JP2016169380A - Ultraviolet curable composition and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet curable composition having excellent discharge stability in an inkjet process and allowing stable formation of a pattern (printed part) with excellent glossiness, and to provide a recorded matter having a pattern (printed part) with excellent glossiness.SOLUTION: The ultraviolet curable composition of the present invention comprises a polymerizable compound and a metal powder. The metal powder includes a surface-treated material as constituent particles, and the metal powder has a volume average particle diameter of 0.2 μm or more and 0.64 μm or less. The metal powder preferably contains a material that is surface treated with a fluorine-based surface treating agent as constituent particles.SELECTED DRAWING: None

Description

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

  Conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.

  However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion.

  On the other hand, a recording method in which a composition containing a pigment or dye is applied to a recording medium by an ink jet method is used. Such a 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 compositions) have been used in order to make the abrasion resistance, water resistance, solvent resistance, etc. particularly excellent (for example, patents). Reference 1).

  However, simply trying to apply metal powder instead of pigment or dye is inferior in droplet ejection stability by the ink jet method, tends to cause ejection failure, and has inherent properties such as glossiness inherent in metal. There was a problem that it was not possible to fully exhibit.

JP 2009-57548 A

  An object of the present invention is to provide an ultraviolet curable composition capable of stably forming a pattern (printed portion) having excellent ejection stability by an inkjet method and excellent gloss, and also having excellent gloss. Another object of the present invention is to provide a recorded matter having a different pattern (printing portion).

Such an object is achieved by the present invention described below.
The ultraviolet curable composition of the present invention comprises a polymerizable compound and a metal powder,
The metal powder includes those subjected to surface treatment as constituent particles,
The volume average particle size of the metal powder is 0.2 μm or more and 0.64 μm or less.

  Thereby, the ultraviolet curable composition which can form stably the pattern (printing part) excellent in the ejection stability by an inkjet method and excellent in the glossiness can be provided.

  In the ultraviolet curable composition of this invention, it is preferable that the said metal powder contains what was surface-treated with the fluorine-type surface treating agent as a constituent particle.

  As a result, the storage stability of the ultraviolet curable composition, the discharge stability over a long period of time can be made sufficiently excellent, and in the recorded matter produced using the ultraviolet curable composition, the metal powder can be used. It can arrange suitably in the outer surface vicinity of a printing part, and can exhibit more effectively the characteristics, such as glossiness which the metal material which comprises metal powder originally has. In addition, even when a polymerizable compound having a low surface tension is used as a constituent material of the ultraviolet curable composition, in a recorded matter produced using the ultraviolet curable composition, the metal powder is surely attached to the printed portion. It can be suitably arranged (leafing) in the vicinity of the outer surface, and the properties such as glossiness inherent in the metal material constituting the metal powder can be more effectively exhibited. Further, the rubbing resistance of the printed portion formed using the ultraviolet curable composition can be made particularly excellent.

  In the ultraviolet curable composition of the present invention, the fluorine-based surface treatment agent is one or more selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate compound, a fluorine-substituted fatty acid, and a fluorine-based isocyanate compound. It is preferable that

  Thereby, characteristics such as storage stability of the ultraviolet curable composition, ejection stability over a long period of time, glossiness of the printed portion, and abrasion resistance can be further improved.

  In the ultraviolet curable composition of the present invention, it is preferable that the metal powder includes, as constituent particles, at least mother particles whose surface is mainly composed of Al that has been surface-treated with a surface treatment agent.

  As a result, it is possible to make the gloss of the recorded matter and the high-class feeling particularly excellent while suppressing an increase in the production cost of the recorded matter. In addition, Al originally exhibits a particularly excellent gloss feeling among various metal materials, but when it is attempted to apply particles composed of Al to the ultraviolet curable composition, the ultraviolet curable composition. The present inventor has found that the storage stability is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation are particularly likely to occur. On the other hand, the average particle diameter of the metal powder is set to a value within a predetermined range, and the surface treatment with the surface treatment agent is performed, even when using particles whose surface is composed of Al. The occurrence of such problems can be reliably prevented. That is, the average particle diameter of the metal powder is a value within a predetermined range, and the metal powder is obtained by surface-treating at least the mother particle whose surface is mainly composed of Al with a surface treatment agent, The effect as described above is particularly remarkable.

  In the ultraviolet curable composition of the present invention, it is preferable that the constituent particles of the metal powder have a scaly shape.

  Thereby, on the recording medium to which the ultraviolet curable composition is applied, the metal powder can be arranged so that the main surface of the particle follows the surface shape of the recording medium, and the metal material constituting the metal powder is The inherent glossiness can be exhibited more effectively in the obtained recorded matter, and the glossiness and luxury of the pattern (printed part) to be formed can be made particularly excellent. In addition, the rub resistance of the recorded material can be made particularly excellent. In addition, in the configuration in which the surface treatment with the surface treatment agent as described above is not performed, the storage stability and the discharge stability of the ultraviolet curable composition are improved when the particles constituting the metal powder are in the form of scales. Although it tends to be low, the particles constituting the metal powder have a predetermined average particle diameter and are subjected to a surface treatment with a surface treatment agent. Even if it constitutes, the occurrence of such a problem can be reliably prevented. That is, when the particles constituting the metal powder have a predetermined average particle diameter, are surface-treated with a surface treatment agent, and have a scaly shape, the effects of these are synergistic. Therefore, it is possible to produce a recorded material that is particularly effective in terms of glossiness and luxury, with particularly excellent productivity.

  In the ultraviolet curable composition of the present invention, the average thickness of the constituent particles of the metal powder is preferably 10 nm or more and 80 nm or less.

  Thereby, the glossiness of a printing part, a high-class feeling, and abrasion resistance can be made further excellent.

In the ultraviolet curable composition of the present invention, the particle size (D ₁₀ ) at a volume cumulative distribution rate of 10% from the fine particle side of the metal powder is preferably 0.10 μm or more and 0.40 μm or less.

  Thereby, the discharge stability of the ultraviolet curable composition by the inkjet method can be made particularly excellent.

In the ultraviolet curable composition of the present invention, the particle diameter (D ₉₀ ) at a volume cumulative distribution rate of 90% from the fine particle side of the metal powder is preferably 0.40 μm or more and 1.10 μm or less.

  Thereby, the discharge stability of the ultraviolet curable composition by the inkjet method can be made particularly excellent.

  In the ultraviolet curable composition of this invention, it is preferable that the half value width in the particle size distribution of the said metal powder is 0.45 micrometer or less.

  Thereby, the discharge stability of the ultraviolet curable composition by the inkjet method can be made particularly excellent.

  In the ultraviolet curable composition of this invention, it is preferable that the polymerizable compound contains a monomer having an alicyclic structure.

  As a result, the storage stability and ejection stability of the ultraviolet curable composition can be made particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable composition can be improved. The property can be made particularly excellent.

  In the ultraviolet curable composition of the present invention, the monomer having the alicyclic structure is tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate, adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl acrylate, tetramethylpiperidyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, mevalonic acid lactone acrylate, dimethylol tricyclodecane diacrylate, dimethylol dicyclo Pentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate Acryloylmorpholine, tetrahydrofurfuryl acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate It is preferable that 1 type or 2 types or more selected from the group which consists of consists of.

  Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable composition can be further improved.

  The ultraviolet curable composition of the present invention includes, as a polymerizable compound other than the monomer having an alicyclic structure, phenoxyethyl acrylate, benzyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, It is preferable to include one or more selected from the group consisting of tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate.

  As a result, the storage stability and ejection stability of the ultraviolet curable composition are excellent, and the reactivity of the ultraviolet curable 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.

  The recorded matter of the present invention is produced by applying the ultraviolet curable composition of the present invention onto a recording medium by an ink jet method and then irradiating with ultraviolet rays.

  As a result, it is possible to provide a recorded matter having a pattern (printing portion) that is excellent in gloss and prevents the occurrence of defects.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<< UV curable composition >>
First, the ultraviolet curable composition of this invention is demonstrated.

  The ultraviolet curable composition of the present invention comprises a polymerizable compound that is polymerized by irradiation with ultraviolet rays and a metal powder.

  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.

  On the other hand, a recording method in which a composition containing a pigment or dye is applied to a recording medium by an ink jet method is used. Such a 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 compositions) have been used in order to make the abrasion resistance, water resistance, solvent resistance, etc. particularly excellent.

  However, simply trying to apply metal powder instead of pigment or dye is inferior in droplet ejection stability by the ink jet method, tends to cause ejection failure, and has inherent properties such as glossiness inherent in metal. There was a problem that it was not possible to fully exhibit.

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 composition (ultraviolet curable inkjet composition) of the present invention includes those subjected to surface treatment as constituent particles of the metal powder, and the volume average particle diameter (D ₅₀ ) of the metal powder. Is 0.2 μm or more and 0.64 μm or less.

