JP2017088821A - Ultraviolet-curable composition and production method for recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curable composition being excellent in storage stability and discharge stability by an inkjet method and capable of being appropriately used for forming a pattern (printed portion) excellent in glossy feeling, and further to provide a recorded matter having the pattern being formed by using the ultraviolet-curable composition and excellent in the glossy feeling.SOLUTION: An ultraviolet-curable composition contains a polymerizable compound, metallic powder, fluorine-containing powder and a defoaming agent. A mean particle diameter of the fluorine-containing powder is equal to 2 nm or more and equal to 50 nm or less. It is preferable that the fluorine-containing powder contain particles constituted of a fluorine-based polymer. It is preferable that constituent particles of the metallic powder have scale-like shapes.SELECTED DRAWING: None

Description

  The present invention relates to an ultraviolet curable composition and a method for producing 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 a dye is applied to a recording medium by a method such as 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, in the case of an ultraviolet curable composition, when a metal powder is applied instead of a pigment or a dye, there is a problem in that the characteristics such as glossiness inherent in the metal cannot be sufficiently exhibited. In addition, the composition is inferior in stability (storage stability), and causes problems such as a decrease in ejection stability due to an increase in viscosity due to gelation. In addition, when a composition containing metal powder is used, there is a problem that a change in appearance due to friction is larger than when a composition containing a pigment or dye is used.

JP 2009-57548 A

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

Such an object is achieved by the present invention described below.
The ultraviolet curable composition of the present invention comprises a polymerizable compound, a metal powder, a fluorine-containing powder, and an antifoaming agent,
The fluorine-containing powder has an average particle size of 2 nm to 50 nm.

  Thereby, the ultraviolet curable composition which can be used suitably for formation of the pattern (printing part) which was excellent in storage stability, the discharge stability by the inkjet method, and was excellent in glossiness and abrasion resistance can be provided. .

  In the ultraviolet curable composition of the present invention, the antifoaming agent is preferably an acrylic antifoaming agent containing fluorine or an acrylic antifoaming agent having no polar functional group.

  Thereby, the discharge stability of the ultraviolet curable composition can be made particularly excellent. In addition, these antifoaming agents have a low molecular weight, and the diffusion and movement speed is much faster than pigments and fluorine-containing particles treated with fluorine-based surface treatment agents. Can do.

  In the ultraviolet curable composition of the present invention, the fluorine-containing powder preferably contains particles composed of a fluorine-based polymer.

  Thereby, a fluorine-containing powder can be easily obtained as a sufficiently small particle size as described above. Moreover, the transparency in the hardened | cured material state which hardened | cured the polymeric compound which comprises an ultraviolet curable composition can be made especially excellent. In addition, the surface energy of the constituent particles becomes particularly small, and the hydrophobic interaction with the polymerizable compound contained in the ultraviolet curable composition is particularly large, so that the particles move to the gas-liquid interface and are easily stabilized. In addition, the fluorine-containing powder is easily fixed on the surface of the recorded matter obtained by ultraviolet curing, and the rub resistance of the recorded matter can be made particularly excellent.

  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, the glossiness and high-class feeling of the pattern (printing part) to be formed can be made particularly excellent.

  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 and high-quality feeling of the pattern (printing part) to be formed can be further improved.

  In the ultraviolet curable composition of the present invention, the average thickness of the constituent particles of the metal powder is preferably larger than the average particle diameter of the fluorine-containing powder.

  Thereby, the glossiness of the printing part formed using an ultraviolet curable composition can be made more excellent.

  In the ultraviolet curable composition of this invention, it is preferable that the average particle diameter of the said metal powder is 200 nm or more and 3.0 micrometers or less.

  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 preferably contains a monomer having an alicyclic structure as the polymerizable compound.

  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, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, and It is preferable that one or more selected from the group consisting of cyclic trimethylolpropane formal acrylate is 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.

  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 method for producing a recorded product of the present invention is characterized in that the production is performed by applying the ultraviolet curable composition of the present invention onto a medium and then irradiating with ultraviolet rays.

  Thereby, a recorded matter having a pattern excellent in glossiness and abrasion resistance can be provided.

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 a dye is applied to a recording medium by a method such as 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, in the case of an ultraviolet curable composition, when a metal powder is applied instead of a pigment or a dye, there is a problem in that the characteristics such as glossiness inherent in the metal cannot be sufficiently exhibited. In addition, the composition is inferior in stability (storage stability), and causes problems such as a decrease in ejection stability due to an increase in viscosity due to gelation. In addition, when a composition containing metal powder is used, there is a problem that a change in appearance due to friction is larger than when a composition containing a pigment or dye is used.

  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 of the present invention contains a fluorine-containing powder and an antifoaming agent in addition to the polymerizable compound and the metal powder, and the average particle size of the fluorine-containing powder is 2 nm or more and 50 nm or less. It is. Thereby, the dispersion stability of the metal powder in the ultraviolet curable composition can be made excellent, and the storage stability of the ultraviolet curable composition and the discharge stability over a long period of time can be made 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 printed part, and the glossiness inherent in the metal material constituting the metal powder is inherent. And the like can be sufficiently exhibited. In addition, the fluorine-containing powder as well as the metal powder can be suitably arranged near the outer surface of the printing part, and the printing part has excellent abrasion resistance, and the appearance change due to friction (for example, a decrease in glossiness, aesthetics) Etc.) can be effectively prevented.

  On the other hand, when the ultraviolet curable composition does not contain a fluorine-containing powder and an antifoaming agent, the rub resistance of the printed portion formed using the ultraviolet curable composition is sufficiently excellent. I can't. Further, the storage stability of the ultraviolet curable composition and the ejection stability by the ink jet method are also lowered.

  Further, even when the ultraviolet curable composition contains a fluorine-containing powder and an antifoaming agent, if the average particle size of the fluorine-containing powder is less than the lower limit, the ultraviolet curable composition is used. The printed part formed in this manner cannot be made sufficiently excellent in abrasion resistance. In addition, the storage stability of the ultraviolet curable composition also decreases.

  Further, even when the ultraviolet curable composition contains a fluorine-containing powder and an antifoaming agent, when the average particle size of the fluorine-containing powder exceeds the upper limit, the glossiness of the printed portion is rapidly increased. And the aesthetics (aesthetic appearance) of the recorded material are drastically reduced. Further, the storage stability of the ultraviolet curable composition and the ejection stability by the ink jet method are also lowered.

  Further, even when the ultraviolet curable composition contains a fluorine-containing powder, if it does not have an antifoaming agent, the ejection stability by the ink jet method is lowered.

