JP2018115243A - Active energy ray-curable composition, active energy ray-curable ink, composition storage container, method and apparatus for forming two-dimensional or three-dimensional image, two-dimensional or three-dimensional image, structure and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition which has high adhesion to a non-permeable base material such as a PET film, glass and metal, has high dispersibility and dischargeability, and is excellent in print density and curability.SOLUTION: An active energy ray-curable composition is a reactive dispersant which contains a pigment, a dispersion agent and a polymerizable compound, where the dispersion agent is a reactive dispersion agent having a reactive double bond group, and the pigment is a pigment other than white with a number average primary diameter (Dn) of 20 nm or more and 60 nm or less. The active energy ray-curable composition is a reactive dispersant which contains a pigment, a dispersion agent and a polymerizable compound, where the dispersion agent is a reactive dispersion agent having a reactive double bond group, and the pigment is a white pigment with a number average primary diameter (Dn) of 205 nm or more and 280 nm or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an active energy ray curable composition, an active energy ray curable ink, a composition container, a two-dimensional or three-dimensional image forming method and apparatus, a two-dimensional or three-dimensional image, a structure, and It relates to molded products.

  The active energy ray curable ink has less odor and quick-drying than solvent-based inks, and therefore can be suitably recorded on a recording medium that does not absorb ink.

  The active energy ray-curable ink is obtained by combining monomers in the active energy ray-curable ink using several kinds of polymerization initiators having different absorption wavelengths according to the type of light source such as a mercury lamp or a metal halide lamp. Harden.

In recent years, the use of active energy ray-curable ink has been expanded, and the demand for printing on various types of substrates has been increasing. In particular, there is an increasing demand for substrates such as glass, metal, and PET films. The adhesion of the printed image is kept good for the base material into which the active energy ray curable ink permeates or even slightly dissolves, but the glass, metal, and PET film are non-penetrating and non-dissolving so that they adhere closely. It was difficult to satisfy the sex.
As a countermeasure for this, a technique has been established to ensure adhesion by printing an image after printing a primer corresponding to these difficult-to-adhere substrates.

  However, the addition of a primer layer has many disadvantages that increase the number of processes and increase the cost. Therefore, there is no primer layer that can simplify the printing process. There was a need for mold inks. In addition, even when a certain level of adhesion can be secured with a clear active energy ray-curable ink that does not contain a colorant, if a colorant is contained, the adhesiveness tends to decrease rapidly, and an improvement in adhesion is desired. It was.

  In a color ink (including white), when a colorant such as a pigment is contained in the ink, it is necessary to contain a pigment dispersant in order to disperse the colorant cleanly in the ink. However, it has been confirmed that the component dissolved in the monomer that is not adsorbed to the pigment by such a pigment dispersant gathers preferentially at the interface with the ink layer at the time of curing and lowers the adhesion. To achieve both pigment dispersibility and substrate adhesion in color inks, use a dispersant that efficiently adsorbs the pigment dispersant to the pigment, minimizes the amount of free dispersant, and does not adversely affect the adhesion as much as possible. It is considered useful.

It has been proposed to use a reactive dispersant as such a dispersant. Patent Document 1 in combination with glass flake pigment, Patent Document 2 in which a manufacturing method is defined in combination with metal oxide particles such as titanium oxide, a specific structure reactive dispersant and 200 nm or less Patent Document 3 in which the metal oxide particles are combined.
However, in any case, adhesion to non-penetrating substrates such as PET, glass, and metal cannot be solved.

On the other hand, the following proposals have been made regarding the amount of dispersant adsorbed on the pigment.
Patent Document 4 devises a method for measuring the adsorption amount of a dispersant to a solid dispersed in a dispersion medium using an NMR spectrum. In Patent Document 5, when carbon black is used as a pigment, an excess dispersant exceeding the saturated adsorption amount is added to improve dispersibility. Patent Document 6 provides a color filter dispersion having excellent dispersibility and light resistance by controlling the amount of dispersant adsorbed to 1.0 to 5.0 mg / m ² with respect to the pigment. Patent Document 7 proposes a UV inkjet ink in which the liberated polymer dispersant not adsorbed on the pigment is 1.0 mass% or less of the total ink. In Patent Document 8, (the ratio of the polymer dispersant to the pigment in the ink excluding the sediment after centrifugation) / (ratio of the polymer dispersant to the pigment in the ink before centrifugation) is 1.0 to An ink-jet ink of 1.5 has been proposed.

However, none of them has a problem of dispersibility and no problem of adhesion. In order to improve the adhesion, simply reducing the amount of the pigment dispersant and reducing the amount of the free dispersant reduces the dispersibility, and even if good dispersibility is initially obtained, Aggregation occurs during storage. Furthermore, if there is a problem in adhesion and dispersibility, the print density and curability deteriorate.
On the other hand, if the pigment dispersibility is to be ensured, the amount of free dispersant will inevitably increase, and the adhesion will be reduced. Until now, no active energy ray-curable composition has been proposed which can achieve both pigment dispersibility and adhesion without primer on non-penetrating substrates such as PET film, glass and metal.

  For this reason, an active energy ray-curable composition having high adhesion to a non-penetrating substrate, good dispersibility, and excellent print density and curability is desired.

  The present invention has been made in view of the above problems, and is an active energy ray-curable composition that has high adhesion to a non-penetrating substrate, has good dispersibility, and is excellent in print density and curability. The purpose is to provide goods.

  In order to solve the above problems, the active energy ray-curable composition of the present invention contains a pigment, a dispersant and a polymerizable compound, and the dispersant is a reactive dispersant having a reactive double bond group. The pigment is a non-white pigment having a number average primary particle size (Dn) of 20 nm to 60 nm.

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type composition which has high adhesiveness also with respect to a non-penetrating base material, has favorable dispersibility, and is excellent in printing density and curability can be provided.

1 is a schematic diagram illustrating an example of an image forming apparatus according to the present invention. It is the schematic which shows the other example of the image forming apparatus which concerns on this invention. It is the schematic which shows the other example of the image forming apparatus which concerns on this invention. It is an adhesion rank sample of JIS-K5600.

  Hereinafter, active energy ray-curable composition, active energy ray-curable ink, composition container, two-dimensional or three-dimensional image forming method and forming apparatus, two-dimensional or three-dimensional image, structure according to the present invention The molded product will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like can be changed within a range that can be conceived by those skilled in the art, and any aspect is possible. As long as the functions and effects of the present invention are exhibited, the scope of the present invention is included.

(Active energy ray-curable composition)
The active energy ray-curable composition of the present invention contains a pigment, a dispersant, and a polymerizable compound, the dispersant is a reactive dispersant having a reactive double bond group, and the pigment has a number average primary particle. It is a pigment other than white having a diameter (Dn) of 20 nm or more and 60 nm or less.
The active energy ray-curable composition of the present invention contains a pigment, a dispersant and a polymerizable compound, the dispersant is a reactive dispersant having a reactive double bond group, and the pigment has a number average. It is a white pigment having a primary particle size (Dn) of 205 nm or more and 280 nm or less.

In the present invention, since the dispersant is a reactive dispersant having a reactive double bond group, the following effects can be expected.
(1) Since the free dispersant dissolved in the monomer reacts with the monomer at the time of curing, it is integrated with the cured film before moving to the substrate interface. For this reason, a dispersing agent does not collect in a base-material interface, and adhesiveness is not reduced.
(2) Since the dispersant present in the portion in contact with the base material also reacts and integrates with the film, the entire film is in close contact with the base material and does not decrease the close contact.
(3) Since the reactive dispersant adsorbed on the pigment also reacts and integrates, the pigment present on the adhesion surface is also integrated and does not deteriorate the adhesion.

  On the other hand, the dispersant having no reactive group is pushed out from the cured film during curing and gathers in the vicinity of the interface with the base material to reduce the adhesion.

  Also, in order to achieve both pigment dispersibility and substrate adhesion, it is necessary to efficiently adsorb the pigment dispersant to the pigment, reduce the amount of free dispersant as much as possible, and not adversely affect the adhesion as much as possible. is important. However, simply reducing the prescription amount of the pigment dispersant and reducing the amount of the free dispersant reduces the dispersibility. Even if good dispersibility is obtained in the initial stage, aggregation occurs during long-term storage. .

  In the present invention, a reactive dispersant is used, and the number average primary particle size (Dn) as a pigment is in a predetermined range. Thereby, the surface area of a pigment can be made into a desired range, and the quantity which a reactive dispersing agent liberates can be controlled. For this reason, the minimum necessary reactive dispersant can be efficiently and firmly adsorbed to the pigment, and good dispersibility can be maintained while suppressing the decrease in adhesion due to the free dispersant. Can do. In addition, because the adsorption power of the dispersant to the pigment is strong, it is possible to achieve dispersion stabilization with a small amount of dispersant, and since it is difficult for the dispersant to be detached, the amount of free dispersant not adsorbed to the pigment can be reduced. It can be less than usual.

<Dispersant>
As the dispersant, a reactive dispersant having a reactive double bond group is used. The reactive dispersant is sometimes referred to as a polymerizable group-containing reactive dispersant.
The reactive dispersant preferably contains a tertiary amino group-containing polyurethane.
The reactive dispersant can be appropriately changed, and for example, Solsperse X300 manufactured by Nippon Lubrizol Corporation can be used.

  The content of the reactive dispersant can be appropriately changed. For example, the content of the reactive dispersant is preferably 0.1 to 0.6 parts by mass with respect to the active energy ray-curable composition.

<Pigment>
The pigment of the present invention includes at least a pigment other than white having a number average primary particle size (Dn) of 20 nm to 60 nm, or a white pigment having a number average primary particle size (Dn) of 205 nm to 280 nm.
As content of the said pigment, 0.1-20 mass% is preferable with respect to the active energy ray hardening-type composition whole quantity.

<< Pigments other than white >>
As the pigment other than white, a pigment having a number average primary particle size (Dn) of 20 nm to 60 nm is used. By setting the number average primary particle size (Dn) of pigments other than white to 20 nm or more and 60 nm or less, good print density and dispersibility can be obtained. If it is smaller than 20 nm, the cohesive force between the particles becomes high and the dispersibility is extremely lowered. If it is larger than 60 nm, the predetermined concentration cannot be obtained.
The number average primary particle size (Dn) of the pigments other than white is preferably 40 nm or more and 60 nm or less, and more preferably 40 nm or more and 55 nm or less.

  Although it does not restrict | limit especially as pigments other than white, For example, carbon black, a cyan pigment, a cyan pigment derivative, etc. are mentioned.

Examples of the cyan pigment include C.I. I. And phthalocyanine pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, and 15: 6, and alkali blue pigments such as Pigment Blue 18 and 56.
Examples of the cyan pigment derivative include an acidic type having a carboxyl group, a sulfone group, and a nitro group at the terminal group, and a basic type having an amino group and an acid amide group.

In addition to these, various pigments and dyes that impart black, magenta, yellow, green, orange, glossy colors such as gold and silver, and the like can be used.
In addition, organic pigments can be used. Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, and quinacridone pigments. , Dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments and other polycyclic pigments, dye chelates (eg basic dye chelates, acid dye chelates), dye lakes (basic dye lakes, acid dyes) Type lake), nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.
These may be used alone or in combination.

  The content of the pigment other than white is preferably 1% by mass or more and 10% by mass or less, and more preferably 2% by mass or more and 5% by mass or less with respect to the total amount of the active energy ray-curable composition. When the content is 1% by mass or more, the print density can be improved, and when the content is 10% by mass or less, the increase in viscosity can be suppressed and the discharge performance can be improved.

Further, the content A of the reactive dispersant adsorbed on the pigment is 30 to 120 mg per 1 g of the pigment, and the content B of the reactive dispersant not adsorbed on the pigment is the reaction. It is preferable that it is 10-50 mass% of the total amount of anionic dispersant.
As described above, the reactive dispersant used in the present invention has an effect of not lowering the adhesion as compared with a general dispersant having no reactive group, but the content of the reactive dispersant is as described above. When satisfy | filling a predetermined range, especially adhesiveness and a dispersibility can be improved simultaneously.

