JP6094055B2 - Manufacturing method of recorded matter - Google Patents

Description

The present invention relates to a method for manufacturing a recorded matter.

Conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.
However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion. In addition, the foil stamping printing has a problem that it is difficult to cope with multi-product production because it has low on-demand property, and gradation-like metallic printing cannot be performed.

  On the other hand, a recording method based on an ink jet method is used as a recording method on a recording medium (base material) using a composition containing a pigment or a dye. The ink jet method is excellent in that it can be suitably applied to formation of a fine pattern and recording on a curved surface portion. In recent years, in the ink jet method, a composition that cures when irradiated with ultraviolet rays (ultraviolet rays), in order to improve particularly the abrasion resistance, water resistance, solvent resistance, etc., and to improve the productivity of recorded matter. Curable ink-jet ink) is used (for example, see Patent Document 1).

  However, in an ultraviolet curable ink-jet ink, when a metal powder is applied instead of a pigment or dye, the gloss inherent in the metal (particularly, the gloss (such as the mirror surface) ( There has been a problem that it is not possible to fully exhibit the characteristics such as the shining feeling)). In particular, when a recorded matter (printed matter) is one in which a printed part is visually recognized (observed) through a recording medium (base material), the printed matter has a dark color tone despite containing a metal powder. As a result, the appearance of the recorded matter (printed portion) is extremely inferior.

JP 2009-57548 A

  An object of the present invention is to provide a recorded matter provided with a printing portion observed through a base material, the printing portion being provided in a desired shape and having an excellent gloss feeling like a mirror surface. In addition, it is possible to efficiently produce a recorded matter that has a printing part that is observed through a substrate, the printing part is provided in a desired shape, and has an excellent gloss feeling like a mirror surface. An object of the present invention is to provide a method for producing a recorded matter that can be produced.

Such an object is achieved by the present invention described below.
The method for producing a recorded matter of the present invention is a method for producing a printed matter comprising a base material and a printing portion, wherein the printing portion provided on the back side of the base material is visually recognized.
A first ink application step in which a first ink containing a first polymerizable compound that is polymerized by irradiation with ultraviolet rays is applied to the surface of a substrate by an inkjet method;
A first curing step of polymerizing and curing the first polymerizable compound;
A second ink application step in which a second ink containing a second polymerizable compound and metal powder that is polymerized by irradiation with ultraviolet rays is applied onto the cured product of the first polymerizable compound by an inkjet method;
A second curing step of polymerizing and curing the second polymerizable compound,
The contact angle of the first ink to the substrate is 30 ° or more and 85 ° or less,
The time from when the first ink droplet lands on the substrate in the first ink application step to when the liquid is cured in the first curing step is within one second. ,
Time from when the droplets of the second ink land on the cured product of the first polymerizable compound in the second ink application step until the curing process is performed on the droplets in the second curing step Is 10 seconds or more.
Accordingly, a printed portion that is observed through the base material is provided, and the printed portion is provided in a desired shape and efficiently produces a recorded matter having an excellent gloss feeling like a mirror surface. It is possible to provide a method for manufacturing a recorded matter.

In the method for producing a recorded matter of the present invention, the viscosity of the first ink at room temperature (25 ° C.) is preferably 5 mPa · s or more and 40 mPa · s or less.
Accordingly, it is possible to more effectively suppress the bleeding at the time of the first ink droplet landing while making the ejection stability of the first ink particularly excellent.
In the method for producing a recorded matter of the present invention, the viscosity of the second ink at room temperature (25 ° C.) is preferably 4 mPa · s or more and 30 mPa · s or less.
This makes it possible to more effectively suppress the bleeding when the second ink droplets land, while making the ejection stability of the second ink particularly excellent, and the gloss of the recorded matter is particularly excellent. Can be.

In the method for producing a recorded matter of the present invention, it is preferable that the surface tension of the first ink at 25 ° C. is 18 mN / m or more and 50 mN / m or less.
Accordingly, it is possible to more effectively suppress the bleeding at the time of the first ink droplet landing while making the ejection stability of the first ink particularly excellent.
In the method for producing a recorded matter of the present invention, the surface tension of the second ink at 25 ° C. is preferably 14 mN / m or more and 40 mN / m or less.
This makes it possible to more effectively suppress the bleeding when the second ink droplets land, while making the ejection stability of the second ink particularly excellent, and the gloss of the recorded matter is particularly excellent. Can be.

In the method for producing a recorded matter of the present invention, the second ink is one or more selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate ester and a phosphate alkyl ester as the metal powder. It is preferable that the surface treatment agent is included.
As a result, the storage stability of the second ink can be made particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter can be made particularly excellent.

In the method for producing a recorded matter of the present invention, the second ink includes the metal powder that has been surface-treated with the fluorine-based silane compound having a chemical structure represented by the following formula (1). Is preferred.
R ¹ SiX ¹ _a R ² _(3-a) (1)
(In Formula (1), 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 second ink can be made particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter can be made particularly excellent.

In the method for producing a recorded matter of the present invention, the second ink includes the metal powder that has been surface-treated with the fluorinated phosphate ester having a chemical structure represented by the following formula (2). It is preferable.
POR _n (OH) _3-n (2)
(In the formula (2), 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 second ink can be made particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter can be made particularly excellent.

In the method for producing a recorded matter of the present invention, the second ink includes the metal powder that has been surface-treated with the alkyl phosphate ester having a chemical structure represented by the following formula (3). It is preferable.
POR _n (OH) _3-n (3)
(In the formula (3), R _{is, CH 3 (CH 2) m} -, CH 3 (CH 2) m (CH 2 O) l -, CH 3 (CH 2) m (CH 2 CH 2 O) l - Or CH ₃ (CH ₂ ) _m O—, n is an integer of 1 to 3, m is an integer of 2 to 18, and l is an integer of 1 to 18.
As a result, the storage stability of the second ink can be made particularly excellent, and the glossiness and abrasion resistance of the printed portion of the recorded matter can be made particularly excellent.

In the method for producing a recorded matter of the present invention, it is preferable that the second ink further includes a basic dispersant having a polymer structure as a dispersant.
Thereby, the glossiness and durability of the recorded matter can be further improved. Further, the storage stability of the second ink can be made particularly excellent.
In the recorded matter manufacturing method of the present invention, it is preferable that the second ink includes a scale-like one as the metal powder.
As a result, the metal powder can be arranged so that the main surface of the metal particles follows the surface shape of the base material (the surface shape of the cured product of the first ink), and the metal material constituting the metal powder inherently exists. The glossiness, etc., can be more effectively exhibited in the recorded matter, and the glossiness and luxury feeling of the printed portion can be made particularly excellent, and the rub resistance of the recorded matter is particularly high. It can be excellent.

In the method for producing a recorded matter of the present invention, it is preferable that both of the first ink and the second ink contain phenoxyethyl acrylate.
Thereby, while making the discharge stability of the first ink and the second ink excellent, the reactivity of the first ink and the second ink after the discharge by the ink jet method is particularly excellent, and the recorded matter The productivity can be made particularly excellent. Further, the adhesion between the cured product of the first ink and the cured product of the second ink can be made particularly excellent, and the reliability and durability of the recorded matter can be made particularly excellent. . Moreover, even if the printing part which should be formed has a fine shape, the printing part of a desired shape can be formed more reliably.

In the method for producing a recorded matter of the present invention, the first ink and the second ink include 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, trimethyl, in addition to the phenoxyethyl acrylate. It is preferable to include at least one selected from the group consisting of propylene glycol diacrylate, 2-hydroxy 3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate.
Thereby, while making the discharge stability of the first ink and the second ink excellent, the reactivity of the first ink and the second ink after the discharge by the ink jet method is particularly excellent, and the recorded matter The productivity can be made particularly excellent. Further, the adhesion between the cured product of the first ink and the cured product of the second ink can be made particularly excellent, and the reliability and durability of the recorded matter can be made particularly excellent. . Moreover, even if the printing part which should be formed has a fine shape, the printing part of a desired shape can be formed more reliably.

  In the method for producing a recorded matter of the present invention, each of the first ink and the second ink is dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopenta. Nyl acrylate, isobornyl acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and at least one selected from the group consisting of methoxytriethylene glycol acrylate are preferable.

  Thereby, while making the discharge stability of the first ink and the second ink excellent, the reactivity of the first ink and the second ink after the discharge by the ink jet method is particularly excellent, and the recorded matter The productivity can be made particularly excellent. Further, the adhesion between the cured product of the first ink and the cured product of the second ink can be made particularly excellent, and the reliability and durability of the recorded matter can be made particularly excellent. . Moreover, even if the printing part which should be formed has a fine shape, the printing part of a desired shape can be formed more reliably.

The recorded matter of the present invention is manufactured using the method of the present invention.
Accordingly, it is possible to provide a recorded matter that includes a printing portion that is observed through a base material, the printing portion is provided in a desired shape, and has an excellent gloss feeling like a mirror surface. it can.

It is sectional drawing which shows typically suitable embodiment of the manufacturing method of the recorded matter of this invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<Method for producing recorded matter>
First, the manufacturing method of the recorded matter of this invention is demonstrated.
The production method of the present invention is a method for producing a recorded matter using an inkjet method.
By the way, conventionally, metal plating, foil press printing using a metal foil, thermal transfer using a metal foil, and the like have been used as a method for producing a decorative product exhibiting a glossy appearance.

However, these methods have a problem that it is difficult to form a fine pattern or to apply to a curved surface portion. In addition, the foil stamping printing has a problem that it is difficult to cope with multi-product production because it has low on-demand property, and gradation-like metallic printing cannot be performed.
On the other hand, a recording method based on an ink jet method is used as a recording method on a recording medium (base material) using a composition containing a pigment or a dye. The ink jet method is excellent in that it can be suitably applied to formation of a fine pattern and recording on a curved surface portion. In recent years, in the ink jet method, a composition that cures when irradiated with ultraviolet rays (ultraviolet rays), in order to make the abrasion resistance, water resistance, solvent resistance, etc. particularly excellent and to improve the productivity of recorded matter. Curable ink-jet ink) is used.

