JP6268946B2 - 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 inkjet method is excellent in that it can be suitably applied to the formation of fine patterns and recording on curved surfaces, can be printed on specific parts on demand, and can be printed with gradation. . In recent years, compositions (ultraviolet curable ink-jet inks) that are cured when irradiated with ultraviolet rays have been used in the ink jet method in order to make the abrasion resistance, water resistance, solvent resistance, etc. particularly excellent. (For example, refer to Patent Document 1).

  However, in the ultraviolet curable ink-jet ink, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. was there. “Glossy” refers to the shiny luster (shiny feeling) that the mirror surface has, or the lame as the observation direction changes when observing a predetermined area of the object. There is a shiny luster (glitter), etc., in which the state of the reflection state changes greatly at each part in the region, but when using UV curable ink jet ink, it expresses the above glitter. There was a problem that it was difficult to do.

JP 2009-57548 A

An object of the present invention is to provide a printed matter with a high-precision printed portion having a glittering glossy feeling (shiny feeling) in which the state of the reflection state changes greatly in each part as the observation direction changes. It is an object of the present invention to provide a method for producing a recorded matter that can efficiently produce the image.

Such an object is achieved by the present invention described below.
The method for producing a recorded matter of the present invention includes 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 a substrate by an inkjet method;
A first curing step of polymerizing and curing the first polymerizable compound by irradiation with ultraviolet rays to form a first layer;
A second ink application step of applying, to the region where the first layer is formed, a second ink containing a second polymerizable compound and metal powder that is polymerized by irradiation with ultraviolet rays, by an inkjet method;
A second curing step of polymerizing and curing the second polymerizable compound by ultraviolet irradiation to form a second layer;
The amount of the first ink applied per unit area in the region is 2.0 g / m ² or more and 20.0 g / m ² or less;
The time from the landing of the droplet of the first ink to the irradiation of the ultraviolet ray on the droplet is 0.0010 seconds or more and 1.0 seconds or less,
The amount of the second ink applied per unit area in the region is 10% by volume or more and less than 80% by volume with respect to the amount of the first ink applied;
The time from the landing of the droplet of the second ink to the irradiation of the ultraviolet ray on the droplet is from 5.0 seconds to 60.0 seconds.
As a result, it is possible to stably produce a printed matter with a precise printing section that has a glittering luster (brilliant feeling) in which the state of the reflection state changes greatly in each part as the observation direction changes. In addition, it is possible to provide a method of manufacturing a recorded matter that can be efficiently manufactured.

In the method for manufacturing a recorded matter of the present invention, the surface roughness Ra of the first layer formed in the first curing step is preferably 3.0 μm or more and 100 μm or less.
Thereby, the 1st layer can exhibit the function as a scaffold at the time of forming the 2nd layer more effectively.
In the recorded matter manufacturing method of the present invention, it is preferable that a droplet amount of the first ink ejected by one ejection operation of the ink jet method is 3 ng or more and 30 ng or less.
As a result, the first layer having a desired shape can be more reliably formed, and the first layer can more effectively exhibit the function as a scaffold when forming the second layer. The surface shape of the second layer can be controlled more reliably, and as a result, it is possible to more reliably produce a recorded matter in which a printing part having an excellent glossy feeling (glittering) like a lame is provided with high accuracy. In addition, the productivity of recorded matter can be made particularly excellent.

In the recorded matter manufacturing method of the present invention, it is preferable that a droplet amount of the second ink ejected by one ejection operation of the ink jet method is 3 ng or more and 30 ng or less.
As a result, the displacement of the landing position of the second ink, excessive wetting and spreading, etc. can be prevented more reliably, and the accuracy of the printed portion of the recorded matter finally obtained can be improved. Productivity can be made particularly excellent.

In the method for producing a recorded matter of the present invention, it is preferable that the metal powder includes a component that has been surface-treated with a surface treatment agent as constituent particles.
Thereby, the gelation of the second ink can be effectively prevented, and the storage stability of the second ink, the ejection stability of the second ink, and the like can be made particularly excellent. In addition, the storage stability of the second ink is excellent, and the affinity with the dispersion medium (second polymerizable compound, etc.) of the metal powder (dispersoid) in the second ink application step described later is also described. Can be suitably adjusted, the metal powder can be suitably arranged in the printing portion of the recorded matter, and the glossiness (glittering) of the printing portion can be made particularly excellent.

In the method for producing a recorded matter of the present invention, the surface treatment agent may be one or more selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate ester, a fluorine-based fatty acid, and an isocyanate compound. preferable.
Thereby, the storage stability of the second ink can be made particularly excellent, and the glossiness (glittering) 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 metal powder includes, as constituent particles, at least mother particles whose surface is mainly composed of Al that has been surface-treated with the surface treatment agent.
As a result, the glossiness inherent in the metal material and the effect of the appropriate arrangement of the metal powder in the printed portion of the recorded matter act synergistically, and the glossiness (glittering) of the printed portion is achieved. It can be made particularly excellent. Further, the gelation of the second ink can be effectively prevented, and the storage stability of the second ink, the ejection stability of the second ink, and the like can be made particularly excellent.

In the method for producing a recorded matter of the present invention, it is preferable that the constituent particles of the metal powder have a scaly shape.
As a result, the metal powder can be arranged so that the main surface of the metal particles follows the surface shape of the second layer, and the glossiness inherent in the metal material constituting the metal powder can be recorded. In addition, the glossiness (glittering) and luxury of the printed part can be made particularly excellent, and the rub resistance of the recorded matter should be particularly excellent. Can do.

In the method for producing a recorded matter of the present invention, the average thickness of the constituent particles of the metal powder is preferably 10 nm to 100 nm.
As a result, the metal powder can be arranged so that the main surface of the metal particles follows the surface shape of the second layer, and the glossiness inherent in the metal material constituting the metal powder can be recorded. In addition, the glossiness (glittering) and luxury of the printed part can be further improved, and the rub resistance of the recorded matter should be further improved. Can do.

In the method for producing a recorded matter of the present invention, it is preferable that the average particle size of the metal powder is 500 nm or more and 3.0 μm or less, and the maximum particle size is 5 μm or less.
Thereby, the glossiness (glitter feeling) and the high-class feeling of the printing part can be further improved. In addition, the storage stability and ejection stability of the second ink can be further improved.

In the method for producing a recorded matter of the present invention, it is preferable that each of the first ink and the second ink includes a monomer having an alicyclic structure as the polymerizable compound.
As a result, the adhesion of the first layer to the substrate, the adhesion of the second layer to the first layer, etc. can be made particularly excellent, and the durability and reliability of the recorded matter are particularly excellent. Can be. In addition, the dispersion stability of the metal powder in the ink and the storage stability of the ink can be made particularly excellent, and the precision, glossiness (glittering), and abrasion resistance of the printed part are particularly excellent. can do.

  In the method for producing a recorded matter of the present invention, the monomer having an alicyclic structure is tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate, adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl acrylate, tetramethylpiperidyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, mevalonic acid lactone acrylate, dimethylol tricyclodecane diacrylate, dimethylol dicyclo Pentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate, Cryroylmorpholine, tetrahydrofurfuryl acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl It is preferable to include one or more selected from the group consisting of acrylates.

  Thereby, the adhesiveness of the first layer to the base material, the adhesiveness of the second layer to the first layer, and the like can be further improved, and the durability and reliability of the recorded matter are further improved. Can be. In addition, the dispersion stability of the metal powder in the ink, the storage stability of the ink, and the ejection stability can be further improved, as well as the accuracy of the printed part, glossiness (glitter feeling), luxury feeling, and abrasion resistance. The property can be further improved.

In the method for producing a recorded matter of the present invention, each of the first ink and the second ink is a phenoxyethyl acrylate, benzyl acrylate, acrylic acid 2 as a polymerizable compound other than the monomer having the alicyclic structure. One or two selected from the group consisting of-(2-vinyloxyethoxy) ethyl, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate It is preferable that the above is included.
As a result, while maintaining excellent storage stability and ejection stability of the ink, the reactivity of the ink after ejection by the inkjet method is particularly excellent, and the productivity of the recorded matter is particularly excellent. In addition, the rub resistance of the pattern to be formed can be made particularly excellent.

In the method for producing a recorded matter of the present invention, it is preferable that a contact angle of the first ink with respect to the substrate is 30 ° or more and 85 ° or less.
As a result, the affinity of the first ink to the substrate is moderately excellent, and the first ink is more than necessary on the substrate while the adhesion of the first layer to the substrate is particularly excellent. Thus, it is possible to more reliably prevent the first layer from having a desired shape.

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 inkjet method is excellent in that it can be suitably applied to the formation of fine patterns and recording on curved surfaces, can be printed on specific parts on demand, and can be printed with gradation. . In recent years, compositions (ultraviolet curable ink-jet inks) that are cured when irradiated with ultraviolet rays have been used in the ink jet method in order to make the abrasion resistance, water resistance, solvent resistance, etc. particularly excellent. Yes.

  However, in the ultraviolet curable ink-jet ink, when a metal powder is applied instead of a pigment or a dye, it is not possible to sufficiently exhibit the properties such as glossiness inherent to the metal. was there. “Glossy” refers to the shiny luster (shiny feeling) that the mirror surface has, or the lame as the observation direction changes when observing a predetermined area of the object. There is a shiny luster (glitter), etc., in which the state of the reflection state changes greatly at each part in the region, but when using UV curable ink jet ink, it expresses the above glitter. There was a problem that it was difficult to do.

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 production method of the present invention includes a first ink application step of applying a first ink containing a first polymerizable compound that is polymerized by irradiation of ultraviolet rays to a substrate by an inkjet method, and the above-mentioned by irradiation of ultraviolet rays. A first curing step for polymerizing and curing the first polymerizable compound to form a first layer; and a second polymerizable compound for polymerizing the region where the first layer is formed by irradiation with ultraviolet rays. And a second ink application step for applying a second ink containing a metal powder by an inkjet method, and a second layer for forming a second layer by polymerizing and curing the second polymerizable compound by ultraviolet irradiation. And the curing amount of the first ink in the region is 2.0 g / m ² or more and 20.0 g / m ² or less, and from the landing of the droplets of the first ink, Purple for the droplet The time until irradiation of the line is 0.0010 seconds or more and 1.0 seconds or less, and the amount of the second ink applied per unit area in the region is 10 with respect to the amount of the first ink applied. The time from the landing of the droplet of the second ink to the irradiation of the ultraviolet ray onto the droplet is 5.0 seconds or more and 60.0 seconds or less. .

  As described above, in the present invention, prior to forming the second layer containing the metal powder by taking a relatively long time for the ultraviolet curing, the second layer is cured by performing the ultraviolet curing in a relatively short time. In addition to forming the first layer as a scaffold, the amount of ink used to form the first layer (ink amount per unit area) and the amount of ink used to form the second layer (ink amount per unit area) By prescribing, the cured product of the first ink droplet can be fixed to a desired part as having a desired shape on various types of substrates, and the first layer (first In the region where the cured product of the ink droplet 1) is formed, the second layer has a surface shape in which the orientation state of the metal powder is suitably controlled and the surface irregularities of the first layer are reflected. Can be formed as (with minute irregularities) . As a result, unintentional wetting and spreading of the ink (excessive wetting and spreading) and repelling of the print pattern due to repelling are reliably prevented, and it has a desired shape and has a lame shape as the observation direction changes. It is possible to stably and efficiently manufacture a recorded matter including a printing unit having a glittering glossy feeling (shiny feeling) in which the state of reflection state varies greatly at each part.