When the content A of the reactive dispersant adsorbed on the pigment is less than 30 mg per 1 g of the pigment, the affinity between the pigment and the dispersion medium cannot be maintained and the pigment dispersibility may be lowered, and the content is more than 120 mg. In some cases, the liquid viscosity is increased and the dischargeability is lowered.
The content A of the reactive dispersant adsorbed on the pigment is more preferably 50 to 100 mg per 1 g of the pigment.

Moreover, it is preferable that content B of the said reactive dispersant which is not adsorb | sucking to a pigment is 10-50 mass% of the said reactive dispersant whole quantity. The dispersant that is not adsorbed on the pigment preferably contains an amount within a certain range in order to maintain a balance with the amount adsorbed on the pigment. When the amount is less than 10% by mass, the amount of the dispersant adsorbed on the pigment tends to shift to the dispersion medium side, and the amount of the dispersant adsorbed on the pigment may decrease. When the amount exceeds 50% by mass, the balance with the amount adsorbed on the pigment cannot be maintained, and the dispersant that is pushed out to the substrate interface before the reaction with the monomer starts to increase or the reaction with the monomer begins. May be present and adhesion may be reduced.
The content of the reactive dispersant adsorbed on the pigment and the content of the reactive dispersant not adsorbed on the pigment can be determined by a measurement method described later.

  When a pigment other than white is included, the volume average particle diameter (Dv) of the active energy ray-curable composition is preferably 100 nm or more and 150 nm or less, and the ratio of the particle diameter of 50 nm or less is 10% by volume or less. The ratio of the diameter of 230 nm or more is preferably 10% by volume or less. If the volume average particle size is smaller than 100 nm, the print density may be reduced. If the volume average particle size is larger than 150 nm, head clogging is likely to occur when recording using an inkjet system, resulting in a decrease in ejection stability. There is.

  Further, when the ratio of the particle diameter of 50 nm or less is 10% by volume or less and the ratio of the particle diameter of 230 nm or more is 10% by volume or less, the adhesion with the substrate can be improved.

  As a method for measuring the volume average particle diameter (Dv) of the active energy ray-curable composition, the active energy ray-curable composition is diluted about 100 times with phenoxyethyl acrylate, and a particle size distribution meter (apparatus name: UPA150, Nikkiso Co., Ltd.).

  The volume average particle size of the active energy ray curable composition means a volume average particle size obtained by subjecting the active energy ray curable composition itself to measurement, and the active energy ray curable composition contains This corresponds to the particle size of a particulate object (specifically, a pigment dispersion containing a pigment).

As the print density, when a cured product (solid image) having an average thickness of 10 μm is produced on a transparent substrate (for example, a film) using the active energy ray-curable composition, the print density is 1.4 or more. Preferably, 1.5 or more is more preferable. At this time, a cured product is produced by irradiating active energy rays with an illuminance of 1 W / cm ² and an irradiation amount of 500 mJ / cm ² .

  As the average thickness, for example, a contact type (pointer type) or eddy current type film thickness meter, for example, an electronic micrometer (manufactured by Anritsu Co., Ltd.) is used, and the average thickness is obtained from an average value of 10 film thicknesses. Can do.

  The print density can be obtained by measuring the density using a reflection spectral densitometer (device name: X-Rite 939, manufactured by X-Rite).

  When a pigment other than white is included, the particle size ratio (Dv / Dn) between the volume average particle size (Dv) of the active energy ray-curable composition and the number average primary particle size (Dn) of the pigment is: It is preferably 1.5 or more and 3.0 or less.

As a pigment other than white, carbon black can be preferably used, and examples thereof include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black and the like.
The carbon black used in the present invention preferably contains an oxidized carbon black having a DBP oil absorption of 35 g / 100 g or more and 55 g / 100 g or less and a pH of 3.5 or less. When the DBP oil absorption is in the above range, the print density can be easily set to 1.4 or more, a good print density can be obtained, and the dispersibility can be improved.

  Oxidized carbon black having a pH of 3.5 or less has many functional groups such as quinone, carboxyl, aldehyde, lactone, and phenol, and can increase the adsorptivity of the dispersant. Thereby, it is easy to make the print density 1.4 or more, a good print density can be obtained, and the dispersibility can be improved.

Examples of carbon blacks that can be suitably used include, for example, Special Black 250 from Orion (Degussa), MOGUL-E from Cabot, and the like.
These carbon blacks are described as examples of carbon blacks that can be used in Japanese Patent Application Laid-Open No. 2012-144681, etc., and are used in Examples in Japanese Patent Application Laid-Open No. 2012-031254.
However, even when the carbon black described in JP 2012-144681 A and JP 2012-031254 A is used, the combination with other materials such as a reactive dispersant, the difference in prescription amount, and construction method Thus, the desired effect in the present invention cannot be obtained. In particular, it is difficult to satisfy the preferred range of the amount of dispersant adsorption in the present invention.

Two or more types of the carbon black may be mixed and used.
The pigment other than white is preferably present as a pigment dispersion containing the pigment in the active energy ray-curable composition.

<< white pigment >>
As the white pigment, a pigment having a number average primary particle size (Dn) of 205 nm or more and 280 nm or less is used. When the number average primary particle size (Dn) of the white pigment is 205 nm or more and 280 nm or less, good concealability (print density) and dispersibility can be obtained. If the number average primary particle size (Dn) of the white pigment is smaller than 205 nm, good concealing property (printing density) cannot be obtained, and if it is larger than 280 nm, it tends to settle and the dispersibility is lowered.

  Examples of white pigments include sulfates of alkaline earth metals such as titanium oxide and barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as finely divided silicic acid and synthetic silicate, calcium silicate , Alumina, hydrated alumina, zinc oxide, talc, clay and the like. These may be used alone or in combination.

  As content of a white pigment, 10 mass% or more and 20 mass% or less are preferable with respect to the active energy ray hardening-type composition whole quantity. When the content is 10% by mass or more, concealability can be improved, and when the content is 20% by mass or less, an increase in viscosity can be suppressed and dischargeability can be improved.

The content C of the reactive dispersant adsorbed on the pigment is 2 to 50 mg per 1 g of the pigment, and the content D of the reactive dispersant not adsorbed on the pigment is the reactive dispersion. It is preferably 5 to 40% by mass of the total amount of the agent.
As described above, the reactive dispersant used in the present invention has an effect of not lowering the adhesion as compared with a general dispersant having no reactive group, but the content of the reactive dispersant is as described above. When satisfy | filling a predetermined range, especially adhesiveness and a dispersibility can be improved simultaneously.

If the content C of the reactive dispersant adsorbed on the pigment is less than 2 mg per 1 g of the pigment, the affinity between the pigment and the dispersion medium cannot be maintained and the pigment dispersibility may be lowered, and the content is more than 50 mg. In some cases, the liquid viscosity is increased and the dischargeability is lowered.
The content C of the reactive dispersant adsorbed on the pigment is more preferably 5 to 30 mg per 1 g of the pigment.

Moreover, it is preferable that content D of the said reactive dispersant which is not adsorb | sucking to a pigment is 5-40 mass% of the said reactive dispersant whole quantity. The dispersant that is not adsorbed on the pigment preferably contains an amount within a certain range in order to maintain a balance with the amount adsorbed on the pigment. When the amount is less than 5% by mass, the amount of the dispersant adsorbed on the pigment tends to shift to the dispersion medium side, and the amount of the dispersant adsorbed on the pigment may decrease. When the amount exceeds 40% by mass, the balance with the amount adsorbed on the pigment cannot be maintained, the viscosity of the dispersion increases, and the dispersant pushed out to the substrate interface before the reaction with the monomer starts. May be present and adhesion may be reduced.
The content of the reactive dispersant adsorbed on the pigment and the content of the reactive dispersant not adsorbed on the pigment can be determined by a measurement method described later.

  In the case of containing a white pigment, the active energy ray-curable composition preferably has a volume average particle diameter (Dv) of 210 nm or more and 300 nm or less, a ratio of a particle diameter of 150 nm or less is 10% by volume or less, and a particle diameter of 380 nm or more. Is preferably 10% by volume or less. When the volume average particle size is smaller than 210 nm, the concealability (print density) may be lowered. When the volume average particle size is larger than 300 nm, head clogging is likely to occur when recording using an ink jet system, and ejection stability. May decrease.

Further, when the ratio of the particle diameter of 150 nm or less is 10% by volume or less and the ratio of the particle diameter of 380 nm or more is 10% by volume or less, the adhesion with the substrate can be improved.
With the particle size distribution as described above, it is possible to achieve both settling properties, ejection stability, and concealment properties (print density).

  As the volume average particle size, the active energy ray-curable composition is diluted about 100 times with phenoxyethyl acrylate in the same manner as the above-mentioned pigments other than white, and a particle size distribution meter (device name: UPA150, Nikkiso Co., Ltd.). And the volume average particle size of the active energy ray-curable composition can be determined by measuring the volume average particle size of the active energy ray-curable composition.

  The volume average particle size of the active energy ray curable composition means a volume average particle size obtained by subjecting the active energy ray curable composition itself to measurement, and the active energy ray curable composition contains This corresponds to the particle size of a particulate object (specifically, a pigment dispersion containing a pigment).

Concealability (printing density) is preferably 81% or more, and 84% or more when a cured product having an average thickness of 10 μm is produced on a transparent substrate using the active energy ray-curable composition. Is more preferable, and 85% or more and 100% or less is particularly preferable. At this time, a cured product is produced by irradiating active energy rays with an illuminance of 1 W / cm ² and an irradiation amount of 500 mJ / cm ² .

  The average thickness is measured using, for example, a contact type (pointer type) or eddy current type film thickness meter, for example, an electronic micrometer (manufactured by Anritsu Co., Ltd.), and obtained from an average value of 10 film thicknesses. be able to.

  As the concealment rate, black paper (trade name: Extra Black, Takeo Co., Ltd., concentration: 1.65) is provided on the side opposite to the side on which the obtained image (cured product) of the transparent substrate is formed. The density of the image (cured product) with respect to black is measured using a reflection spectral densitometer (device name: X-Rite 939, manufactured by X-Rite), and can be calculated based on the following formula.

  Concealment rate (%) = [1− (density of image (cured product) / density of black paper (1.65))] × 100

  When a white pigment is included, the particle size ratio (Dv / Dn) between the volume average particle size (Dv) of the active energy ray-curable composition and the number average primary particle size (Dn) of the pigment is 1. It is preferably 0 or more and 1.2 or less, and more preferably 1.0 or more and 1.1 or less.

  The titanium oxide is preferably rutile type titanium oxide. In the case of rutile titanium oxide, it is possible to suppress a decrease in coating film stability due to photoactivity.

The titanium oxide preferably contains alumina (Al ₂ O ₃ ), silica (SiO ₂ ), zirconium oxide (ZrO ₂ ), zinc oxide (ZnO) or the like as a surface treatment agent. These may be single or plural. Moreover, it is more preferable that the surface treatment which can make the surface of a pigment hydrophilic is made. By making the surface of the pigment hydrophilic, a smaller amount of the reactive dispersant can be efficiently adsorbed to the pigment with a strong adsorption force, so that the amount of the free dispersant can be reduced and the adhesion is improved.

  Furthermore, these surface treatments have an effect of preventing the photocatalytic activity of titanium oxide, and the light resistance of the resulting cured film can be improved.

  The surface treatment method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include known methods such as pigment derivative treatment, resin modification, oxidation treatment, and plasma treatment.

As the titanium oxide, can be a commercially available product, The commercially available product, trade name: TCR-52 (number-average primary particle diameter: 230 nm, surface _treatment: Al _{2 O} 3), trade name: S3618 ( Number average primary particle size: 230 nm, surface treatment: Al ₂ O ₃ ), trade name: D-918 (number average primary particle size: 260 nm, surface treatment: Al ₂ O ₃ , SiO ₂ , ZrO ₂ ) (above, 堺Chemical Industry Co., Ltd.), trade name: JR405 (number average primary particle size: 210 nm, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ ), trade name: JR403 (number average primary particle size: 250 nm, Teika Corporation) Ltd., surface _{treatment: Al 2 O 3, SiO 2} ), trade name: JR701 (number average primary particle diameter: 270 nm, manufactured by Tayca Co., surface _{treatment: Al 2 O 3, SiO 2} , Zn ), Trade name: JR (number average primary particle size: 270nm, Tayca Co., Ltd., surface treatment: no), and the like. These may be used alone or in combination of two or more.