  However, in an ultraviolet curable ink-jet ink, when a metal powder is applied instead of a pigment or dye, the gloss inherent in the metal (particularly, the gloss (such as the mirror surface) ( There has been a problem that it is not possible to fully exhibit the characteristics such as the shining feeling)). In particular, when a recorded matter (printed matter) is one in which a printed part is visually recognized (observed) through a recording medium (base material), the printed matter has a dark color tone despite containing a metal powder. As a result, the appearance of the recorded matter (printed portion) is extremely inferior.

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 manufacturing method of the present invention is a method of manufacturing a printed matter that includes a base material and a printing part, and through which the printing part provided on the back surface side is visually recognized, and is irradiated with ultraviolet rays. A first ink application step of applying the first ink containing the first polymerizable compound to be polymerized to the surface of the substrate by an inkjet method, and a first ink for polymerizing and curing the first polymerizable compound. A second ink application in which a second ink containing a second polymerizable compound and metal powder that is polymerized by irradiation with ultraviolet rays is applied onto the cured product of the first polymerizable compound by an inkjet method. And a second curing step for polymerizing and curing the second polymerizable compound, wherein a contact angle of the first ink to the substrate is 30 ° or more and 85 ° or less, and the first In the ink application process of The time from when the droplet of the first ink lands on the substrate to when the droplet is cured in the first curing step is within one second, and in the second ink application step The time from when the droplets of the second ink land on the cured product of the first polymerizable compound to when the droplets are cured in the second curing step is 10 seconds or more.
Accordingly, a printed portion that is observed through the base material is provided, and the printed portion is provided in a desired shape and efficiently produces a recorded matter having an excellent gloss feeling like a mirror surface. It is possible to provide a method for manufacturing a recorded matter.

Hereinafter, a preferred embodiment of a production method of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of a method for producing a recorded matter of the present invention.
As shown in FIG. 1, in the manufacturing method of the present embodiment, a first ink 2 ′ including a first polymerizable compound 21 ′ that is polymerized by irradiation with ultraviolet rays is applied to the surface of the substrate 1 by an inkjet method. A first ink application step (1a), a first curing step (1b) for polymerizing and curing the first polymerizable compound 21 ′, a second polymerizable compound 32 ′ and a metal that are polymerized by irradiation with ultraviolet rays. A second ink application step (1c) for applying the second ink 3 ′ containing the powder 31 onto the cured product 21 (first layer 2) of the first polymerizable compound 21 ′ by an inkjet method; A second curing step (1d) for polymerizing and curing the second polymerizable compound 32 ′, and a protective film forming step (1e) for forming the protective film 4 so as to cover the second layer 3 ing.

<First ink application step>
In this step, the first ink 2 ′ is applied to the surface of the substrate (recording medium) 1 by an inkjet method (1a).
As the base material 1, a material having optical transparency can be used. In the present invention, “having light transmittance” means having a property of transmitting at least part of light in the visible light region (wavelength region of 380 to 780 nm), and preferably transmitting light in the visible light region. The rate is 70% or more, and more preferably the light transmittance in the visible light region is 80% or more. In this specification, unless otherwise specified, the light transmittance is the light (visible light) transmittance when xenon white light defined in JIS Z 8902 is used as a light source. Point to.

Examples of the constituent material of the substrate 1 include various plastic materials and various glass materials.
Moreover, it is preferable that the base material 1 is comprised by the material whose surface is non-liquid-absorbing (non-absorbing) at least. Thereby, the glossiness and smoothness of the finally obtained recorded matter (printed matter) 10 can be made particularly excellent.

In the present invention, the non-liquid-absorbing recording medium refers to a medium that does not substantially absorb ink, and more specifically, a medium having a contact angle of a droplet after landing of 10 ° or more. Say.
In particular, the substrate 1 is preferably composed of polyester. Thereby, a polymeric compound (especially polymeric compound containing phenoxyethyl acrylate) can be hardened more reliably in a desired shape.

  Examples of the polyester constituting the substrate 1 include polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate, and polyethylene terephthalate is preferable. Thereby, the adhesion between the first layer 2 (particularly, the first layer 2 formed using the first ink 2 ′ containing phenoxyethyl acrylate as the polymerizable compound) and the substrate 1 is particularly excellent. In addition, the heat resistance and the like of the recorded matter 10 finally obtained can be made particularly excellent.

Moreover, the base material 1 may contain components other than the above (other components). Examples of such components include colorants, antifungal agents, preservatives, and antioxidants.
The first ink 2 ′ includes a first polymerizable compound 21 ′ that is polymerized by irradiation with ultraviolet rays. 1st polymeric compound 21 'superposes | polymerizes and hardens | cures in the 1st hardening process explained in full detail later, and forms hardened | cured material 21. FIG.

  The first polymerizable compound 21 'is preferably a liquid. Accordingly, it is not necessary to use a liquid component that is removed (evaporated) in the manufacturing process of the recorded matter, and it is not necessary to provide a process for removing such a liquid component in the manufacture of the recorded matter 10. The productivity can be made particularly excellent. In addition, since it is not necessary to use an organic solvent, it is possible to prevent the occurrence of a volatile organic compound (VOC) problem.

  The first polymerizable compound 21 ′ 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. 2 ′ preferably includes at least a monomer component as the first polymerizable compound 21 ′. Since the monomer is generally a component having a low viscosity as compared with the oligomer component or the like, it is advantageous in making the ejection stability of the first ink 2 'particularly excellent.

  Examples of the monomer as the first polymerizable compound 21 ′ include isobornyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, phenoxyethyl acrylate, isooctyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2 -Ethoxyethyl acrylate, benzyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate , Tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, 2,2,2-trifluoroethyl acrylate 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, Phenyl glycidyl ether acrylate, phenoxy diethylene glycol acrylate, EO modified phenol acrylate, EO modified cresol acrylate, methoxy polyethylene glycol acrylate, dipropylene glycol acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 2-n-butyl-2-ethyl -1,3-propanediol diacrylate, tripropylene glycol dia Relate, tetraethylene glycol diacrylate, 1.9-nonanediol diacrylate, 1,4-butanediol diacrylate, bisphenol A EO modified diacrylate, 1.6-hexanediol diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 300 diacrylate, neopentyl glycol hydroxypivalate diacrylate, 2-ethyl-2-butyl-propanediol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol diacrylate, PO-modified bisphenol A diacrylate, EO-modified hydrogenated bisphenol A diacrylate, dipropylene glycol diacrylate, polyp Pyrene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane EO-modified triacrylate, glycerin PO-added triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, PO-modified trimethylolpropane triacrylate, Tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, 1-adamantylmethyl acrylate, 1-adamantyl acrylate, 2 -Acryloyloxyethyl phthalate, isobornyl acrylate , 3-acryloyloxypropyl acrylate, acryloylmorpholine, lipoxy SP series, dicyclopentanyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, w-carboxyacryloyloxyethyl phthalate, dimethylol dicyclopentane diacrylate, diacrylate Social acrylate / triacrylated mixture, neopentyl glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta / hexaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane PO-modified triacrylate, diethylene glycol diethyl ether, etc. One or more selected from these can be used in combination. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol Propane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate are preferred.

  In particular, the first ink 2 'preferably contains phenoxyethyl acrylate as the first polymerizable compound 21'. Thereby, while making the discharge stability of the first ink 2 ′ excellent, the reactivity of the first ink 2 ′ after discharge by the ink jet method is made particularly excellent, and the productivity of the recorded matter 10 is particularly improved. It can be excellent. In addition, since phenoxyethyl acrylate is highly reactive to ultraviolet rays, the first polymerizable compound 21 ′ can be cured more quickly in the first curing step described in detail later. Even if the printing part to be formed has a fine shape, a printing part having a desired shape can be more reliably formed.

  In addition, the first ink 2 ′ has, as the first polymerizable compound 21 ′, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate in addition to phenoxyethyl acrylate. It is preferable that at least one selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate and 4-hydroxybutyl acrylate is included. Thereby, while making the discharge stability of the first ink 2 ′ excellent, the reactivity of the first ink 2 ′ after discharge by the ink jet method is made particularly excellent, and the productivity of the recorded matter 10 is particularly improved. It can be excellent. In addition, since these compounds are highly reactive to ultraviolet rays, the first polymerizable compound 21 ′ can be cured more quickly in the first curing step described in detail later, and as a result, Even if the printing part to be formed has a fine shape, a printing part having a desired shape can be more reliably formed.

  In addition, the first ink 2 ′ includes dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl as the first polymerizable compound 21 ′. It is preferable to include at least one selected from the group consisting of acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. Thereby, while making the discharge stability of the first ink 2 ′ excellent, the reactivity of the first ink 2 ′ after discharge by the ink jet method is made particularly excellent, and the productivity of the recorded matter 10 is particularly improved. It can be excellent. In addition, since these compounds are highly reactive to ultraviolet rays, the first polymerizable compound 21 ′ can be cured more quickly in the first curing step described in detail later, and as a result, Even if the printing part to be formed has a fine shape, a printing part having a desired shape can be more reliably formed.

  Further, the first ink 2 ′ may include an oligomer in addition to the monomer as the first polymerizable compound 21 ′. In particular, those containing polyfunctional oligomers are preferred. Thereby, the storage stability of the first ink 2 'can be made particularly excellent. Further, it is possible to prevent the viscosity of the first ink 2 'from becoming too low, and it is possible to balance the viscosity with the second ink 3'. In the present invention, among polymerizable compounds, those having a repeating structure in the molecular skeleton and having a molecular weight of 600 or more are called oligomers. As the oligomer, a urethane oligomer whose repeating structure is urethane, an epoxy oligomer whose repeating structure is epoxy, and the like are preferably used.