<Metal powder>
The constituent particles of the metal powder may be those in which at least a part visually recognized (for example, the vicinity of the surface) is made of a metal material, for example, the whole may be made of a metal material. And you may have a base part comprised with the nonmetallic material and a film comprised with the metal material which coat | covers the said base part. Moreover, the surface treatment layer by the surface treatment agent may be provided on the mother particle in which at least the region including the vicinity of the surface is made of a metal material.

  In addition, as a metal material constituting the constituent particles of the metal powder, a single metal, various alloys, or the like can be used, but the metal material is preferably mainly composed of Al.

  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, in this invention, even if it is a case where the particle | grains comprised with Al are used, generation | occurrence | production of the above problems can be prevented reliably. That is, the effect of the present invention is more remarkably exhibited when the metal material constituting the metal powder is mainly composed of Al.

  The metal powder may be produced by any method, but is obtained by forming a film composed of a metal material by a vapor deposition method and then crushing the film. Is preferred. Thereby, in the pattern (printing part) formed using the ultraviolet curable composition of this invention, the glossiness etc. which a metal material 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 a metal powder using such a method, for example, a metal powder can be suitably produced by forming a film composed of a metal material (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, while preventing unintentional oxidation of the metal powder, the productivity of the metal powder is made particularly excellent, and the variation in size, shape, and characteristics among the particles is also improved. It can be particularly small.

  Hereinafter, the case where the constituent particles of the metal powder are obtained by subjecting the base particles (base particles in which at least the region including the vicinity of the surface is made of a metal material) to surface treatment with a surface treatment agent 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 surely arranged (leafing) more appropriately near the outer surface of the printing part, and the metallic material constituting the metal powder originally has glossiness, etc. The characteristics can be exhibited more effectively. Accordingly, the range of selection of the polymerizable compound is widened, and the properties of the ultraviolet curable composition and the recorded matter produced using the ultraviolet curable composition without sacrificing the glossiness of 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 Can be 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 dispersion stability and chemical stability of the metal powder in the UV curable composition are particularly excellent, and the storage stability of the UV curable composition and the discharge stability over a long period of time are particularly excellent. can do. In addition, in a recorded matter produced using an ultraviolet curable composition, metal powder (metal powder surface-treated with a fluorine-based surface treatment agent) is suitably placed near the outer surface of the printing unit together with fluorine-containing powder. It is possible to fully exhibit the properties such as glossiness inherent in the metal material constituting the metal powder, and to make the printed part particularly excellent in abrasion resistance. For example, it is possible to more effectively prevent a reduction in glossiness and a decrease in aesthetics (aesthetic appearance). In particular, the surface treatment agent for the metal powder and the constituent particles of the fluorine-containing powder are commonly made of a fluorine-based material, so that the fluorine-containing powder is located near the constituent particles of the metal powder in the printing section. Therefore, the rub resistance of the printed portion can be made higher and surely excellent, and the above-described effects can be exhibited remarkably. . In addition, since the particles constituting the metal powder are surface-treated with a fluorine-based surface treatment agent, a polymerizable compound having a low surface tension or a polymer having a high viscosity and a low fluidity is used as a constituent material of an ultraviolet curable composition. Even in the case where a compound is used, in a recorded matter produced using an ultraviolet curable composition, the metal powder can be arranged (leafing) more suitably within a desired time near the outer surface of the printing part. The properties such as glossiness inherent in the metal material constituting the metal powder can be exhibited more effectively. 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.

  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. Preferably it is done. 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.

  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.

  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.

  Thereby, the surface treatment can be performed together with the formation of the mother particles, and the productivity of the metal powder and the ultraviolet curable composition can be made particularly excellent. In addition, the surface treatment can be performed with high uniformity on each part of the metal powder. In addition, when the above-mentioned surface treatment agent is used (particularly when a fluorine-based phosphate compound is used), the surface treatment agent works to promote the dispersion of the metal powder, and the energy of grinding by ultrasonic waves is reduced. By efficiently transmitting to individual particles, the film can be pulverized more efficiently in a shorter time, and a metal powder with less variation in size that satisfies the conditions of particle size as described later can be obtained more efficiently. The productivity of the metal powder and the ultraviolet curable composition 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, when the metal powder has been subjected to the surface treatment as described above, the rub resistance of the recorded matter can be made particularly excellent.

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

  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.

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

  The average thickness of the constituent particles of the metal powder is preferably larger than the average particle size of the fluorine-containing powder.

  Thereby, in the recorded matter, it is possible to more effectively prevent the constituent particles of the fluorine-containing powder from being excessively present on the outer surface side (observer's viewpoint side) than the constituent particles of the metal powder. The glossiness of the part can be made more excellent.

The average particle diameter (D ₅₀ ) of the metal powder is preferably 200 nm or more and 3.0 μm or less, more preferably 250 nm or more and 640 nm or less, and further preferably 300 nm or more and 600 nm or less.

  Thereby, the glossiness and high-quality feeling of the recorded matter manufactured using the ultraviolet curable composition can be further improved. In particular, it is possible to more effectively prevent the fluorine-containing powder from being excessively exposed on the outer surface in the printed portion of the recorded matter and inhibiting the texture (such as glossiness) constituting the metal powder. The glossiness and luxury of the product can be further improved. Further, the storage stability and ejection stability of the ultraviolet curable composition can be further improved.

  On the other hand, when the average particle size of the metal powder is less than the lower limit value, the metal powder tends to aggregate in the ultraviolet curable composition, and the storage stability of the ultraviolet curable composition may be reduced. is there. 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.

  Moreover, when the average particle diameter of metal powder exceeds the said upper limit, the discharge stability of the ultraviolet curable composition by an inkjet method may fall.

  In the present invention, the 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 are obtained for each size (particle diameter). This is the particle size (volume average particle diameter) showing exactly 50% of the median when expressed as an accumulation of the abundance ratio. When the constituent particles of the metal powder are scaly, the average particle diameter is determined based on the shape and size when the constituent particles of the metal powder are viewed in plan.

The particle diameter (D ₁₀ ) at a volume cumulative distribution rate of 10% from the fine particle side of the metal powder is preferably 100 nm to 1.1 μm, more preferably 150 nm to 400 nm, and more preferably 180 nm to 350 nm. 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.

The particle diameter (D ₉₀ ) at a volume cumulative distribution rate of 90% from the fine particle side of the metal powder is preferably 300 nm or more and 4.0 μm or less, more preferably 400 nm or more and 1.1 μm or less, and 500 nm or more. More preferably, it is 1.1 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 full width at half maximum in the particle size distribution of the metal powder is preferably 0.50 μm or less, more preferably 0.45 μm or less, and further preferably 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.