As said titanium oxide, what is described in Unexamined-Japanese-Patent No. 2012-214534 and Unexamined-Japanese-Patent No. 2014-185235 can be used conveniently, for example.
However, even when using the titanium oxide described in JP 2012-214534 A and JP 2014-185235 A, the combination with other materials such as a reactive dispersant, the difference in prescription amount, and construction method Thus, the desired effect in the present invention cannot be obtained. In particular, it is difficult to satisfy the preferred range of the amount of dispersant adsorption in the present invention.

  The pigment is preferably present as a pigment dispersion containing the pigment in the active energy ray-curable composition.

<< Measurement Method of Amount of Dispersant Adsorbed on Pigment and Amount of Unadsorbed Dispersant >>
The amount of the dispersant adsorbed on the pigment can be measured by the following method. Weigh 1.5 g of ink (active energy ray-curable composition) into a 1 ml sample holder for centrifugation. This is centrifuged at 10,000 rpm for 1 hour, and the supernatant is removed. Add approximately the same amount of acetone to the amount removed, stir with a spatula, perform centrifugation in the same manner, and perform 4 times in total. This is completely dried with a vacuum dryer. The dry sample 100 mg is accurately weighed in an aluminum cup, heated at 400 ° C. for 2 hours, and the remaining amount is measured.

[Amount of dispersant adsorbed on 1 g of pigment]
= (Weight loss after heating (mg)-pigment weight loss (mg)) / residual amount after heating (mg)
* Pigment single weight loss (mg) is the weight loss (mg) when 100 mg pigment alone is heated at 400 ° C. for 2 hours.

The amount of the dispersant not adsorbed on the pigment (the amount of the unadsorbed dispersant) is obtained as follows when the input amount is known.
(Dispersant prescription amount (parts by mass) / pigment prescription amount (parts by mass)) × 1000 (mg) −dispersant amount adsorbed on 1 g of pigment (mg)

  On the other hand, when the input amount is unknown, it can be obtained, for example, by collecting the supernatant of the above method and measuring it by liquid chromatography or the like.

<Polymerizable compound>
The polymerizable compound used in the present invention preferably contains a monofunctional (meth) acrylate having a cyclic ether structure. The polymerizable compound used in the present invention may contain other polymerizable compounds in addition to this, and the other polymerizable compound is not particularly limited, but for example, a polymerizable unsaturated monomer compound And polymerizable oligomers.

<< Monofunctional (meth) acrylate having cyclic ether structure >>
By including a monofunctional (meth) acrylate having a cyclic ether structure, the adhesion to non-penetrating substrates such as metals, glass, and PET films is further improved in combination with the effect of the reactive dispersant. By having a cyclic ether structure, polarity is increased, adhesion to these polar base materials is increased, and by being monofunctional, curing shrinkage is small, and internal stress is reduced to further increase adhesion. Is presumed to be one of the reasons for improving the adhesion. Further, homopolymers having a glass transition temperature Tg of 0 ° C. or higher are particularly preferred.

  Examples of the monofunctional (meth) acrylate having a cyclic ether structure include acryloylmorpholine (for example, ACMO manufactured by Kojin Co., Ltd.), cyclic trimethylpropane formal acrylate (for example, Biscoat # 200 manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl acrylate (for example, Kyoeisha Chemical Co., Ltd.), isobornyl acrylate (for example, IBXA manufactured by Osaka Organic Chemical Co., Ltd.), etc.

  The content of the monofunctional (meth) acrylate having a cyclic ether structure can be appropriately changed, but is preferably 8% by mass or more and 40% by mass or less based on the total amount of the active energy ray-curable composition, 10 mass% or more and 30 mass% or less are more preferable.

<< Polymerizable unsaturated monomer compound >>
There is no restriction | limiting in particular as said polymerizable unsaturated monomer compound, According to the objective, it can select suitably. Examples thereof include a monofunctional polymerizable unsaturated monomer compound, a bifunctional polymerizable unsaturated monomer compound, a trifunctional polymerizable unsaturated monomer compound, and a tetrafunctional or higher functional unsaturated monomer compound. These may be used alone or in combination of two or more.

  Examples of the monofunctional polymerizable unsaturated monomer compound include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, phenoxyethyl acrylate, isobornyl acrylate, Examples include phenyl glycol monoacrylate, cyclohexyl acrylate, acryloyl morpholine, tetrahydrofurfuryl acrylate, 4-hydroxybutyl acrylate, 2-methyl-2-ethyl-1,3-dioxolan-4-ylmethyl acrylate, and the like. These may be used alone or in combination of two or more.

  Examples of the bifunctional polymerizable unsaturated monomer compound include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, and tetraethylene. Examples include glycol diacrylate and dimethylol tricyclodecane diacrylate. These may be used alone or in combination of two or more.

  Examples of the trifunctional polymerizable unsaturated monomer compound include trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and the like. These may be used alone or in combination of two or more.

  Examples of the tetrafunctional or higher polymerizable unsaturated monomer compound include pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.

  The polymerizable unsaturated monomer compounds may be used singly or in combination of two or more, and two or more different types of polymerizable unsaturated monomer compounds may be used in combination.

  As the polymerizable unsaturated monomer compound, the polyfunctional polymerizable unsaturated monomer compound can increase the curing speed more than the monofunctional polymerizable unsaturated monomer compound, but the viscosity of the composition is increased. Or volume shrinkage may become large, and it tends to be worse in terms of adhesion. Therefore, it is preferable to use a monomer having a small shrinkage rate or to reduce the content of the polyfunctional monomer as much as possible.

  The volume shrinkage of an image cured with the polymerizable unsaturated monomer compound is preferably 15% by volume or less, and more preferably 8% by volume or less.

  There is no restriction | limiting in particular as skin irritation (PI) in the said polymerizable unsaturated monomer compound, Although it can select suitably according to the objective, 1.0 or less is preferable. When the skin irritation is 1.0 or less, irritation to the skin can be reduced, and safety can be improved.

  As the hue of the polymerizable unsaturated monomer compound, the Gardner gray scale is preferably 2 or less, and more preferably colorless and transparent. When the Gardner gray scale is 2 or less, the color of the image portion can be prevented from changing. In addition, as said Gardner gray scale, it can measure according to the color test method-Gardner color number test method of a JIS-0071-2 chemical product.

  As content of the said polymerizable unsaturated monomer compound, 50 mass% or more and 90 mass% or less are preferable with respect to the active energy ray hardening-type composition whole quantity, and 65 mass% or more and 85 mass% or less are more preferable.

<< polymerizable oligomer >>
The polymerizable oligomer preferably has one or more ethylenically unsaturated double bonds. The term “oligomer” means a polymer having 2 to 20 repeating monomer structural units.

  There is no restriction | limiting in particular as a weight average molecular weight of the said polymerizable oligomer, According to the objective, it can select suitably, 1,000 or more and 30,000 or less are preferable in polystyrene conversion, 5,000 or more and 20,000 or less Is more preferable. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

  Examples of the polymerizable oligomer include urethane acrylate oligomers (eg, aromatic urethane acrylate oligomers, aliphatic urethane acrylate oligomers), epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers. These may be used alone or in combination of two or more. Among these, an oligomer having 2 to 5 unsaturated carbon-carbon bonds is preferable, and an oligomer having 2 unsaturated carbon-carbon bonds is more preferable. When the number of unsaturated carbon-carbon bonds is 2 or more and 5 or less, good curability can be obtained.

Commercially available products can be used as the polymerizable oligomer. Examples of the commercially available products include UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 3200B, UV-3300B, UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, UT-5454; Sartomer CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E 5, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN968, CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972, CN973, CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982E75, CN982E N985, CN985B88, CN986, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, C9090, CN9013, C9090 CN9026, CN9028, CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, CN9788, CN9873; EBECRYL210, EBECRYL220L, EBECRYL220L, 5129, EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL873, EBECRYL873 These may be used alone or in combination of two or more.
Moreover, a synthetic product obtained by synthesis can be used instead of a commercial product, and a synthetic product and a commercial product can be used in combination.

  There is no restriction | limiting in particular as skin irritation (PI) in the said polymeric oligomer, Although it can select suitably according to the objective, 1.0 or less is preferable. When the skin irritation is 1.0 or less, irritation to the skin can be reduced, and safety can be improved.

  As the hue of the polymerizable oligomer, the Gardner gray scale is preferably 2 or less, and more preferably colorless and transparent. When the Gardner gray scale is 2 or less, the color of the image portion can be prevented from changing. In addition, as said Gardner gray scale, it can measure according to the color test method-Gardner color number test method of a JIS-0071-2 chemical product.

  The content of the polymerizable oligomer is preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, and more preferably 5% by mass or less with respect to the total amount of the active energy ray-curable composition. Particularly preferred. When the content is 10% by mass or less, the hardness of the obtained cured product can be increased.

<Polymerization initiator>
The polymerization initiator is not particularly limited as long as it can generate active species such as radicals and cations by the energy of active energy rays and initiate polymerization of a polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators and cationic polymerization initiators may be used singly or in combination of two or more, and among them, it is preferable to use a radical polymerization initiator.

  Moreover, as content of the said polymerization initiator, in order to obtain sufficient hardening rate, 5 mass% or more and 20 mass% or less are preferable with respect to the active energy ray hardening-type composition whole quantity.

  Examples of the radical polymerization initiator include aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and the like. Ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds. These may be used alone or in combination of two or more.

  Among these, it is preferable to select according to the wavelength characteristics of an exposure lamp for curing such as a mercury lamp, a metal halide lamp, and a UV-LED lamp, and a thio compound is preferable because it is less susceptible to oxygen inhibition during a thin film, and a thioxanthone compound (Thioxanthone polymerization initiator) is more preferable.

  Commercially available products may be used as the polymerization initiator. Examples of the commercially available products include BASF's Irgacure 819, Irgacure 369, Irgacure 907, Darocur ITX, Lucirin TPO, and Vacure 10 from Stauffer Chemical. 30 or the like. These may be used alone or in combination of two or more.

  As the thioxanthone polymerization initiator, a commercially available product can be used. Examples of the commercially available product include Speedcure DETX (2,4-diethylthioxanthone), Speedcure ITX (2-isopropylthioxanthone) (hereinafter referred to as Lambson). KAYACURE DETX-S (2,4-diethylthioxanthone) (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  The polymerization initiator includes (i) high absorption efficiency of active energy rays, (ii) high solubility in the polymerizable unsaturated monomer compound, (iii) low odor, yellowing, and toxicity. (Iv) Those having characteristics such as not causing a dark reaction are preferable.

In addition to the polymerization initiator, a polymerization accelerator can be used in combination.
The polymerization accelerator is not particularly limited. For example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and amine compounds such as butoxyethyl p-dimethylaminobenzoate. These may be used alone or in combination of two or more.

  When a mixture of the polymerizable unsaturated monomer compound and the polymerization initiator is irradiated with active energy rays (ultraviolet rays), the polymerization initiator generates radicals as shown in the following formulas (I) and (II). generate. The radical causes an addition reaction of the polymerizable unsaturated monomer compound or the polymerizable oligomer to a polymerizable double bond. Further radicals are generated by the addition reaction, and by repeating the addition reaction to the polymerizable double bond of the other polymerizable unsaturated monomer compound or the polymerizable oligomer, the polymerization reaction is performed as shown in the following formula (III). proceed.

  When the hydrogen abstraction type benzophenone polymerization initiator of the formula (I) is used, the reaction may be slowed by the polymerization initiator alone, so the reactivity is increased by using an amine sensitizer in combination. It is preferable. By containing an amine compound that is a polymerization accelerator, there is an effect of supplying hydrogen to the polymerization initiator by a hydrogen abstraction action and an effect of preventing reaction inhibition due to oxygen in the air. In the formulas (I) to (III), R represents an alkyl group, A represents an acrylic monomer main skeleton, and n represents an integer.