  Thereby, it is possible to stably form a pattern (printing portion) excellent in ejection stability by the ink jet method and excellent in gloss.

<Metal powder>
The ultraviolet curable composition of the present invention contains a metal powder.

  The metal powder includes a plurality of particles, and the particles constituting the metal powder are those in which at least a part of the portion visually recognized is made of a metal material, and usually the vicinity of the outer surface is a metal. It is composed of materials.

  In the ultraviolet curable composition of the present invention, the metal powder includes those subjected to surface treatment as constituent particles. That is, the metal powder includes constituent particles having mother particles and a coating film with a surface treatment agent.

(Mother particles)
First, mother particles (particles subjected to a surface treatment with a surface treatment agent) of particles constituting the metal powder will be described.

  The base particles of the particles constituting the metal powder may be any particles as long as at least the region including the vicinity of the surface is composed of a metal material. For example, the entire particle may be composed of a metal material. You may have a base part comprised with the metal material, and a film comprised with the metal material which coat | covers the said base part.

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. The reason why Al is preferable is that the specific gravity (2.70 g / cm ² ) is lower than that of iron or the like. As a result, when particles composed of Al are dispersed in the ultraviolet curable composition, sedimentation proceeds very slowly, so that the ultraviolet curable composition can be stored for a long period of time without causing a concentration change. It becomes possible.

  In addition, the gloss and high quality of the recorded material can be made particularly excellent while suppressing an increase in production cost of the recorded material. Al originally exhibits a particularly excellent gloss feeling among various metal materials, but when the particles composed of Al are applied to the ultraviolet curable composition, the ultraviolet curable composition is preserved. The inventor has found that the stability is particularly low, and problems such as a decrease in ejection stability due to an increase in viscosity due to gelation are particularly likely to occur. On the other hand, the average particle diameter of the metal powder is set to a value within a predetermined range, and the surface treatment with the surface treatment agent is performed, even when using particles whose surface is composed of Al. The occurrence of such problems can be reliably prevented. That is, the average particle diameter of the metal powder is a value within a predetermined range, and the metal powder is obtained by surface-treating at least the mother particle whose surface is mainly composed of Al with a surface treatment agent, The effect as described above is particularly remarkable.

  The mother particles may be manufactured by any method, but when they are composed of Al, a film composed of Al is formed by a vapor deposition method, and then the film is formed. It is preferable to be obtained by pulverizing. Thereby, in the pattern (printing part) formed using the ultraviolet curable composition of this invention, the glossiness etc. which Al originally has 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 reliably obtain a metal powder having a particle size as will be described later, and to suppress variations 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.

(Surface treatment agent)
Next, the surface treating agent for surface treating the mother particles will be described.

  The surface treatment agent has a function of enhancing the dispersion stability of the metal powder (particles) in the ultraviolet curable composition and improving the ejection stability by the ink jet method. Further, if the surface treatment of the metal powder is performed so that the surface energy is lowered, the ultraviolet curable composition can be used even when a polymerizable compound having a low surface tension is used as a constituent material of the ultraviolet curable composition. In the recorded matter manufactured using the metal powder, the metal powder can be reliably arranged (leafing) in the vicinity of the outer surface of the printing part, and the glossiness etc. inherent to the metal material constituting the metal powder The characteristics can be fully exhibited. Accordingly, the range of selection of the polymerizable compound is widened, and the recorded material produced using the characteristics of the ultraviolet curable composition and the ultraviolet curable composition without sacrificing the glossiness inherent in the metal material. Characteristics (for example, viscosity of UV curable composition, storage stability, ejection stability, scratch resistance of recorded matter, etc.) can be easily adjusted.

  Examples of the surface treatment agent include a short-chain compound having an alkyl group that may have a substituent having 2 to 4 carbon atoms, and a substituent having 8 to 20 carbon atoms. Long chain compounds having an alkyl group, silane compounds, phosphoric acid compounds, carboxylic acids, isocyanate compounds, and the like can be used.

  When the alkyl group of the short chain compound and / or the alkyl group of the long chain compound has a substituent, examples of the substituent include a halogeno group such as a fluoro group, a chloro group and a bromo group, a hydroxyl group, and the like. It is done.

  As the silane compound, a compound having a structure in which a hydrogen atom and / or a hydrocarbon group (including those in which part or all of the hydrogen atoms are substituted with other atoms or atomic groups) is directly bonded to a silicon atom is used. be able to.

More specifically, examples of the silane compound include silicon hydride (Si _n H _{2n + 2} (where n is an integer of 1 or more)), H _a SiR _(4-a) (where R is , A hydrocarbon group which may have a substituent, a is an integer of 1 or more and 4 or less.

  As the phosphoric acid compound, for example, a compound (long-chain alkyl phosphate compound) having at least one alkyl group having 6 or more carbon atoms in the molecule can be used.

In particular, the phosphate compound (long-chain alkyl phosphate compound) 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 is O-, n is 1 to 3 an integer, m is 5 or more 19 or less an integer, l is 2 or more and 20 or less an integer.)

  As a result, the storage stability of the ultraviolet curable composition and the ejection stability by the ink jet method are particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable composition are improved. It can be made particularly excellent.

  In formula (1), m is preferably an integer of 5 to 19, but more preferably an integer of 7 to 17. Thereby, the effects as described above are more remarkably exhibited.

  In formula (1), l is preferably an integer of 2 to 20, but more preferably an integer of 4 to 16. Thereby, the effects as described above are more remarkably exhibited.

  As the carboxylic acid, a compound (fatty acid) having a hydrocarbon group and a carboxyl group can be used. Specific examples of such compounds include decanoic acid, tetradecanoic acid, octadecanoic acid, cis-9-octadecenoic acid and the like.

  As the isocyanate compound, a compound having a partial structure represented by —N═C═O can be used. Such a compound modifies the surface of the particle (mother particle) as having a partial structure represented by -NHCOO- by reacting with the metal material constituting the metal powder (mother particle). However, in the partial structure represented by -NHCOO-, the force of hydrogen bonding works. For this reason, the surface of the particles can be subjected to a fine surface treatment, and the above effects can be exhibited remarkably.

  As the isocyanate compound, a compound having at least one isocyanate group in the molecule can be used.

As an isocyanate compound, what has a chemical structure represented by following formula (2) can be used, for example.
RNCO (2)
(In the formula (2), R _{is, CH 3 (CH 2) m} - and is, m is 2 to 18 integers.)

  In formula (2), m is preferably an integer of 3 or more and 14 or less, and more preferably an integer of 4 or more and 12 or less.

  As the surface treatment agent, for example, a fluorine compound (fluorine surface treatment agent) may be used.

  As a result, the chemical stability and dispersion stability of the metal powder in the UV curable composition are sufficiently excellent, and the storage stability of the UV curable composition and the discharge stability over a long period of time are sufficiently excellent. In addition, in the recorded matter produced using the ultraviolet curable composition, the metal powder can be suitably arranged near the outer surface of the printing part, and the metal material constituting the metal powder is originally The properties such as glossiness can be exhibited more effectively. In addition, even when a polymerizable compound having a low surface tension is used as a constituent material of the ultraviolet curable composition, in a recorded matter produced using the ultraviolet curable composition, the metal powder is surely attached to the printed portion. It can be suitably arranged (leafing) in the vicinity of the outer surface, and the properties such as glossiness inherent in the metal material constituting the metal powder can be more effectively exhibited. Accordingly, the range of selection of the polymerizable compound is widened, and the recorded material produced using the characteristics of the ultraviolet curable composition and the ultraviolet curable composition without sacrificing the glossiness inherent in the metal material. Characteristics (for example, viscosity of UV curable composition, storage stability, ejection stability, scratch resistance of recorded matter, etc.) can be easily adjusted. Further, the rubbing resistance of the printed portion formed using the ultraviolet curable composition can be made particularly excellent.

  The fluorine compound (fluorine surface treatment agent) preferably has a perfluoroalkyl structure.

  As a result, the storage stability of the ultraviolet curable composition should be further improved, and the glossiness and rub resistance of the printed portion of the recorded matter produced using the ultraviolet curable composition should be further improved. Can do.

  In addition, the fluorine-based compound (fluorine-based surface treatment agent) may be any compound as long as it contains at least one fluorine atom in the molecule. More specifically, for example, a short-chain compound or a long chain as described above. Compound, silane compound, phosphoric acid compound, carboxylic acid, compound having a structure in which at least part of hydrogen atoms of isocyanate compound is substituted with fluorine atom (fluorine short chain compound, fluorine long chain compound, fluorine silane compound , Fluorine-based phosphoric acid compounds, fluorine-substituted fatty acids, fluorine-based isocyanate compounds, etc.).