Further, in the ultraviolet curable composition of the present invention, the metal powder preferably includes those subjected to surface treatment as its constituent particles, but the surface treatment is applied as a part of the constituent particles of the metal powder. It may contain things that are not. However, even in such a case, the content of the constituent particles subjected to the surface treatment on the entire metal powder is preferably 90% by mass or more, more preferably 95% by mass or more, and 99 More preferably, it is at least mass%.
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 glossiness and abrasion resistance of the printing part formed using an ultraviolet curable composition can be made compatible at a higher level. Further, the storage stability of the ultraviolet curable composition and the discharge stability of the ultraviolet curable composition by the ink jet method can be made particularly excellent.

<Fluorine-containing powder>
As described above, the ultraviolet curable composition of the present invention includes a fluorine-containing powder. In the present invention, the fluorine-containing powder refers to a component other than the metal powder described above, in which the region including at least the surface of the constituent particles is made of a material containing fluorine.

  The fluorine-containing powder preferably has transparency in a cured product state obtained by curing the polymerizable compound constituting the ultraviolet curable composition. Thereby, the aesthetic appearance of the recorded matter manufactured using the ultraviolet curable composition of the present invention can be made particularly excellent.

  The visible light transmittance (wavelength: light transmittance at 600 nm) in the thickness direction of a cured product having a thickness of 100 μm obtained by curing an ultraviolet curable composition having the same composition except that no metal powder is contained. Is preferably 85% or more, and more preferably 90% or more.

  As a result, the fluorine-containing powder easily transmits light for curing the polymerizable compound, so that the curing of the ultraviolet curable composition easily proceeds to the inside when forming a recorded matter, and the ultraviolet curing of the present invention is performed. The aesthetic appearance of the recorded matter produced using the mold composition can be further improved.

  The constituent particles of the fluorine-containing powder may be any particles as long as at least the region including the surface is made of a material containing fluorine. For example, the particles made of a fluorine-based polymer or the surface treated with a fluorine-based surface treatment agent Inorganic fine particles and the like can be used.

  In particular, the fluorine-containing powder preferably includes particles composed of a fluorine-based polymer.

  Thereby, a fluorine-containing powder can be easily obtained as a sufficiently small particle size as described above. Moreover, the transparency in the hardened | cured material state which hardened | cured the polymeric compound which comprises an ultraviolet curable composition can be made especially excellent. In addition, the surface energy of the constituent particles becomes particularly small, and the hydrophobic interaction with the polymerizable compound contained in the ultraviolet curable composition is particularly large, so that the particles move to the gas-liquid interface and are easily stabilized. In addition, the fluorine-containing powder is easily fixed on the surface of the recorded matter obtained by ultraviolet curing, and the rub resistance of the recorded matter can be made particularly excellent.

  In particular, when the fluorine-containing powder includes particles composed of a fluorine-based polymer as constituent particles, the specific gravity is approximately 1.7 to 2.2, which is lighter than a metal such as aluminum. Therefore, the abrasion resistance of the recorded matter is effectively improved with a smaller addition amount.

  When the fluorine-containing powder contains particles composed of a fluorine-based polymer as constituent particles, examples of the fluorine-based polymer include polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, and tetrafluoroethylene. -Ethylene copolymers, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymers, polychlorotrifluoroethylene, polyvinylidene fluoride, etc. are mentioned, among which polytetrafluoroethylene is preferred. Thereby, the surface energy of the fluorine-containing powder becomes particularly small, and the rub resistance of the recorded matter can be effectively improved with a smaller addition amount.

  Further, the constituent particles of the fluorine-containing powder may be constituted by a dendrimer (dendritic polymer).

  Thereby, a fluorine-containing powder can be suitably obtained as a constituent particle having a spherical shape and a small particle diameter as described above. In addition, the particle size distribution of the fluorine-containing powder can be made sharper.

  When the constituent particles of the fluorine-containing powder are composed of dendrimers, examples of the dendrimers (dendrimers containing fluorine atoms) include those having an acrylic skeleton, those having an epoxy skeleton, and polyamidoamine (PAMAM) skeleton. And those having a bis (hydroxymethyl) propanoic acid (MPA) skeleton can be used, and those having an acrylic skeleton are particularly preferable.

  Thereby, the transparency of the constituent particles of the fluorine-containing powder in the printing portion can be made particularly excellent, and the aesthetics (aesthetic appearance) of the recorded matter can be made particularly excellent. In addition, a dendrimer having an acrylic skeleton (a dendrimer containing a fluorine atom) has excellent affinity with a polymerizable compound described in detail later, so that the storage stability of the ultraviolet curable composition is particularly excellent. In addition, the adhesion between the polymer of the polymerizable compound and the dendrimer containing a fluorine atom in the printing part formed using the ultraviolet curable composition can be made particularly excellent, The rub resistance, film strength, etc. can be made particularly excellent.

  When the fluorine-containing powder includes inorganic fine particles treated with a fluorine-based surface treatment agent as constituent particles, examples of the constituent material of the inorganic fine particles (parent particles) include silica, alumina, titania, magnesium oxide, calcium oxide, Examples include mica, carbon black, glass, talc, aluminum hydroxide, magnesium hydroxide, asbestos, iron oxide, zinc oxide, calcium carbonate, barium sulfide, calcium sulfate, graphite, and boron.

  In particular, the inorganic fine particles (mother particles) are preferably composed of a material having an oxide at least on the surface. As a result, the fluorine-based surface treatment agent can react precisely, so that the surface energy of the constituent particles of the fluorine-containing powder becomes very small, and a large amount of fine particles are present on the surface of the recorded matter with a small addition amount, and fixed. Since the formed particles can form a convex shape with a sufficient height, the abrasion resistance can be made particularly excellent.

  The inorganic fine particles (mother particles) are preferably composed of one or more selected from the group consisting of silica, alumina and titania, among the materials described above. As a result, the hardness of the constituent particles of the fluorine-containing powder can be made higher, the treatment with the fluorine-based surface treatment agent can be easily performed, and the surface treatment with a higher density can be performed. Even when the content of the fluorine-containing powder in the composition is further reduced, the recorded material produced using the ultraviolet curable composition has sufficiently excellent abrasion resistance and durability. be able to. In addition, since the transparency of the fluorine-containing powder can be made particularly high, the aesthetic appearance of the recorded matter produced using the ultraviolet curable composition can be more reliably improved.