The first ink 2 'may include components other than those described above (other components). Examples of such components include photopolymerization initiators, slip agents (leveling agents), polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), fixing agents, antifungal agents, antiseptics, Antioxidants, chelating agents, thickeners, sensitizers (sensitizing dyes) and the like can be mentioned.
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 (first 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, from the viewpoints of solubility in the polymerizable compound (first polymerizable compound) and curability, at least one selected from an acylphosphine oxide compound and a thioxanthone compound is preferable, and an acylphosphine oxide compound and a thioxanthone compound are preferable. It is more preferable to use together.

  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 first ink 2 ′ 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 first ink 2 'contains a slip agent, the surface of the first layer 2 becomes smoother due to the leveling action.

Although it does not specifically limit as a slip agent, For example, silicone type surfactants, such as polyester modified silicone and polyether modified silicone, can be used, It is preferable to use polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane. .
The first ink 2 ′ may contain a polymerization inhibitor, but even when it contains a polymerization inhibitor, the content of the polymerization inhibitor in the first ink 2 ′ is: It is preferably 0.6% by mass or less, and more preferably 0.2% by mass or less. Accordingly, since the content of the polymerizable compound (first polymerizable compound) in the first ink 2 ′ can be relatively increased, the first ink 2 ′ is formed. The adhesion of the first layer 2 to the substrate 1 can be made particularly excellent.

The first ink 2 ′ preferably does not contain an organic solvent that is removed (evaporated) in the manufacturing process of the recorded matter 10. Thereby, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented effectively.
The first ink 2 ′ does not contain metal powder.
The contact angle of the first ink 2 ′ with respect to the substrate 1 is not less than 30 ° and not more than 85 °. Thereby, the affinity of the first ink 2 ′ with respect to the substrate 1 is moderately excellent, and the adhesion of the first layer 2 formed in the subsequent step to the substrate 1 is excellent, The first ink 2 ′ can be reliably prevented from spreading more than necessary on the substrate 1, and the first layer 2 can surely have a desired shape. As described above, the contact angle of the first ink 2 ′ with respect to the substrate 1 may be 30 ° or more and 85 ° or less, but is preferably 35 ° or more and 80 ° or less, and is 40 ° or more and 75 ° or less. More preferably. Thereby, the above effects are more remarkably exhibited. In the present invention, as the “contact angle with respect to the substrate”, the contact angle with respect to the substrate of the ink (first ink, second ink) at 25 ° C. measured in accordance with the θ / 2 method is adopted. be able to.

  The viscosity of the first ink 2 ′ at room temperature (25 ° C.) is preferably 5 mPa · s or more and 40 mPa · s or less, and more preferably 6 mPa · s or more and 30 mPa · s or less. Thereby, while making the discharge stability of the first ink 2 ′ particularly excellent, it is possible to more effectively suppress the bleeding when the droplet of the first ink 2 ′ lands, and the desired droplet shape can be obtained. It can be obtained more reliably. In the present invention, the viscosity of the first ink (the same applies to the second ink) can be measured according to JIS Z8809 using a vibration viscometer.

  The surface tension at 25 ° C. of the first ink 2 ′ is preferably 18 mN / m or more and 50 mN / m or less. Thereby, while making the discharge stability of the first ink 2 ′ particularly excellent, it is possible to more effectively suppress the bleeding when the droplet of the first ink 2 ′ lands, and the desired droplet shape can be obtained. It can be obtained more reliably. In the present invention, the surface tension of the first ink (the same applies to the second ink) can be measured according to JIS K 3362.

As a droplet discharge method (inkjet method), a piezo method, a method in which ink is discharged by bubbles generated by heating ink, or the like can be used. From the viewpoint of difficulty, the piezo method is preferable.
Ink discharge by the ink jet method can be performed using a known droplet discharge device.

<First curing step>
Next, the first polymerizable compound 21 ′ is polymerized and cured by irradiating with ultraviolet rays (1b). Thereby, the 1st layer 2 comprised by the hardened | cured material 21 of 1st polymeric compound 21 'is formed.
In this invention, this process is performed so that the following conditions may be satisfied. That is, the time from when the first ink droplets land on the substrate in the first ink application step until the curing treatment for the droplets in this step is within one second. . In this way, by applying the curing process in a sufficiently short time after the landing of the first ink droplet, it is possible to reliably prevent the first ink droplet from spreading more than necessary on the substrate. The layer (first layer) made of the cured product of the first polymerizable compound can surely have a desired shape. As a result, the layer (second layer) formed using the second ink in the step described in detail later also has a desired shape, and the metal powder is suitably arranged in the layer. It can be. As a result, it is possible to reliably obtain a recorded matter provided with a printing portion that is provided in a desired shape and has an excellent glossiness such as a mirror surface.

Thus, in the present invention, the time from when the first ink droplet lands on the substrate in the first ink application step to when the curing treatment is performed on the droplet in this step is within one second. However, it is preferably 0.3 seconds or more and 1.0 seconds or less, and more preferably 0.5 seconds or more and 1.0 seconds or less. This more reliably prevents the polymerization reaction of the first polymerizable compound from proceeding before the first ink has landed on the substrate, and the adhesion of the first layer 2 to the substrate 1 is improved. The effect as described above can be more remarkably exhibited while being particularly excellent.
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.

<Second ink application step>
Next, 2nd ink 3 'is provided on the 1st layer 2 (hardened | cured material 21 of 1st polymeric compound 21') by the inkjet method (1c).
The second ink 3 'includes a metal powder 31 and a second polymerizable compound 32' that is polymerized by irradiation with ultraviolet rays.

By including the metal powder 31, the glossiness of the printed portion of the recorded matter 10 finally obtained can be made excellent.
2nd polymeric compound 32 'superposes | polymerizes and hardens | cures in the 2nd hardening process explained in full detail later, and forms the hardened | cured material 32. FIG.
The metal powder 31 only needs to have at least the vicinity of the surface made of a metal material. For example, the metal powder 31 may be made entirely of a metal material, or may have a base surface made of a non-metal material. The thing of the structure formed by coat | covering the layer comprised with the metal material may be sufficient.

  As the metal material constituting the metal powder 31, a single metal, various alloys, or the like can be used. However, it is preferable that the metal powder 31 is composed mainly of Al at least near the surface. Thereby, the glossiness of the printing part (particularly, the glossiness (shiny feeling) that the mirror surface has) can be made particularly excellent. Further, when the metal powder 31 is mainly composed of Al at least in the vicinity of the surface, in the case where the surface treatment as described in detail later is performed (the particles constituting the metal powder 31 are at least The surface vicinity has a mother particle mainly composed of Al and a layer made of a surface treatment agent that coats it), and the effect obtained by applying the surface treatment with the surface treatment agent as described in detail later is more Prominently demonstrated. In the present specification, the term “mainly” is sufficient if the content rate is the highest among all the constituent components of the target site, and the content rate in the target site is 50% by mass or more. Preferably, it is 80% by mass or more, more preferably 95% by mass or more.

  The metal powder 31 may be produced by any method, but was obtained by forming a film made of a metal material by a vapor deposition method, and then crushing the film. It is preferable. Thereby, the glossiness etc. which the metal material originally has can be expressed more effectively in the printing unit. Moreover, the dispersion | variation in the characteristic between each particle | grain can be suppressed. Moreover, even if it is the comparatively thin metal powder 31, it can manufacture suitably by using the said method.

  When manufacturing the metal powder 31 using such a method, for example, the metal powder 31 can be preferably manufactured by forming a film made of a metal material (film formation) on a base material. it can. As the substrate, for example, a plastic film such as polyethylene terephthalate can be used. The base material may have a release agent layer (for example, a release agent layer composed of a polymer release agent) on the film formation surface.

Moreover, it is preferable that the said grinding | pulverization is performed by providing an ultrasonic vibration to the said film | membrane in a liquid. Thereby, the metal powder 31 having a particle size as described later can be obtained easily and reliably, and the occurrence of variations in size, shape, and characteristics among the particles can be suppressed.
Further, when pulverizing by the above method, the liquid is selected from the group consisting of diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, tripropylene glycol dimethyl ether, triethylene glycol diethyl ether and diethylene glycol diethyl ether. It is preferable to use one containing at least one kind. As a result, the productivity of the metal powder 31 is made particularly excellent while preventing unintentional oxidation of the metal powder 31, and the variation in size, shape, and characteristics among the particles is particularly small. can do.

  The metal powder 31 may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably has a scaly shape. Thereby, the metal powder 31 can be arranged so that the main surface of the metal particles follows the surface shape of the substrate 1 (surface shape of the first layer 2), and the metal material constituting the metal powder 31 is originally The glossiness and the like possessed can be more effectively exhibited in the recorded matter 10, and the glossiness and luxury feeling of the printed portion can be made particularly excellent. Even if the recorded material 10 does not have the protective film 4 as described later, the recorded material 10 can be made particularly excellent in abrasion resistance.

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

The average particle size of the metal powder 31 is preferably 500 nm or more and 2.0 μm or less, and more preferably 800 nm or more and 1.8 μm or less. Thereby, the glossiness of a printing part and a high-class feeling can be made further excellent. In addition, the storage stability and ejection stability of the second ink 3 ′ can be further improved. In the present invention, the average particle diameter refers to the average particle diameter based on the number, and the average of the diameters of perfect circles having the same area as the area S ₁ when observed from the direction in which the projected area is maximized. Refers to the value.

  Moreover, the particles (metal particles) constituting the metal powder 31 may be subjected to surface treatment. Thereby, the gelation of the second ink 3 ′ can be effectively prevented, and the storage stability of the second ink 3 ′, the discharge stability of the second ink 3 ′, etc. are particularly excellent. It can be. In addition, by including the surface-treated metal particles, the storage stability of the second ink 3 ′ is excellent, and the metal powder 31 (dispersoid) in the second ink application step described later is used. The affinity with the dispersion medium (second polymerizable compound 32 ′ and the like) can be suitably adjusted, and the metal powders 31 can be suitably arranged in the printing portion of the recorded matter 10. The glossiness can be made particularly excellent.