<Other ingredients>
The active energy ray-curable composition of the present invention may contain other known components as necessary. Other components are not particularly limited. For example, conventionally known surfactants, polymerization inhibitors, organic solvents, leveling agents, antifoaming agents, fluorescent whitening agents, penetration enhancers, wetting agents (humectants) ), Fixing agents, viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusting agents, and thickeners.

<< Polymerization inhibitor >>
Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methoquinone, 2,2′-dihydroxy-3,3′-di ( α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, p-benzoquinone, di-t-butyldiphenylamine, 9,10-di-n-butoxycyantracene, 4,4 ′-[1,10-dioxo-1 , 10-decandiylbis (oxy)] bis [2,2,6,6-tetramethyl] -1-piperidinyloxy, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol and the like. It is done.

  As content of the said polymerization inhibitor, 0.005 mass% or more and 3 mass% or less are preferable with respect to the polymerization initiator whole quantity. When the content is 0.005% by mass or more, storage stability can be improved, an increase in viscosity can be suppressed under a high temperature environment, and when it is 3% by mass or less, curability can be improved.

<< Surfactant >>
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, a higher fatty acid type surfactant, a silicone type surfactant, a fluorine-type surfactant, etc. are mentioned.

  As content of the said surfactant, 0.1 mass% or more and 3 mass% or less are preferable with respect to the active energy ray hardening-type composition whole quantity, and 0.2 mass% or more and 1 mass% or less are more preferable. When the content is 0.1% by mass or more, wettability can be improved, and when it is 3% by mass or less, curability can be improved. When the content is within a more preferable range, wettability and leveling properties can be improved.

<< Organic solvent >>
The active energy ray-curable composition of the present invention may contain an organic solvent, but it is preferable not to contain it if possible. By not containing organic solvent (for example, VOC (Volatile Organic Compounds) free), there is no residue of volatile organic solvent in the cured film, it is possible to obtain printing site safety and prevent environmental pollution. It becomes. The “organic solvent” means what is generally called a volatile organic compound (VOC), and examples thereof include ether, ketone, xylene, ethyl acetate, cyclohexanone, toluene and the like. It should be distinguished from the functional monomer. Further, “does not contain” an organic solvent means that it does not contain substantially, and its content is preferably less than 0.1% by mass.

<Method for producing active energy ray-curable composition>
As a method for producing the active energy ray-curable composition, a dispersion machine using a pigment, if necessary, a dispersant, a polymerizable unsaturated monomer, and the like using a medium such as a ball mill, a kitty mill, a disk mill, a pin mill, or a dyno mill. The pigment dispersion can be prepared by mixing the mixture with a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a surfactant, and the like. Further, a medialess dispersion device such as a disper or a homogenizer may be used.

  The absorbance characteristics differ depending on the difference in these materials, content, dispersion method, etc., and therefore, in order to obtain the active energy ray-curable composition having the predetermined absorbance of the present invention, an appropriate material is selected. , It is necessary to optimize the content and prepare the dispersion method and the ink adjustment method under the optimum conditions.

<Viscosity>
The viscosity of the active energy ray-curable composition of the present invention may be appropriately adjusted according to the use and application means, and is not particularly limited. For example, when applying a discharge means that discharges the composition from a nozzle The viscosity in the range of 20 ° C. to 65 ° C., desirably the viscosity at 25 ° C. is preferably 3 to 40 mPa · s, more preferably 5 to 15 mPa · s, and particularly preferably 6 to 12 mPa · s. Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. In addition, the above-mentioned viscosity uses a cone rotor (1 ° 34 '× R24) with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., with a rotation speed of 50 rpm and a constant temperature circulating water temperature of 20 ° C. It can be measured by appropriately setting in the range of ~ 65 ° C. VISCOMATE VM-150III can be used for temperature adjustment of circulating water.

<Other physical properties>
The active energy ray-curable composition is preferably printed on a PET film with a film thickness of 5 to 15 μm, and the cross-cut adhesion when evaluated by the evaluation method of JIS-K5600-5-6 is preferably classification 0 or 1. . If the evaluation method of JIS-K5600-5-6 is not at the level of classification 0 or 1, adhesion problems may occur when actually used as a product. A sample of the adhesion rank is shown in FIG.

  The active energy ray-curable composition preferably has sensitivity to light-emitting diode light having an emission peak in a wavelength range of 360 nm to 400 nm. The phrase “having sensitivity to light emitting diode light” means that it has a property of being polymerized and cured in the presence or absence of a polymerization initiator by irradiation with light emitting diode light.

<Active energy rays>
Active energy rays used for curing the active energy ray-curable composition of the present invention include polymerizable components in the composition such as electron rays, α rays, β rays, γ rays, and X rays in addition to ultraviolet rays. There is no particular limitation as long as it can provide the energy necessary for proceeding the polymerization reaction. In particular, when a high energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Among these, the active energy ray is preferably light emitting diode light (LED).

  There is no restriction | limiting in particular as a light source of the said active energy ray, Although it can select suitably, For example, a mercury lamp, a metal halide lamp, UV-LED lamp etc. are mentioned.

  The mercury lamp is a quartz glass arc tube filled with high-purity mercury (Hg) and a small amount of rare gas. The main wavelength is 365 nm, and ultraviolet rays of 254 nm, 303 nm, and 313 nm are efficiently used. It is characterized by high radiation and short wavelength UV output.

  The metal halide lamp is a lamp in which a metal is enclosed in the form of a halide in addition to mercury in an arc tube, and emits an active energy ray spectrum over a wide range from 200 nm to 450 nm. Compared to a mercury lamp, it is 300 nm to 450 nm. It is characterized by high output of long wavelength ultraviolet rays.

  The UV-LED lamp has a feature that the environmental load can be reduced by the LED system with a long life and low power consumption, and there is no generation of ozone, and the apparatus can be made compact, and the active energy ray curable composition of the present invention is used. It is preferable as a lamp used for curing.

(Use)
The active energy ray-curable composition of the present invention is not particularly limited as long as the active energy ray-curable material is generally used in the field, and can be appropriately selected according to the purpose. For example, a molding resin, It can be used for paints, adhesives, insulating materials, release agents, coating materials, sealing materials, various resists, various optical materials, and the like.

  Furthermore, the active energy ray-curable composition of the present invention is not only used as an ink to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional model). Can also be used.

  As the three-dimensional modeling material, for example, the three-dimensional modeling method may be used as a binder between powder particles used in the powder lamination method, which is one of the three-dimensional modeling methods, and the additive manufacturing method as shown in FIGS. It may be used as a three-dimensional constituent material (model material) or a support member (support material) used in (optical modeling method).

In FIG. 2, an example of a material jet method (stereolithography method) in which an active energy ray-curable composition is ejected onto a predetermined region, and a material obtained by irradiating and curing an active energy ray is sequentially stacked to perform three-dimensional modeling. It is shown.
Moreover, as shown in FIG. 3, the active energy ray 4 is irradiated to the storage pool (container) 1 of the active energy ray-curable composition 5 to form a cured layer 6 having a predetermined shape on the movable stage 3, It can be utilized as a three-dimensional object constituent material in an optical modeling method for performing three-dimensional modeling by sequentially stacking these.

  A three-dimensional modeling apparatus for modeling a three-dimensional modeled object using such an active energy ray-curable composition can use a known one, and is not particularly limited. A thing provided with a supply means, a discharge means, an active energy ray irradiation means, etc. can be used.

  The present invention also includes a cured product obtained by curing the active energy ray-curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate such as a recording medium. . The molded product is obtained by subjecting a cured product or structure formed in a sheet shape or a film shape to a molding process such as heat stretching or punching, for example, an automobile, an OA device, an electric -It is suitably used for applications that require the surface to be molded after decorating, such as meters for electronic devices and cameras, and panels for operation units.

  The substrate is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include paper, plastic, metal, ceramic, glass, and composite materials thereof. From the viewpoint of workability, plastic is preferable. A substrate is preferred. Moreover, when the stretchability of the cured product in the present invention is expressed as a stretchability at 180 ° C. by a ratio of (length after tensile test−length before tensile test) / (length before tensile test), It is preferably 50% or more, and more preferably 100% or more.

(Active energy ray curable ink)
The active energy ray curable ink of the present invention (hereinafter sometimes referred to as “ink”) is made of the active energy ray curable composition of the present invention and is preferably used for inkjet.

The static surface tension at 25 ° C. of the active energy ray-curable ink is preferably 20 mN / m or more and 40 mN / m or less, and more preferably 28 mN / m or more and 35 mN / m or less.
The static surface tension was measured at 25 ° C. using a static surface tension meter (manufactured by Kyowa Interface Science Co., Ltd., CBVP-Z type). The static surface tension assumes specifications of a commercially available inkjet discharge head such as GEN4 manufactured by Ricoh Printing Systems Co., Ltd., for example.

(Composition container)
The composition storage container of the present invention means a container in which the active energy ray-curable composition is stored, and is suitable for use in the above applications. For example, when the active energy ray-curable composition of the present invention is used for ink, the container in which the ink is stored can be used as an ink cartridge or an ink bottle. In this operation, it is not necessary to directly touch the ink, and the fingers and clothes can be prevented from being stained. In addition, foreign matters such as dust can be prevented from entering the ink. Further, the shape, size, material, and the like of the container itself may be suitable for use and usage, and are not particularly limited, but the material is a light-shielding material that does not transmit light, or the container is shielded from light. It is desirable to be covered with an adhesive sheet.

(Image Forming Method and Image Forming Apparatus)
The image forming method of the present invention includes an irradiation step of irradiating active energy rays in order to cure at least the active energy ray-curable composition, and the image forming apparatus of the present invention irradiates active energy rays. An irradiating means for carrying out, and an accommodating part for accommodating the active energy ray-curable composition, and the container may be accommodated in the accommodating part. Furthermore, you may have the discharge process and discharge means which discharge an active energy ray hardening-type composition. A method for discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

  FIG. 1 is an example of an image forming apparatus provided with an ink jet ejection unit. Ink is ejected to the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d including ink cartridges and discharge heads of active energy ray curable inks of yellow, magenta, cyan, and black. Is done. Thereafter, the light is cured by irradiating active energy rays from the light sources 24a, 24b, 24c, and 24d for curing the ink, thereby forming a color image. Thereafter, the recording medium 22 is conveyed to the processing unit 25 and the printed matter winding roll 26. Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied by the ink discharge unit. If necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. In addition, for a recording medium that moves intermittently according to the ejection head width, a serial method in which ink is ejected onto the recording medium by moving the head, or the recording medium is moved continuously and held at a fixed position. Any ink jet recording apparatus of a line system in which ink is ejected from a head onto a recording medium can be applied.

The recording medium 22 is not particularly limited, and examples thereof include paper, a film, a metal, a composite material thereof, and the like, and may be a sheet shape. Moreover, even if it is the structure which enables only single-sided printing, the structure which also enables double-sided printing may be sufficient.
Further, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and the active energy ray may be irradiated from the light source 24d after printing a plurality of colors. Thereby, energy saving and cost reduction can be achieved.

  The image formed by the active energy ray-curable composition or ink of the present invention is not only printed on a smooth surface such as ordinary paper or resin film, but also printed on a printed surface having irregularities. Moreover, what was printed on the to-be-printed surface which consists of various materials, such as a metal and a ceramic, is also included. Further, by stacking two-dimensional images, it is possible to form an image having a stereoscopic effect (an image composed of two and three dimensions) or a three-dimensional object.

  FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) used in the present invention. The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to transfer the first active energy ray-curable composition from the molded article ejection head unit 30 to the support. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is discharged from the discharge head units 31 and 32, and these respective compositions are discharged by the adjacent ultraviolet irradiation means 33 and 34. It is laminated while curing.