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 ′ containing a first polymerizable compound 21 ′ that is polymerized by irradiation with ultraviolet rays is applied to at least a surface of a substrate (recording medium) by an inkjet method. ) A first ink application step (1a) applied to the surface of 1 and a first polymerizable compound 21 ′ which is polymerized and cured by irradiation with ultraviolet rays to form a cured product 21, thereby forming a first layer 2 Curing step (1b) and a second polymerizable compound that is polymerized by irradiation with ultraviolet rays in a region where the first layer 2 is formed (a region where the second layer 3 as a film without a gap is to be formed) A second ink application step (1c) in which the second ink 3 ′ containing 32 ′ and the metal powder 31 is applied by an inkjet method; and the second polymerizable compound 32 ′ is polymerized and cured by irradiation with ultraviolet rays. The cured product 32 is used to form the second layer 3 And a second curing step (1d).

<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).
The substrate 1 may be any material, and any of absorptive or nonabsorptive materials may be used. For example, paper (plain paper, inkjet dedicated paper, etc.), plastic material, metal, ceramics, wood, Natural fibers / synthetic fibers such as shells, cotton, polyester, and wool, non-woven fabrics, etc. can be used, but at least the surface (site to which the first ink 2 'is applied) is a non-liquid-absorbing material (for example, plastic Preferably, it is composed of materials, metals, ceramics, shells, etc. Thereby, when the non-absorptive (non-liquid absorbing) thing is used as the base material 1, control of the shape of the hardened | cured material 21 of 1st ink 2 'can be performed more suitably.

In the present invention, the non-absorbing recording medium means a material that does not substantially absorb ink, and more specifically, a recording medium having a contact angle of 10 ° or more after landing. Say.
Especially, it is preferable that the base material 1 is what the surface was comprised with polyester at least. Thereby, 1st polymeric compound 21 '(especially 1st polymeric compound 21' containing the monomer which has an alicyclic structure explained in full detail later) 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. Thus, the first layer 2 (particularly, the first layer 2 formed using the first ink 2 ′ containing a monomer having an alicyclic structure, which will be described in detail later, as the first polymerizable compound 21 ′). In particular, the adhesion between the substrate and the substrate 1 can be made particularly excellent, and the heat resistance and the like of the finally obtained recorded matter 10 can be made particularly excellent.

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 a liquid. Accordingly, it is not necessary to use a liquid component that is removed (evaporated) in the manufacturing process of the recorded matter 10, 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 of 10 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 for making the ejection stability of the first ink 2 'particularly excellent.
In particular, the first ink 2 ′ preferably contains a monomer having an alicyclic structure as the first polymerizable compound 21 ′. Thereby, while being able to make especially the adhesiveness with respect to the base material 1 of the hardened | cured material 21 (1st layer 2) formed at a 1st hardening process, the hardened | cured material controlled to the desired shape 21 (first layer 2) can be formed more easily.

  Examples of the monomer having an alicyclic structure include tris (2- (meth) acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, and γ-butyrolactone (meth) acrylate. N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meta ) Acrylate, mevalonic acid lactone (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclope Tanyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, phenylglycidyl ether (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) Examples include acrylate, di (meth) acrylated isocyanurate, tri (meth) acrylated isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate, adamantyl acrylate, γ -Butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl acrylate, tetramethylpiperidyl acrylate, 2-methyl-2-ada N-yl acrylate, 2-ethyl-2-adamantyl acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl acrylate, mevalonic acid lactone acrylate, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate, acryloyl morpholine, and tetrahydrofluoro It is preferable to include one or more selected from the group consisting of furyl acrylate. Thereby, while being able to make the adhesiveness with respect to the base material 1 of the hardened | cured material 21 (1st layer 2) formed at a 1st hardening process further excellent, the hardened | cured material controlled to the desired shape 21 (first layer 2) can be formed more easily. In addition, the storage stability and ejection stability of the first ink 2 'can be further improved.

  Among these, from the viewpoint of further improving the curing speed of the first ink 2 ′ and the productivity of the recorded product 10 in the first curing step, tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl are used. Acrylate, γ-butyrolactone acrylate, N-vinylpyrrolidone, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, acryloylmorpholine, and tetrahydrofurfuryl It is preferable to include one or more selected from the group consisting of acrylates, more preferably to include acryloylmorpholine and / or γ-butyrolactone acrylate, Even more preferably those containing a lactone acrylate.

Moreover, when it includes one or more selected from the group consisting of cyclohexyl acrylate, tetrahydrofurfuryl acrylate, and benzyl acrylate, the flexibility of the cured product 21 (first layer 2) is further improved. Can be.
In addition, when the ink contains one or more selected from the group consisting of γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, isobornyl acrylate, and tetrahydrofurfuryl acrylate, the first ink It is possible to make the shrinkage rate at the time of curing of 2 ′ smaller, and to more effectively prevent undesired wrinkles and the like from occurring in the cured product 21 (first layer 2).

The content of the monomer having an alicyclic structure in the first ink 2 ′ is preferably 40% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 88% by mass or less, and 55% by mass. % To 85% by mass is more preferable. The first ink 2 ′ may contain two or more compounds as a monomer having an alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.
The monomer having an alicyclic structure preferably has 5 or more, more preferably 6 or more constituent atoms of a cyclic structure formed by a covalent bond. Thereby, the storage stability of the first ink 2 ′ can be made particularly excellent.

  The first ink 2 ′ preferably contains a monofunctional monomer containing a hetero atom in the alicyclic structure (monofunctional monomer having a heterocyclic ring not showing aromaticity) as a monomer having an alicyclic structure. Thereby, particularly excellent ejection stability can be obtained over a long period of time. Examples of such monofunctional monomers include tris (2- (meth) acryloyloxyethyl) isocyanurate, γ-butyrolactone (meth) acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth) acrylate. , Tetramethylpiperidyl (meth) acrylate, mevalonic acid lactone (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, and the like.

  The content of the monofunctional monomer (monofunctional monomer containing a hetero atom in the alicyclic structure) in the first ink 2 ′ is preferably 10% by mass or more and 80% by mass or less, and 15% by mass or more and 75%. It is more preferable that the amount is not more than mass%. Thereby, hardening shrinkage can be controlled more effectively. The first ink 2 'may include two or more compounds as a monofunctional monomer including a hetero atom in the alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.

The polymerizable compound constituting the first ink 2 ′ may include a monomer having no alicyclic structure.
Examples of such monomers (monomers having no alicyclic structure) include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, and dipropylene. Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate lauryl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, isooctyl (meth) acrylate, stearyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2-hydride Xylethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, EO-modified 2-ethylhexyl (meth) acrylate , Phenoxydiethylene glycol (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate Dipropylene glycol (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1.9-nonanediol di (meth) acrylate 1,4-butanediol di (meth) acrylate, bisphenol A EO-modified di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 300 di (meth) ) Acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, polyethylene glycol 00 di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A EO-modified di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, trimethylolpropane EO-modified tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate 2- (meth) acryloyloxyethyl phthalate, 3- (meth) acryloyloxypropyl acrylate, w-carboxy (meth) acryloyloxyethyl Examples include phthalate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta / hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but phenoxyethyl acrylate, benzyl acrylate, acrylic acid 2- (2- Vinyloxyethoxy) ethyl, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and one or more selected from the group consisting of 4-hydroxybutyl acrylate Is preferred. By including such a monomer having no alicyclic structure in addition to the monomer having an alicyclic structure, the storage stability and ejection stability of the first ink 2 ′ are improved, and the ink jet method is used. The reactivity of the first ink 2 ′ after ejection can be made particularly excellent, and the productivity of the recorded matter 10 can be made particularly excellent.
In particular, in the case of containing 2- (2-vinyloxyethoxy) ethyl acrylate, the curing rate of the first ink 2 ′ when irradiated with ultraviolet rays and the productivity of the recorded matter 10 may be further improved. it can.

Moreover, when it contains phenoxyethyl acrylate and / or 2-hydroxy 3-phenoxypropyl acrylate, the flexibility of the cured product 21 (first layer 2) can be further improved.
Further, in the case of containing phenoxyethyl acrylate, the shrinkage rate at the time of curing of the first ink 2 ′ is made smaller, and it is more effective that unintentional wrinkles and the like occur in the cured product 21 (first layer 2). Can be prevented.

  The content of the monomer other than the monomer having an alicyclic structure in the first ink 2 ′ is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. . As a result, the curing rate of the first ink 2 ′ and the flexibility of the cured product 21 (first layer 2) are made particularly excellent, and the shrinkage rate during curing is further easily adjusted. Note that the first ink 2 'may include two or more compounds as monomers having no alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.

  The first ink 2 ′ may contain an oligomer (including dimer, trimer, etc.), a prepolymer, etc. in addition to the monomer as the polymerizable compound. As the oligomer and prepolymer, for example, those having the above-described monomer as a constituent component can be used. It is preferable that the first ink 2 'contains a polyfunctional oligomer. Thereby, the storage stability of the first ink 2 'can be made particularly excellent. In addition, for example, when the first ink 2 ′ does not contain a metal powder, the viscosity of the first ink 2 ′ can be prevented from becoming too low, and the second ink 3 ′ The balance of the viscosity can be suitably adjusted. As the oligomer, a urethane oligomer whose repeating structure is urethane, an epoxy oligomer whose repeating structure is epoxy, and the like are preferably used.

  The content of the polymerizable compound in the first ink 2 ′ 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. Thereby, the storage stability, ejection stability, and curability of the first ink 2 'can be further improved. The first ink 2 'may include two or more compounds as the polymerizable compound. In this case, it is preferable that the total content of these compounds is a value within the above range.

The first ink 2 'may include components other than those described above (other components). Such components include, for example, colorants, metal powders, photopolymerization initiators, slip agents (leveling agents), polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), fixing agents, anti-blocking agents. Examples include glazes, preservatives, antioxidants, chelating agents, thickeners, and sensitizers (sensitizing dyes).
When 1st ink 2 'contains a coloring agent, the color tone of the printing part which has the 1st layer 2 and the 2nd layer 3 can be adjusted suitably. Further, when the first ink 2 ′ contains a colorant, for example, even if the base material 1 is made of a highly transparent material, the concealability can be improved, and the printing portion (particularly, The visibility of the printing part (second layer 3)) by the second ink 3 'can be enhanced.

  Further, the first ink 2 'may include a metal powder as described as a constituent component of the second ink 3' which will be described in detail later. Thereby, even if the base material 1 is made of a highly transparent material, it can exhibit a particularly high concealing property, and a printing part (particularly, a printing part (second printing by the second ink 3 ′) The layer 3)) can be improved in visibility, and the glossiness of the printed portion can be supplementarily enhanced. As a result, the glossiness of the printed portion of the recorded matter 10 can be made particularly excellent. it can. In addition, when 1st ink 2 'contains a metal powder, in the 1st layer 2 formed using 1st ink 2', the said metal powder is the 2nd layer 3 explained in full detail behind. It is not necessary to orderly arrange like the metal powder 31 in the inside. This is because the metal powder in the first layer 2 only has a function of supplementarily enhancing the glossiness of the entire printing portion, and the glossiness of the entire printing portion is in the second layer 3. This is because the metal powder 31 is dominant.

  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, at least one selected from an acylphosphine oxide compound and a thioxanthone compound is preferable from the viewpoint of solubility in a polymerizable compound (first 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 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.
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 first polymerizable compound 21 ′ in the first ink 2 ′ can be relatively high, the first ink 2 ′ is formed using the first ink 2 ′. The adhesion of the layer 2 to the substrate 1 can be made particularly excellent.

Further, the first ink 2 ′ may include a dispersant and a substance A, which will be described in detail later as components of the second ink 3 ′. Thereby, the same effect as described in detail later can be obtained.
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.