The surface treatment agent used for the surface treatment is not particularly limited. For example, phosphoric acid alkyl ester, fluorine-based silane compound, fluorine-based phosphate ester, silane coupling agent, higher fatty acid, fatty acid metal salt, unsaturated organic acid , Organic titanate, organic aluminate, resin acid, polyethylene glycol and the like.
Among these, the second ink 3 ′ is surface-treated with one or more surface treatment agents selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate ester, and a phosphate alkyl ester as the metal powder 31. It is preferable to include those prepared. Thereby, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness of the printed part of the recorded matter 10 can be made particularly excellent. Even if the recorded matter 10 does not have the protective film 4 as described later, the rub resistance of the printed portion of the recorded matter 10 can be made particularly excellent.

Hereinafter, among the surface treatment agents, a fluorine-based silane compound, a fluorine-based phosphate ester, and a phosphate alkyl ester will be described in detail.
First, among the surface treatment agents, the fluorine-based silane compound will be described in detail.
As the fluorine-based silane compound, a silane compound having at least one fluorine atom in the molecule can be used.
In particular, the fluorinated silane compound as the surface treatment agent preferably has a chemical structure represented by the following formula (1).

R ¹ SiX ¹ _a R ² _(3-a) (1)
(In Formula (1), 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.)

Thereby, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness of the printed part of the recorded matter 10 can be made particularly excellent. Even if the recorded matter 10 does not have the protective film 4 as described later, the rub resistance of the printed portion of the recorded matter 10 can be made particularly excellent.
Examples of R ¹ in the formula (1) include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. in which a part or all of 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.

Specific examples of the fluorine-based silane compound represented by the formula (1) include dimethyldimethoxysilane, diethyldiethoxysilane, 1-propenylmethyldichlorosilane, propyldimethylchlorosilane, propylmethyldichlorosilane, propyltrichlorosilane, and propyltriethoxy. Silane, propyltrimethoxysilane, styrylethyltrimethoxysilane, tetradecyltrichlorosilane, 3-thiocyanatepropyltriethoxysilane, p-tolyldimethylchlorosilane, p-tolylmethyldichlorosilane, p-tolyltrichlorosilane, p-tolyltrimethoxy Silane, p-tolyltriethoxysilane, di-n-propyldi-n-propoxysilane, diisopropyldiisopropoxysilane, di-n-butyldi-n-butyroxysilane Di-sec-butyldi-sec-butyroxysilane, di-t-butyldi-t-butyroxysilane, octadecyltrichlorosilane, octadecylmethyldiethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyldimethylchlorosilane, octadecylmethyldichlorosilane, octadecyl Methoxydichlorosilane, 7-octenyldimethylchlorosilane, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane, octylmethyldichlorosilane, octyldimethylchlorosilane, octyltrichlorosilane, 10-undecenyldimethylchlorosilane, undecyltri Chlorosilane, vinyldimethylchlorosilane, methyloctadecyldimethoxysilane, methyldodecyldiethoxy Silane, methyloctadecyldimethoxysilane, methyloctadecyldiethoxysilane, n-octylmethyldimethoxysilane, n-octylmethyldiethoxysilane, triacontyldimethylchlorosilane, triaconyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri -N-propoxysilane, methyl isopropoxy silane, methyl-n-butoxy silane, methyl tri-sec-butoxy silane, methyl tri-t-butoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tri-n-propoxy silane, ethyl isopropoxy silane , Ethyl-n-butyroxysilane, ethyltri-sec-butyroxysilane, ethyltri-t-butyroxysilane, n-propylto Limethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, hexadecyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-propyltriethoxysilane, Isobutyltriethoxysilane, n-hexyltriethoxysilane, hexadecyltriethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-octadecyltriethoxysilane, 2- [2- (trichlorosilyl) ethyl] Pyridine, 4- [2- (trichlorosilyl) ethyl] pyridine, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,3- (trichlorosilylmethyl) heptacosane, dibenzyldimethoxysilane, Benzyldiethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenyldimethylethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, Benzylmethyldimethoxysilane, benzyldimethylmethoxysilane, benzyldimethoxysilane, benzyldiethoxysilane, benzylmethyldiethoxysilane, benzyldimethylethoxysilane, benzyltriethoxysilane, dibenzyldimethoxysilane, dibenzyldiethoxysilane, 3-acetoxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane, allyltrimethoxysilane Allyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 6- (aminohexylaminopropyl) trimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenylethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, ω-aminoundecyltrimethoxysilane, amyltriethoxysilane, benzoxacilepin dimethyl ester, 5- (bicycloheptenyl) trie Xysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 8-bromooctyltrimethoxysilane, bromophenyltrimethoxysilane, 3-bromopropyltrimethoxysilane, n-butyltrimethoxysilane, 2-chloro Methyltriethoxysilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- (chloromethyl) phenyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, -Cyanoethyltrimethoxysilane, cyanomethylphenethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 2- (3-cyclohexenyl) ethyltrimethoxysilane, 2- (3-cyclohexenyl) ethyltriethoxysilane, 3-cyclo Hexenyltrichlorosilane, 2- (3-cyclohexenyl) ethyltrichlorosilane, 2- (3-cyclohexenyl) ethyldimethylchlorosilane, 2- (3-cyclohexenyl) ethylmethyldichlorosilane, cyclohexyldimethylchlorosilane, cyclohexylethyl Dimethoxysilane, cyclohexylmethyldichlorosilane, cyclohexylmethyldimethoxysilane, (cyclohexylmethyl) trichlorosilane, cyclohexyltrichlorosilane, cyclohexyl Limethoxysilane, cyclooctyltrichlorosilane, (4-cyclooctenyl) trichlorosilane, cyclopentyltrichlorosilane, cyclopentyltrimethoxysilane, 1,1-diethoxy-1-silacyclopent-3-ene, 3- (2,4-dinitro Phenylamino) propyltriethoxysilane, (dimethylchlorosilyl) methyl-7,7-dimethylnorpinane, (cyclohexylaminomethyl) methyldiethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, N, N- Diethyl-3-aminopropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (furfuryloxymethyl) triethoxy Silane, 2-hydroxy-4- (3-triethoxypropoxy) diphenyl ketone, 3- (p-methoxyphenyl) propylmethyldichlorosilane, 3- (p-methoxyphenyl) propyltrichlorosilane, p- (methylphenethyl) methyl Dichlorosilane, p- (methylphenethyl) trichlorosilane, p- (methylphenethyl) dimethylchlorosilane, 3-morpholinopropyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltri Methoxysilane, 1,2,3,4,7,7, -hexachloro-6-methyldiethoxysilyl-2-norbornene, 1,2,3,4,7,7, -hexachloro-6-triethoxysilyl- 2-norbornene, 3-iodopropyltrimethoxylane, 3-isocyanatopropyltriethoxysilane, (mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, methyl {2- (3-trimethoxysilylpropylamino) ethylamino} -3-propionate, 7-octenyltrimethoxysilane, RN-α-phenethyl-N′-tri Ethoxysilylpropylurea, S-N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane, phenethyl Dimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltrimethoxy Silane, N- (triethoxysilylpropyl) dansilamide, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 2- (triethoxysilylethyl) -5- (chloroacetoxy) bicycloheptane, ( S) -N-triethoxysilylpropyl-O-menth carbamate, 3- (triethoxysilylpropyl) -p-nitrobenzamide, 3- (triethoxysilyl) propylsuccinic anhydride, N- [5 (Trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethylammonium chloride, phenyl vinyl Diethoxysilane, 3-thiocyanatopropyltriethoxysilane, N- {3- (triethoxysilyl) propyl} phthalamic acid, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxysilyl) ) Ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N-trimethoxysilylpropyl-N, N, N-tributylammonium Bro Id, N-trimethoxysilylpropyl-N, N, N-tributylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, vinylmethyldiethoxylane, vinyltriethoxysilane, vinyltrimethoxy Silane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldichlorosilane, vinylphenyldichlorosilane, vinylphenyldiethoxysilane, vinylphenyldimethylsilane, vinylphenylmethylchlorosilane, vinyltriphenoxysilane, vinyltris t-butoxysilane, adamantylethyltrichlorosilane, allylphenyltrichlorosilane, (aminoethylaminomethyl) phenethyltrimethoxy Silane, 3-aminophenoxydimethylvinylsilane, phenyltrichlorosilane, phenyldimethylchlorosilane, phenylmethyldichlorosilane, benzyltrichlorosilane, benzyldimethylchlorosilane, benzylmethyldichlorosilane, phenethyldiisopropylchlorosilane, phenethyltrichlorosilane, phenethyldimethylchlorosilane, phenethylmethyldisilane Chlorosilane, 5- (bicycloheptenyl) trichlorosilane, 5- (bicycloheptenyl) triethoxysilane, 2- (bicycloheptyl) dimethylchlorosilane, 2- (bicycloheptyl) trichlorosilane, 1,4-bis (trimethoxysilyl) Ethyl) benzene, bromophenyltrichlorosilane, 3-phenoxypropyldimethylchlorosilane, 3-pheno Shi propyl trichlorosilane, t- butyl phenyl chlorosilane, t- butyl phenyl silane, t- butyl phenyl dichlorosilane, p-(t-butyl) phenethyl dimethylchlorosilane, p-(t-butyl) phenethyl trichlorosilane, 1,
3- (chlorodimethylsilylmethyl) heptacosane, ((chloromethyl) phenylethyl) dimethylchlorosilane, ((chloromethyl) phenylethyl) methyldichlorosilane, ((chloromethyl) phenylethyl) trichlorosilane, ((chloromethyl) phenyl Ethyl) trimethoxysilane, chlorophenyltrichlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethylmethyldichlorosilane, 3-cyanopropylmethyldiethoxysilane, 3-cyanopropylmethyldichlorosilane, 3-cyanopropylmethyldichlorosilane, 3- Some or all of the hydrogen atoms of silane compounds such as cyanopropyldimethylethoxysilane, 3-cyanopropylmethyldichlorosilane, and 3-cyanopropyltrichlorosilane In may be mentioned compounds having a structure resulting from substitution.