  In particular, when the mother particles (inorganic fine particles) are composed of silica, the following effects can be obtained. That is, silica is a material having a high reactivity with a fluorine-based silane compound as a fluorine-based surface treatment agent, and a material having particularly high transparency and high hardness (Mohs hardness 7). For this reason, it is possible to further improve the abrasion resistance and durability of the recorded matter produced using the ultraviolet curable composition. Moreover, the aesthetic appearance of the recorded matter manufactured using the ultraviolet curable composition can be further improved. Further, since silica is an inexpensive and highly versatile material, it is also preferable from the viewpoint of reducing the production cost of the ultraviolet curable composition and the recorded material, and stably supplying the ultraviolet curable composition and the recorded material.

  Further, when the mother particles are made of alumina, the following effects can be obtained. That is, alumina is a material having high reactivity with a fluorine-based silane compound as a fluorine-based surface treatment agent, and a material having particularly high transparency and high hardness (Mohs hardness 9). For this reason, it is possible to further improve the abrasion resistance and durability of the recorded matter produced using the ultraviolet curable composition. Moreover, the aesthetic appearance of the recorded matter manufactured using the ultraviolet curable composition can be further improved. Alumina is an inexpensive and highly versatile material, and is therefore preferable from the viewpoint of reducing the production cost of the ultraviolet curable composition and recorded material, and the stable supply of the ultraviolet curable composition and recorded material.

Further, when the mother particle is composed of titania, the following effects can be obtained. That is, titania is a material with particularly high transparency and high hardness (Mohs hardness 7 to 7.5). For this reason, it is possible to further improve the abrasion resistance and durability of the recorded matter produced using the ultraviolet curable composition. Moreover, the aesthetic appearance of the recorded matter manufactured using the ultraviolet curable composition can be further improved. In addition, titania is an inexpensive and highly versatile material, so it is also preferable from the viewpoint of reducing the production cost of the ultraviolet curable composition and recorded material, and the stable supply of the ultraviolet curable composition and recorded material. In addition, titania has extremely high stability and high resistance to reactive gases such as hydrogen fluoride, hydrogen sulfide, SO ₃ and chlorine.

  When the fluorine-containing powder contains inorganic fine particles treated with a fluorine-based surface treatment agent as constituent particles, as the fluorine-based surface treatment agent, one containing at least one fluorine atom in the molecule can be used, For example, the fluorine compound (fluorine surface treatment agent) described as the surface treatment agent for the metal powder (mother particles) described above can be used. More specifically, for example, it has a structure in which at least a part of hydrogen atoms of the short chain compound, long chain compound, silane compound, phosphoric acid compound, carboxylic acid, and isocyanate compound as described above is substituted with a fluorine atom. Examples of the compound include fluorine short chain compounds, fluorine long chain compounds, fluorine silane compounds, fluorine phosphate compounds, fluorine-substituted fatty acids, and fluorine isocyanate compounds.

  In particular, when fluorine-based silane compounds are used, the reactivity with silica and alumina is high, so that inorganic fine particles composed of these inorganic materials are treated with a fluorine-based silane compound as a fluorine-based surface treatment agent. The constituent particles of the powder can be more stably dispersed in the ultraviolet curable composition.

  In addition, when a fluorine-based phosphate compound is used, surface treatment can be effectively performed with inorganic fine particles composed of iron oxide, aluminum, alumina, or the like. Further, since the surface treatment agent of the phosphoric acid compound is resistant to acid, the recorded matter obtained under an acidic environment exhibits excellent durability and weather resistance.

  In addition, when fluorine-substituted fatty acids (fluorinated fatty acids) are used, inorganic fine particles composed of these inorganic materials are treated with fluorine-substituted fatty acids as fluorine-based surface treatment agents because of their high reactivity with calcium carbonate and titania. The constituent particles of the resulting fluorine-containing powder can be more stably dispersed in the ultraviolet curable composition.

  In addition, when a fluorine-based isocyanate compound is used, the binding force between the base particles (inorganic fine particles) and the surface treatment agent can be made particularly strong.

  When the fluorine-containing powder contains inorganic fine particles treated with a fluorine-based surface treatment agent as constituent particles, the fluorine-based surface treatment agent used for the surface treatment of the inorganic fine particles and the surface treatment of the constituent particles of the metal powder are used. The fluorine-based surface treatment agent may be the same type of surface treatment agent. As a result, the surface characteristics (interfacial energy, charged state, etc.) of both the metal powder and the fluorine-containing powder are similar, so that the dispersion stability in the UV curable composition is particularly excellent, and the viscosity is increased over a longer period. And increase in particle size can be effectively suppressed.

As described above, the average particle diameter (D ₅₀ ) of the fluorine-containing powder may be 2 nm or more and 50 nm or less, preferably 2 nm or more and 10 nm or less, and more preferably 3.0 nm or more and 9 nm or less. .
Thereby, the effects as described above are more remarkably exhibited.

When the thickness of the metal powder is T _M [μm] and the average particle size of the fluorine-containing powder is D _F [μm], it is preferable that the relationship 0.05 ≦ D _F / T _M ≦ 0.7 is satisfied. 0.07 ≦ D _F / T _M ≦ 0.5 is more preferable, and 0.10 ≦ D _F / T _M ≦ 0.35 is more preferable.

  Thereby, in the recorded matter, it is possible to more effectively prevent the constituent particles of the fluorine-containing powder from being excessively present on the outer surface side (observer's viewpoint side) than the constituent particles of the metal powder. In addition, the glossiness of the portion can be made more excellent, and the rub resistance of the recorded matter can be made particularly excellent.

When the average particle diameter of the metal powder is D _M [μm] and the average particle diameter of the fluorine-containing powder is D _F [μm], it is preferable that the relationship of 10 ≦ D _M / D _F ≦ 300 is satisfied, and 15 ≦ It is more preferable to satisfy the relationship of D _M / D _F ≦ 200, and it is even more preferable to satisfy the relationship of 25 ≦ D _M / D _F ≦ 150.

  As a result, the glossiness of the printed portion can be made more excellent, and the recorded material can be made particularly excellent in abrasion resistance.

  The particles constituting the fluorine-containing powder may have any shape such as a spherical shape, a spindle shape, a needle shape (bar shape), a scale shape, etc., but preferably have a spherical shape.

  Thereby, the abrasion resistance of the recorded matter produced using the ultraviolet curable composition can be made particularly excellent. Moreover, when the particle | grains which comprise a fluorine-containing powder are spherical, the content rate of the fluorine-containing powder in an ultraviolet curable composition (in a printing part) shall be high, and the above-mentioned fluorine-containing powder is included. It is possible to more effectively prevent the fluorine-containing powder from exerting an adverse effect on the appearance of the recorded matter while exhibiting the effect of the above-described effect more effectively.