  By using such a compound as a surface treating agent, the effects as described above are more remarkably exhibited. In particular, the surface free energy of the constituent particles of the metal powder can be reduced more effectively, the difference in the interfacial energy with the polymerizable compound is increased, and the hydrophobic interaction works more strongly. The metal powder can be more effectively arranged on the surface of the recorded matter. As a result, the glossiness of the recorded matter can be made particularly excellent.

  In particular, when a fluorine-based silane compound is used, recorded matter produced using an ultraviolet curable composition exhibits particularly excellent durability and weather resistance, and the film hardness can be maintained for a longer period.

  In addition, since the surface treatment agent for phosphoric acid compounds is resistant to acid, when a fluorine-based phosphoric acid compound is used, the recorded material produced using the ultraviolet curable composition has excellent durability even in an acidic environment. Shows weather resistance.

  In addition, when fluorine-substituted fatty acids (fluorinated fatty acids) are used, surface treatment can be performed more effectively on mother particles composed of noble metals such as gold, silver and platinum, copper and aluminum, etc. Since a film having a small group and high crystallinity (surface treatment layer) can be formed, surface free energy can be effectively reduced. As a result, smaller particles can be effectively arranged on the surface of the recorded material, and the abrasion resistance can be further improved.

  In addition, when a fluorine-based isocyanate compound is used, a finer surface treatment can be applied to the mother particles, and the bond strength with the mother particles can be made stronger, and the durability of the metal powder Therefore, the abrasion resistance can be maintained for a longer period.

The fluorine-based silane compound preferably has a chemical structure represented by the following formula (3).
R ¹ SiX ¹ _a R ² _(3-a) (3)
(In Formula (3), R ¹ represents a hydrocarbon group in which part or all of the hydrogen atoms are substituted with fluorine atoms, X ¹ represents a hydrolyzable group, an ether group, a chloro group, or a hydroxyl group; ² represents an alkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 3 inclusive.)

  As a result, the storage stability of the ultraviolet curable composition and the ejection stability by the ink jet method are particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable composition are improved. It can be made particularly excellent.

Examples of R ¹ in the formula (3) include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. in which part or all of the hydrogen atoms are substituted with fluorine atoms, and are further included in the molecular structure. At least a part of hydrogen atoms (hydrogen atoms not substituted with fluorine atoms) may be substituted with an amino group, a carboxyl group, a hydroxyl group, a thiol group, etc., and -O-, -S in the carbon chain A hetero atom such as-, -NH-, -N =, or an aromatic ring such as benzene may be sandwiched. Specific examples of R ¹ include, for example, a phenyl group, a benzyl group, a phenethyl group, a hydroxyphenyl group, a chlorophenyl group, an aminophenyl group, a naphthyl group, an anthrenyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, Pyrenyl group, thienyl group, pyrrolyl group, cyclohexyl group, cyclohexenyl group, cyclopentyl group, cyclopentenyl group, pyridinyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Butyl group, tert-butyl group, octadecyl group, n-octyl group, chloromethyl group, methoxyethyl group, hydroxyethyl group, aminoethyl group, cyano group, mercaptopropyl group, vinyl group, allyl group, acryloxyethyl group, Methacryloxyethyl group, glycidoxypropyl Group, acetoxy group and the like.

The fluorine-based silane compound having a perfluoroalkyl structure _{(C n F 2n + 1)} , for example, those represented by the following formula (4).
_{C n F 2n + 1 (CH} 2) m SiX 1 a R 2 (3-a) (4)
(In Formula (4), X ¹ represents a hydrolyzable group, an ether group, a chloro group, or a hydroxyl group, R ² represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 14) M is an integer of 2 to 6, and a is an integer of 1 to 3.

Specific examples of the compound having such a structure include CF ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF _3. (CF ₂ ) ₅ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ —CH _{2 CH 2 -Si (OCH 3) 3} , CF 3 (CF 2) 11 -CH 2 CH 2 -Si (OC 2 H 5) 3, CF 3 (CF 2) 3 -CH 2 CH 2 -Si (CH 3) _{(OCH 3) 2, CF 3} (CF 2) 7 -CH 2 CH 2 -Si (CH 3) (OCH 3) 2, CF 3 (CF 2) 8 -CH 2 CH 2 -Si (CH 3) (OC _{2 H 5) 2, CF 3} (CF 2) _{8 -CH 2 CH 2 -Si (C} 2 H 5) (OC 2 H 5) 2 and the like.

Further, as the fluorine-based silane compound may be used those having a perfluoroalkyl ether structure _{(C n F 2n + 1 O} ) in place of the above-mentioned perfluoroalkyl structure _{(C n F 2n + 1)} .

The fluorine-based silane compound having a perfluoroalkyl ether structure _{(C n F 2n + 1 O} ), for example, those represented by the following formula (5).
_{C p F 2p + 1 O (} C p F 2p O) r (CH 2) m SiX 1 a R 2 (3-a) (5)
(In Formula (5), X ¹ represents a hydrolyzable group, an ether group, a chloro group, or a hydroxyl group, R ² represents an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 4 inclusive. Yes, r is an integer from 1 to 10, m is an integer from 2 to 6, and a is an integer from 1 to 3.

Specific examples of the compound having such a structure include CF ₃ O (CF ₂ O) ₆ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ , CF ₃ O (C ₃ F ₆ O) ₄ —CH. ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ O (C ₃ F ₆ O) ₂ (CF ₂ O) ₃ —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ , CF ₃ O (C ₃ F ₆ O _{) 8 -CH 2 CH 2 -Si (} OCH 3) 3, CF 3 O (C 4 F 9 O) 5 -CH 2 CH 2 -Si (OCH 3) 3, CF 3 O (C 4 F 9 O) 5 _{-CH 2 CH 2 -Si (CH 3} ) (OC 2 H 5) 2, CF 3 O (C 3 F 6 O) 4 -CH 2 CH 2 -Si (C 2 H 5) (OCH 3) 2 and the like Can be mentioned.

  As the fluorine-based phosphate compound, a phosphate compound having at least one fluorine atom in the molecule can be used.

In particular, the fluorine-based phosphoric acid compound preferably has a chemical structure represented by the following formula (6).
POR _n (OH) _3-n (6)
(In the formula (6), R _{is, CF 3 (CF 2) m} -, CF 3 (CF 2) m (CH 2) l -, CF 3 (CF 2) m (CH 2 O) l -, CF 3 (CF ₂ ) _m (CH ₂ CH ₂ O) ₁ —, CF ₃ (CF ₂ ) _m O—, or CF ₃ (CF ₂ ) _m (CH ₂ ) ₁ O—, and n is 1 or more and 3 or less. 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 composition and the ejection stability by the ink jet method are particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable composition are improved. It can be made particularly excellent.

  In formula (6), 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 (6), l is preferably an integer of 1 to 14, but more preferably an integer of 1 to 10. Thereby, the effects as described above are more remarkably exhibited.

  As the fluorine-substituted fatty acid (fluorinated fatty acid), a fatty acid having at least one fluorine atom in the molecule can be used.

Examples of the fluorine-substituted fatty acid include CF ₃ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₃ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —COOH, CF _3. (CF ₂ ) ₆ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₇ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₉ —CH ₂ CH ₂ —COOH, and esters thereof may be mentioned. However, among these, CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —COOH is preferable.

  As a result, the metal particles such as silicon, aluminum, magnesium, and titanium constituting the mother particle can be strongly bonded by a dehydration reaction by heating, and a dense film can be formed. Can be lowered.

  As the fluorine-based isocyanate compound, a compound having at least one fluorine atom and at least one isocyanate group in the molecule can be used.

As a fluorine-type isocyanate compound, what has a chemical structure represented by following formula (7) can be used, for example.
RfNCO (7)
(In the formula (7), Rf _{is, CF 3 (CF 2) m} -, _{or, CF 3 (CF 2) m} (CH 2) l - is and, m is 2 to 18 integer, l is It is an integer from 1 to 18.)

  Thereby, the storage stability of the ultraviolet curable composition and the ejection stability by the inkjet method can be made particularly excellent. Further, in a recorded matter produced using an ultraviolet curable composition, the metal powder can be more suitably arranged (leafing) near the outer surface of the printed part, and the glossiness of the printed part of the produced recorded matter Can be made particularly excellent. Further, the rubbing resistance of the printed part of the recorded matter to be produced can be made particularly excellent.

  In formula (7), m is preferably an integer of 3 or more and 14 or less, and more preferably an integer of 4 or more and 12 or less. Thereby, the effects as described above are more remarkably exhibited.

  In formula (7), 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.

  Moreover, the metal powder may be surface-treated with a plurality of types of surface treatment agents. In such a case, the same particles may be subjected to a surface treatment with a plurality of types of surface treatment agents, and the metal powder includes a plurality of types of particles that have been subjected to a surface treatment with different surface treatment agents. There may be.