  Further, the first ink 2 ′ preferably contains a component common to the second ink 3 ′ described in detail later (particularly, the polymerizable compound having the same composition), and the second ink More preferably, it has the same composition as 3 ′. Thereby, setting, adjustment, and the like of the ejection conditions of the ink (first ink 2 'and second ink 3') by the inkjet method are facilitated. Further, since the affinity between the first layer 2 formed using the first ink 2 'and the second ink 3' can be made particularly excellent, the second ink 3 ' Unintentional wet spreading and the like can be more effectively prevented, and the second layer 3 can be selectively formed in the region where the first layer 2 is formed more reliably. As a result, the accuracy of the printing unit can be increased easily and more reliably. In the finally obtained recorded matter 10, the first layer 2 formed using the first ink 2 ′ and the second layer 3 formed using the second ink 3 ′ The adhesion can be made particularly excellent, and the durability and reliability of the recorded matter 10 can be made particularly excellent.

  The contact angle of the first ink 2 ′ with respect to the substrate 1 is preferably 30 ° or more and 85 ° or less, more preferably 35 ° or more and 80 ° or less, and 40 ° or more and 75 ° or less. Further preferred. As a result, 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 particularly excellent. The first ink 2 ′ can be more reliably prevented from spreading more than necessary on the substrate 1, and the first layer 2 has a desired shape more reliably. be able to. In the present invention, as the “contact angle with respect to the substrate”, the contact angle of the ink with respect to the substrate at 25 ° C. measured in accordance with the θ / 2 method can be adopted.

  The viscosity of the first ink 2 ′ at room temperature (25 ° C.) is preferably 4 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 ejection stability of the first ink 2 ′ particularly excellent, it is possible to more effectively suppress the bleeding when the first ink 2 ′ is landed on the droplet, and the first ink 2 ′. The droplets can be cured in a desired shape 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 14 mN / m or more and 50 mN / m or less. Thereby, while making the ejection stability of the first ink 2 ′ particularly excellent, it is possible to more effectively suppress the bleeding when the first ink 2 ′ is landed on the droplet, and the first ink 2 ′. The droplets can be cured in a desired shape 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.

The driving amount per unit area of the first ink 2 ′ in the region to which the first ink 2 ′ is applied in this step (region in which the first layer 2 is formed) is 2.0 g / m ² or more and 20 0.0 g / m ² or less. By setting the amount of the first ink 2 ′ to be within the above range, the first layer 2 having a desired shape can be reliably formed in a later step, and in the later step, the first layer 2 The function as a scaffold for forming the second layer 3 on the first layer 2 can be surely exhibited. Moreover, since the 1st layer 2 (the 1st layer 2 which has an unevenness | corrugation on the surface) of a desired shape can be formed reliably, the unevenness | corrugation of the surface of the 1st layer 2 is made into the 2nd layer 3. It can be formed as having a reflected surface shape (having minute irregularities). As a result, it is possible to reliably obtain the recorded matter 10 in which the printing unit having a glittering glossy feeling (glittering feeling), in which the state of the reflection state changes greatly in each part as in the case of changing the observation direction, is accurately provided. Can be manufactured.

  On the other hand, when the amount of the first ink 2 ′ applied is less than the lower limit value, the first layer 2 obtained by curing the first ink 2 ′ becomes the second layer 3 as described above. The function as a scaffold for forming the film cannot be sufficiently exhibited, and the recorded matter 10 in which the printing part is provided with high accuracy cannot be obtained. Further, when the amount of the first ink 2 ′ applied is less than the lower limit value, the first layer 2 obtained by curing the first ink 2 ′ has a desired shape (the surface has irregularities, the The second layer 3 formed on the first layer 2 is provided with irregularities having an appropriate height difference on the surface. I can't. As a result, it is not possible to form a printed part having a glittering feeling. Further, when the amount of the first ink 2 ′ applied exceeds the upper limit, the first layer 2 obtained by curing the first ink 2 ′ has the second layer 3 as described above. The function as a scaffold during formation cannot be sufficiently exhibited, and the recorded matter 10 in which the printing portion is provided with high accuracy cannot be obtained.

As described above, the driving amount per unit area of the first ink 2 ′ in the region to which the first ink 2 ′ is applied (region in which the first layer 2 is formed) is 2.0 g / m ^2. above 20.0 g / ^{m 2} may be equal to or less than, the at 3.0 g / ^{m 2} or more 18.0 g / ^{m 2} or less is preferably, 5.0 g / ^{m 2} or more 16.0 g / ^{m 2} or less Is more preferable. Thereby, the effects as described above are more remarkably exhibited.

  The droplet amount of the first ink 2 ′ ejected by one ejection operation of the inkjet method is preferably 3 ng to 30 ng, more preferably 5 ng to 25 ng, and more preferably 7 ng to 20 ng. More preferably. As a result, the first layer 2 having a desired shape can be more reliably formed in a later step, and further, when the second layer 3 is formed on the first layer 2 in a later step. Printing that has the function as a scaffold more effectively and can control the surface shape of the second layer 3 more reliably, and as a result, has an excellent glossy feeling (glittering) It is possible to more reliably manufacture the recorded matter 10 with the portions provided with high precision, and to make the recorded matter 10 particularly excellent in productivity.

  On the other hand, when the droplet amount of the first ink 2 ′ ejected by one ejection operation of the ink jet method is less than the lower limit value, the productivity of the recorded matter 10 is lowered. In addition, when the amount of droplets of the first ink 2 ′ ejected by one ejection operation of the inkjet method is less than the lower limit value, the first layer 2 has unevenness on the surface with a sufficiently large difference in height. As a result, it may be difficult to make the printed portion of the recorded matter 10 have a glittering feeling (excellent glossiness such as a glitter). . Further, when the droplet amount of the first ink 2 ′ ejected by one ejection operation of the ink jet method exceeds the upper limit value, the first layer 2 may be formed depending on the composition of the first ink 2 ′. It becomes difficult to have a desired shape, and the first layer 2 obtained by curing the first ink 2 ′ functions as a scaffold when forming the second layer 3 as described above. And it is difficult to reliably control the surface shape of the second layer 3, and the final printed matter 10 has a glittery feeling (excellent glossiness such as glitter). ), It may be difficult to make the accuracy sufficiently good.

<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 with the material containing the hardened | cured material 21 of 1st polymeric compound 21 'is formed.
This step is performed so as to satisfy the following conditions. That is, the time from when the droplet of the first ink 2 ′ lands on the substrate 1 in the first ink application step described above to when the ultraviolet ray is applied to the droplet in this step is 0.0010 seconds or more. It is performed so that it becomes 1.0 second or less. As described above, by performing the curing process in a sufficiently short time from the landing of the droplet of the first ink 2 ′, the droplet of the first ink 2 ′ spreads more than necessary on the substrate 1. And the like, and the cured product 21 (first layer 2) of the first polymerizable compound 21 ′ can be reliably made to have a desired shape at a desired site. The adhesion between the substrate 1 and the cured product 21 (first layer 2) can be reliably improved. As a result, the second layer 3 formed by using the second ink 3 ′ in the process described in detail later also has a desired shape, and the metal powder 31 is preferably used in the second layer 3. Can be arranged. As a result, the recording is provided with a desired shape, and has a printing section having a glittering glossy feeling (shiny feeling) in which the state of the reflection state changes greatly at each site as the observation direction changes. The thing 10 can be obtained reliably. In particular, the above effects can be stably obtained for various types of base materials 1.

  In contrast, the time from the landing of the droplet of the first ink 2 'on the substrate 1 in the first ink application step to the irradiation of the ultraviolet rays on the droplet in this step is less than the lower limit value. If so, the adhesion between the substrate 1 and the cured product 21 (first layer 2) is lowered, and the curing reaction proceeds before the droplets of the first ink 2 'land on the substrate 1. This will increase the defective product rate. Further, when the time period from the landing of the droplet of the first ink 2 ′ on the substrate 1 in the first ink application step to the irradiation of the ultraviolet ray on the droplet in this step exceeds the upper limit value, Depending on the type of the base material 1, the first ink 2 ′ is excessively wet spread on the base material 1 or the first ink 2 ′ applied on the base material 1 is repelled. It becomes difficult to accurately form the layer 2 having a desired shape. As a result, the accuracy of the printed portion cannot be sufficiently improved in the finally obtained recorded matter 10. Further, when the time period from the landing of the droplet of the first ink 2 ′ on the substrate 1 in the first ink application step to the irradiation of the ultraviolet ray on the droplet in this step exceeds the upper limit value, It becomes difficult to form the first layer 2 having unevenness with a sufficiently large difference in height on the surface, and as a result, the printed portion 10 of the finally obtained recorded matter 10 has a glittering feeling (like a glitter). In some cases, it is not possible to achieve a sufficiently superior glossiness.

  As described above, the time from the landing of the droplet of the first ink 2 ′ on the substrate 1 in the first ink application step to the irradiation of the ultraviolet ray on the droplet in this step is 0.0010. However, it is preferably 0.005 seconds or more and 0.8 seconds or less, and more preferably 0.008 seconds or more and 0.5 seconds or less. Thereby, the effect mentioned above is exhibited more notably.

Also, in this step, the time from when the first ink 2 'droplet starts to be irradiated with ultraviolet rays until the degree of cure of the first polymerizable compound 21' contained in the droplet reaches 90%. Is preferably 0.5 seconds or shorter, more preferably 0.3 seconds or shorter, and even more preferably 0.2 seconds or shorter. As described above, the curing reaction proceeds in a sufficiently short time, so that the unintentional deformation of the cured product 21 (first layer 2) can be more reliably prevented.
In addition, the measurement of a cure degree can be performed using various apparatuses, such as DSC-60 (made by Shimadzu Corp.).
As the ultraviolet light source, for example, a mercury lamp, a metal halide lamp, an ultraviolet light emitting diode (UV-LED), an ultraviolet laser diode (UV-LD), or the like can be used. Among these, ultraviolet light emitting diodes (UV-LED) and ultraviolet laser diodes (UV-LD) are preferable from the viewpoints of small size, long life, high efficiency, and low cost.

  The surface roughness Ra of the first layer 2 formed in this step is preferably 3.0 μm or more and 100 μm or less, more preferably 5.0 μm or more and 50 μm or less, and 12.0 μm or more and 30 μm or less. More preferably. Thereby, the function as a scaffold at the time of forming the 2nd layer 3 as mentioned above can be exhibited more effectively. In addition, in this invention, surface roughness Ra means the value measured based on JISB0601.

<Second ink application step>
Next, the second ink 3 ′ is applied on the first layer 2 (the region where the first layer 2 is formed) by an 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.

  The amount of the second ink 3 ′ per unit area in the region is 10% by volume or more and less than 80% by volume with respect to the amount of the first ink 2 ′. Thereby, the second ink 3 ′ can selectively cover the inside of the region without a gap, and the second layer 3 formed in the second curing step, which will be described in detail later, can be applied to a desired portion. It can be selectively formed with high precision (formed so as to selectively cover the inside of the region without a gap). Further, the second layer 3 has a surface shape (small unevenness) reflecting the unevenness of the surface of the first layer 2 and the orientation state of the metal powder 31 is suitably controlled. The recorded material 10 that can be finally obtained has a glittering luster (glittering feeling) in which the state of change in the reflection state is greatly different in each part as the observation direction changes. it can.

  On the other hand, if the amount of the second ink 3 ′ applied per unit area in the region is less than the lower limit value, it becomes difficult for the second ink 3 ′ to cover the region without a gap. In the finally obtained recorded matter, a high-quality and excellent glitter feeling cannot be obtained. In addition, when the amount of the second ink 3 ′ applied per unit area in the region exceeds the upper limit (80% by volume or more), it is difficult to keep the second ink 3 ′ in the region. The second ink 3 ′ protrudes out of the above range, making it impossible to form a highly accurate printed part, or the surface of the second layer 3 reflecting the irregularities of the surface of the first layer 2. It cannot be formed as having a shape (small unevenness), and the recorded matter 10 having an excellent glossy feeling (glittering) like a glitter may not be obtained.

