition according to claim 1, wherein the metal powder is a powder whose surface is mainly composed of Al and is surface-treated with an alkyl phosphate.   The ultraviolet curable ink jet composition according to claim 1, wherein the metal powder has a scaly shape.   The ultraviolet curable inkjet composition according to any one of claims 1 to 3, wherein the phosphoric acid alkyl ester contains only C, H, P, and O as constituent elements. The ultraviolet curable inkjet composition according to any one of claims 1 to 4, wherein the metal powder includes a surface treated with the alkyl phosphate ester having a chemical structure represented by the following formula (1).
POR _n (OH) _3-n (1)
(In the formula (1), R _{is, CH 3 (CH 2) m} -, CH 3 (CH 2) m (CH 2 O) l -, CH 3 (CH 2) m (CH 2 CH 2 O) l - Or CH ₃ (CH ₂ ) _m O—, n is an integer of 1 to 3, m is an integer of 2 to 18, and l is an integer of 1 to 18.   The ultraviolet curable ink jet composition according to claim 1, wherein the metal powder has an average particle size of 500 nm to 3.0 μm.   The ultraviolet curable ink jet composition according to any one of claims 1 to 6, wherein the polymerizable compound contains phenoxyethyl acrylate.   As the polymerizable compound, in addition to the phenoxyethyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy 3-phenoxypropyl acrylate, and 4 The ultraviolet curable inkjet composition according to claim 7, comprising at least one selected from the group consisting of -hydroxybutyl acrylate.   Examples of the polymerizable compound include dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate. And at least one selected from the group consisting of methoxytriethylene glycol acrylate. The ultraviolet curable ink jet composition according to any one of claims 1 to 8. The ultraviolet curable inkjet composition according to any one of claims 1 to 9, wherein the ultraviolet curable inkjet composition further comprises a substance A having a partial structure represented by the following formula (5).

Claims satisfying a relationship of 0.01 ≦ X _A / X _M ≦ 0.8, where X _A [mass%] is the content of the substance A and X _M [mass%] is the metal powder. Item 11. The ultraviolet curable inkjet composition according to any one of Items 1 to 10.   A recorded matter produced by applying the ultraviolet curable inkjet composition according to claim 1 onto a recording medium and then irradiating with ultraviolet rays.