The fluorine-based silane compound (surface treatment agent) preferably has a perfluoroalkyl structure (C _n F _{2n + 1} ). Thereby, the storage stability of the second ink 3 ′ can be further improved, and the glossiness of the printed portion of the recorded matter 10 can be further improved. Even if the recorded material 10 does not have the protective film 4 as described later, the recorded material 10 can be made particularly excellent in abrasion resistance.
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.

Next, among the surface treatment agents, the fluorine-based phosphate ester will be described in detail.
As the fluorine-based phosphate ester, a phosphate ester having at least one fluorine atom in the molecule can be used.
In particular, the fluorine-based phosphate ester preferably has a chemical structure represented by the following formula (2).

POR _n (OH) _3-n (2)
(In the formula (2), 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.)

Thereby, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness of the printed part of the recorded matter 10 can be made particularly excellent. Even if the recorded material 10 does not have the protective film 4 as described later, the recorded material 10 can be made particularly excellent in abrasion resistance.
In formula (2), m is preferably an integer of 3 to 14, but more preferably an integer of 4 to 12. Thereby, the effects as described above are more remarkably exhibited.

In formula (2), 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.
Further, fluorine-based phosphate ester (surface treatment agent) is preferably one having a perfluoroalkyl structure _{(C n F 2n + 1)} . Thereby, the storage stability of the second ink 3 ′ can be further improved, and the glossiness of the printed portion of the recorded matter 10 can be further improved. Even if the recorded material 10 does not have the protective film 4 as described later, the recorded material 10 can be made particularly excellent in abrasion resistance.

Next, among the surface treatment agents, the alkyl phosphate ester will be described in detail.
The phosphoric acid alkyl ester has a structure in which at least a part of OH groups of phosphoric acid is esterified with a functional group containing an alkyl group (C _n H _{2n + 1} — (where n is an integer of 1 or more)). It is.
It is preferable that the phosphoric acid alkyl ester contains only C, H, P, and O as constituent elements. As a result, the gloss and rub resistance of the recorded product 10 finally obtained can be made particularly excellent, and the recorded product 10 can be manufactured at a lower cost than when a fluorine-based phosphate is used. can do.
In particular, the phosphoric acid alkyl ester preferably has a chemical structure represented by the following formula (3).

POR _n (OH) _3-n (3)
(In the formula (3), R _{is, CH 3 (CH 2) m} -, CH 3 (CH 2) m (CH 2 O) l -, CH 3 (CH 2) m (CH 2 CH 2 O) l - Or CH ₃ (CH ₂ ) _m O—, n is an integer of 1 to 3, m is an integer of 2 to 18, and l is an integer of 1 to 18.

Thereby, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness of the printed part of the recorded matter 10 can be made particularly excellent. Even if the recorded material 10 does not have the protective film 4 as described later, the recorded material 10 can be made particularly excellent in abrasion resistance.
In formula (3), m is preferably an integer of 3 or more and 14 or less, but more preferably an integer of 4 or more and 12 or less. Thereby, the effects as described above are more remarkably exhibited.

In formula (3), 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.
Preferable specific examples of the phosphoric acid alkyl ester include, for example, ((CH ₃ ) ₂ CHO) ₂ P (═O) (OH), ((CH ₃ ) ₂ CHO) P (═O) (OH) ₂ , ( _{C 2 H 5 O) 2 P} (= O) (OH), (C 2 H 5 O) P (= O) (OH) 2, (CH 3 O) 2 P (= O) (OH), (C _{4 H 9 O) P (=} O) (OH) 2, (C 3 H 7 O) 2 P (= O) (OH), 2 and the like (C 3 H 7 O) P (= O) (OH) Can be mentioned.

  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 of using the surface treatment agent as described above can be more effectively exhibited. In addition, even when an oxide film is formed on the surface of the particles to be the mother particles before the surface treatment with the surface treatment agent, the oxide film can be reliably removed, and the oxide film is removed. In this state, the surface treatment with the surface treatment agent can be performed, so that the glossiness of the manufactured metal powder 31 can be made particularly excellent. Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, hyposulfite, nitrous acid, hyponitrous acid, phosphorous acid, and the following. Protic acids such as phosphorous acid can be used. Of these, hydrochloric acid, phosphoric acid, and acetic acid are preferable. On the other hand, as the base, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide or the like can be used. Of these, sodium hydroxide and potassium hydroxide are preferred.

The content of the metal powder in the second ink 3 ′ is preferably 0.5% by mass or more and 10.0% by mass or less, and more preferably 1.0% by mass or more and 5.0% by mass or less. preferable.
The second polymerizable compound 32 ′ is preferably a liquid. Accordingly, it is not necessary to use a liquid component that is removed (evaporated) in the manufacturing process of the recorded matter, and it is not necessary to provide a process for removing such a liquid component in the manufacture of the recorded matter 10. The productivity can be made particularly excellent. In addition, since it is not necessary to use an organic solvent, it is possible to prevent the occurrence of a volatile organic compound (VOC) problem.

The second ink 3 ′ preferably contains the same compound as the first polymerizable compound 21 ′ constituting the first ink 2 ′ as the second polymerizable compound 32 ′. As a result, the adhesion between the first layer 2 and the second layer 3 can be made particularly excellent, and the durability and reliability of the recorded matter 10 can be made particularly excellent.
The second polymerizable compound 32 ′ 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. 32 'preferably contains at least a monomer component as the second polymerizable compound 32'. Since the monomer is generally a component having a low viscosity as compared with the oligomer component or the like, it is advantageous in making the ejection stability of the second ink 32 'particularly excellent.

  Examples of the monomer as the second polymerizable compound 32 ′ include isobornyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, phenoxyethyl acrylate, isooctyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2 -Ethoxyethyl acrylate, benzyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate , Tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, 2,2,2-trifluoroethyl acrylate 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, Phenyl glycidyl ether acrylate, phenoxy diethylene glycol acrylate, EO modified phenol acrylate, EO modified cresol acrylate, methoxy polyethylene glycol acrylate, dipropylene glycol acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 2-n-butyl-2-ethyl -1,3-propanediol diacrylate, tripropylene glycol dia Relate, tetraethylene glycol diacrylate, 1.9-nonanediol diacrylate, 1,4-butanediol diacrylate, bisphenol A EO modified diacrylate, 1.6-hexanediol diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 300 diacrylate, neopentyl glycol hydroxypivalate diacrylate, 2-ethyl-2-butyl-propanediol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol diacrylate, PO-modified bisphenol A diacrylate, EO-modified hydrogenated bisphenol A diacrylate, dipropylene glycol diacrylate, polyp Pyrene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane EO-modified triacrylate, glycerin PO-added triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, PO-modified trimethylolpropane triacrylate, Tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, 1-adamantylmethyl acrylate, 1-adamantyl acrylate, 2 -Acryloyloxyethyl phthalate, isobornyl acrylate , 3-acryloyloxypropyl acrylate, acryloylmorpholine, lipoxy SP series, dicyclopentanyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, w-carboxyacryloyloxyethyl phthalate, dimethylol dicyclopentane diacrylate, diacrylate Social acrylate / triacrylated mixture, neopentyl glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta / hexaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane PO-modified triacrylate, diethylene glycol diethyl ether, etc. One or more selected from these can be used in combination. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol Propane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate are preferred.

  In particular, the second ink 3 ′ preferably contains phenoxyethyl acrylate as the second polymerizable compound 32 ′. Thereby, while making the ejection stability of the second ink 32 ′ excellent, the reactivity of the second ink 32 ′ after ejection by the ink jet method is made particularly excellent, and the productivity of the recorded matter 10 is particularly improved. It can be excellent. In addition, when the first ink 2 ′ and the second ink 3 ′ contain phenoxyethyl acrylate as a common component, the adhesion between the first layer 2 and the second layer 3 is particularly excellent. The reliability and durability of the recorded matter 10 can be made particularly excellent. Further, from the difference in affinity between the surface of the first layer 2 and the other portion of the second ink 3 ′, the pattern (the shape of the second layer 3) by the second ink 3 ′ is more The desired shape can be ensured.

  In addition, the second ink 3 ′ includes, as the second polymerizable compound 32 ′, 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, in addition to phenoxyethyl acrylate. It is preferable that at least one selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate and 4-hydroxybutyl acrylate is included. Thereby, while making the ejection stability of the second ink 32 'excellent, the reactivity of the third ink 3' after ejection by the ink jet method is made particularly excellent, and the productivity of the recorded matter 10 is particularly improved. It can be excellent. In addition to the phenoxyethyl acrylate, both the first ink 2 ′ and the second ink 3 ′ are 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate. , 2-hydroxy-3-phenoxypropyl acrylate, and at least one selected from the group consisting of 4-hydroxybutyl acrylate, particularly excellent adhesion between the first layer 2 and the second layer 3 The reliability and durability of the recorded matter 10 can be made particularly excellent. Further, from the difference in affinity between the surface of the first layer 2 and the other portion of the second ink 3 ′, the pattern (the shape of the second layer 3) by the second ink 3 ′ is more The desired shape can be ensured.

  In addition, the second ink 3 ′ includes dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl as the second polymerizable compound 32 ′. It is preferable to include at least one selected from the group consisting of acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate. Thereby, while making the ejection stability of the second ink 3 ′ excellent, the reactivity of the second ink 3 ′ after ejection by the ink jet method is made particularly excellent, and the productivity of the recorded matter 10 is particularly improved. It can be excellent. Further, both the first ink 2 ′ and the second ink 3 ′ are dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl. In the case of including at least one selected from the group consisting of acrylate, acryloylmorpholine, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate, the first layer 2 and the second layer 3 The adhesion can be made particularly excellent, and the reliability and durability of the recorded matter 10 can be made particularly excellent. Further, from the difference in affinity between the surface of the first layer 2 and the other portion of the second ink 3 ′, the pattern (the shape of the second layer 3) by the second ink 3 ′ is more The desired shape can be ensured.