  In addition, when the particles constituting the fluorine-containing powder are spindle-shaped or rod-shaped, the specific surface area of the particles constituting the fluorine-containing powder is increased, so that the UV curable composition applied on the recording medium tends to float. Thus, it can be arranged more suitably in the vicinity of the outer surface of the printed part, and even with a relatively small content, it can have excellent abrasion resistance.

  In addition, when the particles that make up the fluorine-containing powder are spindle-shaped, the spindle increases in area by aligning and contacting the spindle-shaped major axis direction with the surface, or hardens in a state of deeply entering the recorded material. -Since it is fixed, there is also an effect that the rub resistance of the recorded matter becomes stronger.

  The content of the fluorine-containing powder in the ultraviolet curable composition is preferably 0.010% by mass or more and 5.0% by mass or less, more preferably 0.050% by mass or more and 4.0% by mass or less. Preferably, it is 0.10 mass% or more and 3.0 mass% or less.

  Thereby, the glossiness and abrasion resistance of the printing part formed using an ultraviolet curable composition can be made compatible at a higher level.

When the content of the metal powder in the ultraviolet curable composition is X _M [% by mass] and the content of the fluorine-containing powder is X _F [% by mass], 0.05 ≦ X _F / X _M ≦ 0.5 It is preferable to satisfy this relationship, and it is more preferable to satisfy the relationship of 0.07 ≦ X _F / X _M ≦ 0.45.

  Thereby, in the recorded matter manufactured using an ultraviolet curable composition, glossiness and abrasion resistance can be made compatible at a higher level.

<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 in a liquid state, and preferably functions as a dispersion medium for dispersing the metal powder and the fluorine-containing 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.

<Antifoaming agent>
The ultraviolet curable composition of the present invention contains an antifoaming agent as an additive.

  Since the antifoaming agent can reduce the surface tension of the ultraviolet curable composition and significantly reduce bubbles generated at the meniscus position in the vicinity of the nozzle, the discharge stability in the inkjet of the ultraviolet curable composition can be improved.

  In contrast, when the ultraviolet curable composition did not contain an antifoaming agent, pigments and fluorine-containing particles treated with a fluorine-based surface treatment agent having a low surface free energy were generated in the ultraviolet curable composition. By being easy to arrange in the gas-liquid interface in a bubble, a bubble can exist stably for a long time. As a result, ejection energy generated from piezo elements in the inkjet method is absorbed and attenuated by stabilized bubbles, resulting in ejection failure, reduced droplet weight, decreased droplet flying speed, and flight direction bending. Causes various problems. Therefore, the discharge stability cannot be made sufficiently excellent, and the uniformity of the ultraviolet curable composition is significantly deteriorated.

  In particular, by using an acrylic antifoaming agent containing fluorine or an acrylic antifoaming agent having no polar functional group as the antifoaming agent, the discharge stability can be made particularly excellent. Since these antifoaming agents have a small molecular weight and are much faster in diffusion and movement speed than pigments and fluorine-containing particles treated with a fluorine-based surface treatment agent, the generation of bubbles can be more effectively suppressed.

  Specific examples of the fluorine-containing acrylic antifoaming agent that can be used in the present invention include BYK-3440 (by Big Chemie) and BYK-3441 (by Big Chemie).

  The acrylic antifoaming agent having no polar functional group that can be used in the present invention is a functional group such as a hydroxyl group, amino group, carboxyl group, cyano group, or ketone group having a high electronegativity as a polar functional group. It is an acrylic copolymer that is not present in the molecule, and specific examples thereof include DISPERBYK-354 (manufactured by Big Chemie), DISPERBYK-392 (manufactured by Big Chemie), and the like.

  The content of the antifoaming agent is preferably 1.5% by weight or less, and more preferably 0.1% by weight or more and 1.0% by weight or less.

  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 antifoaming agent may contain two or more compounds as an acrylic antifoaming agent containing fluorine or an acrylic antifoaming agent having no polar functional group.

  In this case, it is preferable that the total content of these compounds is a value within the above range. If the content of the antifoaming agent in the ultraviolet curable composition is too high, the concentration of the excess antifoaming agent that does not act on defoaming increases, so that the metal powder and fluorine are present near the outer surface of the ultraviolet curable composition. It may be difficult to arrange the contained powder suitably, and it may be difficult to make the finally obtained recorded matter (printed part) sufficiently glossy and scratch resistant.

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

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

  The reason why such an excellent effect can be obtained is considered to be as follows. That is, by including a monomer having an alicyclic structure, the dispersion stability of the fluorine-containing powder and the metal powder in the ultraviolet curable composition can be made particularly excellent, and the fluorine in the ultraviolet curable composition can be improved. Aggregation and sedimentation of the contained powder and metal powder can be suitably prevented over a long period of time. Such an effect synergistically works with the effect of including a fluorine-containing powder and a metal powder satisfying predetermined conditions, so that the storage stability of the ultraviolet curable composition is particularly excellent. In addition, it is considered that the glossiness and 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, γ-butyrolactone (meth) acrylate, N -Vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, mevalon Acid lactone (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenta (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-adaman 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, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate And one or more selected from the group consisting of cyclic trimethylolpropane formal acrylate.

  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, The dispersion stability of the metal powder and fluorine-containing powder and the ejection stability by the ink jet method can be further improved, and in the recorded matter produced using the ultraviolet curable composition, the metal powder is printed on the printed part. Can be arranged more suitably in the vicinity of the outer surface, and the glossiness of the obtained recorded product 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. -Gamma-butyrolactone acrylate, N-vinylpyrrolidone, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, acryloylmorpholine, cyclic trimethylol propane formal acrylate, And preferably one or more selected from the group consisting of tetrahydrofurfuryl acrylate, acryloylmorpholine and / or γ-butyrolactone accelerator It is more preferable that it contains γ-butyrolactone 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 It is preferable to include one or more selected from the group consisting of acryloylmorpholine, and to include 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 and the fluorine-containing powder is particularly excellent, and particularly excellent discharge stability can be 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 and the fluorine-containing powder is particularly excellent, and particularly excellent discharge stability can be 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, for example, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated orthophenylphenol (meth) acrylate, and (meth) acrylic acid 2- ( 2-vinyloxyethoxy) ethyl, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 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-tri Fluoroethyl (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-butanediol 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, polypropylene 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-added tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, 2- (meth) acryl Leuoxyethyl phthalate, 3- (meth) acryloyloxypropyl acrylate, w-carboxy (meth) acryloyloxyethyl phthalate, ditrime Examples include roll propane tetra (meth) acrylate, dipentaerythritol penta / hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., but phenoxyethyl acrylate, benzyl acrylate, acrylic acid 2- (2-vinyloxyethoxy) ) It preferably contains one or more selected from the group consisting of ethyl, dipropylene glycol diacrylate, tripropylene 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, in the recorded matter produced using the ultraviolet curable composition, the fluorine-containing powder can be more suitably arranged near the outer surface of the printed part, and the obtained recorded matter has further excellent abrasion resistance. can do.