As described above, the amount of the second ink 3 ′ per unit area in the region may be 10% by volume or more and less than 80% by volume with respect to the amount of the first ink 2 ′. It is preferably 15% by volume or more and 70% by volume or less with respect to the amount of the first ink 2 ′, and is 17% by volume or more and 60% by volume or less with respect to the amount of the first ink 2 ′. Is more preferable. Thereby, the effects as described above are more remarkably exhibited.
A specific value of the amount of the second ink 3 ′ applied per unit area in the region is preferably 1.5 g / m ² or more and 7.0 g / m ² or less. Thereby, the effects as described above are more remarkably exhibited.

The droplet amount of the second ink 3 ′ ejected by one ejection operation of the inkjet method is preferably 3 ng or more and 30 ng or less, more preferably 5 ng or more and 25 ng or less, and more preferably 7 ng or more and 20 ng or less. More preferably. Thereby, the displacement of the landing position of the second ink 3 ′, excessive wetting spread, etc. can be more reliably prevented, and the accuracy of the printed portion of the recorded matter 10 finally obtained is particularly excellent. The productivity of the recorded matter 10 can be made particularly 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 is composed of a plurality of particles. Constituent particles of the metal powder 31 (in the case where the surface treatment described in detail later is performed, the mother particles of the metal powder 31; hereinafter the same) are composed of a metal material at least near the surface. For example, the entire surface may be made of a metal material, or the base portion made of a non-metal material may be covered with a layer made of a metal material. May be.

  As the metal material constituting the metal powder 31, metals or various alloys as a single substance can be used, but the constituent particles of the metal powder 31 are preferably composed mainly of Al at least near the surface. . Thereby, the glossiness (glittering) of a printing part can be made especially excellent. Further, in the case where the constituent particles of the metal powder 31 are at least in the vicinity of the surface mainly composed of Al, in the case where the surface treatment described in detail later is performed (the particles constituting the metal powder 31) However, at least in the vicinity of the surface, it has a mother particle mainly composed of Al and a layer made of a surface treatment agent that coats the mother particle). The effect is more remarkable. 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.

  When the pulverization is performed by the above method, the liquid includes alcohols such as methanol, ethanol, propanol, and butanol, n-heptane, n-octane, decane, dodecane, tetradecane, toluene, xylene, and cymene. , Hydrocarbon compounds such as durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol n-butyl ether, tripropy N-glycol dimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, ether compounds such as p-dioxane, propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, Polar compounds such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dimethyl sulfoxide, cyclohexanone and acetonitrile can be preferably used. By using such a liquid, the productivity of the metal powder 31 is made particularly excellent while preventing unintentional oxidation or the like of the metal powder 31, and the size and shape between the particles. The variation in characteristics can be made particularly small.

  The constituent particles of the metal powder 31 may have any shape such as a spherical shape, a spindle shape, or a needle shape, but preferably have 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 second layer 3, and the glossiness etc. inherent to the metal material constituting the metal powder 31 can be obtained. In addition, the recorded matter 10 can be exhibited more effectively, and the glossiness (glittering) and luxury of the printed portion can be made particularly excellent, and the rub resistance of the recorded matter 10 is particularly excellent. Can be.

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

When the constituent particles of the metal powder 31 have a scaly shape, the average thickness of the constituent particles is preferably 10 nm or more and 100 nm or less, and more preferably 20 nm or more and 80 nm or less. Thereby, the effect by the above-mentioned particle | grains being scaly is exhibited more notably.
The average particle size of the metal powder 31 is preferably 500 nm or more and 3.0 μm or less, and more preferably 800 nm or more and 2.5 μm or less. Thereby, the glossiness (glitter feeling) and the high-class feeling of the printing part can be further improved. In addition, the storage stability and ejection stability of the second ink 3 ′ can be further improved. In the present specification, the “average particle diameter” refers to a volume-based average particle diameter (volume average particle diameter (D ₅₀ )). Examples of the measuring apparatus include a laser diffraction / scattering particle size analyzer Microtrac MT-3000 (manufactured by Nikkiso Co., Ltd.).
Further, the maximum particle size of the metal powder 31 is preferably 5 μm or less, and more preferably 4.5 μm or less. Thereby, the storage stability and ejection stability of the second ink 3 ′ can be further improved.

  Further, the constituent particles (metal particles) of 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 (glitter feeling) can be made particularly excellent.

The surface treatment agent used for the surface treatment is not particularly limited. For example, phosphoric acid alkyl ester, higher fatty acid, fluorine-based silane compound, fluorine-based phosphate ester, fluorine-based fatty acid, isocyanate compound, silane coupling agent, fatty acid. Examples thereof include metal salts, unsaturated organic acids, organic titanates, organic aluminates, resin acids, polyethylene glycols and the like.
Among them, the second ink 3 ′ is one or more surface treatment agents selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate ester, a fluorine-based fatty acid, and an isocyanate compound as the metal powder 31. It is preferable to include those subjected to surface treatment. As a result, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness (glittering) and abrasion 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, a fluorine-based fatty acid, an isocyanate compound, and an alkyl phosphate 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.)
As a result, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness (glittering) and abrasion 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) trieth Sisilane, 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-iodopropyltrimethoxyra , 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′- Triethoxysilylpropylurea, S-N-α-phenethyl-N′-triethoxysilylpropylurea, phenethyltrimethoxysilane, phenethylmethyldimethoxysilane, phenethyldimethylmethoxysilane, phenet Tildimethoxysilane, phenethyldiethoxysilane, phenethylmethyldiethoxysilane, phenethyldimethylethoxysilane, phenethyltriethoxysilane, (3-phenylpropyl) dimethylchlorosilane, (3-phenylpropyl) methyldichlorosilane, N-phenylaminopropyltri Methoxysilane, 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- [ -(Trimethoxysilyl) -2-aza-1-oxo-pentyl] caprolactam, 2- (trimethoxysilylethyl) pyridine, N- (trimethoxysilylethyl) benzyl-N, N, N-trimethylammonium chloride, phenyl Vinyldiethoxysilane, 3-thiocyanatopropyltriethoxysilane, N- {3- (triethoxysilyl) propyl} phthalamic acid, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxy Silyl) ethylphenylsulfonyl azide, β-trimethoxysilylethyl-2-pyridine, trimethoxysilylpropyldiethylenetriamine, N- (3-trimethoxysilylpropyl) pyrrole, N-trimethoxysilylpropyl-N, N, N-tributyl Ammonium Romide, 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) phenethyltrimeth Sisilane, 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-fluoro Roh 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} ). As a result, the storage stability of the second ink 3 ′ can be further improved, and the glossiness (glittering) and abrasion resistance of the printed portion of the recorded matter 10 can be further improved.
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.)

As a result, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness (glittering) and abrasion resistance of the printed portion of the recorded matter 10 can be made particularly excellent.
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)} . As a result, the storage stability of the second ink 3 ′ can be further improved, and the glossiness (glittering) and abrasion resistance of the printed portion of the recorded matter 10 can be further improved.

Next, among the surface treatment agents, the fluorinated fatty acid will be described in detail.
As the fluorinated fatty acid, a fatty acid having at least one fluorine atom in the molecule can be used.
Examples of the fluorinated fatty acid include CF ₃ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₃ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —COOH, CF _3. (CF ₂ ) ₆ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₇ —CH ₂ CH ₂ —COOH, CF ₃ (CF ₂ ) ₉ —CH ₂ CH ₂ —COOH, etc. CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —COOH is preferred. Thereby, the metal atom constituting the mother particle can be strongly bonded by a dehydration reaction by heating and a dense film can be formed, so that the surface energy of the particle can be effectively reduced.

Next, an isocyanate compound is demonstrated in detail among surface treating agents.
As the isocyanate compound, a compound having at least one isocyanate group in the molecule can be used.
As an isocyanate compound, what has a chemical structure represented by following formula (6) can be used.
RNCO (6)
(In the formula (6), R _{is, CH 3 (CH 2) m} - and is, m is 2 to 18 integers.)

Thereby, the dispersion stability of the metal powder 31 in the second ink 3 ′ and the storage stability of the second ink 3 ′ can be made particularly excellent. Moreover, since the dispersion stability with respect to various dispersion media is improved, the range of selection of the dispersion media (for example, the second polymerizable compound 32 ′) of the metal powder 31 in the second ink 3 ′ is expanded. Further, the ejection stability of the second ink 3 ′ by the ink jet method can be made particularly excellent.
In formula (6), m is preferably an integer of 3 or more and 14 or less, and more preferably an integer of 4 or more and 12 or less. Thereby, the effects as described above are more remarkably exhibited.

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

  Thereby, the storage stability of the second ink 3 ′ can be made particularly excellent. Further, in the recorded matter 10 manufactured using the second ink 3 ′, the metal powder 31 can be more suitably arranged (leafing) in the vicinity of the outer surface of the second layer 3. The glossiness (glitter feeling) of the ten printed portions can be made particularly excellent. Further, the rubbing resistance of the printed portion of the recorded matter 10 to be manufactured can be made particularly excellent.

In formula (7), m is preferably an integer of 3 or more and 14 or less, and more preferably an integer of 4 or more and 12 or less. Thereby, the effects as described above are more remarkably exhibited.
In formula (7), l is preferably an integer of 1 or more and 14 or less, more preferably an integer of 1 or more and 10 or less. Thereby, the effects as described above are more remarkably exhibited.

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 finally obtained recorded material 10 can have particularly high glossiness (sparkle feeling) and abrasion resistance, and can be recorded at a lower cost than when a fluorine-based phosphate ester is used. Article 10 can be manufactured.
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.

As a result, the storage stability of the second ink 3 ′ can be made particularly excellent, and the glossiness (glittering) and abrasion resistance of the printed portion of the recorded matter 10 can be made particularly excellent.
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. It is preferred to do so. As a result, the surface of the mother particles can be more reliably modified by chemical bonding with the surface treatment agent, and the effects 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 a liquid. Accordingly, it is not necessary to use a liquid component that is removed (evaporated) in the manufacturing process of the recorded matter 10, 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 of 10 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. 3 ′ 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 for making the ejection stability of the second ink 3 ′ particularly excellent.

  In particular, the second ink 3 ′ preferably contains a monomer having an alicyclic structure as the second polymerizable compound 32 ′. Thereby, the dispersion stability of the metal powder 31 in the second ink 3 ′ and the storage stability of the second ink 3 ′ can be made particularly excellent, and the second ink 3 ′ is used. The gloss (glitter) and abrasion resistance of the printed portion of the recorded matter 10 to be manufactured can be made particularly excellent. Moreover, the adhesiveness with respect to the hardened | cured material 21 (1st layer 2) etc. of the hardened | cured material 32 (2nd layer 3) formed at a 2nd hardening process can be made especially excellent.

  Examples of the monomer having an alicyclic structure include tris (2- (meth) acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, and γ-butyrolactone (meth) acrylate. N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meta ) Acrylate, mevalonic acid lactone (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclope Tanyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, phenylglycidyl ether (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) Examples include acrylate, di (meth) acrylated isocyanurate, tri (meth) acrylated isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate, adamantyl acrylate, γ -Butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl acrylate, tetramethylpiperidyl acrylate, 2-methyl-2-ada N-yl acrylate, 2-ethyl-2-adamantyl acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl acrylate, mevalonic acid lactone acrylate, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate, acryloyl morpholine, and tetrahydrofluoro It is preferable to include one or more selected from the group consisting of furyl acrylate. As a result, the gloss (glitter) and luxury of the recorded product 10 to be manufactured can be further improved. In addition, the cured product 32 (second layer 3) formed in the second curing step can be further improved in adhesion to the first layer 2, and can be cured in a desired shape. The object 32 can be formed more easily. In addition, the storage stability and ejection stability of the second ink 3 'can be further improved.