In addition, the second ink 3 ′ may include an oligomer in addition to the monomer as the second polymerizable compound 32 ′. In particular, those containing polyfunctional oligomers are preferred. Thereby, the storage stability of the second ink 3 ′ can be made particularly excellent.
The content of the second polymerizable compound 32 ′ in the second ink 3 ′ 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 second ink 3 ′ can be further improved, and the glossiness of the recorded matter 10 can be further improved. Even if the recorded material 10 does not have the protective film 4 as described later, the recorded material 10 can be made particularly excellent in abrasion resistance. The second ink 3 ′ may include two or more compounds as the second polymerizable compound 32 ′. In this case, it is preferable that the total content of these compounds is a value within the above range.

The second ink 3 ′ preferably includes a basic dispersant having a polymer structure (hereinafter also referred to as “basic polymer dispersant”). Thereby, the glossiness and durability of the recorded matter 10 can be further improved. Further, the storage stability of the second ink 3 ′ can be made particularly excellent.
In the present invention, the basic polymer dispersant is not particularly limited as long as it shows basicity and has a polymer structure.

The polymer structure constituting the basic polymer dispersant is not particularly limited. For example, an acrylic polymer structure (including a copolymer), a methacrylic polymer structure (including a copolymer), and polyurethane. Examples thereof include a polymer structure, a hydroxyl group-containing carboxylic acid ester structure, a polyether polymer structure, and a silicone polymer structure.
The amine value of the basic polymer dispersant is not particularly limited, but is preferably 3 mgKOH / g or more and 80 mgKOH / g or less, more preferably 10 mgKOH / g or more and 70 mgKOH / g or less.

  Specific examples of the basic polymer dispersant include DISPERBYK-116 (manufactured by BYK Chemie), DISPERBYK-182 (manufactured by BYK Chemy), DISPERBYK-183 (manufactured by BYK Chemy), DISPERBYK-184 (manufactured by BYK Chemy), DISPERBYK- 2155 (manufactured by Big Chemie), DISPERBYK-2164 (manufactured by Big Chemie), DISPERBYK-108 (manufactured by Big Chemie), DISPERBYK-112 (manufactured by Big Chemie), DISPERBYK-198 (manufactured by BYK Chemie), DISPERBYK-2150 (manufactured by Big Chemie) ), PAA-1112 (manufactured by Nittobo Co., Ltd.) and the like.

The content of the basic polymer dispersant in the second ink 3 ′ is preferably 0.01% by mass or more and 5.0% by mass or less, and preferably 0.1% by mass or more and 2.0% by mass or less. More preferably. As a result, the storage stability, ejection stability, and curability of the second ink 3 ′ can be further improved, and the glossiness, durability, and the like of the recorded matter can be further improved. it can. The second ink 3 ′ may contain two or more compounds as a basic polymer dispersant. In this case, it is preferable that the total content of these compounds is a value within the above range.
Moreover, it is preferable that 2nd ink 3 'contains the substance A which has the partial structure shown by following formula (6).

  The second ink 3 ′ contains the substance A having such a chemical structure (in particular, together with the metal powder 31 and the basic polymer dispersant that have been subjected to the surface treatment as described above). The storage stability and curability of the second ink 3 ′ can be made particularly excellent. Further, in the recorded matter 10, the glossiness and luxury feeling inherent in the metal material constituting the metal powder 31 are more effectively exhibited, and the glossiness and durability of the recorded matter are particularly excellent. be able to.

In the formula (6), R ¹ may be a hydrogen atom, a hydrocarbon group or an alkoxyl group (a chain or alicyclic hydrocarbon group bonded to an oxygen atom), particularly a hydrogen atom, methyl It is preferably a group or an octyloxy group. Thereby, the storage stability and ejection stability of the second ink 3 ′ can be further improved, and the gloss and durability of the recorded matter 10 can be further improved.

In Formula (6), 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. Thereby, the storage stability and ejection stability of the second ink 3 ′ can be further improved, and the gloss and durability of the recorded matter 10 can be further improved.

  The content of the substance A in the second ink 3 'is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 3.0% by mass or less. As a result, the storage stability, ejection stability, and curability of the second ink 3 ′ can be further improved, and the glossiness, durability, and the like of the recorded matter 10 can be further improved. Can do. The second ink 3 ′ may include 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 31 is X _M [mass%], the relationship of 0.01 ≦ X _A / X _M ≦ 0.8 is satisfied. Preferably, it is more preferable to satisfy the relationship of 0.05 ≦ X _A / X _M ≦ 0.4. By satisfying such a relationship, the storage stability and ejection stability of the second ink 3 ′ can be further improved, and the gloss and durability of the recorded matter 10 can be further improved. It can be.

  The second ink 3 ′ may include components other than those described above (other components). Examples of such components include dispersants other than basic polymer dispersants, photopolymerization initiators, slip agents (leveling agents), polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants). Coloring agents other than metal powders, fixing agents, antifungal 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 (second 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 (second polymerizable compound) and curability, and an acylphosphine oxide compound and a thioxanthone compound are preferable. It is more preferable to use together.

  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 second ink 3 ′ 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.
If the second ink 3 'contains a slip agent, the surface of the recorded matter becomes smooth due to the leveling action. For this reason, even if the recorded matter 10 does not have the protective film 4 as described later, it is possible to make the recorded matter 10 particularly excellent in abrasion resistance.

Although it does not specifically limit as a slip agent, For example, silicone type surfactants, such as polyester modified silicone and polyether modified silicone, can be used, It is preferable to use polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane. .
The second ink 3 ′ may contain a polymerization inhibitor, but even when it contains a polymerization inhibitor, the content of the polymerization inhibitor in the second ink 3 ′ is: It is preferably 0.6% by mass or less, and more preferably 0.2% by mass or less. Accordingly, since the content of the polymerizable compound (second polymerizable compound) in the second ink 3 ′ can be relatively increased, the second ink 3 ′ is formed. The adhesion of the second layer 3 to the first layer 2 can be made particularly excellent.

The second ink 3 ′ preferably does not contain an organic solvent that is removed (evaporated) in the manufacturing process of the recorded matter 10. Thereby, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented effectively.
The contact angle of the second ink 3 ′ with respect to the first layer 2 is preferably 10 ° or more and 90 ° or less, and more preferably 30 ° or more and 60 ° or less. Further, the contact angle of the second ink 3 ′ with respect to the substrate 1 is preferably 10 ° or more, and more preferably 10 ° or more and 60 ° or less. By satisfying such a condition, the affinity of the second ink 3 ′ for the first layer 2 is made excellent, and the second layer 3 formed in a later step with respect to the first layer 2 is made. While making the adhesiveness excellent, it is possible to reliably prevent the second ink 3 ′ from spreading to the surface of the substrate 1 (region where the first layer 2 is not formed). The second layer 3 can surely have a desired shape. In the present invention, as the “contact angle with respect to the first layer”, the contact angle with respect to the first layer of the second ink at 25 ° C. measured in accordance with the θ / 2 method can be adopted.

  The viscosity of the second ink 3 ′ at room temperature (25 ° C.) is preferably 4 mPa · s or more and 30 mPa · s or less, and more preferably 8 mPa · s or more and 23 mPa · s or less. Thereby, while making the ejection stability of the second ink 3 ′ particularly excellent, it is possible to more effectively suppress the bleeding when the second ink 3 ′ lands on the droplets, and the desired droplet shape Can be obtained more reliably, and the gloss of the recorded matter 10 can be made particularly excellent.

  The surface tension of the second ink 3 ′ at 25 ° C. is preferably 14 mN / m or more and 40 mN / m or less, and more preferably 20 mN / m or more and 35 mN / m or less. Thereby, while making the ejection stability of the second ink 3 ′ particularly excellent, it is possible to more effectively suppress the bleeding when the second ink 3 ′ lands on the droplets, and the desired droplet shape Can be obtained more reliably, and the gloss of the recorded matter 10 can be made particularly excellent.

This step can be performed by employing a droplet discharge method (inkjet method) as described in the first ink application step. In addition, this process may be performed by the same system as the first ink application process, or may be performed by a system different from the first ink application process.
In addition, this step may be performed using the same apparatus (droplet discharge device) as that used in the first ink application step, or different from that used in the first ink application step. An apparatus (droplet discharge apparatus) may be used.

<Second curing step>
Next, the second polymerizable compound 32 ′ is polymerized and cured by irradiating with ultraviolet rays (1d). Thereby, the 2nd layer 3 to which the metal powder 31 was fixed is formed of the hardened | cured material 32 of 2nd polymeric compound 32 '.
In particular, after the droplet of the second ink 3 ′ has landed on the first layer 2 (cured product 21 of the first polymerizable compound 2 ′) in the second ink application step described above, the liquid in this step is used. The time until the curing treatment for the droplets is 10 seconds or longer. Thereby, the second ink 3 ′ can be sufficiently wet and spread on the first layer 2. Thereby, the 2nd layer 3 of a desired shape can be formed reliably. In addition, after the second ink 3 ′ has landed, the second polymerizable compound 32 ′ can be polymerized and cured in a state where the metal powders 31 included in the second ink 3 ′ are suitably arranged. A preferable arrangement of the metal powder 31 can be fixed.

As described above, after the droplet of the second ink 3 ′ has landed on the first layer 2 (cured product 21 of the first polymerizable compound 2 ′) in the second ink application step, The time until the droplet is cured may be 10 seconds or longer, but is preferably 10 seconds or longer and 120 seconds or shorter, and more preferably 10 seconds or longer and 90 seconds or shorter. As a result, the above-described effects can be exhibited more remarkably, and the productivity of the recorded matter 10 can be made particularly excellent.
In this step, as the ultraviolet ray source, those described in the first ink application step can be used. In addition, this process may be performed using the same ultraviolet light source used in the first ink application process, or an ultraviolet light source different from that used in the first ink application process may be used. May be performed.