  More specifically, for example, the second active energy ray-curable composition is ejected from the support ejection head units 31 and 32 on the model support substrate 37 and solidified by irradiation with active energy rays. After forming the first support layer having the reservoir, the first active energy ray-curable composition is discharged from the ejection head unit 30 for a molded article into the reservoir and is solidified by irradiation with active energy rays. Then, the step of forming the first modeled object layer is repeated a plurality of times while lowering the stage 38 movable in the vertical direction in accordance with the number of stacking, thereby stacking the support layer and the modeled object layer to form the three-dimensional modeled object 35. Is produced. Thereafter, the support laminate 36 is removed as necessary. In FIG. 2, only one shaped article discharge head unit 30 is provided, but two or more shaped article discharge head units 30 may be provided.

(2D or 3D image)
The two-dimensional or three-dimensional image of the present invention is formed by applying and curing either the active energy ray-curable composition of the present invention or the active energy ray-curable ink of the present invention on a substrate. .
The two-dimensional or three-dimensional image recorded by the active energy ray-curable composition of the present invention is not only recorded on a smooth surface such as ordinary paper or resin film, but also recorded on a recording surface having irregularities. And those recorded on a recording surface made of various materials such as metals and ceramics.

Examples of the two-dimensional image include characters, symbols, figures, combinations thereof, and solid images.
Examples of the three-dimensional image include a three-dimensional model.
There is no restriction | limiting in particular as average thickness of the said three-dimensional molded item, According to the objective, it can select suitably, 10 micrometers or more are preferable.

Since the two-dimensional or three-dimensional image uses either the active energy ray-curable composition of the present invention or the active energy ray-curable ink of the present invention, the two-dimensional image formed on the non-penetrating substrate. Alternatively, the three-dimensional image has excellent water resistance such that good adhesion can be maintained even after being immersed in water.
The two-dimensional or three-dimensional image is preferably cured using light-emitting diode light.

(Structure)
As a structure of this invention, it has a base material and the two-dimensional or three-dimensional image of this invention on the said base material. There is no restriction | limiting in particular as said base material, According to the objective, it can select suitably, What was mentioned above can be used.

(Molded product)
The molded product of the present invention is formed by stretching at least one selected from the two-dimensional or three-dimensional image of the present invention and the structure of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

(Preparation of pigment dispersion 1)
<Preparation of Pigment Dispersion A1>
45 parts by mass of carbon black A (trade name: Special Black 250: manufactured by Orion), 5 parts by mass of a polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.), and cyclic trimethylpropane formal acrylate 100 parts by mass (manufactured by Osaka Organic Industrial Chemical Co., Ltd.) was placed in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling rate: 45% by volume) and dispersed at a rotation temperature of 25 ° C. for 96 hours at 70 rpm. Then, 75 parts by mass of cyclic trimethylpropane formal acrylate (manufactured by Osaka Organic Industrial Chemical Co., Ltd.) was added and dispersed for 30 minutes, and then placed in a 1 L sand mill filled with zirconia beads having a diameter of 0.1 mm (filling rate: 80% by volume). Disperse at a peripheral speed of 8 m / sec and a dispersion temperature of 25 ° C. for 3 hours. Thus, [Pigment dispersion A1] was produced.

<Preparation of pigment dispersion B1>
45 parts by mass of carbon black A (trade name: Special Black 250: manufactured by Orion), 4 parts by mass of a polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.), and cyclic trimethylpropane formal acrylate 80 parts by mass (manufactured by Osaka Organic Industrial Chemical Co., Ltd.) was dispersed at 5,000 revolutions using a homogenizer at a dispersion temperature of 35 ° C. for 20 minutes, and then filled with zirconia beads having a diameter of 0.3 mm (filling rate: 90% by volume) ) Was added to a 1 L sand mill, and the peripheral speed was 10 m / second and the dispersion temperature was 30 ° C. for 1 hour, and then 96 parts by mass of cyclic trimethylpropane formal acrylate (manufactured by Osaka Organic Industrial Chemical Co., Ltd.) was added for 20 minutes. Dispersed to produce [Pigment Dispersion B1].

<Preparation of Pigment Dispersion C1>
45 parts by mass of carbon black B (trade name: Special Black 350: manufactured by Orion), 3 parts by mass of a polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.), and acryloylmorpholine (Kojin) Co., Ltd.) 83 parts by mass was placed in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling ratio: 43% by volume) and dispersed at a temperature of 25 ° C. for 70 hours at 70 rpm, followed by acryloylmorpholine ( [Pigment dispersion C1] was prepared by adding 94 parts by mass of Kojin Co., Ltd.

<Preparation of Pigment Dispersion D1>
45 parts by mass of carbon black C (trade name: MOGUL-L: manufactured by Cabot), 7 parts by mass of a polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.), and tetrahydrofurfuryl acrylate After putting 67 parts by mass (manufactured by Kyoeisha Chemical Co., Ltd.) into a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling ratio: 45% by volume), the dispersion temperature was 25 ° C. and 70 rotations / minute for 200 hours. 106 parts by mass of furfuryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was added to prepare [Pigment Dispersion D1].

<Preparation of pigment dispersion E1>
45 parts by mass of carbon black B (trade name: Special Black 350: manufactured by Orion), 8 parts by mass of a polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.), and 4-hydroxybutyl acrylate 79 parts by mass (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was dispersed with a homogenizer at a dispersion temperature of 35 ° C. for 15 minutes at 8,000 rpm, and then filled with zirconia beads having a diameter of 0.3 mm (filling rate: 80% by volume) ) And then dispersed for 1 hour at a dispersion temperature of 30 ° C. and a peripheral speed of 8 m / sec, 93 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added [Pigment Dispersion E1 ] Was produced.

<Preparation of Pigment Dispersion F1>
[Pigment Dispersion] except that carbon black A (trade name: Special Black 250, manufactured by Orion) was changed to carbon black D (trade name: Special Black 550, manufactured by Orion) in the production of [Pigment Dispersion A1]. [Pigment dispersion F1] was prepared in the same manner as in preparation of A1].

<Preparation of Pigment Dispersion G1>
In the production of [Pigment Dispersion B1], except that Carbon Black A (trade name: Special Black 250, manufactured by Orion) was changed to Carbon Black E (trade name: MOGUL-E, manufactured by Cabot), [Pigment Dispersion [Pigment Dispersion G1] was prepared in the same manner as in Preparation of Body B1].

<Preparation of pigment dispersion H1>
45 parts by mass of carbon black F (trade name: MA14, manufactured by Mitsubishi Chemical Corporation), 5 parts by mass of a polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.), and 4-hydroxybutyl After dispersing 105 parts by mass of acrylate (Osaka Organic Chemical Co., Ltd.) with a homogenizer at a dispersion temperature of 35 ° C. for 15 minutes at 8,000 rpm, 4-hydroxybutyl acrylate (Osaka Organic Chemical Co., Ltd.) Add 70 parts by mass and place in a sand mill filled with zirconia beads having a diameter of 0.5 mm (filling rate: 75% by volume) and disperse [pigment dispersion H1] at a dispersion temperature of 25 ° C. and a peripheral speed of 8 m / sec for 1 hour. Produced.

<Preparation of Pigment Dispersion I1> (Comparative Example 1 Dispersion)
Preparation of [Pigment Dispersion D1] except that the dispersant was changed to a dicarboxylic acid ester copolymer (trade name: DISPERBYK-168, manufactured by Big Chemie Japan Co., Ltd.). Similarly, [Pigment Dispersion I1] was produced.

<Preparation of Pigment Dispersion J1> (Comparative Example 2 Dispersion)
45 parts by mass of carbon black G (trade name: # 850, manufactured by Mitsubishi Chemical Corporation), 15 parts by mass of an amine group-containing acrylic block copolymer (dispersant, trade name: BYKJET-9151, manufactured by BYK Japan Japan) 165 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) is placed in a 500 mL ball mill filled with zirconia beads having a diameter of 1 mm (filling rate: 48% by volume), and the dispersion temperature is 35 ° C. and 70 rpm for 240 hours. [Pigment dispersion J1] was produced.

<Preparation of Pigment Dispersion K1> (Comparative Example 3 Dispersion)
Carbon black H (trade name: # 5, manufactured by Mitsubishi Chemical Corporation) 45 parts by mass, comb-type resin dispersant for fatty acid amine having polyethyleneimine as a main skeleton (dispersant, trade name: Solsperse 39000, manufactured by Nippon Louvre Resol Co., Ltd.) ) 5 parts by mass and 175 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) are placed in a 500 mL ball mill filled with zirconia beads having a diameter of 1 mm (filling ratio: 46% by volume), and the dispersion temperature is 35 ° C. and 70 revolutions / minute. Then, [Pigment dispersion K1] was produced for 280 hours.

<Preparation of Pigment Dispersion L1> (Comparative Example 4 Dispersion)
In the production of [Pigment Dispersion A1], except that carbon black A (trade name: Special Black 250, manufactured by Orion) was changed to carbon black H (trade name: # 5, manufactured by Mitsubishi Chemical Corporation), [Pigment [Pigment dispersion L1] was produced in the same manner as in the production of Dispersion A1].

<Preparation of Pigment Dispersion M1>
In the production of [Pigment Dispersion A1], except that the carbon black A (trade name: Special Black 250, manufactured by Orion) was changed to a blue pigment (trade name: TM Blue 3490E, primary particle diameter 50 nm), [Pigment Dispersion [Pigment Dispersion M1] was prepared in the same manner as in Preparation of Body A1].

  The compositions of the obtained pigment dispersions A1 to M1 are shown in Table 1.

Example 1
[Pigment dispersion A1] 15 parts by mass, 60 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.), 5 parts by mass of tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), pentaerythritol triacrylate (Shin Nakamura) Chemical Industry Co., Ltd.) 5 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF) 6 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl -Phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 5 parts by mass, 2,4-diethylthioxanthone (trade name: Speedcure DETX, manufactured by Lambson) 3.5 parts by mass, p-methoxyphenol (Nippon Kayaku) 0.2 parts by mass) Ether-modified polydimethylsiloxane mixed (trade name BYK3510, BYK Chemie Japan KK) 0.3 part by weight the active energy ray-curable composition 1].

(Example 2)
[Pigment dispersion A1] 15 parts by mass, 40 parts by mass of tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 35 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.), urethane acrylate oligomer (trade name: EBECRYL8402) Daicel Cytec Co., Ltd.) 6 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE 369, manufactured by BASF) 3.5 parts by mass, p- 0.2 parts by mass of methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) and 0.3 parts by mass of acrylic functional group-containing modified polydimethylsiloxane 1 (trade name: BYK-3576, manufactured by Big Chemy Japan Co., Ltd.) [Active energy ray-curable composition 2] was obtained.

(Example 3)
[Active energy ray-curable composition 3] was obtained in the same manner as in Example 1 except that [Pigment dispersion A1] was changed to [Pigment dispersion B1] in Example 1.

Example 4
[Pigment dispersion C1] 15 parts by mass, 40 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.), 26 parts by mass of tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), pentaerythritol triacrylate (Shin Nakamura) Chemical Industries, Ltd.) 7 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF) 5 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl -Phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 3 parts by mass, 2,4-diethylthioxanthone (trade name: Speedcure DETX, manufactured by Lambson) 3.5 parts by mass, p-methoxyphenol (Nippon Kayaku) 0.2 parts by mass) Ether-modified polydimethylsiloxane mixed (trade name BYK3510, BYK Chemie Japan KK) 0.3 part by weight the active energy ray-curable composition 4].

(Example 5)
[Pigment dispersion D1] 15 parts by mass, 35 parts by mass of isobornyl acrylate (Osaka Organic Chemical Co., Ltd.), 2-methyl-2-ethyl-1,3-dioxolan-4-ylmethyl acrylate (Osaka Organic Chemical) 25 parts by mass manufactured by Kogyo Co., Ltd., 20 parts by mass of dimethylol tricyclodecane diacrylate (manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Osaka Organic Chemical Co., Ltd.) 4.5 parts by mass, p-methoxyphenol (Nippon Kayaku Co., Ltd.) 0.2 parts by mass, and crosslinkable functional group-containing modified polyether 0.3 parts by mass were mixed. [Active energy ray-curable composition 5] was obtained.