  Among these, when the ink contains one or more selected from the group consisting of acryloylmorpholine, tetrahydrofurfuryl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, and N-vinylpyrrolidone, the second ink 3 ′ The dispersion stability of the metal powder 31 in the inside can be further improved, and in the recorded matter 10 manufactured using the second ink 3 ′, the metal powder 31 is applied to the outer surface of the second layer 3. It can be arranged more suitably in the vicinity, and the gloss (glitter feeling) of the obtained recorded product 10 can be further improved.

  From the viewpoint of further improving the curing speed of the second ink 3 ′ and the productivity of the recorded product 10 in the second curing step, tris (2-acryloyloxyethyl) isocyanurate and dicyclopentenyloxyethyl are used. Acrylate, γ-butyrolactone acrylate, N-vinylpyrrolidone, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, acryloylmorpholine, and tetrahydrofurfuryl It is preferable to include one or more selected from the group consisting of acrylates, more preferably to include acryloylmorpholine and / or γ-butyrolactone acrylate, and γ-butyro Even more preferably those containing a click tons acrylate.

Moreover, when it includes one or more selected from the group consisting of cyclohexyl acrylate, tetrahydrofurfuryl acrylate, and benzyl acrylate, the flexibility of the cured product 32 (second layer 3) is further improved. Can be.
From the viewpoint of further improving the abrasion resistance of the second layer 3 formed by curing the second ink 3 ′, tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl are used. Acrylate, adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, It preferably contains one or more selected from the group consisting of isobornyl acrylate and acryloylmorpholine, and contains γ-butyrolactone acrylate and / or N-vinylcaprolactam. More preferable.

  In the case where the ink contains one or more selected from the group consisting of γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, isobornyl acrylate, and tetrahydrofurfuryl acrylate, the second ink The shrinkage rate at the time of 3 ′ curing is made smaller, and a reduction in glossiness (glittering) due to undesired wrinkles or the like in the cured product 32 (second layer 3) is more effectively prevented. be able to.

  The content of the monomer having an alicyclic structure in the second ink 3 ′ is preferably 40% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 88% by mass or less, and 55% by mass. % To 85% by mass is more preferable. Thereby, the dispersion stability of the metal powder 31 is made particularly excellent, and particularly excellent discharge stability is obtained over a long period of time. In particular, even if the second ink 3 ′ does not contain a dispersant, the above excellent effects can be obtained.

On the other hand, when the content of the monomer having an alicyclic structure in the second ink 3 ′ is less than the lower limit, the dispersibility of the metal powder 31 is reduced, and the droplet discharge stability by the ink jet method is reduced. May be reduced. In this case, the temporal stability of the droplet discharge of the second ink 3 ′ may also be lowered. Further, when the content of the monomer having an alicyclic structure in the second ink 3 ′ exceeds the upper limit value, the dispersion stability of the metal powder 31 is excessively improved, so that it is imparted to the recording medium 1. In the second ink 3 ′, the internal abundance ratio of the metal powder 31 is increased, and it becomes difficult to suitably arrange the metal powder 31 near the outer surface of the applied second ink 3 ′. There is a possibility that glossiness (sparkle feeling) and abrasion resistance of the recorded matter 10 to be obtained may be lowered. The second ink 3 ′ may include two or more compounds as a monomer having an alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.
The monomer having an alicyclic structure preferably has 5 or more, more preferably 6 or more constituent atoms of a cyclic structure formed by a covalent bond. Thereby, the storage stability of the second ink 3 ′ can be made particularly excellent.

  The second ink 3 ′ preferably contains a monofunctional monomer containing a hetero atom in the alicyclic structure (monofunctional monomer having a heterocyclic ring not showing aromaticity) as a monomer having an alicyclic structure. Thereby, the dispersion stability of the metal powder 31 is made particularly excellent, and particularly excellent discharge stability is obtained over a long period of time. In particular, even if the second ink 3 ′ does not contain a dispersant, the above excellent effects can be obtained. Examples of such monofunctional monomers include tris (2- (meth) acryloyloxyethyl) isocyanurate, γ-butyrolactone (meth) acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl (meth) acrylate. , Tetramethylpiperidyl (meth) acrylate, mevalonic acid lactone (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, and the like.

  The content of the monofunctional monomer (monofunctional monomer containing a hetero atom in the alicyclic structure) in the second ink 3 ′ is preferably 10% by mass or more and 80% by mass or less, and 15% by mass or more and 75%. It is more preferable that the amount is not more than mass%. As a result, it is possible to produce a recorded product 10 that includes a printing unit that suppresses curing shrinkage, has less scattering, and is more excellent in gloss (glitter). The second ink 3 'may contain two or more compounds as a monofunctional monomer containing a hetero atom in the alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.

The polymerizable compound constituting the second ink 3 ′ may include a monomer having no alicyclic structure.
Examples of such monomers (monomers having no alicyclic structure) include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, and dipropylene. Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate lauryl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, isooctyl (meth) acrylate, stearyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2-hydride Xylethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, EO-modified 2-ethylhexyl (meth) acrylate , Phenoxydiethylene glycol (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate Dipropylene glycol (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1.9-nonanediol di (meth) acrylate 1,4-butanediol di (meth) acrylate, bisphenol A EO-modified di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 300 di (meth) ) Acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, polyethylene glycol 00 di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A EO-modified di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, trimethylolpropane EO-modified tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate 2- (meth) acryloyloxyethyl phthalate, 3- (meth) acryloyloxypropyl acrylate, w-carboxy (meth) acryloyloxyethyl Examples include phthalate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta / hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but phenoxyethyl acrylate, benzyl acrylate, acrylic acid 2- (2- Vinyloxyethoxy) ethyl, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and one or more selected from the group consisting of 4-hydroxybutyl acrylate Is preferred. By including such a monomer having no alicyclic structure in addition to the monomer having an alicyclic structure, the storage stability and ejection stability of the second ink 3 ′ are improved, and the ink jet method is used. The reactivity of the second ink 3 ′ after ejection can be made particularly excellent, the productivity of the recorded matter 10 can be made particularly excellent, and the formed pattern has particularly excellent abrasion resistance and the like. Can be.

In particular, in the case where the material contains phenoxyethyl acrylate, the metal powder 31 can be more suitably arranged in the vicinity of the outer surface of the second layer 3 in the manufactured recorded material 10, and the glossy feeling (shiny feeling) of the recorded material 10. Can be further improved.
Further, in the case of containing 2- (2-vinyloxyethoxy) ethyl acrylate, the curing rate of the second ink 3 ′ when irradiated with ultraviolet rays and the productivity of the recorded matter 10 may be further improved. it can.
Moreover, when it contains phenoxyethyl acrylate and / or 2-hydroxy 3-phenoxypropyl acrylate, the flexibility of the cured product 32 (second layer 3) can be further improved.

In addition, from the viewpoint of further improving the abrasion resistance of the printed portion, it is selected from the group consisting of 2- (2-vinyloxyethoxy) ethyl acrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate. It is preferable that 1 type or 2 types or more are included, and it is more preferable that 2- (2-vinyloxyethoxy) ethyl acrylate is included.
Further, in the case of containing phenoxyethyl acrylate, the shrinkage rate at the time of curing of the second ink 3 ′ is made smaller, and glossiness due to undesired wrinkles or the like occurring in the cured product 32 (second layer 3). It is possible to more effectively prevent a reduction in (shininess).

  The content of the monomer other than the monomer having an alicyclic structure in the second ink 3 ′ is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. . This further facilitates the adjustment of the curing speed, flexibility, shrinkage rate during curing, and the like of the second ink 3 '. Note that the second ink 3 ′ may include two or more compounds as monomers having no alicyclic structure. In this case, it is preferable that the sum of these contents is a value within the above range.

  The second ink 3 ′ may include an oligomer (including a dimer, a trimer, etc.), a prepolymer, and the like as a polymerizable compound in addition to the monomer. As the oligomer and prepolymer, for example, those having the above-described monomer as a constituent component can be used. It is preferable that the second ink 3 'contains a polyfunctional oligomer. As a result, the storage stability of the second ink 3 ′ can be improved, and the printed portion formed can have particularly excellent abrasion resistance. As the oligomer, a urethane oligomer whose repeating structure is urethane, an epoxy oligomer whose repeating structure is epoxy, and the like are preferably used.

  The content of the polymerizable compound in the 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. Thereby, the storage stability, ejection stability, and curability of the second ink 3 ′ can be further improved. Note that the second ink 3 ′ may contain two or more compounds as the polymerizable compound. In this case, it is preferable that the total content of these compounds is a value within the above range.

The second ink 3 ′ may contain a dispersant. Thereby, the dispersion stability of the metal powder 31 in the second ink 3 ′ can be made excellent, and the storage stability of the second ink 3 ′ can be made more excellent.
In particular, the second ink 3 ′ may include a basic dispersant having a polymer structure (hereinafter also referred to as “basic polymer dispersant”). Thereby, the storage stability of the second ink 3 ′ can be further improved.
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. Accordingly, the storage stability, ejection stability, and curability of the second ink 3 ′ can be further improved, and the gloss (glitter), durability, and the like of the recorded matter 10 are further improved. Can be. 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 (8).

  The second ink 3 ′ contains the substance A having such a chemical structure (in particular, together with the metal powder 31 subjected to the surface treatment as described above), thereby preserving the second ink 3 ′. Stability and curability can be made particularly excellent. Further, in the recorded matter 10, the glossiness / luxury feeling inherent in the metal material constituting the metal powder 31 is more effectively exhibited, and the glossiness (glitter feeling) and durability of the recorded matter 10 are particularly enhanced. It can be excellent.

In the formula (8), 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 (glitter) and durability of the recorded matter 10 can be further improved. Can do.

In Formula (8), R ^{2 to} R ⁵ may be independently a hydrogen atom or a hydrocarbon group, but are preferably an alkyl group having 1 to 3 carbon atoms, and is a methyl group. Is more preferable. Thereby, the storage stability and ejection stability of the second ink 3 ′ can be further improved, and the gloss (glitter) and durability of the recorded matter 10 can be further improved. Can do.

  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. Accordingly, the storage stability, ejection stability, and curability of the second ink 3 ′ can be further improved, and the gloss (glitter), durability, and the like of the recorded matter 10 are further improved. Can be. 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 (glitter) and durability of the recorded matter 10 can be improved. Furthermore, it can be made excellent.

The second ink 3 ′ may contain components other than those described above (other components). Examples of such components include colorants, photopolymerization initiators, slip agents (leveling agents), polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), fixing agents, antifungal agents, Examples include antiseptics, antioxidants, chelating agents, thickeners, and sensitizers (sensitizing dyes).
As a photoinitiator, the thing similar to having demonstrated as a structural component of a 1st ink can be used, for example. Thereby, the same effect as described above can be obtained.

  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 material 10 becomes smooth due to the leveling action, and the abrasion resistance is improved.
The slip agent is not particularly limited. For example, a silicone-based surfactant such as polyester-modified silicone, polyether-modified silicone, and acrylic silicone can be used, and polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane is used. It is preferable.