  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 a fluorine-containing powder and a metal powder satisfying predetermined conditions, and further includes an alicyclic structure-containing monomer. The storage stability and curability 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 and the fluorine-containing 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 polymer structure having an acid group (hereinafter also referred to as “acid group-containing polymer dispersant”).

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

  The acid group-containing polymer dispersant is not particularly limited as long as it has an acid group such as carboxylic acid, phosphoric acid, and sulfonic acid group and has a polymer structure.

  The polymer structure constituting the acid group-containing polymer dispersant is not particularly limited. For example, an acrylic polymer structure (including a copolymer), a methacrylic polymer structure (including a copolymer), Examples thereof include polyurethane-based polymer structures, hydroxyl group-containing carboxylic acid ester structures, polyether-based polymer structures, and silicone-based polymer structures.

  The acid value of the acid group-containing polymer dispersant is not particularly limited, but is preferably 3 mgKOH / g or more and 200 mgKOH / g or less, more preferably 10 mgKOH / g or more and 120 mgKOH / g or less.

  Specific examples of the polymer dispersant having an acid group that can be used in the present invention include DISPERBYK-102 (manufactured by BYK Chemie), DISPERBYK-106 (manufactured by BYK Chemie), DISPERBYK-110 (manufactured by BYK Chemie), DISPERBYK- 111 (by Big Chemie), DISPERBYK-140 (by Big Chemie), DISPERBYK-142 (by Big Chemie), DISPERBYK-145 (by Big Chemie), DISPERBYK-118 (by Big Chemie), DISPERBYK-180 (by Big Chemie) ), DISPERBYK-191 (made by Big Chemie), DISPERBYK-2095 (made by Big Chemie), DISPERBYK-2096 (made by Big Chemie), Price Surf A212 (Daiichi Kogyo Seiyaku), Prisurf A215C (Daiichi Kogyo Seiyaku), Prisurf A208N (Daiichi Kogyo Seiyaku), Prisurf A219B (Daiichi Kogyo Seiyaku), PN-411 (Ajinomoto Fine Techno Co. ), PA-111 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 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 an acidic polymer dispersant (acid group-containing polymer dispersant). In this case, it is preferable that the total content of these compounds is a value within the above range. If the content of the dispersant in the ultraviolet curable composition is too high, the concentration of the surplus dispersant that does not act on the dispersion increases, so that the so-called polymer dispersion depletion effect causes the metal powder and the fluorine-containing powder. Osmotic pressure generated when the particles are close to each other promotes particle aggregation, resulting in an increase in the average particle diameter and further separation / sedimentation of the pigment from the ultraviolet curing component. As a result, in the ultraviolet curable composition applied to the recording medium, the uniformity of the metal powder and the fluorine-containing powder is lowered and the fluidity of the powder particles is greatly reduced. It becomes difficult to arrange the metal powder and fluorine-containing powder in the vicinity of the outer surface, and it is difficult to make the final printed matter (printed part) sufficiently glossy and scratch resistant. There is a possibility.

<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 0.3 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. Further, in the present invention, even when the content of the polymerization inhibitor is relatively low, the storage stability and ejection stability of the ultraviolet curable composition can be made sufficiently 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 according to the present invention will be described.

  The recorded matter according to the present invention is produced by applying the ultraviolet curable composition as described above onto a medium (recording medium) and then irradiating with ultraviolet rays.

  Such a recorded matter has a pattern (printing portion) excellent in glossiness and abrasion resistance.

  As described above, the ultraviolet curable 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 according to 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 recorded matter according to the present invention include console lids, switch bases, center clusters, interior panels, emblems, center consoles, meter interiors such as meter nameplates, operation units (key switches) of various electronic devices, For example, display parts such as decorative parts, indicators, logos and the like that exhibit decorative properties are included.

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

  For example, in the above-described embodiment, the case where the recorded matter according to the present invention is composed of a recording medium (base material) and a printing unit has been mainly described. However, the recorded matter according to the present invention is a recording medium ( In addition to the base material) and 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 was formed was added to 99 parts by mass of diethylene glycol diethyl ether as CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O ( P) (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. Thus, a dispersion of metal powder in the base particles made of Al consists of _{CF 3 (CF 2) 5 (} CH 2) 2 O (P) (OH) 2 scaly particles surface-treated by the obtained It was.

The volume average particle size (D ₅₀ ) 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, metal The particle diameter (D ₉₀ ) at a volume cumulative distribution rate of 90% from the fine particle side of the powder was 0.77 μm, and the half width in the particle size distribution of the metal powder was 0.32 μm.

Next, a dispersion of the metal powder is prepared by using a fluorine-containing powder (volume average particle diameter (D ₅₀ ): 7 nm) composed of highly branched dendrimers having an acrylic skeleton and spherical particles, and a monomer having an alicyclic structure (polymerizability). Γ-butyrolactone acrylate as a compound), phenoxyethyl acrylate as a monomer having no alicyclic structure (polymerizable compound), substance A having a chemical structure represented by the following formula (9), basic polymer dispersant DISPERBYK-182 (manufactured by Big Chemie) as a photopolymerization initiator, Irgacure 819 (manufactured by Ciba Japan), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, and Speedcure DETX as a photopolymerization initiator (Made by Lambson) and mixed with the production for recording To give an object (ultraviolet-curable composition).

(Examples 2 to 20)
The constituent particles of the metal powder and the constituent particles of the fluorine-containing powder are configured as shown in Table 1, and the types and ratios of the raw materials used for the preparation of the recorded product manufacturing composition (ultraviolet curable composition) are changed. Thus, a composition for producing a recorded matter (ultraviolet curable composition) was produced in the same manner as in Example 1 except that the compositions shown in Tables 2 and 3 were used.

(Comparative Example 1)
A composition for producing recorded matter (ultraviolet curable composition) was produced in the same manner as in Example 1 except that the composition did not contain fluorine-containing powder.

(Comparative Examples 2 and 3)
A composition for producing recorded matter (ultraviolet curable composition) was produced in the same manner as in Example 1 except that the particle size distribution of the fluorine-containing powder was different.