  The surface treatment agent as described above may be directly treated on the mother particles. However, after the mother particles are treated with an acid or a base, the mother particles are treated with the surface treatment agent. It is preferred to do so. As a result, the surface of the mother particles can be more reliably modified by chemical bonding with the surface treatment agent, and the effects as described above can be more effectively exhibited. 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.

  Further, as described above, the surface treatment of the mother particles with the surface treatment agent may be performed when, for example, forming a mother particle by pulverizing a metal film formed by a vapor deposition method in a liquid. It may be performed by including a surface treatment agent therein.

  As a result, the surface treatment proceeds in parallel with the formation of uniform mother particles, so the surface can be immediately treated on the pulverized clean surface, and the quality and production of metal powder and UV-curable composition. The property can be made particularly excellent. In addition, when the above-described surface treatment agent is used (particularly when a fluorine-based phosphate compound is used), the solution in which the mother particles are dispersed is obtained by appropriately inhibiting the aggregation of the surface-treated mother particles. The fluidity of the film can be increased, the film can be pulverized more efficiently, and a metal powder satisfying the particle size conditions as described above can be obtained more efficiently. The quality and productivity can be further improved.

  When multiple types of surface treatment are performed on the same particle, the surface treatment may be performed in a plurality of steps corresponding to each surface treatment agent, or surface treatment with multiple types of surface treatment agents in the same step. May be performed.

  The particles constituting the metal powder may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably have a scaly shape.

  Thereby, on the recording medium to which the ultraviolet curable composition is applied, the metal powder can be arranged so that the main surface of the particle follows the surface shape of the recording medium, and the metal material constituting the metal powder is The inherent glossiness can be exhibited more effectively in the obtained recorded matter, and the glossiness and luxury of the pattern (printed part) to be formed can be made particularly excellent. In addition, the rub resistance of the recorded material can be made particularly excellent. In addition, in the configuration in which the surface treatment with the surface treatment agent as described above is not performed, the storage stability and the discharge stability of the ultraviolet curable composition are improved when the particles constituting the metal powder are in the form of scales. Although it tends to be low, the particles constituting the metal powder have a predetermined average particle diameter and are subjected to a surface treatment with a surface treatment agent. Even if it constitutes, the occurrence of such a problem can be reliably prevented. That is, when the particles constituting the metal powder have a predetermined average particle diameter, are surface-treated with a surface treatment agent, and have a scaly shape, the effects of these are synergistic. Therefore, it is possible to produce a recorded material that is particularly effective in terms of glossiness and luxury, with particularly excellent productivity.

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.

When the particles constituting the metal powder are scaly, the average thickness of the particles is preferably from 10 nm to 80 nm, and more preferably from 20 nm to 70 nm. The ratio (S ₁ / S ₀ ) and thickness can be determined by observation using, for example, a transmission electron microscope or a scanning electron microscope. Specific examples of these apparatuses include a transmission electron microscope (TEM, JOEL JEM-2000EX), a field emission scanning electron microscope (FE-SEM, Hitachi S-4700), a scanning transmission electron microscope (STEM, Hitachi High-Technologies). "HD-2000" manufactured by the company). Here, the average thickness means an average value of values obtained by performing thickness measurement 10 times.

  Thereby, the effect by the above-mentioned particle | grains being scaly is exhibited more notably.

The volume average particle diameter (D ₅₀ ) of the metal powder is 0.2 μm or more and 0.64 μm or less.
Since the metal powder is subjected to surface treatment and has a predetermined average particle diameter, the excellent effects as described above can be obtained.

  On the other hand, when the volume average particle diameter of the metal powder is less than the lower limit, the metal powder is likely to aggregate in the ultraviolet curable composition, and the storage stability of the ultraviolet curable composition is significantly reduced. . In addition, by causing such agglomeration, unintentional color unevenness or the like is likely to occur in a printed portion formed using the ultraviolet curable composition.

  On the other hand, when the volume average particle size of the metal powder exceeds the upper limit, the ejection stability of the ultraviolet curable composition by the ink jet method is rapidly lowered.

The volume average particle diameter (D ₅₀ ) of the metal powder may be 0.2 μm or more and 0.64 μm or less, preferably 0.25 μm or more and 0.60 μm or less, and 0.30 μm or more and 0.55 μm or less. More preferably.
Thereby, the effects as described above are more remarkably exhibited.

  In the present invention, the volume average particle diameter means a median diameter of a volume distribution measured by using a laser diffraction / scattering method for a particle dispersion, and a large number of measurement results (particle diameter). When expressed as an accumulation of each abundance ratio, it is a particle size that shows exactly 50% of the median in the accumulation. Examples of the measuring apparatus include a laser diffraction / scattering particle size analyzer Microtrac MT-3000 (manufactured by Nikkiso Co., Ltd.) and the like. The volume average particle diameter (D50) in Examples described later is a value measured by the above-mentioned Microtrac MT-3000.

The particle diameter (D ₁₀ ) at a volume cumulative distribution rate of 10% from the fine particle side of the metal powder is preferably 0.10 μm or more and 0.40 μm or less, and more preferably 0.15 μm or more and 0.35 μm or less. Preferably, it is 0.20 μm or more and 0.30 μm or less.

  Thereby, the particle size distribution of the metal powder can be made sharper, and the discharge stability of the ultraviolet curable composition by the ink jet method can be made particularly excellent.

The particle size (D ₉₀ ) at a volume cumulative distribution rate 90% from the fine particle side of the metal powder is preferably 0.40 μm or more and 1.10 μm or less, more preferably 0.45 μm or more and 0.95 μm or less. Preferably, it is 0.50 μm or more and 0.85 μm or less.

  Thereby, the particle size distribution of the metal powder can be made sharper, and the discharge stability of the ultraviolet curable composition by the ink jet method can be made particularly excellent.

The half width (distance between D ₂₅ and D ₇₅ , quartile range) in the particle size distribution of the metal powder is preferably 0.45 μm or less, more preferably 0.40 μm or less, and 0.35 μm or less. More preferably.

  Thereby, the particle size distribution of the metal powder can be made sharper, and the discharge stability of the ultraviolet curable composition by the ink jet method can be made particularly excellent.

In addition, the ultraviolet curable composition of the present invention includes those in which the volume average particle diameter of the metal powder is within the predetermined range as described above and the surface treatment is performed as the constituent particles of the metal powder. As long as it is possible, some of the constituent particles of the metal powder may include those not subjected to the surface treatment, but even in such a case, the surface treatment was performed on the entire metal powder. The content of the constituent particles is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.
Thereby, the effects as described above are more remarkably exhibited.

  The content of the metal powder in the ultraviolet curable composition is preferably 0.9% by mass or more and 29% by mass or less, and more preferably 1.2% by mass or more and 19.3% by mass or less.

  Thereby, the discharge stability of the ultraviolet curable composition by the inkjet method can be made particularly excellent, and the glossiness of the printed part formed using the ultraviolet curable composition is made particularly excellent. be able to.

<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 composition.

  The polymerizable compound is a liquid and preferably functions as a dispersion medium for dispersing the metal powder in the ultraviolet curable composition.

  As a result, it is not necessary to use a dispersion medium that is removed (evaporated) separately in the production process of the recorded material, and it is not necessary to provide a process for removing the dispersion medium in the production of the recorded material. The property can be made particularly excellent. Moreover, since it is not necessary to use what is generally used as an organic solvent as a dispersion medium, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented. Moreover, the adhesiveness of the printing part formed using an ultraviolet curable 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 composition is excellent in media compatibility.

  The polymerizable compound may be any component that can be polymerized by irradiation with ultraviolet rays. For example, various monomers, various oligomers (including dimers, trimers, etc.) can be used, but ultraviolet curable compositions are polymerizable. The 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 composition particularly excellent.

  In particular, the ultraviolet curable composition preferably contains a monomer having an alicyclic structure as the polymerizable compound.

  By including a monomer having an alicyclic structure together with a metal powder (a metal powder surface-treated with a surface treatment agent as described above), the storage stability and ejection stability of the ultraviolet curable composition are particularly excellent. In addition, the gloss and the abrasion resistance of the printed portion of the recorded matter produced using the ultraviolet curable composition can be made particularly excellent.

  Examples of the monomer having an alicyclic structure include tris (2- (meth) acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, and γ-butyrolactone (meth) acrylate. N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meta ) Acrylate, mevalonic acid lactone (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclope Tanyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, phenylglycidyl ether (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) Examples include acrylate, di (meth) acrylated isocyanurate, tri (meth) acrylated isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate, adamantyl acrylate, and γ-butyrolactone acrylate. N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl acrylate, tetramethylpiperidyl acrylate, 2-methyl-2-ada Nethyl acrylate, 2-ethyl-2-adamantyl acrylate, mevalonic acid lactone acrylate, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl Acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) It is preferable that 1 type (s) or 2 or more types selected from the group which consists of methyl acrylate are included.

  Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable composition can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable composition can be further improved.

  Among these, in the case where the composition contains one or more selected from the group consisting of acryloylmorpholine, tetrahydrofurfuryl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, and N-vinylpyrrolidone, In addition to improving the dispersion stability of the metal powder in the ink jet and the ejection stability by the ink jet method, in the recorded matter manufactured using the ultraviolet curable composition, the metal powder is disposed near the outer surface of the printing part. Therefore, the gloss of the obtained recorded matter can be further improved.

  Further, from the viewpoint of further improving the curing rate of the ultraviolet curable composition upon irradiation with ultraviolet rays and the productivity of the recorded matter, tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate. -To, γ-butyrolactone acrylate, N-vinylpyrrolidone, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, acryloylmorpholine, and tetrahydrofurfuryl acrylate It is preferable to include one or more selected from the group consisting of acryloylmorpholine and / or γ-butyrolactone acrylate, and more preferable to include γ-butyrolac Even more preferably those containing a down acrylate.

  Moreover, when it contains 1 type or 2 or more types selected from the group which consists of cyclohexyl acrylate, tetrahydrofurfuryl acrylate, and benzyl acrylate, the flexibility of the printing part formed by hardening | curing an ultraviolet curable composition Can be further improved.

  Further, from the viewpoint of further improving the abrasion resistance of the printed part formed by curing the ultraviolet curable composition, tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate , Adamantyl acrylate, γ-butyrolactone acrylate, N-vinyl caprolactam, N-vinyl pyrrolidone, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate And one or more selected from the group consisting of acryloylmorpholine, preferably γ-butyrolactone acrylate and / or N-vinylcaprolactam. More preferred.

  In addition, when it contains one or more selected from the group consisting of γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, isobornyl acrylate, and tetrahydrofurfuryl acrylate, an ultraviolet curable composition Reduce shrinkage when curing the product, and more effectively prevent a decrease in glossiness caused by unintentional wrinkles in the printed part formed by curing the UV curable composition Can do.

  The content of the monomer having an alicyclic structure in the ultraviolet curable composition is preferably 40% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 88% by mass or less, and 55% by mass. More preferably, it is 85 mass% or less.

  Thereby, the dispersion stability of the metal powder is particularly excellent, and particularly excellent discharge stability is obtained over a long period of time. In particular, even if the ultraviolet curable composition does not contain a dispersant, the above excellent effects can be obtained. The ultraviolet curable composition may contain two or more compounds as a monomer having an alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.

The monomer having an alicyclic structure preferably has 5 or more, more preferably 6 or more constituent atoms of a cyclic structure formed by a covalent bond.
Thereby, the storage stability of the ultraviolet curable composition can be made particularly excellent.

  The ultraviolet curable composition preferably contains a monofunctional monomer containing a hetero atom in the alicyclic structure (monofunctional monomer having a heterocyclic ring not showing aromaticity) as the monomer having an alicyclic structure.

  Thereby, the dispersion stability of the metal powder is particularly excellent, and particularly excellent discharge stability is obtained over a long period of time. In particular, even if the ultraviolet curable composition does not contain a dispersant, the above excellent effects can be obtained. Examples of such monofunctional monomers include tris (2- (meth) acryloyloxyethyl) isocyanurate, γ-butyrolactone (meth) acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth) acrylate. , Tetramethylpiperidyl (meth) acrylate, mevalonic acid lactone (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, and the like.

  The content of the monofunctional monomer (monofunctional monomer containing a hetero atom in the alicyclic structure) in the ultraviolet curable composition is preferably 10% by mass to 80% by mass, and more preferably 15% by mass to 75% by mass. % Or less is more preferable.

  Thereby, it can use suitably for manufacture of the recorded matter provided with the pattern (printing part) which suppressed cure shrinkage, has few scattering, and was more excellent in glossiness. The ultraviolet curable composition may contain two or more compounds as a monofunctional monomer containing a hetero atom in the alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.

  In the present invention, the polymerizable compound constituting the ultraviolet curable composition may include a monomer having no alicyclic structure.

  Examples of such monomers (monomers having no alicyclic structure) include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, and dipropylene. Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate lauryl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, isooctyl (meth) acrylate, stearyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 3,3-tetrafluoropropyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, EO-modified 2-ethylhexyl (meth) acrylate, phenoxydiethylene glycol (meth) ) Acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dipropylene glycol (meth) Acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1.9-nonanediol di (meth) acrylate, 1,4-butane Diol di (meth) acrylate, bisphenol A EO-modified di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 300 di (meth) acrylate, neopentyl glycol Hydroxypivalate di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, polyethylene glycol 600 di (meth) acrylate, Ripropylene glycol di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, glycerin PO addition Tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate, 3- (meta ) Acryloyloxypropyl acrylate, w-carboxy (meth) acryloyloxyethyl phthalate, ditrimethylolpropane tetra (meth) acrylate, dipentaery Examples include pentol / hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, phenoxyethyl acrylate, benzyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene It is preferable to include one or more selected from the group consisting of glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate.

  In addition to the monomer having an alicyclic structure, by including such a monomer having no alicyclic structure, the storage stability and ejection stability of the ultraviolet curable composition are improved, and ejection by an inkjet method is performed. The reactivity of the later ultraviolet curable composition is particularly excellent, the productivity of the recorded matter can be particularly excellent, and the rub resistance of the pattern to be formed is particularly excellent. be able to.

  In particular, when it contains phenoxyethyl acrylate, in the recorded matter produced using the ultraviolet curable composition, the metal powder can be more suitably arranged in the vicinity of the outer surface of the printing portion, and the glossiness of the obtained recorded matter. Can be further improved.

  Further, when it contains 2- (2-vinyloxyethoxy) ethyl acrylate, the curing rate of the ultraviolet curable composition when irradiated with ultraviolet rays and the productivity of recorded matter can be further improved.

  Moreover, when it contains phenoxyethyl acrylate and / or 2-hydroxy 3-phenoxypropyl acrylate, the flexibility of the printed part formed by curing the ultraviolet curable composition may be further improved. it can.

  Further, from the viewpoint of further improving the abrasion resistance of the printed part formed by curing the ultraviolet curable composition, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, and It is preferable that it contains 1 type, or 2 or more types selected from the group consisting of tripropylene glycol diacrylate, and it is more preferable that it contains 2- (2-vinyloxyethoxy) ethyl acrylate.

  In addition, when it contains phenoxyethyl acrylate, the shrinkage rate at the time of curing of the ultraviolet curable composition should be smaller, and unintentional wrinkles or the like may occur in the printed part formed by curing the ultraviolet curable composition. It is possible to more effectively prevent a decrease in glossiness due to.

  The content of the monomer other than the monomer having an alicyclic structure in the ultraviolet curable composition is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

  This further facilitates adjustment of the curing rate, flexibility, shrinkage rate during curing, and the like of the ultraviolet curable composition. The ultraviolet curable composition may contain two or more compounds as a monomer having no alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.

  The ultraviolet curable composition may contain oligomers (including dimers, trimers, etc.), prepolymers, etc., in addition to monomers, as polymerizable compounds. As the oligomer and prepolymer, for example, those having the above-described monomer as a constituent component can be used. The ultraviolet curable composition preferably contains a polyfunctional oligomer.

  As a result, the storage stability of the ultraviolet curable composition and the ejection stability by the inkjet method can be made excellent, and the rub resistance of the formed pattern can be made particularly excellent. 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 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 composition can be further improved, and the glossiness and abrasion resistance of the recorded matter produced using the ultraviolet curable composition can be improved. The properties and the like can be further improved. The ultraviolet curable 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 composition of this invention contains the substance A which has a partial structure shown by following formula (8).

  The ultraviolet curable composition contains the substance A having such a chemical structure together with the metal powder subjected to the surface treatment as described above, and further includes the monomer having an alicyclic structure, thereby ultraviolet curing. The storage stability, curability, and ejection stability by the ink jet method of the mold composition can be made particularly excellent. In addition, in the recorded matter produced using the ultraviolet curable composition, the metallic material constituting the metal powder can more effectively exhibit the glossiness and luxury feeling inherent in the metal material, The rubbing resistance can be made particularly excellent, and the durability of the recorded matter can be made particularly excellent.

In the formula (8), R ¹ may be an oxygen atom, a hydrogen atom, a hydrocarbon group or an alkoxyl group (a chain or alicyclic hydrocarbon group bonded to an oxygen atom). An atom, a methyl group, or an octyloxy group is preferred.

  As a result, the storage stability and ejection stability of the ultraviolet curable composition can be further improved, and the glossiness and abrasion resistance of the printed part formed using the ultraviolet curable composition can be further increased. It can be excellent.