<Protective film formation process>
Next, the protective film 4 is formed on the side of the substrate 1 on which the printed layers (the first layer 2 and the second layer 3) are provided to obtain a recorded matter (1e). Thus, in this embodiment, the protective film 4 is formed. As described above, in this embodiment, since the second layer 3 is covered with the protective film 4, the durability (rubbing resistance, etc.) of the recorded matter is particularly excellent.

In the configuration shown in the figure, the protective film 4 is formed on the entire surface side of the base material 1 on which the printing portion is provided. It may be selectively formed on only a part of the.
Examples of the constituent material of the protective film 4 include polyester resins such as polyethylene terephthalate, thermoplastic resins such as acrylic resins, thermosetting resins such as epoxy resins, and inorganic materials such as titanium oxide and zinc oxide. Further, the protective film 4 may contain an additive such as an ultraviolet absorber.
Examples of the method for forming the protective film 4 include coating methods such as a roll coater, various printing methods such as an inkjet method, and fusion of a sheet-like member (protective film forming member).

《Recordings》
Next, the recorded matter of the present invention will be described.
The recorded matter of the present invention is manufactured by using the method of the present invention as described above, and the printed portion provided on the back side of the printed material is visually recognized through a base material. Such a recorded matter is provided with a printing section which is provided in a desired shape and has an excellent gloss feeling like a mirror surface.
The recorded matter of the present invention may be used for any purpose, and may be applied to, for example, a decorative article or other items. Specific examples of the recorded material of the present invention include console interiors for vehicles such as console lids, switch bases, center clusters, interior panels, emblems, center consoles, meter nameplates, operation parts (key switches) of various electronic devices, decorations. Display items such as decorative parts, indicators, logos, etc. that exhibit properties.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, in the manufacturing method of the present invention, in addition to the steps as described above, there may be further steps (a pretreatment step, an intermediate treatment step, a post treatment step).
Further, the ink set according to the present invention (the set of the first ink and the second ink) may be any one that includes at least one kind of the first ink and the second ink as described above, For example, two or more types of first ink may be provided, or two or more types of second ink may be provided.
In the embodiment described above, the case where the protective film is provided has been representatively described. However, in the present invention, the protective film may not be provided.

Next, specific examples of the present invention will be described.
[1] Manufacture of recorded matter (Example 1)
First, an ink set including the first ink and the second ink was manufactured as follows.

<Manufacture of ink set>
<Production of first ink>
Phenoxyethyl acrylate as the first polymerizable compound, 4-hydroxybutyl acrylate as the first polymerizable compound, tetrahydrofurfuryl acrylate as the first polymerizable compound, Irgacure 819 as the photopolymerization initiator (Ciba Japan) The first ink was obtained by mixing Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator and Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator. The viscosity of the first ink at room temperature (25 ° C.) was 18.1 mPa · s. Further, the surface tension of the first ink at 25 ° C. was 35 mN / m.

<Manufacture of second ink>
First, a film made of polyethylene terephthalate having a smooth surface (surface roughness Ra of 0.02 μm or less) was prepared.
Next, silicone oil was applied to the entire one surface of the film.
Next, a film made of Al was formed on the side coated with silicone oil by vapor deposition.

Next, a polyethylene terephthalate film (base material) on which an Al film was formed was placed in a liquid composed of diethylene glycol diethyl ether, and ultrasonic vibration was applied. As a result, scaly Al particles (particles to be mother particles) were obtained.
Next, the Al particles obtained as described above were converted into CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ and CF ₃ (CF ₂ ) as fluorine-based phosphate esters. ₅ (CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) and a mixture of 5% (mass ratio 5:95) in a 1% by mass propanol solution and stirred for 10 seconds, Surface treatment with phosphoric acid ester was performed to obtain a metal powder.
The average particle diameter of the metal powder thus obtained was 0.8 μm, and the average thickness was 60 nm.

  Next, DISPERBYK-183 (manufactured by Big Chemie) as a dispersant (basic polymer dispersant) having a basic polymer structure, a metal powder, a phenoxyethyl acrylate as a second polymerizable compound, a second 4-hydroxybutyl acrylate as a polymerizable compound, tetrahydrofurfuryl acrylate as a second polymerizable compound, Irgacure 819 (manufactured by Ciba Japan) as a photopolymerization initiator, Speedcure TPO (ACETO) as a photopolymerization initiator The second ink was obtained by mixing with Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator and substance A having a chemical structure represented by the following formula (7). The viscosity of the second ink at room temperature (25 ° C.) was 15.1 mPa · s. The surface tension of the second ink at 25 ° C. was 26.8 mN / m.

As described above, an ink set including the first ink and the second ink was obtained.
<Manufacture of recorded materials>
Using the ink set obtained as described above, a recorded matter was produced as follows.
<First ink application step>
First, a droplet discharge device installed in a chamber (thermal chamber) is prepared, and the first ink is made of a non-porous, non-liquid-absorbing polyethylene terephthalate base (Diafoil G440E 38 μm thickness manufactured by Mitsubishi Plastics). ) In a predetermined pattern.

<First curing step>
Next, by irradiating with ultraviolet rays, the first polymerizable compound was polymerized and cured to form a first layer composed of a cured product of the first polymerizable compound.
In this step, the time (T ₁ ) from when the first ink droplet lands on the substrate in the first ink application step to when the droplet is cured (T ₁ ) is 0.9 seconds. Went to.
Further, as the ultraviolet source, RX FireFly UV Light System (manufactured by Phoseon) was used.

<Second ink application step>
Next, the second ink was selectively applied to the surface of the first layer from a different droplet discharge head of the same droplet discharge apparatus used in the second ink application step.
<Second curing step>
Next, the second polymerizable compound was polymerized and cured by irradiating ultraviolet rays to form a second layer composed of a cured product of the second polymerizable compound and metal powder.
In this step, the time (T ₂ ) from when the second ink droplet lands on the first layer in the second ink application step to when the curing treatment for the droplet is performed is 60 seconds. went.
Further, as the ultraviolet ray source, the same one as used in the first curing step (RX FireFly UV Light System (manufactured by Phoseon)) was used.

<Protective film formation process>
Next, a protective film made of an acrylic resin was formed on the entire surface side of the substrate on which the printed layers (first layer and second layer) were provided by a bar coater to obtain a recorded matter. The adhesion amount of the acrylic resin (the constituent material of the protective film) per unit area of the substrate was 2.2 g / m ² .

(Examples 2 to 10)
A recorded matter was produced in the same manner as in Example 1 except that the composition of the ink constituting the ink set, T ₁ and T ₂ were as shown in Tables 1 to 3.
(Comparative Example 1)
A recorded matter was produced in the same manner as in Example 1 except that the first ink application step and the first curing step were omitted.
(Comparative Example 2)
Except that the time T ₂ of the from the droplets of the second ink landed on the first layer in the second ink application step until subjected to a curing treatment for the droplet to be 2 seconds, the comparison A recorded matter was produced in the same manner as in Example 1.

(Comparative Example 3)
A recorded matter was produced in the same manner as in Example 1 except that the composition of the first ink and the composition of the substrate were as shown in Tables 1 and 2.
(Comparative Example 4)
Except that the time T ₁ of the after droplets of the first ink landed on the substrate in the first ink application step until subjected to a curing treatment for the droplet to be 10 seconds, the Example 1 Recorded materials were produced in the same manner as described above.

(Comparative Example 5)
Except that the time T ₂ of the from the droplets of the second ink landed on the first layer in the second ink application step until subjected to a curing treatment for the droplet to be 2 seconds, the above described A recorded matter was produced in the same manner as in Example 1.
(Comparative Example 6)
A recorded matter was produced in the same manner as in Comparative Example 1 except that the metal powder constituting the second ink was made into a spherical shape that had not been scaled.