(Comparative Example 4)
A composition for producing a recorded matter (ultraviolet curable composition) was produced in the same manner as in Example 1 except that the composition did not contain an antifoaming agent.

About each said Example and a comparative example, the structure of the metal powder and fluorine-containing powder which are contained in the composition for recording material manufacture is put together in Table 1, and the composition of the composition for recording material manufacture is summarized in Table 2, Table 3. Showed. In the table, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (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 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: CH ₃ (CH ₂ ) ₁₁ — (OCH ₂ CH ₂ ) ₂ —O—PO (OH) ₂ as “LP”, octyltriethoxysilane as an alkylsilane compound as “OTS”, CH ₃ (CH ₂ ) ₇ O—PO (OH) ₂ is “AP1”, polytetrafluoroethylene is “PTFE”, acrylic skeleton dendrimer is “FA-1”, epoxy skeleton dendrimer is “FE-1”, bis (hydroxy Methyl) propanoic acid skeleton dendrimer as “FMP-1”, γ-butyrolactone acrylate as a monomer (polymerizable compound) having an alicyclic structure as “BLA”, tetrahydrofluor as a monomer having a alicyclic structure (polymerizable compound) Furyl acrylate is “THFA”, N-vinyl carbonate as a monomer (polymerizable compound) having an alicyclic structure Prolactam is “VC”, N-vinylpyrrolidone is “VP” as a monomer (polymerizable compound) having an alicyclic structure, “AMO” is acryloylmorpholine as a monomer (polymerizable compound) having an alicyclic structure, “TAOEI” is tris (2-acryloyloxyethyl) isocyanurate as a monomer having a ring structure (polymerizable compound), and “DCPTeOEA” is dicyclopentenyloxyethyl acrylate as a monomer having a alicyclic structure (polymerizable compound). , “AA” for adamantyl acrylate as a monomer (polymerizable compound) having an alicyclic structure, “DMTCDDA” for dimethylol tricyclodecane diacrylate as a monomer (polymerizable compound) having an alicyclic structure, As a monomer (polymerizable compound) Methylol dicyclopentane diacrylate is “DMDCPTA”, dicyclopentenyl acrylate is “DCPTeA” as a monomer having an alicyclic structure (polymerizable compound), and dicyclopentanyl is a monomer having a alicyclic structure (polymerizable compound) "DCPTaA" acrylate, "IBA" isobornyl acrylate as a monomer having an alicyclic structure (polymerizable compound), "CHA" cyclohexyl acrylate as a monomer having a alicyclic structure (polymerizable compound), alicyclic Diacrylated isocyanurate as a monomer having a structure (polymerizable compound) “DAI”, triacrylated isocyanurate as a monomer having an alicyclic structure (polymerizable compound) “TAI”, monomer having an alicyclic structure ( Γ- as a polymerizable compound) “BLM” for butyrolactone methacrylate, “THF” for tetrahydrofurfuryl methacrylate as a monomer (polymerizable compound) having an alicyclic structure, and “dicyclopentenyloxyethyl methacrylate” for a monomer (polymerizable compound) having an alicyclic structure “ “DCPTeOEM”, “AM” for adamantyl methacrylate as a monomer (polymerizable compound) having an alicyclic structure, “PMPM” for pentamethylpiperidyl methacrylate as a monomer (polymerizable compound) having an alicyclic structure, having an alicyclic structure Tetramethylpiperidyl methacrylate as a monomer (polymerizable compound) is “TMPM”, 2-methyl-2-adamantyl methacrylate as a monomer (polymerizable compound) having an alicyclic structure is “MAM”, 2-ethyl-2-adamantyl methacrylate as a monomer (polymerizable compound) “EAM”, mevalonic acid lactone methacrylate as a monomer (polymerizable compound) “MLM”, monomer having an alicyclic structure ( Dicyclopentenyl methacrylate as a polymerizable compound) is “DCPTeM”, dicyclopentanyl methacrylate as a monomer having an alicyclic structure (polymerizable compound) is “DCPTaM”, and a monomer having an alicyclic structure (polymerizable compound) Isobornyl methacrylate of “IBM”, cyclohexyl methacrylate as a monomer (polymerizable compound) having an alicyclic structure (CHM), and cyclohexanespiro-2- (1) as a monomer having an alicyclic structure (polymerizable compound) , 3-Dioxolan-4-yl “CHDOLA” methyl acrylate, “MEDOLA” methyl (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate as a monomer (polymerizable compound) having an alicyclic structure, and an alicyclic structure Phenoxyethyl acrylate as a monomer (polymerizable compound) that does not have "PEA", dipropylene glycol diacrylate as a monomer (polymerizable compound) that does not have an alicyclic structure as "DPGDA", has an alicyclic structure Tripropylene glycol diacrylate as a monomer (polymerizable compound) is “TPGDA”, 2-hydroxy-3-phenoxypropyl acrylate as a monomer (polymerizable compound) having no alicyclic structure is “HPPA”, an alicyclic structure 4-Hydroxybuty as a monomer (polymerizable compound) having no carbon Acrylate “HBA”, ethyl carbitol acrylate as a monomer (polymerizable compound) having no alicyclic structure “ECA”, methoxytriethylene glycol as a monomer having no alicyclic structure (polymerizable compound) “MTEGA” for acrylate, “TBA” for t-butyl acrylate as a monomer (polymerizable compound) having no alicyclic structure, and “BA” for benzyl acrylate as a monomer (polymerizable compound) having no alicyclic structure "" (VEEA) "2- (2-hydroxyethoxy) ethyl acrylate as a monomer (polymerizable compound) having no alicyclic structure," benzyl methacrylate "as a monomer (polymerizable compound) having no alicyclic structure "BM", urethane acrylate as a monomer (polymerizable compound) having no alicyclic structure “UA”, DISPERBYK-118 (BIC Chemie, acid value: 36 mgKOH / g) as an acidic polymer dispersant is “D1”, DISPERBYK-2090 (BIC Chemie, acid value: 61 mgKOH, as an acidic polymer dispersant) / G) is “D2”, Prisurf A219B as an acidic polymer dispersant (Daiichi Kogyo Seiyaku Co., Ltd., acid value: 50 mg KOH / g) is “D3”, a compound represented by the above formula (9) (substance A) ) Is “A1”, the compound represented by the following formula (10) (substance A) is “A2”, the compound represented by the following formula (11) (substance A) is “A3”, and the following formula (12) The substance A represented is "A4", BYK-3441 as an antifoaming agent is "B3441", DISPERBYK-354 as an antifoaming agent is "D354", and DISPERBYK- as an antifoaming agent 92 “D392”, Irgacure 819 (manufactured by Ciba Japan) “ic819”, Speedure TPO (manufactured by ACETO) “scTPO”, Speedcure DETX (manufactured by Lambson) “scDETX”, BYK-350 (BIC Chemie) "BY350", hydroquinone monomethyl ether "MEHQ", LHP-96 (Enomoto Kasei Co., Ltd.) "LHP", LF-1982 (Enomoto Kasei Co., Ltd.) "LF-1", LF-1984 (Enomoto) "LF-2" is shown. 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. In addition, with respect to the metal powder constituting the composition for producing recorded matter (ultraviolet curable composition) of each of the above examples, each of the 10 metal particles was observed and observed from the direction in which the projected area was maximized. The area S ₁ [μm ² ] at the time (when viewed in plan) and the ratio to the area S ₀ [μm ² ] when observed from the direction in which the area when observed is the maximum among the directions orthogonal to the observation direction When (S ₁ / S ₀ ) was determined and the average value of these was determined, the average value of S ₁ / S ₀ was 19 or more. Moreover, in the Example and comparative example using what gave the surface treatment as a metal powder, all the content rate of the constituent particle to which the surface treatment was given with respect to the whole metal powder was 99 mass% or more. . Further, the visible light transmittance (wavelength) in the thickness direction of a cured product having a thickness of 100 μm obtained by curing a composition having the same composition as the ultraviolet curable composition of each of the above examples except that the metal powder is not included. : Transmittance of light at 600 nm) was 90% or more in all cases.