(Example 6)
[Active energy ray-curable composition 6] was obtained in the same manner as in Example 4 except that [Pigment dispersion C1] was changed to [Pigment dispersion E1] in Example 4.

(Example 7)
[Pigment dispersion F1] 15 parts by mass, 67 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Hitachi Chemical Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF) ) 5 parts by mass, 2,4-diethylthioxanthone (trade name: Speedcure DETX, manufactured by Lambson) 3.5 parts by mass, p-methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) 0.2 parts by mass and polyether-modified poly 0.3 part by mass of dimethylsiloxane (trade name: BYK3510, manufactured by Big Chemie Japan Co., Ltd.) was mixed to obtain [active energy ray-curable composition 7].

(Example 8)
[Pigment dispersion G1] 15 parts by mass, 38 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.), 20 parts by mass of isobornyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.), dipentaerythritol pentaacrylate (manufactured by Sartomer) 15 parts by mass, 5 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product) Name: LUCIRIN TPO, manufactured by BASF) 3 parts by mass, 2-isopropylthioxanthone (trade name: Speedcure ITX, manufactured by Lambson) 3.5 parts by mass, 2,6-di-tert-butyl-p-cresol (Nippon Kayaku) 0.2 parts by mass and acrylic officer 0.3 parts by mass of functional group-containing modified polydimethylsiloxane 2 (trade name: BYK-3575, manufactured by Big Chemie Japan Co., Ltd.) was mixed to obtain [active energy ray-curable composition 8].

Example 9
[Pigment dispersion H1] 15 parts by mass, 30 parts by mass of tripropylene glycol diacrylate (made by Shin-Nakamura Chemical Co., Ltd.), 5 parts by mass of pentaerythritol triacrylate (made by Shin-Nakamura Chemical Co., Ltd.), 4-hydroxybutyl acrylate (Osaka Organic Chemical Co., Ltd.) 38 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF) 5 parts by mass, 2,4,6-trimethyl Benzoyl-diphenyl-phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 3 parts by mass, 2,4-diethylthioxanthone (trade name: Speedcure DETX, manufactured by Lambson) 3.5 parts by mass, p-methoxyphenol ( Nippon Kayaku Co., Ltd.) 0.2 quality Parts and polyether-modified polydimethylsiloxane (trade name: BYK-3510, manufactured by BYK Chemie Japan Co., Ltd.) were mixed 0.3 part by weight the active energy ray curable composition 9].

(Example 10)
[Active energy ray-curable composition 10] was obtained in the same manner as in Example 1 except that [Pigment dispersion A1] was changed to [Pigment dispersion M1] in Example 1.

(Comparative Example 1)
[Active energy ray-curable composition 11] was obtained in the same manner as in Example 4 except that [Pigment dispersion C1] was changed to [Pigment dispersion I1] in Example 4.

(Comparative Example 2)
[Active energy ray-curable composition 12] was obtained in the same manner as in Example 4, except that [Pigment dispersion C1] was changed to [Pigment dispersion J1] in Example 4.

(Comparative Example 3)
[Active energy ray-curable composition 13] was obtained in the same manner as in Example 4 except that [Pigment dispersion C1] was changed to [Pigment dispersion K1] in Example 4.

(Comparative Example 4)
[Active energy ray-curable composition 14] was obtained in the same manner as in Example 1, except that [Pigment Dispersion A1] was changed to [Pigment Dispersion L1] in Example 1.

  Tables 2 and 3 show the compositions of the active energy ray-curable compositions obtained in the above Examples and Comparative Examples.

(Measurement of amount of dispersant adsorbed on pigment, amount of unadsorbed dispersant, ratio)
About the obtained active energy ray-curable composition, the amount of dispersant adsorbed on the pigment, the amount of unadsorbed dispersant, and the ratio were measured as follows. The results are shown in Table 4.

  The amount of the dispersant adsorbed on the pigment is 1.5 g of ink (active energy ray-curable composition) in a 1 ml sample holder for centrifugation, and this is centrifuged at 10,000 rpm for 1 hour, and the supernatant portion Remove. To this was added approximately the same amount of acetone, and the mixture was stirred with a spatula and centrifuged in the same manner for a total of 4 times. This was completely dried with a vacuum dryer, 100 mg of the dried sample was accurately measured in an aluminum cup, heated at 400 ° C. for 2 hours, the remaining amount was measured, and the following calculation formula was obtained.

[Amount of dispersant adsorbed on 1 g of pigment]
= (Weight loss after heating (mg)-pigment weight loss (mg)) / residual amount after heating (mg)
* Pigment single weight loss (mg) is the weight loss (mg) when 100 mg pigment alone is heated at 400 ° C. for 2 hours.

The amount of unadsorbed dispersant was determined by the following formula.
(Dispersant prescription amount (parts by mass) / pigment prescription amount (parts by mass)) × 1000 (mg) −dispersant amount adsorbed on 1 g of pigment (mg)

(Measurement of particle size and evaluation)
The volume average particle diameter, volume particle diameter, and number average primary particle diameter of the pigment of the active energy ray-curable composition were determined as follows. Further, “adhesion” (glass / PET / aluminum), “print density”, and “curability” were evaluated as follows. The results are shown in Table 5.

<Number average primary particle size of pigment>
As the number average primary particle size of the pigment, the obtained active energy ray-curable composition was measured with a scanning electron microscope (device name: SU3500, manufactured by Hitachi High-Technologies Corporation) in a 10,000-fold field of view. The constant direction diameter at the interval between two parallel lines in a fixed direction sandwiching the primary particles of 200 to 500 primary particles was measured and obtained from the average value of the cumulative distribution.

<Volume average particle diameter of active energy ray-curable composition>
The volume average particle size of the active energy ray-curable composition was obtained by diluting the obtained active energy ray-curable composition with phenoxyethyl acrylate about 100 times, and measuring the particle size distribution meter (device name: UPA150, Nikkiso Co., Ltd.). Was used to measure the volume particle size and volume average particle size of the active energy ray-curable composition. From the obtained volume particle size, the content of the active energy ray curable composition having a volume particle size of 170 nm or less and the content of the active energy ray curable composition having a volume particle size of 380 nm or more were calculated.

<Adhesion>
Using the obtained active energy ray-curable composition, an image (cured product) of 10 cm × 10 cm having an average thickness of 10 μm was obtained. The solid part of the obtained image (cured product) was cut with a cutter knife into a base pattern at intervals of 1 mm according to JIS K5600, and cellophane adhesive tape (trade name: Scotch Mending Tape (18 mm), manufactured by 3M Japan Co., Ltd.) Then, the “adhesiveness” of the following substrate was evaluated based on the following evaluation criteria while looking with a loupe (trade name: PEAK No. 1961 (× 10), manufactured by Tokai Sangyo Co., Ltd.).

-Evaluation criteria-
◎: JIS K5600 crosscut evaluation rank classification 0 level ○: JIS K5600 crosscut evaluation rank classification 1 level △: JIS K5600 crosscut evaluation rank classification 2 or 3 levels ×: JIS K5600 crosscut evaluation rank classification 4 level or less

-Base material-
Glass: Matsunami Glass Industrial Co., Ltd. S9213 standard large water polish t1.3
Aluminum: Panac Alvet 9-100
PET film: Toyobo E-5100

<Print density>
The obtained active energy ray-curable composition was placed on a recording medium (trade name: Cosmo Shine A4300 coated PET film, manufactured by Toyobo Co., Ltd., average thickness: 100 μm, color: transparent) and a printer (device name: SG7100, Inc.). A solid image of 10 cm × 10 cm was obtained using an evaluation printer modified from Ricoh. Using the obtained solid image, a UV-LED device for inkjet printers (device name: UV-LED module (single-pass water-cooled, manufactured by USHIO INC.)) Has an illuminance of 1 W / cm ² and an irradiation amount of 500 mJ / Curing treatment was performed so as to be cm ² , and a 10 cm × 10 cm image (cured product) having an average thickness of 10 μm was obtained.
In addition, the ultraviolet-ray intensity meter (apparatus name: UM-10) and the light-receiving part (apparatus name: UM-400) (above, Konica Minolta Co., Ltd. product) were used for the measurement of irradiation amount. Moreover, as a measuring method of the said average thickness, thickness was measured using the electronic micrometer (made by Anritsu Co., Ltd.), and it calculated | required from the average value of 10 thicknesses. The printer for evaluation was changed to an MH2620 head (manufactured by Ricoh Co., Ltd.), which uses a conveyance and drive unit of the device name: SG7100 (manufactured by Ricoh Co., Ltd.) and can heat-discharge the head part and can handle high viscosity ink. It is.

  The obtained image (cured material) of the recording medium was measured for the density of the image (cured material) with respect to black using a reflection spectral densitometer (device name: X-Rite 939, manufactured by X-Rite), and the print density. did.

<Curing property>
Using the obtained active energy ray-curable composition, an image (cured product) of 10 cm × 10 cm having an average thickness of 10 μm was obtained in the same manner as the evaluation of the concealing property. The obtained image (cured material) was subjected to 10 reciprocating frictions with a white cotton cloth attached to a clock meter (device name: NO416, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) with a load of 50 g / cm ² . Then, using a reflection spectral densitometer (device name: X-Rite 939, manufactured by X-Rite), the density of the white cotton cloth before and after the reciprocating friction was measured, and the concentration before and after the reciprocating friction was determined from the concentration after the reciprocating friction. A value obtained by subtracting the concentration was calculated, and “curability” was evaluated based on the following evaluation criteria.

-Evaluation criteria-
A: Less than 0.001 B: More than 0.001 and less than 0.005 Δ: More than 0.005 and less than 0.009 ×: More than 0.009

As is apparent from the results in Table 5, it can be seen that the active energy ray-curable composition (active energy ray-curable ink) using the reactive dispersant of the present invention can achieve both adhesion, print density, and curability.
Among those using a reactive dispersant, those having a pigment adsorption amount and a free dispersant amount within a specific range and those containing a monofunctional (meth) acrylate having a cyclic ether structure are particularly good. In addition, since the carbon characteristics having a specific range and the particle size characteristics having a specific range have good dispersibility, the printing density is also good.

(Preparation of pigment dispersion 2)
<Preparation of Pigment Dispersion A2>
110 parts by mass of titanium oxide A (trade name: TCR-52, manufactured by Sakai Chemical Co., Ltd., surface treatment: Al ₂ O ₃ ), polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.) ) 5 parts by mass and 60 parts by mass of cyclic trimethylpropane formal acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) were placed in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling rate: 45% by volume) at 70 rpm. After dispersion at a dispersion temperature of 25 ° C. for 96 hours, 50 parts by mass of cyclic trimethylpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added and dispersed for 30 minutes, followed by filling with zirconia beads having a diameter of 0.1 mm (filling) (Rate: 80% by volume) in a 1L sand mill, the peripheral speed is 8 m / sec, and the dispersion temperature is 25 ° C. for 3 hours. Thus, [Pigment Dispersion A2] was produced.

<Preparation of pigment dispersion B2>
110 parts by mass of titanium oxide A (trade name: TCR-52, manufactured by Sakai Chemical Co., Ltd., surface treatment: Al ₂ O ₃ ), polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.) ) 3 parts by mass and 62 parts by mass of cyclic trimethylpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) using a homogenizer at 5,000 revolutions and a dispersion temperature of 35 ° C. for 20 minutes, then a diameter of 0.3 mm The sample was placed in a 1 L sand mill filled with zirconia beads (filling rate: 90% by volume) and dispersed at a peripheral speed of 10 m / second and a dispersion temperature of 30 ° C. for 1 hour, and then cyclic trimethylpropane formal acrylate (Osaka Organic Chemical Co., Ltd.) 50 parts by mass) were added and dispersed for 20 minutes to prepare [Pigment Dispersion B2].