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 second polymerizable compound 32 ′ in the second ink 3 ′ can be relatively increased, the second ink 3 ′ is formed using the second ink 3 ′. The adhesion of the layer 3 to the first layer 2 and the like 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 30 ° or more and 85 ° or less, more preferably 35 ° or more and 80 ° or less, and 40 ° or more and 75 ° or less. Is more preferable. 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. It is possible to reliably prevent the second ink 3 'from spreading to the surface of the substrate 1 (a region where the first layer 2 is not formed) and the like while making the adhesion excellent. 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 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 40 mPa · s or less, and more preferably 6 mPa · s or more and 30 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 unintentional bleeding at the time of the droplet landing of the second ink 3 ′, and to record the recorded matter. The glossiness (shiny feeling) of 10 can be made particularly excellent.

  The absolute value of the difference between the viscosity of the first ink 2 ′ at room temperature (25 ° C.) and the viscosity of the second ink 3 ′ at room temperature (25 ° C.) is preferably 1.0 mPa · s or less. , 0.6 mPa · s or less is more preferable, and 0.4 mPa · s or less is more preferable. Thereby, setting, adjustment, and the like of the ejection conditions of the ink (first ink 2 'and second ink 3') by the inkjet method are facilitated.

  The surface tension at 25 ° C. of the second ink 3 ′ is preferably 14 mN / m or more and 50 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 unintentional bleeding at the time of the droplet landing of the second ink 3 ′, and to record the recorded matter. The glossiness (shiny feeling) of 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 '.
This step is performed so as to satisfy the following conditions. That is, after the droplets of the second ink 3 ′ ejected in the second ink application step described above land on the region where the first layer 2 is formed, the droplets (second The time required to irradiate the ink 3 ′ droplets) with ultraviolet rays is 5.0 seconds or more and 60.0 seconds or less. In this way, a relatively long time from the landing of the droplet of the second ink 3 ′ (after the droplet of the first ink 2 ′ has landed on the substrate 1 in the first ink application step, The second ink 3 ′ is sufficiently applied to the surface of the first layer 2 by performing a curing process by ultraviolet irradiation after a time longer than the time until the droplets are irradiated with ultraviolet rays in the curing step. Since the second polymerizable compound 32 ′ is cured after the metal powder 31 takes a suitable arrangement in the second ink 3 ′ that is wet and spreads and has fluidity, the surface shape of the first layer 2 is changed. The reflected shape of the second layer 3 is formed, and the metal powder 31 is suitably arranged in the second layer 3. Then, combined with the necessary and sufficient amount of the second ink 3 ′ applied in the second ink application step, the reflection state is reflected at each part like a lame as the observation direction changes. It is possible to obtain a glittering glossy feeling (shiny feeling) in which the state of change is greatly different.

  On the other hand, the time from the landing of the droplet of the second ink 3 ′ to the region in the second ink application step to the irradiation of the ultraviolet ray on the droplet in this step is less than the lower limit value. Before the second ink 3 ′ is sufficiently wet spread on the surface of the first layer 2, and before the metal powder 31 takes a suitable arrangement in the second ink 3 ′, the second polymerizable compound 32. The curing reaction of 'will proceed and the second layer 3 that has lost its fluidity is formed, so that the formed second layer 3 sufficiently reflects the surface shape of the first layer 2. In other words, it is not possible to obtain an excellent gloss (glitter). In addition, when the time from the landing of the droplet of the second ink 3 ′ to the area in the second ink application step to the irradiation of the ultraviolet ray on the droplet in this step exceeds the upper limit, recording is performed. Productivity of the article 10 decreases. Further, the second ink 3 ′ protrudes out of the above range, and a high-precision printed portion cannot be formed.

  As described above, the time from the landing of the droplet of the second ink 3 ′ in the second ink application step to the region until the irradiation of the droplet with the ultraviolet ray in this step is 5.0 seconds. Although it may be 60.0 seconds or more, it is preferably 6.0 seconds or more and 30.0 seconds or less, and more preferably 7.0 seconds or more and 20.0 seconds or less. Thereby, the effect mentioned above is exhibited more notably.

  In this step, the time from the start of irradiation of the second ink 3 ′ with the ultraviolet rays until the degree of cure of the second polymerizable compound 32 ′ contained in the second droplet reaches 90%. Is preferably 0.5 seconds or shorter, more preferably 0.3 seconds or shorter, and even more preferably 0.2 seconds or shorter. As described above, the curing reaction proceeds in a sufficiently short time, so that the unintentional deformation of the cured product 32 (second layer 3) can be more reliably prevented. Further, it is advantageous for further improving the productivity of the recorded matter 10.

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 ray source as used in the first ink application process, or an ultraviolet ray source different from that used in the first ink application process may be used. May be performed.
The surface roughness Ra of the second layer 3 formed in this step is preferably 1.0 μm or more and 10 μm or less, and more preferably 2.0 μm or more and 9.0 μm or less. Thereby, it is possible to make the recorded material 10 particularly excellent in glossiness (shininess).

《Recordings》
Next, the recorded matter of the present invention will be described.
The recorded matter of the present invention is manufactured using the method of the present invention as described above. Such a recorded matter is accurately provided with a printing portion having a glittering glossy feeling (shiny feeling) in which the state of the reflection state changes greatly in each part like a lame as the observation direction changes. It is.

  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 present invention, the same ink may be used in common as the first ink and the second ink.

  In the above-described embodiment, the first layer is formed as a film-like material (a combination of the first ink droplets) covering the surface of the substrate in a predetermined region. As described above, in the present invention, the first layer is not a combination of the first ink droplets in a predetermined region, for example, and is provided in a plurality of scattered dots. There may be.

Next, specific examples of the present invention will be described.
[1] Manufacture of recorded matter (Example 1)
First, inks (first ink and second ink) were produced as follows.
<< Manufacture of ink (first ink, 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 added to 99 parts by mass of diethylene glycol diethyl ether as CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O ( P) (OH) ₂ : 1 part by mass was placed in a dissolved liquid, and 27 kHz ultrasonic vibration was applied at 55 ° C. for 3 hours. Thus, a dispersion of metal powder in the base particles made of Al consists of _{CF 3 (CF 2) 5 (} CH 2) 2 O (P) (OH) 2 scaly particles surface-treated by the obtained It was.
The average particle size of the metal powder thus obtained was 0.9 μm, the maximum particle size was 2.0 μm, and the average thickness was 60 nm.

  Next, γ-butyrolactone acrylate as a monomer having an alicyclic structure (polymerizable compound), phenoxyethyl acrylate as a monomer having no alicyclic structure (polymerizable compound), 9) Substance A having a chemical structure represented by 9), DISPERBYK-182 (manufactured by Big Chemie) as a basic polymer dispersant, Irgacure 819 (manufactured by Ciba Japan) as a photopolymerization initiator, and photopolymerization initiator The ink was obtained by mixing with Speedcure TPO (manufactured by ACETO) and Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator.

<Manufacture of recorded materials>
Using the ink obtained as described above as the first ink and the second ink, a recorded matter was produced as follows. In the method described below, the first ink application step and the second ink application step are as follows: substrate conveyance speed: 350 mm / second, resolution: 720 × 720 dpi, substrate-nozzle surface distance (gap) 1 mm.

<First ink application step>
First, a droplet discharge device installed in a chamber (thermal chamber) is prepared, and a first ink is placed on a surface of a non-porous, non-liquid-absorbing polycarbonate substrate with a predetermined pattern (four 5 A square pattern of .0 cm square was placed in two vertical and horizontal directions so that the corresponding sides were parallel, and the pattern was set so that a gap of 0.5 mm existed between them (see FIG. 1 (1a)). The amount (X ₁ ) of the first ink applied in the region where the first ink was applied was 10.0 g / m ² .

<First curing step>
Next, by irradiating with ultraviolet rays, the first polymerizable compound was polymerized and cured to form a film-like first layer made of a material containing a cured product of the first polymerizable compound (FIG. 1 (1b)).
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 starts to be irradiated with ultraviolet rays is 0.010. I went to the second.
Further, as the ultraviolet light source (light source), RX FireFly UV Light System (manufactured by Phoseon) was used.

<Second ink application step>
Next, a region where the first layer is formed (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 Selectively granted. The second ink ejection amount (X ₂ ) in the region to which the second ink was applied (region in which the first layer was formed) was 5.0 g / m ² .

<Second curing step>
Next, by irradiating with ultraviolet rays, the second polymerizable compound is polymerized and cured to form a film-like second layer composed of a material containing a cured product of the second polymerizable compound and metal powder. did.
In this step, the second ink droplet lands on the region where the first layer is formed in the second ink application step (the surface of the first layer), and then the ultraviolet ray is irradiated to the droplet. The time (T ₂ ) until the start was set to 10.0 seconds.
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.

(Examples 2 to 20)
The composition of the ink used for manufacturing the recorded material is shown in Table 1, Table 2, Table 4, and Table 5, the type of base material (recording medium) used for manufacturing the recorded material, and the first ink ejection amount X _1. The time T ₁ from when the first ink droplets land on the substrate in the first ink application step until the start of ultraviolet irradiation on the droplets, the second ink ejection amount X _2. Time T ₂ from when the droplet of the second ink has landed on the region where the first layer is formed (the surface of the first layer) until the start of irradiation of ultraviolet rays to the droplet A recorded matter was produced in the same manner as in Example 1 except that the conditions were as shown in Table 7.

(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 after surface landing droplets of the second ink of the substrate before the start of irradiation of ultraviolet rays with respect to the droplet to be 1.0 seconds, the comparative examples A recorded matter was produced in the same manner as in Example 1.

(Comparative Example 3)
Same as Example 1 except that the amount of first ink applied (X ₁ ) in the region (region where the first ink is applied) in the first ink application step is 1.9 g / m ^2. In this way, recorded matter was manufactured.
(Comparative Example 4)
The same as in Example 1 except that the first ink ejection amount (X ₁ ) in the region (region to which the first ink was applied) in the first ink application step was 21.0 g / m ^2. In this way, recorded matter was manufactured.

(Comparative Example 5)
The time (T ₁ ) from when the first ink droplet lands on the substrate in the first ink application step to when the droplet starts to be irradiated with ultraviolet rays (T ₁ ) is 0.0001 seconds. Produced a recorded material in the same manner as in Example 1.
(Comparative Example 6)
The time (T ₁ ) from when the first ink droplet lands on the substrate in the first ink application step to when the droplet starts to be irradiated with ultraviolet rays (T ₁ ) is 1.1 seconds. Produced a recorded material in the same manner as in Example 1.

(Comparative Example 7)
The second ink application amount (X ₂ ) in the region (region where the first layer is formed) in the second ink application step is 0.9 g / m ² (the first ink injection amount in the region). A recorded matter was produced in the same manner as in Example 1 except that the ratio of the second ink ejection amount to 9 vol.

(Comparative Example 8)
The second ink application amount (X ₂ ) in the region (region where the first layer is formed) in the second ink application step is 8.1 g / m ² (the first ink injection amount in the region). A recorded matter was produced in the same manner as in Example 1 except that the ratio of the amount of the second ink to be set to 81 vol%.

(Comparative Example 9)
After the second ink droplet has landed on the region where the first layer has been formed in the second ink application step (the surface of the first layer), irradiation of ultraviolet rays is started on the droplet. A recorded matter was produced in the same manner as in Example 1 except that the time (T ₂ ) was 4.9 seconds.
(Comparative Example 10)
After the second ink droplet has landed on the region where the first layer has been formed in the second ink application step (the surface of the first layer), irradiation of ultraviolet rays is started on the droplet. A recorded matter was produced in the same manner as in Example 1 except that the time (T ₂ ) was 61.0 seconds.
(Comparative Example 11)
The same procedure as in Comparative Example 10 except that spherical Al particles manufactured using the gas atomization method were used as the base particles of the constituent particles of the metal powder contained in the first ink and the second ink. The recorded material was manufactured.