[2] Droplet discharge stability evaluation (discharge stability evaluation)
Using the compositions for producing recorded matter of each of the above Examples and Comparative Examples, evaluation by tests as shown below was performed.

  First, a droplet discharge device installed in a chamber (thermal chamber) and the recorded product manufacturing compositions of each of the examples and comparative examples were prepared, and the driving waveform of the piezoelectric element was optimized at 25 ° C., 50 In an environment of% RH, with respect to each composition for producing a recorded product, the average discharge speed of droplets while continuously discharging from each nozzle of a droplet discharge head having a nozzle hole size of 22 μm in diameter at a frequency of 20 kHz, The weight of the ink was measured. Next, the situation at the time when 1 million (1000000) droplets are continuously ejected from each nozzle is captured in a computer as a photographed image, and a defective nozzle (missing, ejection bending, ejection speed reduction accompanied by ink weight change, etc.) The total number of nozzles not discharging normally) was taken in and counted. Dropout in this case is a state in which droplets do not come out of the nozzle hole or abnormal discharge in the form of spray, and discharge bending is normal in which discharge is performed in the normal direction of the nozzle surface This shows a state where the flight is bent in a range of ± 5 degrees or more with respect to the state. The discharge speed was reduced as a defective nozzle by 3% or more of the discharge average speed calculated and set in advance. If the occurrence probability of this defective nozzle (ratio of defective nozzles to the total number of evaluated nozzles) is small, it can be determined that the ejection stability is high.

[2.1] Bending defect occurrence rate A: The occurrence probability of bending defects is less than 0.5%.
B: Bending defect occurrence probability is 0.5% or more and less than 1.0%.
C: The occurrence probability of bending failure is 1.0% or more and less than 5.0%.
D: Bending defect occurrence probability is 5.0% or more and less than 10.0%.
E: The probability of occurrence of bending failure is 10.0% or more.

[2.2] Occurrence rate of omission (discharge omission)
A: Occurrence probability of missing defects is less than 0.5%.
B: Occurrence probability of missing defects is 0.5% or more and less than 1.0%.
C: Occurrence probability of missing defects is 1.0% or more and less than 2.0%.
D: Occurrence probability of missing defect is 2.0% or more and less than 5.0%.
E: Occurrence probability of missing defects is 5.0% or more.

[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 60 ° C. environment for 20 days and then filtered with a capsule filter having a filtration accuracy of 3 μm (manufactured by Yamachine Filter). The concentration before and after the passage of 1 L was measured, the loss due to filter filtration of coarse particles due to insufficient dispersion was determined by the concentration reduction rate, and evaluated according to the following criteria.

A: The ink density reduction rate is less than 5%.
B: The ink density reduction rate is 5% or more and less than 10%.
C: The ink density reduction rate is 10% or more and less than 20%.
D: The ink density reduction rate is 20% 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, a composition for producing a recorded product is ejected in a predetermined pattern onto a base material (recording medium) having a curved surface portion formed by using polycarbonate (manufactured by Asahi Glass Co., Ltd., Carboglass polish 2 mm thick). 365 nm, 380 nm Ultraviolet light having a spectrum having a maximum value at a wavelength of 395 nm was irradiated with an irradiation intensity of 160 mW / cm ² for 10 seconds to cure the composition for producing a recorded material on the substrate. Then, it heated at 80 degreeC for 1 hour, and the interior panel as a recorded material was obtained.

  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 320 or more.
B: Glossiness is 250 or more and less than 320.
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 according to the present invention had excellent gloss and appearance, and was excellent in the scratch 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, satisfactory results were not obtained.

Claims (11)

A polymerizable compound, a metal powder, a fluorine-containing powder, and an antifoaming agent,
An ultraviolet curable composition, wherein the fluorine-containing powder has an average particle size of 2 nm to 50 nm.   The ultraviolet curable composition according to claim 1, wherein the antifoaming agent is an acrylic antifoaming agent containing fluorine or an acrylic antifoaming agent having no polar functional group.   The ultraviolet curable composition according to claim 1, wherein the fluorine-containing powder contains particles composed of a fluorine-based polymer.   The ultraviolet curable composition according to any one of claims 1 to 3, wherein the constituent particles of the metal powder have a scaly shape.   The ultraviolet curable composition according to claim 4, 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 claim 4 or 5, wherein the average thickness of the constituent particles of the metal powder is larger than the average particle diameter of the fluorine-containing powder.   The ultraviolet curable composition according to any one of claims 1 to 6, wherein an average particle size of the metal powder is 200 nm or more and 3.0 µm or less.   The ultraviolet curable composition according to any one of claims 1 to 7, 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 Drofurfuryl acrylate, cyclohexane spiro-2- (1,3-dioxolan-4-yl) methyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, and cyclic tri The ultraviolet curable composition according to claim 8, comprising one or more selected from the group consisting of methylolpropane formal acrylate.   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 8 or 9, comprising one or more selected from the group consisting of -phenoxypropyl acrylate and 4-hydroxybutyl acrylate.   A method for producing a recorded matter, comprising producing the ultraviolet curable composition according to any one of claims 1 to 10 on a medium and then irradiating with ultraviolet rays.