<Preparation of Pigment Dispersion C2>
Titanium oxide B (trade name: JR405, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ ) Trade name: 110 parts by mass, polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.) ) 2 parts by mass and 63 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) are placed in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling ratio: 43% by volume), and the dispersion temperature is 25 ° C. and 70 rotations / min. Then, after 180 hours, 50 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) was added to prepare [Pigment Dispersion C2].

<Preparation of Pigment Dispersion D2>
110 parts by mass of titanium oxide C (trade name: JR403, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ ), polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.) ) 6 parts by mass and 59 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) are placed in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling rate: 45% by volume), and the dispersion temperature is 70 ° C. at 25 ° C. After 200 hours per minute, 50 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was added to prepare [Pigment Dispersion D2].

<Preparation of pigment dispersion E2>
110 parts by mass of titanium oxide B (trade name: JR405, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ ), 10% by mass of a polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.) And 50 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) using a homogenizer at a dispersion temperature of 35 ° C. for 15 minutes at 8,000 rpm, and then zirconia beads having a diameter of 0.3 mm. After putting in a filled sand mill (filling rate: 80% by volume) and dispersing for 1 hour at a dispersion temperature of 30 ° C. and a peripheral speed of 8 m / second, 55 mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) Part was added to prepare [Pigment Dispersion E2].

<Preparation of Pigment Dispersion F2>
In the production of [Pigment Dispersion A2], titanium oxide A (trade name: TCR-52, manufactured by Sakai Chemical Co., Ltd., surface treatment: Al ₂ O ₃ ) was used as titanium oxide D (trade name: JR, manufactured by TAICA Corporation). [Pigment Dispersion F2] was prepared in the same manner as [Pigment Dispersion A2] except that the surface treatment was changed to None.

<Preparation of Pigment Dispersion G2>
In the preparation of [Pigment Dispersion B2], titanium oxide A (trade name: TCR-52, manufactured by Sakai Chemical Co., Ltd., surface treatment: Al ₂ O ₃ ) was used as titanium oxide E (D-918, Sakai Chemical Industry Co., Ltd.). Ltd., surface _treatment: was changed to _{Al 2 O 3, SiO 2,} ZrO 2) , in the same manner as the preparation of pigment dispersion B2], to prepare the pigment dispersion G2].

<Preparation of pigment dispersion H2>
110 parts by mass of titanium oxide F (JR701, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ , ZnO), polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.) ) 5 parts by mass and 110 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) are placed in a 500 mL ball mill filled with zirconia beads having a diameter of 1 mm (filling ratio: 48% by volume), and the dispersion temperature is 35 ° C. at 70 rpm. For 240 hours to prepare [Pigment Dispersion H2].

<Preparation of Pigment Dispersion I2> (Comparative Example 5 Dispersion)
The preparation of [Pigment Dispersion D2] is the same as that of [Pigment Dispersion D2] except that the dispersant is changed to a dicarboxylic acid ester copolymer (trade name: DISPERBYK-168, Big Chemie Japan Co., Ltd.). Thus, [Pigment Dispersion I2] was produced.

<Preparation of Pigment Dispersion J2> (Comparative Example 6 Dispersion)
Titanium oxide G (trade name: JR301, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ ) 110 parts by mass, polymerizable group-containing reactive dispersant (trade name: Solsperse X300, manufactured by Nippon Lubrizol Co., Ltd.) 15 masses Part, and 100 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) in a 500 mL ball mill filled with zirconia beads having a diameter of 1 mm (filling rate: 48% by volume), at a dispersion temperature of 35 ° C. at 70 rotations / minute, 240 [Pigment dispersion J2] was produced by allowing time.

<Preparation of Pigment Dispersion K2> (Comparative Example 7 Dispersion)
110 parts by mass of titanium oxide H (trade name: R45M, manufactured by Sakai Chemical Industry Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ ), comb-type resin dispersant of fatty acid amine having polyethyleneimine as a main skeleton (trade name: Solsperse) 39000, manufactured by Nippon Ruble Resor Co., Ltd.) and 20 parts by mass of phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) were placed in a 500 mL ball mill filled with zirconia beads having a diameter of 1 mm (filling ratio: 46% by volume) and dispersed temperature. Was 280 hours at 35 ° C. at 70 rpm, and 45 parts by mass of phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) was added and dispersed for 10 hours to prepare [Pigment Dispersion K2].

<Preparation of Pigment Dispersion L2> (Comparative Example 8 Dispersion)
110 parts by mass of titanium oxide I (trade name: R21, manufactured by Sakai Chemical Industry Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ ), amine group-containing acrylic block copolymer (dispersant, trade name: BYKJET-9151, BIC 10 parts by mass of Chemie Japan Co., Ltd.) and 50 parts by mass of phenoxyethyl acrylate (Osaka Organic Chemical Co., Ltd.) were placed in a 500 mL ball mill filled with zirconia beads having a diameter of 1 mm (filling ratio: 46% by volume), and the dispersion temperature was 35. After 280 hours at 70 rpm at 70 ° C., 55 parts by mass of phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) was added and dispersed for 10 hours to prepare [Pigment Dispersion L2].

<Preparation of Pigment Dispersion M2> (Comparative Example 9 Dispersion)
In the production of [Pigment Dispersion A2], titanium oxide A (trade name: TCR-52, manufactured by Sakai Chemical Co., Ltd., surface treatment: Al ₂ O ₃ ) was replaced with titanium oxide J (trade name: TTO55, manufactured by Ishihara Sangyo Co., Ltd.). [Surface treatment: Ai ₂ O ₃ , primary particle diameter 35 nm] [Pigment dispersion M2] was prepared in the same manner as [Pigment dispersion A2].

  The compositions of the obtained pigment dispersions A2 to M2 are shown in Table 6.

(Example 11)
[Pigment dispersion A2] 30 parts by mass, 45 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.), 5 parts by mass of tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), pentaerythritol triacrylate (Shin Nakamura) Chemical Industry Co., Ltd.) 5 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF) 6 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl -Phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 5 parts by mass, 2,4-diethylthioxanthone 1 (trade name: Speedcure DETX, manufactured by Lambson) 3.5 parts by mass, p-methoxyphenol (Nipponization) Yakuhin Co., Ltd.) 0.2 parts by mass Ether-modified polydimethylsiloxane mixed (trade name BYK3510, BYK Chemie Japan KK) 0.3 part by weight the active energy ray curable composition 15.

(Example 12)
[Pigment dispersion A2] 30 parts by mass, tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass, acryloylmorpholine (manufactured by Kojin Co., Ltd.) 35 parts by mass, urethane acrylate oligomer (trade name: EBECRYL8402) Daicel Cytec Co., Ltd.) 6 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE 369, manufactured by BASF) 3.5 parts by mass, p- 0.2 parts by mass of methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) and 0.3 parts by mass of acrylic functional group-containing modified polydimethylsiloxane 1 (trade name: BYK-3576, manufactured by Big Chemy Japan Co., Ltd.) [Active energy ray-curable composition 16] was obtained.

(Example 13)
[Active energy ray-curable composition 17] was obtained in the same manner as in Example 11 except that [Pigment dispersion A2] was changed to [Pigment dispersion B2] in Example 11.

(Example 14)
[Pigment dispersion C2] 30 parts by mass, 40 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.), 11 parts by mass of tripropylene glycol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.), pentaerythritol triacrylate (Shin Nakamura) Chemical Industries, Ltd.) 7 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF) 5 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl -Phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 3 parts by mass, 2,4-diethylthioxanthone 1 (trade name: Speedcure DETX, manufactured by Lambson) 3.5 parts by mass, p-methoxyphenol (Nipponization) 0.2 parts by mass) Rieteru modified polydimethylsiloxane were mixed (trade name BYK3510, BYK Chemie Japan KK) 0.3 part by weight the active energy ray curable composition 18.

(Example 15)
[Pigment Dispersion D2] 30 parts by mass, isobornyl acrylate (Osaka Organic Chemical Co., Ltd.) 20 parts by mass, 2-methyl-2-ethyl-1,3-dioxolan-4-ylmethyl acrylate (Osaka Organic Chemical) 25 parts by mass manufactured by Kogyo Co., Ltd., 20 parts by mass of dimethylol tricyclodecane diacrylate (manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Osaka Organic Chemical Co., Ltd.) 4.5 parts by mass, p-methoxyphenol (Nippon Kayaku Co., Ltd.) 0.2 parts by mass, and crosslinkable functional group-containing modified polyether 0.3 parts by mass were mixed. [Active energy ray-curable composition 19] was obtained.

(Example 16)
[Active energy ray-curable composition 20] was obtained in the same manner as in Example 14 except that [Pigment dispersion C2] was changed to [Pigment dispersion E2] in Example 14.

(Example 17)
[Pigment Dispersion F2] 30 parts by mass, 57 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Hitachi Chemical Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF) ) 8 parts by mass, 2,4-diethylthioxanthone 2 (trade name: KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass, p-methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) 0.2 mass Part and 0.3 part by mass of polyether-modified polydimethylsiloxane (trade name: BYK3510, manufactured by Big Chemie Japan Co., Ltd.) were mixed to obtain [active energy ray-curable composition 21].

(Example 18)
[Pigment Dispersion G2] 30 parts by mass, 35 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.), 5 parts by mass of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), dipentaerythritol pentaacrylate (manufactured by Sartomer) 15 parts by mass, 5 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product) Name: LUCIRIN TPO, manufactured by BASF) 5 parts by mass, 2-isopropylthioxanthone (trade name: SpeedcureITX, manufactured by Lambson) 4.5 parts by mass, 2,6-di-tert-butyl-p-cresol (Nippon Kayaku) 0.2 parts by mass and acrylic functionality 0.3 part by mass of group-containing modified polydimethylsiloxane 2 (trade name: BYK-3575, manufactured by Big Chemie Japan Co., Ltd.) was mixed to obtain [active energy ray-curable composition 22].

(Example 19)
[Pigment dispersion H2] 30 parts by mass, 5 parts by mass of tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts by mass of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 4-hydroxybutyl acrylate (Osaka Organic Chemical Co., Ltd.) 45 parts by mass, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE 819, manufactured by BASF) 6 parts by mass, 2,4,6-trimethyl Benzoyl-diphenyl-phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 5 parts by mass, 2,4-diethylthioxanthone 1 (trade name: Speedcure DETX, manufactured by Lambson) 3.5 parts by mass, p-methoxyphenol (Nippon Kayaku Co., Ltd.) 0.2 The amount unit, and polyether-modified polydimethylsiloxane mixed (trade name BYK-3510, BYK Chemie Japan KK) 0.3 part by weight the active energy ray curable composition 23.

(Comparative Example 5)
[Active energy ray-curable composition 24] was obtained in the same manner as in Example 14 except that [Pigment dispersion C2] was changed to [Pigment dispersion I2] in Example 14.

(Comparative Example 6)
[Active energy ray-curable composition 25] was obtained in the same manner as in Example 14 except that [Pigment dispersion C2] was changed to [Pigment dispersion J2] in Example 14.

(Comparative Example 7)
[Active energy ray-curable composition 26] was obtained in the same manner as in Example 14, except that [Pigment dispersion C2] was changed to [Pigment dispersion K2] in Example 14.

(Comparative Example 8)
[Active energy ray-curable composition 27] was obtained in the same manner as in Example 14, except that [Pigment dispersion C2] was changed to [Pigment dispersion L2] in Example 14.

(Comparative Example 9)
[Active energy ray-curable composition 28] was obtained in the same manner as in Example 11 except that [Pigment dispersion A2] was changed to [Pigment dispersion M2] in Example 11.

  Tables 7 and 8 show the compositions of the active energy ray-curable compositions obtained in the above Examples and Comparative Examples.

(Measurement of amount of dispersant adsorbed on pigment, amount of unadsorbed dispersant, ratio)
About the obtained active energy ray-curable composition, the amount of dispersant adsorbed on the pigment, the amount of unadsorbed dispersant, and the ratio were measured as follows. The results are shown in Table 9.