For each of the examples and comparative examples, the ink compositions are summarized in Tables 1 to 6, and the constituent materials of the base material used for the production of the recorded material, the first ink ejection amount X ₁ [g in the region, / M ² ], a time T ₁ [second] from the landing of the first ink droplet to the irradiation of the ultraviolet light onto the droplet, a second ink ejection amount X ₂ [g / m ² ] in the region, Time T ₂ [seconds] from the landing of the second ink droplet to the irradiation of the ultraviolet light onto the droplet, the ratio R [volume%] of the second ink ejection amount to the first ink ejection amount in the region. ] Are collectively shown in Table 7. In the table, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ as the fluorine-based phosphate compound is “FAP1”, and (CF ₃ (CF ₂ ) as the fluorine-based silane compound is used. ) ₇ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ) as “FAS1” and (CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ) as a fluorine-based silane compound as “FAS2” ”, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ COOH as a fluorinated fatty acid is“ FFA1 ”, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ NCO as an isocyanate compound is“ IS1 ”, and the isocyanate compound is CF ₃ (CF ₂ ) ₇ NCO is “IS2”, and CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ NCO as an isocyanate compound is “IS3”. CH ₃ (CH ₂ ) ₇ NCO as an acid compound is “IS4”, CH ₃ (CH ₂ ) ₁₂ NCO as an isocyanate compound is “IS5”, and CH ₃ (CH ₂ ) ₁₇ NCO as an isocyanate compound is “IS6”. CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) (OH) ₂ as an isocyanate compound is “S1”, and CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ O (P) as an isocyanate compound (OH) (OCH ₂ CH ₃ ) is “S2”, CF ₃ (CF ₂ ) ₅ —CH ₂ CH ₂ —Si (OC ₂ H ₅ ) ₃ as an isocyanate compound is “S3”, and CF ₃ is an isocyanate compound. —CH ₂ CH ₂ —Si (OCH ₃ ) ₃ as “S4”, CH ₃ (CH ₂ ) ₇ O—PO (O H) ₂ for “S5”, γ-butyrolactone acrylate as a monomer having an alicyclic structure (polymerizable compound) as “BLA”, and tetrahydrofurfuryl acrylate as a monomer having an alicyclic structure (polymerizable compound) as “THFA” ”,“ VC ”for N-vinylcaprolactam as a monomer (polymerizable compound) having an alicyclic structure,“ VP ”for N-vinylpyrrolidone as a monomer (polymerizable compound) having an alicyclic structure, "AMO" for acryloylmorpholine as a monomer (polymerizable compound) having "TAOEI" for tris (2-acryloyloxyethyl) isocyanurate as a monomer (polymerizable compound) having an alicyclic structure, monomer having an alicyclic structure Dicyclopentenyloxyethyl acrylate as (polymerizable compound) “DCPTeOEA”, “AA” as a monomer having an alicyclic structure (polymerizable compound) “AA”, dimethylol tricyclodecane diacrylate as a monomer having a alicyclic structure (polymerizable compound) “DMTCDDA”, fat Dimethylol dicyclopentane diacrylate as a monomer having a ring structure (polymerizable compound) is “DMDCPTA”, dicyclopentenyl acrylate as a monomer having an alicyclic structure (polymerizable compound) is “DCPTeA”, and an alicyclic structure is Dicyclopentanyl acrylate as a monomer (polymerizable compound) having “DCPTaA”, isobornyl acrylate as a monomer having an alicyclic structure (polymerizable compound) “IBA”, and monomer having an alicyclic structure (polymerizable) Shiku as a compound) “CHA” is hexyl acrylate, “DAI” is a diacrylated isocyanurate as a monomer (polymerizable compound) having an alicyclic structure, and “TAI” is a triacrylated isocyanurate as a monomer (polymerizable compound) having an alicyclic structure. ”,“ BLM ”for γ-butyrolactone methacrylate as a monomer (polymerizable compound) having an alicyclic structure,“ THFM ”for tetrahydrofurfuryl methacrylate as a monomer (polymerizable compound) having an alicyclic structure, Dicyclopentenyloxyethyl methacrylate as a monomer (polymerizable compound) having “DCPTeOEM”, adamantyl methacrylate as a monomer having a cycloaliphatic structure (polymerizable compound) as “AM”, and a monomer having a cycloaliphatic structure (polymerizable compound) Penta as Tilpiperidyl methacrylate is “PMPM”, tetramethylpiperidyl methacrylate is “TMPM” as a monomer (polymerizable compound) having an alicyclic structure, and 2-methyl-2-adamantyl is a monomer having a alicyclic structure (polymerizable compound) "MAM" methacrylate, 2-ethyl-2-adamantyl methacrylate as monomer (polymerizable compound) having alicyclic structure "EAM", mevalonic acid lactone methacrylate as monomer having alicyclic structure (polymerizable compound) “MLM”, dicyclopentenyl methacrylate as a monomer having an alicyclic structure (polymerizable compound) “DCPTeM”, dicyclopentanyl methacrylate as a monomer having an alicyclic structure (polymerizable compound) “DCPTaM”, fat Has a ring structure Isobornyl methacrylate as a monomer (polymerizable compound) is “IBM”, monomer having a cycloaliphatic structure (polymerizable compound) is “CHM”, monomer having a cycloaliphatic structure (polymerizable compound) Cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl acrylate as “CHDOLA”, (2-methyl-2-ethyl-1,3-dioxolane as a monomer (polymerizable compound) having an alicyclic structure -4-yl) methyl acrylate as "MEDOLA", phenoxyethyl acrylate as a monomer (polymerizable compound) having no alicyclic structure as "PEA", as a monomer having no alicyclic structure (polymerizable compound) Dipropylene glycol diacrylate is “DPGDA”, a model that does not have an alicyclic structure. Tripropylene glycol diacrylate as a monomer (polymerizable compound) is “TPGDA”, 2-hydroxy-3-phenoxypropyl acrylate is “HPPA” as a monomer having no alicyclic structure (polymerizable compound), and an alicyclic structure is 4-Hydroxybutyl acrylate as a monomer (polymerizable compound) that does not have "HBA", ethyl carbitol acrylate as a monomer (polymerizable compound) that does not have an alicyclic structure as "ECA", has an alicyclic structure Methoxytriethylene glycol acrylate as a monomer (polymerizable compound) that does not have "MTEGA", t-butyl acrylate as a monomer (polymerizable compound) that does not have an alicyclic structure as "TBA", has an alicyclic structure Benzyl acrylate as a monomer (polymerizable compound) “VEEA” is 2- (2-hydroxyethoxy) ethyl acrylate as a monomer (polymerizable compound) having no alicyclic structure, and “benzyl methacrylate” is a monomer (polymerizable compound) having no alicyclic structure. "BM", urethane acrylate as a monomer having no alicyclic structure (polymerizable compound) as "UA", DISPERBYK-182 as a basic polymer dispersant (by Big Chemie, amine value: 13 mgKOH / g) D2 ", DISPERBYK-2155 (produced by BYK Chemie, amine value: 48 mgKOH / g) as a basic polymer dispersant is" D5 ", and the compound (substance A) represented by the above formula (9) is" A1 ", The compound (substance A) represented by the following formula (10) is “A2”, the compound (substance A) represented by the following formula (11) is “A3”, Substance A represented by formula (12) is “A4”, Irgacure 819 (manufactured by Ciba Japan) is “ic819”, Speedcure TPO (manufactured by ACETO) is “scTPO”, and Speedcure DETX (manufactured by Lambson) is “ scDETX ", UV-3500 (manufactured by Big Chemie)" UV3500 ", hydroquinone monomethyl ether" MEHQ ", 1,2-hexanediol" 1,2HD ", trimethylolpropane" TMP ", Surfynol 465 (day Shinsei Chemical Co., Ltd.) “S465”, triethanolamine “TEA”, glycerin “GL”, LHP-96 (Enomoto Kasei Co., Ltd.) “LHP”, LF-1984 (Enomoto Kasei Co., Ltd.) “ LF ", Polyflow 401 (manufactured by Nissin Chemical Industry Co., Ltd.)," PF401 ", Polycar Bonate is indicated by “PC” and polyethylene terephthalate is indicated by “PET”. Moreover, about Example 15, the composition of the constituent material of a mother particle showed the content rate of each element with the weight ratio about Example 15. In addition, the viscosity at 25 ° C. of the ink used in each of the examples measured according to JIS Z8809 using a vibration viscometer is a value in the range of 6 mPa · s to 30 mPa · s. Met. Further, the surface tension at 25 ° C. of the ink used in each of the above examples measured in accordance with JIS K 3362 was a value within the range of 14 mN / m to 50 mN / m. In addition, for the first ink used in each of the examples, the contact angle with respect to the substrate at 25 ° C. measured in accordance with the θ / 2 method was 40 ° or more and 75 ° or less. In addition, for the second ink used in each of the above examples, the contact angle with respect to the first layer at 25 ° C. measured in accordance with the θ / 2 method was 30 ° or more and 85 ° or less. . In addition, for the second ink used in each of the above examples, the contact angle with respect to the substrate at 25 ° C. measured according to the θ / 2 method was 40 ° or more and 75 ° or less. In addition, regarding the metal powder constituting the ink used in each of the above-described embodiments, an arbitrary 10 metal particles are observed, and the area S when observed from the direction in which the projected area is maximized (when viewed in plan). ₁ [μm ² ] and a 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, When these average values were obtained, the average values of S ₁ / S ₀ were all 19 or more. D2 and D5 are both basic and have a polymer structure (basic polymer dispersant). In addition, the base materials used in the above Examples and Comparative Examples were all non-porous and non-absorbing. In each of the above-described examples and comparative examples, the amount of liquid droplets in one ejection operation of the first ink and the amount of liquid droplets in one ejection operation of the second ink are both 7 ng or more and 20 ng. The value was within the following range. In each of the above embodiments, the time from when the first ink droplet starts to be irradiated with ultraviolet rays until the degree of cure of the first polymerizable compound contained in the droplet reaches 90%. In addition, the time from the start of irradiation of the second ink droplet with ultraviolet rays to the time when the degree of cure of the second polymerizable compound contained in the droplet reaches 90% is 0.1. It was less than a second. Further, for the recorded matter of each Example, the surface roughness Ra of the second layer was measured in accordance with JIS B 0601.
In either case, it was 2.0 μm or less and 8.0 μm or less. Moreover, about each said Example, when surface roughness Ra of the 1st layer was measured based on JISB0601, all were 15 micrometers or more and 20 micrometers or less.

[2] Evaluation of recorded matter Each recorded matter obtained as described above was evaluated as follows.
[2.1] Print section shape (print section accuracy)
Each recorded matter produced in each of the above examples and comparative examples was observed from the surface side where the printing portion (first layer, second layer) of the base material was provided. Evaluation was made according to the criteria of the stage.

A: The average gap between adjacent square solid patterns is 0.3 mm or more and 0.7 mm.
Less than.
B: The average gap between adjacent square solid patterns is 0.2 mm or more and 0.3 mm
Or less than 0.7 mm and less than 0.8 mm.
C: The average gap between adjacent square solid patterns is 0.1 mm or more and 0.2 mm
Or 0.8 mm or more and less than 0.9 mm.
D: The average gap between adjacent square solid patterns is 0 mm (contact) or more and 0.1
Less than mm or 0.9 mm or more.