In Formula (8), 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 composition can be further improved, and the glossiness and abrasion resistance of the printed part formed using the ultraviolet curable composition can be further increased. It can be excellent.

  The content of the substance A in the ultraviolet curable composition is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass or less. .

  As a result, the storage stability, ejection stability, and curability of the ultraviolet curable composition can be further improved, and the glossiness and abrasion resistance of the recorded matter produced using the ultraviolet curable composition can be improved. The properties and the like can be further improved. The ultraviolet curable 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 composition can be further improved, and the gloss of the printed part formed using the ultraviolet curable composition can be improved. The feeling and abrasion resistance can be further improved.

<Dispersant>
The ultraviolet curable composition of the present invention may contain a dispersant.

  Thereby, the dispersion stability of the metal powder in the ultraviolet curable composition can be further improved, and the storage stability of the ultraviolet curable composition can be further improved.

  In particular, the ultraviolet curable composition of the present invention may include a dispersant having a basic polymer structure (hereinafter also referred to as “basic polymer dispersant”).

  Thereby, the storage stability of the ultraviolet curable composition can be further improved.

  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.

  When the ultraviolet curable composition contains a dispersant, the content of the dispersant in the ultraviolet curable composition is preferably 5.0% by mass or less, and 0.01% by mass or more and 2.0% by mass. The following is more preferable.

  As a result, the gloss of the recorded matter produced using the ultraviolet curable composition is sufficiently excellent, and the storage stability, ejection stability, and curability of the ultraviolet curable composition are further improved. can do. The ultraviolet curable 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. In addition, if the content of the dispersant in the ultraviolet curable composition is too high, the dispersion stability of the metal powder is excessively improved, so that in the ultraviolet curable composition applied to the recording medium, the interior of the metal powder As the abundance ratio increases, it becomes difficult to properly arrange the metal powder in the vicinity of the outer surface of the applied UV curable composition, and the glossiness and abrasion resistance of the finally obtained recorded matter (printed part) are reduced. It may be difficult to make it sufficiently good.

<Other ingredients>
The ultraviolet curable 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), solvents, polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), colorants, fixing agents, and antifungal agents. Agents, preservatives, 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 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 composition contains a slip agent, the surface of the recorded matter becomes smooth due to the leveling action, and the abrasion resistance is improved.

  The slip agent is not particularly limited. For example, silicone surfactants such as polyester-modified silicone, polyether-modified silicone, and polyacrylate-modified silicone, and polymer surfactants such as polyacrylate and polyester can be used. It is preferable to use polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, or polyacrylate-modified dimethylsiloxane.

  The ultraviolet curable composition of the present invention may contain a polymerization inhibitor, but even if it contains a polymerization inhibitor, the content of the polymerization inhibitor in the ultraviolet curable composition is 0.6 mass% or less is preferable, and 0.2 mass% or less is more preferable.

  Thereby, since the content of the polymerizable compound in the ultraviolet curable composition can be made relatively high, particularly the abrasion resistance of the printed part formed using the ultraviolet curable composition, etc. It can be excellent.

  Moreover, it is preferable that the ultraviolet curable 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 composition of the present invention, measured according to JIS Z8809 using a vibration viscometer, is preferably 25 mPa · s or less, and preferably 3 mPa · s. It is more preferably 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 composition as described above onto a recording medium by an ink jet method and then irradiating with ultraviolet rays.

  Such a recorded matter has a pattern (printing portion) that is excellent in gloss and prevents the occurrence of defects.

  As described above, the ultraviolet curable 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 composition of the present invention is excellent in adhesion to a recording medium, the recording medium may be any type, and either absorbing or non-absorbing may be used. For example, natural fibers / synthetic fibers such as paper (plain paper, ink jet dedicated paper, etc.), plastic materials, metals, ceramics, wood, shells, cotton, polyester, wool, etc., non-woven fabrics, etc. can be used. Further, the shape of the recording medium is not particularly limited, and any shape such as a sheet shape may be used.

  As a droplet discharge method (inkjet method), a piezo method or a method of discharging ink by bubbles generated by heating the ink can be used. From the viewpoint of difficulty, etc., the piezo method is preferable.

  The ultraviolet curable composition can be discharged by an inkjet method using a known droplet discharge device.

  The ultraviolet curable composition discharged by the inkjet 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.

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

  As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.

  For example, in the embodiment described above, the case where the recorded matter of the present invention is composed of a recording medium (base material) and a printing unit has been mainly described. However, the recorded matter of the present invention is a recording medium (base material). ) In addition to the printing unit, it may have other configurations.

Next, specific examples of the present invention will be described.
[1] Production of composition for producing recorded matter (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 is formed is diethylene glycol diethyl ether: 99 parts by mass of CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O— as a fluorine-based surface treatment agent. PO- (OH) ₂ : 1 part by mass was placed in a dissolved liquid, and 27 kHz ultrasonic vibration was applied at 55 ° C. for 3 hours. Accordingly, dispersion of _{CF 3 (CF 2) 5 (} CH 2) 2 O-PO- (OH) metal _{powder 2} surface treatment with consists scaly particles subjected to the mother particles made of Al is obtained It was.

The volume average particle size of the metal powder thus obtained was 0.45 μm, the particle size (D ₁₀ ) at a volume cumulative distribution rate of 10% from the fine particle side of the metal powder was 0.28 μm, and the fine particle side of the metal powder. The particle size (D ₉₀ ) at a volume cumulative distribution rate of 90% from 0.76 was 0.76 μm, and the half-value width in the particle size distribution of the metal powder was 0.32 μm. These values were obtained by measurement using Microtrac MT-3000 (manufactured by Nikkiso Co., Ltd.).

  Next, the dispersion of the metal powder has acryloylmorpholine as a monomer (polymerizable compound) having an alicyclic structure, phenoxyethyl acrylate as a monomer (polymerizable compound) having no alicyclic structure, and an alicyclic structure. Tetrahydrofurfuryl acrylate as a monomer (polymerizable compound), DISPERBYK-2155 (manufactured by Big Chemie) as a basic polymer dispersant, a substance A having a chemical structure represented by the following formula (9), a photopolymerization initiator Irgacure 819 (manufactured by Ciba Japan), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, and LF-1984 (manufactured by Enomoto Kasei) Mixed with the composition for producing recorded matter ( UV curable composition) was obtained.

(Examples 2 to 20)
By configuring the constituent particles of the metal powder as shown in Table 1, and changing the type and ratio of the raw materials used for the preparation of the composition for producing recorded matter (ultraviolet curable composition), Tables 2 and A composition for producing a recorded matter (ultraviolet curable composition) was produced in the same manner as in Example 1 except that the composition shown in FIG.

(Comparative Example 1)
Example 1 except that a liquid (diethylene glycol diethyl ether) containing no surface treatment agent was used when applying ultrasonic vibration to a polyethylene terephthalate film (base material) on which an Al film was formed. In the same manner as described above, a composition for producing recorded matter (ultraviolet curable composition) was produced. That is, the composition for producing recorded matter (ultraviolet curable composition) of this comparative example contains only particles that have not been subjected to surface treatment as constituent particles of the metal powder.

(Comparative Examples 2 and 3)
Recording was performed in the same manner as in Example 1 except that the particle size distribution of the metal powder was changed by changing the application time of ultrasonic vibration to the polyethylene terephthalate film (base material) on which the Al film was formed. A product manufacturing composition (ultraviolet curable composition) was manufactured.

(Comparative Example 4)
Scale-like metal powder obtained in the same manner as in Example 1, 1,2-hexanediol, trimethylolpropane, Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.), triethanolamine, and glycerin Then, polyflow 401 (manufactured by Nissin Chemical Industry Co., Ltd.) and ion-exchanged water were mixed to produce a composition for producing recorded matter. That is, the composition for producing a recorded product of this comparative example does not contain a polymerizable compound (binder) that is cured by irradiation with ultraviolet rays.

(Comparative Example 5)
A composition for producing a recorded material in the same manner as in Comparative Example 1 except that a spherical Al powder produced using a gas atomizing method (not subjected to a surface treatment with a surface treatment agent) was used as the metal powder. (Ultraviolet curable composition) was produced.