  The amount of the dispersant adsorbed on the pigment is 1.5 g of ink (active energy ray-curable composition) in a 1 ml sample holder for centrifugation, and this is centrifuged at 10,000 rpm for 1 hour, and the supernatant portion Removed. To this was added approximately the same amount of acetone, and the mixture was stirred with a spatula and centrifuged in the same manner for a total of 4 times. This was completely dried with a vacuum dryer, 100 mg of the dried sample was accurately measured in an aluminum cup, heated at 400 ° C. for 2 hours, and the remaining amount was measured.

[Amount of dispersant adsorbed on 1 g of pigment]
= (Weight loss after heating (mg)-pigment weight loss (mg)) / residual amount after heating (mg)
* Pigment single weight loss (mg) is the weight loss (mg) when 100 mg pigment alone is heated at 400 ° C. for 2 hours.

The amount of unadsorbed dispersant was determined by the following formula.
(Dispersant prescription amount (parts by mass) / pigment prescription amount (parts by mass)) × 1000 (mg) −dispersant amount adsorbed on 1 g of pigment (mg)

(Measurement of particle size and evaluation)
The volume average particle diameter, volume particle diameter, and number average primary particle diameter of the pigment of the active energy ray-curable composition were determined as follows. Further, “adhesion” (glass / PET / aluminum), “hiding ratio”, and “curability” were evaluated as follows. The results are shown in Table 10.

<Number average primary particle size of pigment>
As the number average primary particle size of the pigment, the obtained active energy ray-curable composition was measured with a scanning electron microscope (device name: SU3500, manufactured by Hitachi High-Technologies Corporation) in a 10,000-fold field of view. The constant direction diameter at the interval between two parallel lines in a fixed direction sandwiching the primary particles of 200 to 500 primary particles was measured and obtained from the average value of the cumulative distribution.

<Volume average particle diameter of active energy ray-curable composition>
The volume average particle size of the active energy ray-curable composition was obtained by diluting the obtained active energy ray-curable composition with phenoxyethyl acrylate about 100 times, and measuring the particle size distribution meter (device name: UPA150, Nikkiso Co., Ltd.). Was used to measure the volume particle size and volume average particle size of the active energy ray-curable composition. From the obtained volume particle size, the content of the active energy ray-curable composition having a volume particle size of 150 nm or less and the content of the active energy ray-curable composition having a volume particle size of 380 nm or more were calculated.

<Adhesion>
Using the obtained active energy ray-curable composition, an image (cured product) of 10 cm × 10 cm having an average thickness of 10 μm was obtained. The solid part of the obtained image (cured product) was cut with a cutter knife into a base pattern at intervals of 1 mm according to JIS K5600, and cellophane adhesive tape (trade name: Scotch Mending Tape (18 mm), manufactured by 3M Japan Co., Ltd.) Then, the “adhesiveness” of the following substrate was evaluated based on the following evaluation criteria while looking with a loupe (trade name: PEAK No. 1961 (× 10), manufactured by Tokai Sangyo Co., Ltd.).

-Evaluation criteria-
◎: JIS K5600 crosscut evaluation rank classification 0 level ○: JIS K5600 crosscut evaluation rank classification 1 level △: JIS K5600 crosscut evaluation rank classification 2 or 3 levels ×: JIS K5600 crosscut evaluation rank classification 4 level or less

-Base material-
Glass: Matsunami Glass Industrial Co., Ltd. S9213 standard large water polish t1.3
Aluminum: Panac Alvet 9-100
PET film: Toyobo E-5100

<Concealment (print density)>
The obtained active energy ray-curable composition was placed on a recording medium (trade name: Cosmo Shine A4300 coated PET film, manufactured by Toyobo Co., Ltd., average thickness: 100 μm, color: transparent) and a printer (device name: SG7100, Inc.). A solid image of 10 cm × 10 cm was obtained using an evaluation printer modified from Ricoh. Using the obtained solid image, a UV-LED device for inkjet printers (device name: UV-LED module (single-pass water-cooled, manufactured by USHIO INC.)) Has an illuminance of 1 W / cm ² and an irradiation amount of 500 mJ / Curing treatment was performed so as to be cm ² , and a 10 cm × 10 cm image (cured product) having an average thickness of 10 μm was obtained.
In addition, the ultraviolet-ray intensity meter (apparatus name: UM-10) and the light-receiving part (apparatus name: UM-400) (above, Konica Minolta Co., Ltd. product) were used for the measurement of irradiation amount. Moreover, as a measuring method of the said average thickness, thickness was measured using the electronic micrometer (made by Anritsu Co., Ltd.), and it calculated | required from the average value of 10 thicknesses. The printer for evaluation was changed to an MH2620 head (manufactured by Ricoh Co., Ltd.), which uses a conveyance and drive unit of the device name: SG7100 (manufactured by Ricoh Co., Ltd.) and can heat-discharge the head part and can handle high viscosity ink. It is.

A black paper (trade name: Extra Black, manufactured by Takeo Co., Ltd., density: 1.65) is placed on the side of the recording medium opposite to the side on which the obtained image (cured product) is formed. Name: X-Rite 939 (manufactured by X-Rite) was used to measure the density of the image (cured product) with respect to black, and the concealment rate was calculated based on the following formula to evaluate “concealability”. The higher the concealment rate, the better the concealment property.
Concealment rate (%) = [1− (density of image (cured product) / density of black paper (1.65))] × 100

<Curing property>
Using the obtained active energy ray-curable composition, an image (cured product) of 10 cm × 10 cm having an average thickness of 10 μm was obtained in the same manner as the evaluation of the concealing property. The obtained image (cured material) was subjected to 10 reciprocating frictions with a white cotton cloth attached to a clock meter (device name: NO416, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) with a load of 50 g / cm ² . Then, using a reflection spectral densitometer (device name: X-Rite 939, manufactured by X-Rite), the density of the white cotton cloth before and after the reciprocating friction was measured, and the concentration before and after the reciprocating friction was determined from the concentration after the reciprocating friction. A value obtained by subtracting the concentration was calculated, and “curability” was evaluated based on the following evaluation criteria.

-Evaluation criteria-
A: Less than 0.001 B: More than 0.001 and less than 0.005 Δ: More than 0.005 and less than 0.009 ×: More than 0.009

As is clear from the results in Table 10, the active energy ray-curable composition (active energy ray-curable ink) using the reactive dispersant of the present invention has both adhesion, hiding properties (print density), and curability. I understand that I can do it.
Among those using a reactive dispersant, those having a pigment adsorption amount and a free dispersant amount within a specific range and those containing a monofunctional (meth) acrylate having a cyclic ether structure are particularly good. In addition, since the carbon characteristics having a specific range and the particle size characteristics having a specific range have good dispersibility, the printing density is also good.

DESCRIPTION OF SYMBOLS 21 Supply roll 22 Recording medium 23a, 23b, 23c, 23d Printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Printed product winding roll 39 Forming apparatus 30 Modeling object discharge head unit 31, 32 Support body discharge head Units 33 and 34 Ultraviolet irradiation means 36 Support layered portion 38 Stage

JP 2011-032311 A JP 2013-129778 A Japanese Patent No. 5407114 JP 2011-053094 A JP 2013-112691 A JP 2009-108213 A JP 2005-263898 A JP 2006-342201 A

Claims (28)

Containing pigments, dispersants and polymerizable compounds,
The dispersant is a reactive dispersant having a reactive double bond group,
The active energy ray-curable composition, wherein the pigment is a pigment other than white having a number average primary particle size (Dn) of 20 nm to 60 nm. The content A of the reactive dispersant adsorbed on the pigment is 30 to 120 mg per 1 g of the pigment,
The active energy ray-curable composition according to claim 1, wherein the content B of the reactive dispersant not adsorbed on the pigment is 10 to 50% by mass of the total amount of the reactive dispersant. .   The volume average particle diameter (Dv) of the active energy ray-curable composition is 100 nm or more and 150 nm or less, the ratio of the particle diameter of 50 nm or less is 10 vol% or less, and the ratio of the particle diameter of 230 nm or more is 10 vol% or less. The active energy ray-curable composition according to claim 1 or 2.   The particle size ratio (Dv / Dn) between the volume average particle size (Dv) of the active energy ray-curable composition and the number average primary particle size (Dn) of the pigment is 1.5 or more and 3.0 or less. The active energy ray hardening-type composition in any one of Claims 1-3 characterized by the above-mentioned.   The active energy ray-curable composition according to claim 1, wherein the pigment contains carbon black.   6. The active energy ray-curable composition according to claim 5, wherein the carbon black contains an oxidized carbon black having a DBP oil absorption of 35 g / 100 g or more and 55 g / 100 g or less and a pH of 3.5 or less. Containing pigments, dispersants and polymerizable compounds,
The dispersant is a reactive dispersant having a reactive double bond group,
The active energy ray-curable composition, wherein the pigment is a white pigment having a number average primary particle size (Dn) of 205 nm or more and 280 nm or less. The content C of the reactive dispersant adsorbed on the pigment is 2 to 50 mg per 1 g of the pigment,
The active energy ray-curable composition according to claim 7, wherein the content D of the reactive dispersant not adsorbed on the pigment is 5 to 40% by mass of the total amount of the reactive dispersant. .   The volume average particle diameter (Dv) of the active energy ray-curable composition is 210 nm or more and 300 nm or less, the ratio of the particle diameter of 150 nm or less is 10% by volume or less, and the ratio of the particle diameter of 380 nm or more is 10% by volume or less. The active energy ray-curable composition according to claim 7 or 8.   The particle size ratio (Dv / Dn) between the volume average particle size (Dv) of the active energy ray-curable composition and the number average primary particle size (Dn) of the pigment is 1.0 or more and 1.2 or less. The active energy ray-curable composition according to any one of claims 7 to 9.   The active energy ray-curable composition according to claim 7, wherein the pigment contains rutile-type titanium oxide.   The active energy ray-curable composition according to claim 11, wherein the titanium oxide contains at least one selected from alumina, silica, zirconium oxide and zinc oxide as a surface treatment agent.   The active energy ray-curable composition according to claim 1, wherein the polymerizable compound contains a monofunctional (meth) acrylate having a cyclic ether structure.   The active energy ray-curable composition according to claim 1, wherein the reactive dispersant contains a tertiary amino group-containing polyurethane.   The active energy ray-curable composition is printed on a PET film with a film thickness of 5 to 15 μm, and the cross-cut adhesion when evaluated by the evaluation method of JIS-K5600-5-6 is classification 0 or 1. The active energy ray-curable composition according to any one of claims 1 to 14,   The active energy ray-curable composition according to claim 1, which is sensitive to light-emitting diode light having an emission peak in a wavelength range of 360 nm to 400 nm.   The active energy ray-curable composition according to claim 1, which is a three-dimensional modeling material.   An active energy ray-curable ink comprising the active energy ray-curable composition according to claim 1.   The active energy ray-curable ink according to claim 18, wherein the active energy ray-curable ink is used for inkjet.   An active energy ray-curable composition according to any one of claims 1 to 17 is contained in a container.   An accommodating part that accommodates the active energy ray-curable composition according to any one of claims 1 to 17, and an irradiation means for irradiating the active energy ray-curable composition with active energy rays. An apparatus for forming a two-dimensional or three-dimensional image, comprising:   The apparatus for forming a two-dimensional or three-dimensional image according to claim 21, further comprising ejection means for ejecting the active energy ray-curable composition by an ink jet recording method.   A method for forming a two-dimensional or three-dimensional image, comprising an irradiation step of irradiating the active energy ray-curable composition according to any one of claims 1 to 17 with an active energy ray.   The method for forming a two-dimensional or three-dimensional image according to claim 23, further comprising a discharge step of discharging the active energy ray-curable composition by an ink jet recording method.   The method for forming a two-dimensional or three-dimensional image according to claim 23 or 24, wherein the active energy ray is light-emitting diode light.   A two-dimensional or three-dimensional image obtained by irradiating and curing the active energy ray-curable composition according to any one of claims 1 to 17 with an active energy ray.   A structure having a base material and the two-dimensional or three-dimensional image according to claim 26 on the base material. A molded product obtained by stretching at least one selected from the two-dimensional or three-dimensional image according to claim 26 and the structure according to claim 27.