[2.2] Appearance evaluation of recorded matter (glitter feeling)
Each recorded matter produced in each of the above Examples and Comparative Examples was visually observed from the side where the printing unit (first layer, second layer) was provided, and the aesthetic appearance (aesthetics) was as follows. Evaluation was made according to the criteria of the stage.
A: As the observation direction changes, the reflection state changes greatly at each part, like a lamé, and it has a glittering and glossy feeling (glitter feeling), and has an extremely excellent appearance. ing.
B: As the observation direction changes, the reflection state changes greatly in each part, like a lamé, and it has a sparkling glossy feeling (glittering) and has a very good appearance. doing.
C: As the observation direction changes, the reflection state changes greatly in each part, like a lamé, and it has a glittering, high-grade gloss (glitter), and has an excellent appearance. ing.
D: As the viewing direction changes, the reflection state changes greatly in each part, like a lamé, with a sparkling and high-class luster (glitter), and an excellent appearance Have.
E: It is inferior to a glittering feeling and has a slightly poor appearance.
F: Inferior to glitter and appearance is poor.
G: Inferior to glitter and very poor appearance.

[2.3] Abrasion Resistance With respect to the recorded matter according to each of the examples and comparative examples, when 48 hours have elapsed since the manufacture of the recorded matter, the glossiness of the pattern forming portion is measured by a gloss meter (MINOLTA MULTI GLOSS 268). Was measured under the condition of a turning angle of 60 °. Thereafter, using a Southerland Love Tester, a rub resistance test using a film made of polyethylene terephthalate (Mitsubishi Resin, Diafoil G440E) as a companion paper was performed according to JIS K5701, and the same conditions as described above. Also for the recorded matter after the rubbing test, the glossiness (turning angle 60 °) was measured, the reduction rate of the glossiness before and after the rubbing resistance test was determined, and evaluated according to the following criteria.

A: The reduction rate of glossiness is less than 10%.
B: The reduction rate of glossiness is 10% or more and less than 17%.
C: The reduction rate of glossiness is 17% or more and less than 27%.
D: The reduction rate of glossiness is 27% or more and less than 30%.
E: Gloss reduction rate is 30% or more, or the surface of the substrate is exposed due to metal particles falling off.

[3] Evaluation of ink used for production of recorded matter The following evaluation was performed on each recorded matter obtained as described above.
[3.1] Evaluation of droplet discharge stability (discharge stability evaluation)
The ink used in each of the examples was evaluated by the following tests.
First, a droplet discharge device installed in a chamber (thermal chamber) and the ink used in each of the above examples are prepared, and the driving waveform of the piezo element is optimized, in an environment of 25 ° C. and 50% RH. For each ink, 2000 million (2,000,000) droplets were continuously discharged from each nozzle of the droplet discharge head. Thereafter, the operation of the droplet discharge device was stopped, and the liquid droplet discharge device was left in an environment of 25 ° C. and 50% RH for 360 hours in a state where each flow path was filled with each ink.

  Thereafter, 4 million droplets (4000000 droplets) were continuously discharged from each nozzle of the droplet discharge head in an environment of 25 ° C. and 50% RH. The average deviation amount d from the center target position of the center position of each of the landed droplets of the 4000000 droplets ejected from a designated nozzle near the center of the droplet ejection head after being left for 360 hours. Values were obtained and evaluated according to the following five-step criteria. It can be said that the smaller the value is, the more effectively the occurrence of flight bending is prevented.

A: The average value of the shift amount d is less than 0.07 μm.
B: The average value of the shift amount d is 0.07 μm or more and less than 0.14 μm.
C: The average value of the shift amount d is 0.14 μm or more and less than 0.17 μm.
D: The average value of the shift amount d is 0.17 μm or more and less than 0.21 μm.
E: The average value of the shift amounts d is 0.21 μm or more.

[3.2] Frequency characteristics of ink A droplet discharge device installed in a chamber (thermal chamber) and the ink used in each of the above examples were prepared, and the driving waveform of the piezoelectric element was optimized at 25 ° C. In an environment of 50% RH, for each ink, droplet ejection was performed while changing the frequency (frequency) of the piezo element from all nozzles of the droplet ejection head. The droplet discharge time at each frequency was 20 minutes. The frequency range that can be actually used was evaluated according to the following four-stage criteria, with the number of undischarged nozzles being less than 1% of the total number of nozzles after 20 minutes of discharge being the highest frequency that can be actually used. It can be said that the larger this value, the better the frequency characteristics.
A: 15 kHz or more.
B: 11 kHz or more and less than 15 kHz.
C: 5 kHz or more and less than 11 kHz.
D: Less than 5 kHz.

[3.3] Evaluation of ink storage stability (long-term stability evaluation)
[3.3.1] Sedimentability Each of the inks used in the above examples was placed in a microtube having a height of 3 cm and allowed to stand in an environment of 40 ° C., and the supernatant transparent layer (including metal powder) The time until the thickness of the layer not formed was 2 mm was measured and evaluated according to the following criteria.
A: The period until the thickness of the transparent layer of the supernatant becomes 2 mm is 2 weeks or more.
B: The period until the thickness of the transparent layer of the supernatant becomes 2 mm is 1 week or more and less than 2 weeks.
C: The period until the thickness of the supernatant transparent layer becomes 2 mm is 3 days or more and less than 1 week.
D: The period until the thickness of the transparent layer of the supernatant is 2 mm is less than 3 days.

[3.3.2] Generation of foreign matter (aggregates) on the filter The ink used in each of the above examples was allowed to stand in an environment of 40 ° C. for 60 days, and then a membrane filter having a filtration accuracy of 10 μm was used. 10 mL was passed under reduced pressure. Thereafter, the number of foreign matters (aggregates) derived from the ink present on the filter was counted and evaluated according to the following criteria.
A: Foreign matter (aggregate) is not recognized on the filter.
B: The number of foreign matters (aggregates) present on the filter is 1 or more and 4 or less.
C: The number of foreign matters (aggregates) present on the filter is 5 or more and 29 or less.
D: There are 30 or more foreign substances (aggregates) present on the filter.

[3.4] Rate of increase in viscosity The ink used in each of the above examples was measured in accordance with JIS Z8809 using a vibration viscometer after being left for 30 days in an environment of 60 ° C. The viscosity at 25 ° C. of the ink used in each example was measured, the rate of increase in viscosity immediately after production was determined, and evaluated according to the following criteria.

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

[3.5] Curability About the ink used in each of the above examples, the ink was introduced into an Epson inkjet printer; PM800C, and a diafoil G440E (thickness: 38 μm) manufactured by Mitsubishi Plastics Co., Ltd. was used as the recording medium. Solid printing was performed at an amount of 9 g / m ^2. Immediately after printing, the LED-UV lamp; Foseon RX RXrefly (gap 6 mm, peak wavelength 395 nm, 1000 mW / cm ² ) was used to irradiate ultraviolet rays. It was confirmed whether it was cured or not, and evaluated according to the following five-step criteria. Whether or not the ink was cured was determined by rubbing the surface with a cotton swab and not adhering uncured ink. In addition, whether it corresponds to the irradiation amount of the following AE can be calculated by how many seconds the lamp is irradiated.

A: Cured with an ultraviolet irradiation dose of less than 100 mJ / cm ² .
B: It hardened | cured with the ultraviolet irradiation amount of 100 mJ / cm < ² > or more and less than 200 mJ / cm < ² >.
C: Cured with an ultraviolet irradiation amount of 200 mJ / cm ² or more and less than 500 mJ / cm ² .
D: It hardened | cured with the ultraviolet irradiation amount of 500 mJ / cm < ² > or more and less than 1000 mJ / cm < ² >.
E: It hardens | cures by the ultraviolet irradiation amount of 1000 mJ / cm < ² > or more. Or it does not cure at all.
These results are shown in Tables 8 and 9.

  As is apparent from Table 8, the recorded matter of the present invention is provided with a printing portion having a desired shape with high precision, and has an excellent gloss feeling (each part like a lame as the observation direction changes). The appearance of the reflection state changed greatly, and the appearance of the gloss (shiny) was excellent, and the printed part was excellent in abrasion resistance. In the present invention, the excellent results as described above were obtained regardless of the type of the substrate. Further, as apparent from Table 9, the ink used in the present invention was excellent in droplet ejection stability, storage stability, and curability. On the other hand, in the comparative example, a satisfactory result was 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

Claims (14)

A first ink application step of applying a first ink containing a first polymerizable compound that is polymerized by irradiation of ultraviolet rays to a substrate by an inkjet method;
A first curing step of polymerizing and curing the first polymerizable compound by irradiation with ultraviolet rays to form a first layer;
A second ink application step of applying, to the region where the first layer is formed, a second ink containing a second polymerizable compound and metal powder that is polymerized by irradiation with ultraviolet rays, by an inkjet method;
A second curing step of polymerizing and curing the second polymerizable compound by ultraviolet irradiation to form a second layer;
The amount of the first ink applied per unit area in the region is 2.0 g / m ² or more and 20.0 g / m ² or less;
The time from the landing of the droplet of the first ink to the irradiation of the ultraviolet ray on the droplet is 0.0010 seconds or more and 1.0 seconds or less,
The amount of the second ink applied per unit area in the region is 10% by volume or more and less than 80% by volume with respect to the amount of the first ink applied;
A method for producing a recorded matter, characterized in that the time from the landing of the droplet of the second ink to the irradiation of the ultraviolet ray onto the droplet is 5.0 seconds or more and 60.0 seconds or less.   2. The method for producing a recorded matter according to claim 1, wherein a surface roughness Ra of the first layer formed in the first curing step is 3.0 μm or more and 100 μm or less.   The method for producing a recorded matter according to claim 1 or 2, wherein a droplet amount of the first ink ejected by one ejection operation of the inkjet method is 3 ng or more and 30 ng or less.   The method for producing a recorded matter according to any one of claims 1 to 3, wherein a droplet amount of the second ink ejected by one ejection operation of the ink jet method is 3 ng to 30 ng.   The method for producing a recorded matter according to any one of claims 1 to 4, wherein the metal powder includes a component subjected to a surface treatment with a surface treatment agent as constituent particles.   The method for producing a recorded matter according to claim 5, wherein the surface treatment agent is one or more selected from the group consisting of a fluorine-based silane compound, a fluorine-based phosphate ester, a fluorine-based fatty acid, and an isocyanate compound.   The method for producing a recorded matter according to claim 5 or 6, wherein the metal powder includes, as constituent particles, at least mother particles whose surface is mainly composed of Al and surface-treated with the surface treatment agent.   The method for producing a recorded matter according to any one of claims 1 to 7, wherein the constituent particles of the metal powder have a scaly shape.   The method for producing a recorded matter according to claim 8, wherein the average thickness of the constituent particles of the metal powder is 10 nm to 100 nm.   10. The method for producing a recorded matter according to claim 1, wherein the metal powder has an average particle size of 500 nm to 3.0 μm and a maximum particle size of 5 μm or less.   The method for producing a recorded matter according to any one of claims 1 to 10, wherein each of the first ink and the second ink includes a monomer having an alicyclic structure as the polymerizable compound.   Monomers having the alicyclic structure are tris (2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate, adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl acrylate, Tetramethylpiperidyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, mevalonic acid lactone acrylate, dimethylol tricyclodecane diacrylate, dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, di Cyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate, acryloylmorpholine, tetra The group consisting of drofurfuryl acrylate, cyclohexane spiro-2- (1,3-dioxolan-4-yl) methyl acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate The method for producing recorded matter according to claim 11, comprising one or more selected from the group consisting of:   The first ink and the second ink are both polymerizable compounds other than the monomer having an alicyclic structure, such as phenoxyethyl acrylate, benzyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, The composition according to claim 11 or 12, comprising one or more selected from the group consisting of dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate. A method for producing the recorded matter. The method for producing a recorded matter according to any one of claims 1 to 13, wherein a contact angle of the first ink with respect to the base material is 30 ° or more and 85 ° or less .

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