For each of the examples and comparative examples, the composition and the like of the first ink constituting the ink set are summarized in Table 1, the composition and the like of the second ink are summarized in Table 2, and the liquid of the first ink Table 3 summarizes the time from the landing of the droplet to the curing treatment on the droplet and the time from the landing of the second ink droplet to the curing treatment on the droplet. In the table, 4-hydroxybutyl acrylate is “B1”, tetrahydrofurfuryl acrylate is “B2”, phenoxyethyl acrylate is “B3”, tripropylene glycol diacrylate is “B4”, and dipropylene glycol diacrylate is “B5”. ”, N-vinylcaprolactam“ B6 ”, dimethyloltricyclodecane diacrylate“ B7 ”, 2-hydroxy3-phenoxypropyl acrylate“ B8 ”, 2- (2-hydroxyethoxy) ethyl acrylate“ B9 ” ”Acryloylmorpholine“ B10 ”, dicyclopentenyl acrylate“ B11 ”, dimethylol dicyclopentane diacrylate“ B12 ”, urethane acrylate“ B14 ”, dicyclopentanyl acrylate“ B15 ”, ethyl Carbitol acrylate "B16", methoxytriethylene glycol acrylate "B17", benzyl methacrylate "B18", Irgacure 819 (Ciba Japan) "Z1", Speedcure TPO (Lambson) "Z2" Speedcure DETX (manufactured by Lambson) “Z3”, UV-3500 (manufactured by Big Chemie) “Z4”, hydroquinone monomethyl ether “Z5”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) A mixture (5:95 by mass ratio) of (OH) ₂ and CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) is designated as “S1”, CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O—PO (OH) ₂ as “S2”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ for “S3”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) (OCH ₂ CH ₃ ) for “S4”, CF ₃ (CF ₂ ) ₁ (CH ₂ ) ₃ P (O) (OCH ₂ CH ₃ ) is “S5”, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O—PO (OH) (OC ₂ H ₅ ) is “S6” DISPERBYK-183 (by Big Chemie, amine value: 17 mgKOH / g) is “D1”, DISPERBYK-182 (by Big Chemie, amine value: 13 mgKOH / g) is “D2”, DISPERBYK-184 (by Big Chemie, amine) Value: 15 mgKOH / g) is “D3”, DISPERBYK-116 (BIC Chemie, amine value: 65 mgKOH / g) is “D4”, DISPERBYK-2155 (bit Chemie's product, amine value: 48 mgKOH / g) is “D5”, DISPERBYK-2164 (Bic Chemie product, amine value: 14 mgKOH / g) is “D6”, PAA-1112 (manufactured by Nittobo) is “D7”, Emanon 4110 (dispersant with a polymer structure but not basic, manufactured by Kao Corporation) “D′ 1”, Nonion P-208 (dispersant without a polymer structure, manufactured by NOF Corporation) “D′ 2”, the compound (substance A) represented by the above formula (7) is “A1”, the compound represented by the following formula (8) (substance A) is “A2”, and the following formula (9) The compound (substance A) represented is represented by “A3”, and the substance A represented by the following formula (10) is represented by “A4”. Further, the observation is performed for each of 10 arbitrary metal particles contained in each second ink, and the area S ₁ [μm ² ] when observed from the direction in which the projected area is maximized (when viewed in plan) The ratio (S ₁ / S ₀ ) to the area S ₀ [μm ² ] when observed from the direction in which the area when observed is the maximum among the directions orthogonal to the observation direction is determined, and the average value thereof is The results are shown in Table 1. In the table, the column “θ ₁ ” indicates the contact angle of the ink (first ink, second ink) with respect to the substrate at 25 ° C. measured in accordance with the θ / 2 method. The column “θ ₂ ” shows the contact angle with respect to the first layer of the second ink at 25 ° C. measured in accordance with the θ / 2 method, and the column “viscosity” shows the vibration viscometer. Used, the viscosity at 25 ° C. of the ink measured according to JIS Z 8809 is shown, and the “surface tension” column shows the surface tension at 25 ° C. of the ink measured according to JIS K 3362. . In the table, the time from when the first ink droplets land on the substrate in the first ink application step until the curing process is performed on the droplets in the first curing step is T ₁ [seconds]. The time from when the second ink droplets land on the first layer in the second ink application step to when the second curing step performs the curing process on the droplets is T ₂ [seconds] ]. D1 to D7 are all basic and have a polymer structure (basic polymer dispersant). The base materials used in the examples and comparative examples all have a light (visible light) transmittance of 90% or more when xenon white light defined by JIS Z 8902 is used as a light source. And it was non-porous and non-absorbing. In each of the above examples, the time until the first ink droplets were completely cured was within 1 second after the landing of the first ink droplets on the substrate. In each of the above embodiments, the time until the second ink droplets are completely cured is within one second after the landing of the second ink droplets on the first layer. .

[2] Evaluation The following evaluation was performed on each recorded matter obtained as described above.
[2.1] Shape of printing part The surface opposite to the surface provided with the printing part (first layer, second layer) of the substrate for each recorded matter produced in each of the examples and comparative examples. Visual observation was performed from the side, and the shape of the printed portion was evaluated according to the following seven-stage criteria.
A: The printing part is formed as designed, and the fine shape is also faithfully expressed.
B: The printing part is formed almost as designed.
C: The printed part is not formed as designed due to unintentional wetting and spreading of the ink.

[2.2] Appearance evaluation of recorded matter Each recorded matter produced in each of the above examples and comparative examples is opposite to the surface on which the printed portion (first layer, second layer) of the substrate is provided. It observed visually from the surface side, and evaluated the aesthetic appearance (aesthetics) according to the following seven-stage criteria.
A: It has a glossy feeling full of luxury like a mirror surface, and has an extremely excellent appearance.
B: It has a glossy feeling full of luxury like a mirror surface, and has a very excellent appearance.
C: Glossy with a high-class feeling like that of a mirror surface, and an excellent appearance.
D: Glossy with a high-class feeling like that of a mirror surface, 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.

[2.3] Glossiness The glossiness of the printed portion of each recorded matter produced in each of the above Examples and Comparative Examples was measured according to JIS H 8686 / JIS K 7105 using a Suga Test Machine “ICM-1T”. Was measured and evaluated according to the following criteria. The glossiness was measured from the side opposite to the side of the substrate on which the printing parts (first layer, second layer) were provided.
A: Glossiness is 75 or more.
B: The glossiness is 50 or more and less than 75.
C: Glossiness is 30 or more and less than 50.
D: Glossiness is less than 30.

[2.4] Abrasion Resistance A recorded matter was produced in the same manner as described above except that the protective film forming step was omitted for each of the above Examples and Comparative Examples. With regard to the recorded matter thus obtained, when 48 hours have passed since the production of the recorded matter, a film made of polyethylene terephthalate (Mitsubishi Plastics Corporation, Dia. A rub resistance test using foil G440E) was performed. Before and after the rub resistance test, the glossiness (turning angle 60 °) is measured by the same method as described in [2.3] above, and the reduction rate of the glossiness before and after the rub resistance test is obtained. The evaluation was made according to the following criteria.

A: The reduction rate of glossiness is less than 5%.
B: The reduction rate of glossiness is 5% or more and less than 13%.
C: The reduction rate of glossiness is 13% or more and less than 23%.
D: The reduction rate of glossiness is 23% or more and less than 27%.
E: Gloss reduction rate is 27% or more, or the surface of the substrate is exposed due to metal particles falling off.
These results are shown in Table 4.

  As is apparent from Table 4, the recorded matter of the present invention is provided with a printing portion having a desired shape, and has an excellent gloss feeling (particularly the gloss feeling (shiny feeling that the mirror surface has)). Had an appearance. In addition, the printed portion was excellent in abrasion resistance. On the other hand, in the comparative example, satisfactory results were not obtained.

  DESCRIPTION OF SYMBOLS 10 ... Recorded matter 1 ... Base material (recording medium) 2 ... 1st layer 2 '... 1st ink 21 ... Hardened | cured material 21' ... 1st polymeric compound 3 ... 2nd layer 3 '... 2nd Ink 31 ... Metal powder 32 ... Cured product 32 '... Second polymerizable compound 4 ... Protective film

Claims (14)

A manufacturing method of a printed matter comprising a base material and a printing part, wherein the printing part provided on the back surface side through the base material is visually recognized,
A first ink application step in which a first ink containing a first polymerizable compound that is polymerized by irradiation with ultraviolet rays is applied to the surface of a substrate by an inkjet method;
A first curing step of polymerizing and curing the first polymerizable compound;
A second ink application step in which a second ink containing a second polymerizable compound and metal powder that is polymerized by irradiation with ultraviolet rays is applied onto the cured product of the first polymerizable compound by an inkjet method;
A second curing step of polymerizing and curing the second polymerizable compound,
The contact angle of the first ink to the substrate is 30 ° or more and 85 ° or less,
The time from when the first ink droplet lands on the substrate in the first ink application step to when the liquid is cured in the first curing step is within one second. ,
Time from when the droplets of the second ink land on the cured product of the first polymerizable compound in the second ink application step until the curing process is performed on the droplets in the second curing step For 10 seconds or more.   The method for producing a recorded matter according to claim 1, wherein the viscosity of the first ink at room temperature (25 ° C.) is not less than 5 mPa · s and not more than 40 mPa · s.   The method for producing a recorded matter according to claim 1 or 2, wherein the viscosity of the second ink at room temperature (25 ° C) is 4 mPa · s or more and 30 mPa · s or less.   The method for producing a recorded matter according to any one of claims 1 to 3, wherein the surface tension of the first ink at 25 ° C is 18 mN / m or more and 50 mN / m or less.   The method for producing a recorded matter according to any one of claims 1 to 4, wherein the surface tension of the second ink at 25 ° C is 14 mN / m or more and 40 mN / m or less.   The second ink is surface-treated with one or more surface treatment agents selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate ester, and a phosphate alkyl ester as the metal powder. The method for producing a recorded matter according to any one of claims 1 to 5, wherein: The method for producing a recorded matter according to claim 6, wherein the second ink includes, as the metal powder, a surface treated with the fluorine-based silane compound having a chemical structure represented by the following formula (1). .
R ¹ SiX ¹ _a R ² _(3-a) (1)
(In Formula (1), 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.) 8. The recorded matter according to claim 6, wherein the second ink includes, as the metal powder, a surface treated with the fluorine-based phosphate ester having a chemical structure represented by the following formula (2). Manufacturing method.
POR _n (OH) _3-n (2)
(In the formula (2), 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.) The said 2nd ink contains what was surface-treated with the said phosphoric acid alkylester which has a chemical structure represented by following formula (3) as said metal powder. 2. A method for producing a recorded matter according to 1.
POR _n (OH) _3-n (3)
(In the formula (3), R _{is, CH 3 (CH 2) m} -, CH 3 (CH 2) m (CH 2 O) l -, CH 3 (CH 2) m (CH 2 CH 2 O) l - Or CH ₃ (CH ₂ ) _m O—, n is an integer of 1 to 3, m is an integer of 2 to 18, and l is an integer of 1 to 18.   The method for producing a recorded matter according to any one of claims 1 to 9, wherein the second ink further includes a dispersant having a basic polymer structure.   The method for producing a recorded matter according to any one of claims 1 to 10, wherein the second ink includes a scale-like one as the metal powder.   The method for producing a recorded matter according to any one of claims 1 to 11, wherein each of the first ink and the second ink contains phenoxyethyl acrylate.   In addition to the phenoxyethyl acrylate, the first ink and the second ink are 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy 3- The method for producing a recorded matter according to claim 12, comprising at least one selected from the group consisting of phenoxypropyl acrylate and 4-hydroxybutyl acrylate.   The first ink and the second ink are all dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acryloyl morpholine. 14. The method for producing a recorded matter according to claim 1, comprising at least one selected from the group consisting of tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, and methoxytriethylene glycol acrylate.

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