About each said Example and comparative example, the structure of the metal powder contained in the composition for recorded material manufacture was put together in Table 1, and the composition of the composition for recorded material manufacture was shown collectively in Table 2, Table 3. In the table, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O—PO— (OH) ₂ as the fluorine-based phosphate compound is “FAP1”, and (CF ₃ (CF ₂ ) as the fluorine-based silane compound is used. ₇ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ) as “FAS1”, and (CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ) as a fluorine-based silane compound as “FAS2” CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ COOH as a fluorine-substituted fatty acid is “FFA1”, and CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ NCO as a fluorine-based isocyanate compound is “IS1”. Lauryl phosphate as an acid compound: CH ₃ (CH ₂ ) ₁₁ — (OCH ₂ CH ₂ ) ₂ —O—PO (OH) ₂ as “LA”, alkyl ether phosphate compound Laureth -2 phosphate _{Te: CH 3 (CH 2) 11} - (OCH 2 CH 2) 2 -O-PO (OH) 2 to "LP", "OTS" octyltriethoxysilane as alkylsilane compound, CH ₃ (CH ₂ ) ₇ O—PO (OH) ₂ is “AP1”, γ-butyrolactone acrylate as a monomer (polymerizable compound) having an alicyclic structure is “BLA”, and monomer having an alicyclic structure (polymerizable) Tetrahydrofurfuryl acrylate as a compound) is “THFA”, N-vinylcaprolactam is “VC” as a monomer (polymerizable compound) having an alicyclic structure, and N— is a monomer having a alicyclic structure (polymerizable compound). “VP” for vinylpyrrolidone, “AMO” for acryloylmorpholine as a monomer (polymerizable compound) having an alicyclic structure, “TAOEI” is tris (2-acryloyloxyethyl) isocyanurate as a monomer (polymerizable compound) having an alicyclic structure, and “DCPTeOEA is dicyclopentenyloxyethyl acrylate as a monomer (polymerizable compound) having an alicyclic structure. "Adamantyl acrylate as a monomer (polymerizable compound) having an alicyclic structure" AA, dimethylol tricyclodecane diacrylate as a monomer having a alicyclic structure (polymerizable compound) "DMTCDDA", alicyclic structure Dimethylol dicyclopentane diacrylate as a monomer (polymerizable compound) having dimethyl ring, “DMDCPTA”, dicyclopentenyl acrylate as a monomer having a alicyclic structure (polymerizable compound) “DCPTeA”, monomer having an alicyclic structure ( Dicyclopentanyl acrylate as a compatible compound) as “DCPTaA”, isobornyl acrylate as a monomer having an alicyclic structure (polymerizable compound) as “IBA”, and monomer having a alicyclic structure (polymerizable compound) The cyclohexyl acrylate is “CHA”, the diacrylated isocyanurate as a monomer (polymerizable compound) having an alicyclic structure is “DAI”, and the triacrylated isocyanurate as a monomer (polymerizable compound) having an alicyclic structure is “ “TAI”, “BLM” as γ-butyrolactone methacrylate as a monomer (polymerizable compound) having an alicyclic structure, “THM” as tetrahydrofurfuryl methacrylate as a monomer (polymerizable compound) having an alicyclic structure, and alicyclic structure As a monomer (polymerizable compound) having Dicyclopentenyloxyethyl methacrylate is “DCPTeOEM”, adamantyl methacrylate is “AM” as a monomer (polymerizable compound) having an alicyclic structure, and pentamethylpiperidyl methacrylate is a monomer (polymerizable compound) having an alicyclic structure. “PMPM”, tetramethylpiperidyl methacrylate as a monomer having an alicyclic structure (polymerizable compound) as “TMPM”, 2-methyl-2-adamantyl methacrylate as a monomer having an alicyclic structure (polymerizable compound) as “MAM” ”,“ EAM ”as 2-ethyl-2-adamantyl methacrylate as a monomer (polymerizable compound) having an alicyclic structure,“ MLM ”as mevalonic acid lactone methacrylate as a monomer (polymerizable compound) having an alicyclic structure, Alicyclic structure Dicyclopentenyl methacrylate as a monomer (polymerizable compound) having “DCPTeM”, dicyclopentanyl methacrylate as a monomer having a alicyclic structure (polymerizable compound) as “DCPTaM”, monomer having an alicyclic structure (polymerization) Isobornyl methacrylate as an ionic compound) "IBM", cyclohexyl methacrylate as a monomer (polymerizable compound) having an alicyclic structure "CHM", cyclohexane spiro as a monomer having an alicyclic structure (polymerizable compound) 2- (1,3-Dioxolan-4-yl) methyl acrylate is “CHDOLA”, and (2-methyl-2-ethyl-1,3-dioxolane-4-) as a monomer (polymerizable compound) having an alicyclic structure Yl) Methyl acrylate "MEDOLA", alicyclic Phenoxyethyl acrylate as a monomer that does not have a structure (polymerizable compound) is “PEA”, dipropylene glycol diacrylate as a monomer that does not have an alicyclic structure (polymerizable compound) is “DPGDA”, and an alicyclic structure is “TPGDA” is tripropylene glycol diacrylate as a monomer (polymerizable compound) having no alicyclic structure, “HPPA” is 2-hydroxy-3-phenoxypropyl acrylate as a monomer (polymerizable compound) having no alicyclic structure, 4-Hydroxybutyl acrylate as a monomer having no ring structure (polymerizable compound) is “HBA”, Ethyl carbitol acrylate as a monomer having no alicyclic structure (polymerizable compound) is “ECA”, alicyclic Methoxytriethyl as a monomer without structure (polymerizable compound) Renglycol acrylate is “MTEGA”, t-butyl acrylate as a monomer (polymerizable compound) having no alicyclic structure is “TBA”, and benzyl acrylate is a monomer having no alicyclic structure (polymerizable compound) “BA”, 2- (2-hydroxyethoxy) ethyl acrylate as a monomer having no alicyclic structure (polymerizable compound) “VEEA”, as a monomer having no alicyclic structure (polymerizable compound) “BM” is benzyl methacrylate, “UA” is a urethane acrylate as a monomer (polymerizable compound) having no alicyclic structure, DISPERBYK-182 (basic polymer dispersant, amine value: 13 mgKOH / g) “D2”, DISPERBYK-2155 as a basic polymer dispersant (BIC “M5, amine value: 48 mg KOH / g)” is “D5”, the compound represented by the above formula (9) (substance A) is “A1”, and the compound represented by the following formula (10) (substance A) is "A2", the compound (substance A) represented by the following formula (11) is "A3", the substance A represented by the following formula (12) is "A4", and Irgacure 819 (manufactured by Ciba Japan) is " ic819 ", Speedcure TPO (manufactured by ACETO)" scTPO ", Speedcure DETX (manufactured by Lambson)" scDETX ", BYK-350 (manufactured by BYK Chemie)" BYK350 ", hydroquinone monomethyl ether" MEHQ ", 1, 2-hexanediol is “1,2HD”, trimethylolpropane is “TMP”, Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) is “S” 65, triethanolamine “TEA”, glycerin “GL”, LHP-96 (manufactured by Enomoto Kasei Co., Ltd.) “LHP”, LF-1982 (manufactured by Enomoto Kasei Co., Ltd.) “LF-1”, LF-1984 (LF-2) is indicated by “LF-2” and Polyflow 401 (manufactured by Nissin Chemical Industry) is indicated by “PF401”. Moreover, about Example 15, the composition of the constituent material of a mother particle showed the content rate of each element with the weight ratio about Example 15. In addition, the viscosity at 20 ° C. of the composition for producing recorded matter (ultraviolet curable composition) of each of the above examples measured according to JIS Z8809 using a vibration viscometer is 3 mPa · s. The value was within the range of 15 mPa · s or less. Further, regarding the metal powder constituting the composition for producing recorded matter (ultraviolet curable composition) of each of the above-mentioned examples, a transmission electron microscope (TEM, JOEL JEM-2000EX) is used for any 10 metal particles. The area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan) and the area when observed out of the directions orthogonal to the observation direction are maximum. When the ratio (S ₁ / S ₀ ) with respect to the area S ₀ [μm ² ] when observed from the direction to be obtained and the average value thereof was determined, the average values of S ₁ / S ₀ were all 19 or more. Met. D2 and D5 are both basic and have a polymer structure (basic polymer dispersant). In the compositions for manufacturing recorded matter (ultraviolet curable compositions) of the above Examples and Comparative Examples 2 to 4, the content of the constituent particles subjected to the surface treatment on the entire metal powder is 99. It was more than mass%.

[2] Frequency characteristics (discharge stability) of the composition for producing recorded matter
A droplet discharge device installed in a chamber (thermal chamber) and the recorded product manufacturing compositions of the above examples and comparative examples were prepared, and the drive waveform of the piezoelectric element was optimized, at 25 ° C. and 50% RH. In this environment, droplets were ejected from each nozzle of a droplet ejection head having a nozzle hole size of 22 μm while changing the frequency (frequency) of the piezo element. . The droplet discharge time at each frequency was 20 minutes. Evaluate the actual usable frequency range according to the following four criteria, with the number of undischarged nozzles being less than 0.5% of the total number of nozzles as the maximum frequency that can be actually used after 20 minutes of discharge. did. It can be said that the larger this value, the better the frequency characteristics.

A: 15 kHz or more.
B: 11 kHz or more and less than 15 kHz.
C: 5 kHz or more and less than 11 kHz.
D: Less than 5 kHz.

[3] Storage stability evaluation of composition for producing recorded matter (long-term stability evaluation)
[3.1] Dispersibility The compositions for producing recorded products of the above Examples and Comparative Examples were left in a 40 ° C. environment for 60 days and then filtered with a capsule filter having a filtration accuracy of 3 μm (manufactured by Yamachine Filter). Measure the content of metal powder before and after passing through 1L (content of metal powder in the composition for producing recorded matter), and filter the coarse particles due to insufficient dispersion. It calculated | required by the decreasing rate of the content rate, and evaluated according to the following references | standards.

A: The reduction rate of the metal powder content is less than 5%.
B: The reduction rate of the content rate of the metal powder is 5% or more and less than 10%.
C: The reduction rate of the content rate of the metal powder is 10% or more and less than 20%.
D: The reduction rate of the content rate of the metal powder is 20% or more and less than 40%.
E: Reduction rate of content of metal powder is 40% or more.

[3.2] Increasing rate of viscosity The compositions for producing recorded products of the respective Examples and Comparative Examples were allowed to stand for 60 days in an environment of 40 ° C., and then compliant with JIS Z8809 using a vibration viscometer. The viscosities at 20 ° C. of the compositions for producing recorded products of the respective Examples measured above were measured to determine the rate of increase in viscosity immediately after production, and evaluated according to the following criteria.

A: Increase rate of viscosity is less than 5%.
B: Increase rate of viscosity is 5% or more and less than 10%.
C: Increase rate of viscosity is 10% or more and less than 18%.
D: Increase rate of viscosity is 18% or more and less than 23%.
E: The rate of increase in viscosity is 23% or more, or generation of foreign matter is observed.

[4] Curability About the composition for producing recorded matter of each of the above Examples and Comparative Examples, it was introduced into an Epson inkjet printer; PM800C, and Diafoil G440E (thickness: 38 μm) manufactured by Mitsubishi Plastics Co., Ltd. was used as a recording medium. Using the ink amount wet of 9 g / m ² , solid printing is performed, and immediately after printing, an LED-UV lamp; Foseon RX RXrefly (gap 6 mm, peak wavelength 395 nm, 1000 mW / cm ² ) is used for irradiation with ultraviolet rays. It was confirmed whether or not the composition for producing recorded matter 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. 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 200 mJ / cm ² .
B: It hardened | cured by the ultraviolet irradiation amount of 200 mJ / cm < ² > or more and less than 350 mJ / cm < ² >.
C: It hardened | cured with the ultraviolet irradiation amount of 350 mJ / cm < ² > or more and less than 500 mJ / cm < ² >.
D: It hardened | cured with the ultraviolet irradiation amount of 500 mJ / cm < ² > or more and less than 1000 mJ / cm < ² >.
E: It hardens | cures by the ultraviolet irradiation amount of 1000 mJ / cm < ² > or more. Or it does not cure at all.

[5] Manufacture of recorded matter An interior panel as a recorded matter was produced as follows using the composition for producing recorded matter of each Example and Comparative Example.
First, the composition for producing recorded matter was put into an ink jet apparatus.

  Thereafter, the composition for producing recorded matter was discharged in a predetermined pattern onto a base material (recording medium) having a curved surface portion formed using polycarbonate (manufactured by Asahi Glass Co., Ltd., Carboglass polish 2 mm thick).

Then, after heating at 60 ° C. for 5 minutes, ultraviolet rays having a spectrum having maximum values at wavelengths of 365 nm, 380 nm, and 395 nm are irradiated for 10 seconds with an irradiation intensity of 160 mW / cm ^2, and the composition for producing recorded matter on the substrate is used. Was cured to obtain an interior panel as a recorded material.

  Using the method as described above, 10 interior panels (recorded materials) were manufactured using the recorded product manufacturing 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 molded product was used.

[6] Evaluation of recorded matter The following evaluation was performed on each recorded matter obtained as described above.

[6.1] Appearance evaluation of recorded matter Each recorded matter produced in each of the above examples and comparative examples was visually observed and evaluated according to the following seven criteria.

A: It has a glossy feeling rich in luxury and has an extremely excellent appearance.
B: It has a glossy feeling full of luxury and has a very excellent appearance.
C: It has a glossiness with a high-class feeling and has an excellent appearance.
D: Glossy with a high-class feeling and a good appearance.
E: Inferior gloss and appearance is slightly poor.
F: Inferior glossiness and poor appearance.
G: Inferior glossiness and extremely poor appearance.

[6.2] Glossiness About the pattern formation part of each recorded matter manufactured in each of the above Examples and Comparative Examples, the glossiness at a turning angle of 60 ° was measured using a glossmeter (MINOLTA MULTI GLOSS 268), Evaluation was made according to the following criteria.

A: Glossiness is 350 or more.
B: Glossiness is 250 or more and less than 350.
C: Glossiness is 150 or more and less than 250.
D: Glossiness is less than 150.

[6.3] Abrasion resistance With respect to the recorded matter according to each of the above examples and comparative examples, when 48 hours have elapsed from the production of the recorded matter, a load of 500 g is applied in accordance with JIS L0849 using a Gakushin type fastness tester. Then, the cloth was rubbed 30 times, and the glossiness (grinding angle 60 °) of the recorded material after the cloth was rubbed was measured by the same method as described in [6.2] above. The reduction rate of glossiness 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 50%.
E: The reduction rate of glossiness is 50% or more.

  These results are shown in Table 4. In Table 4, “M1” represents a recorded material produced using a polycarbonate substrate, “M2” represents a recorded material produced using a polyethylene terephthalate substrate, and a low density polyethylene substrate. “M3” is a recorded matter manufactured using a biaxially oriented polypropylene base material, and “M4” is a recorded matter manufactured using a biaxially oriented polypropylene base material. Indicated by “M5”.

  As is apparent from Table 4, the composition of the present invention (ultraviolet curable composition) 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. Further, by using the composition (ultraviolet curable composition) of the present invention, stable and excellent results were obtained regardless of the type of the recording medium. On the other hand, in the comparative example, a satisfactory result was not obtained.

Claims (13)

Containing a polymerizable compound and a metal powder;
The metal powder includes those subjected to surface treatment as constituent particles,
The ultraviolet curable composition, wherein the metal powder has a volume average particle size of 0.2 μm or more and 0.64 μm or less.   2. The ultraviolet curable composition according to claim 1, wherein the metal powder includes a component that has been surface-treated with a fluorine-based surface treatment agent as constituent particles.   The ultraviolet curing according to claim 2, wherein the fluorine-based surface treatment agent is one or more selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate compound, a fluorine-substituted fatty acid, and a fluorine-based isocyanate compound. Mold composition.   The ultraviolet curable composition according to any one of claims 1 to 3, wherein the metal powder includes, as constituent particles, at least mother particles whose surface is mainly composed of Al and surface-treated with a surface treatment agent. object.   The ultraviolet curable composition according to any one of claims 1 to 4, wherein the constituent particles of the metal powder have a scaly shape.   The ultraviolet curable composition according to claim 5, wherein an average thickness of the constituent particles of the metal powder is 10 nm or more and 80 nm or less. The ultraviolet curable composition according to any one of claims 1 to 6, wherein a particle diameter (D ₁₀ ) at a volume cumulative distribution rate of 10% from the fine particle side of the metal powder is 0.10 µm or more and 0.40 µm or less. object. The ultraviolet curable composition according to any one of claims 1 to 7, wherein a particle diameter (D ₉₀ ) at a volume cumulative distribution rate of 90% from the fine particle side of the metal powder is 0.40 µm or more and 1.10 µm or less. object.   The ultraviolet curable composition according to any one of claims 1 to 8, wherein a half width in a particle size distribution of the metal powder is 0.45 µm or less.   The ultraviolet curable composition according to any one of claims 1 to 9, comprising a monomer having an alicyclic structure as the polymerizable compound.   Monomers having the alicyclic structure are tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate, adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl acrylate, Tetramethylpiperidyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, mevalonic acid lactone acrylate, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, di Cyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate, acryloylmorpholine, tetra The group consisting of drofurfuryl acrylate, cyclohexane spiro-2- (1,3-dioxolan-4-yl) methyl acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate The ultraviolet curable composition according to claim 10, comprising one or more selected from the group consisting of:   As polymerizable compounds other than the monomer having the alicyclic structure, phenoxyethyl acrylate, benzyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy 3 The ultraviolet curable composition according to claim 10 or 11, comprising one or more selected from the group consisting of -phenoxypropyl acrylate and 4-hydroxybutyl acrylate.   A recorded matter produced by applying the ultraviolet curable composition according to any one of claims 1 to 12 onto a recording medium by an inkjet method and then irradiating with ultraviolet rays.