JP6701730B2 - Active energy ray-curable composition, active energy ray-curable ink, composition container, two-dimensional or three-dimensional image forming method and forming apparatus, structure, and molded product - Google Patents

Description

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

  Since the active energy ray-curable ink has less odor and is quick-drying as compared with the solvent-based ink, it can be suitably recorded on a recording medium that does not absorb the ink.

The active energy ray-curable ink, depending on the type of light source such as a mercury lamp or a metal halide lamp, using several types of polymerization initiators having different absorption wavelengths, by combining the monomers in the active energy ray-curable ink. Let it harden.
In recent years, an ultraviolet light emitting diode having a peak emission wavelength at 365 nm or 385 nm, which consumes less power, is often used from the viewpoint of power saving.
The functions required for the active energy ray-curable ink include, for example, efficient curing at the peak emission wavelength, high density of the cured print image, stable ejection from the head, and storage. It is important that the ink properties are stable.
If the pigment contained in the active energy ray-curable ink is not properly dispersed in a monomer or the like as a dispersion medium, not only the desired color density cannot be obtained, but also the particle size is large and the viscosity is high, so that the ejection property from the head is improved. There is a problem that

In order to properly disperse the pigment in the monomer, it is important that the pigment and the monomer have an affinity and that the pigment particles do not aggregate due to steric hindrance or charge repulsion. Therefore, (1) a method of containing a dispersant which holds a site adsorbed to the pigment and a site having a high affinity with the monomer, (2) a method of encapsulating the pigment with a material having a high monomer affinity, (3) Methods such as modifying the pigment to make it a self-dispersible pigment have been taken.
JP-A-2009-57546 (Patent Document 1) has excellent dispersibility by using a polymer dispersant of poly(ethyleneimine)-poly(12-hydroxystearic acid) graft polymer such as Solsperse 24000GR as a dispersant. Proposed UV inkjet ink.
Japanese Unexamined Patent Application Publication No. 2011-53094 (Patent Document 2) proposes a method of measuring an adsorption amount of a dispersant with respect to a solid dispersed in a dispersion medium using an NMR spectrum.
Japanese Patent Application Laid-Open No. 2013-112691 (Patent Document 3) improves dispersibility by adding an excessive dispersant at a saturated adsorption amount or more when carbon black is used as a pigment.
JP-A-2009-108213 (Patent Document 4) discloses a dispersion liquid for a color filter which is excellent in dispersibility and light resistance by controlling the amount of a dispersant adsorbed to a pigment to 1.0 to 5.0 mg/m ^2. providing.
Japanese Patent Application Laid-Open No. 2009-52010 discloses a color filter dispersion liquid in which the dispersibility of brominated zinc phthalocyanine, which is a pigment, is enhanced by using a block copolymer dispersant having an amine value of 80 to 150 mgKOH/g. providing.
Japanese Patent Laid-Open No. 2005-263898 (Patent Document 6) proposes a UV inkjet ink in which a free polymeric dispersant that is not adsorbed on a pigment is 1.0% by mass or less of the total ink.
Japanese Patent Application Laid-Open No. 2006-342201 (Patent Document 7) discloses (ratio of polymer dispersant to pigment in ink excluding sediment after centrifugation)/(polymer dispersant to pigment in ink before centrifugation). An inkjet ink having a ratio of 1.0 to 1.5 is proposed.

However, a black pigment composition or an inkjet ink that can obtain good dispersibility with a small amount of a dispersant adsorbed to a pigment has not been found so far. Therefore, it has been difficult to satisfy the characteristics such as dispersibility, dischargeability, curability, and film strength. Further, neither a black pigment composition nor an ink capable of satisfying both of the above characteristics and filter filterability (liquid permeability) has been found.
An object of the present invention is to provide an active energy ray-curable composition having high dispersibility and dischargeability, and excellent hiding properties, curability and liquid permeability.

As a means for solving the above problems, the present invention contains a carbon black, a dispersant and a polymerizable compound, and when the content ratio of the dispersant to the carbon black is 1 (mass basis) of the carbon black. And 0.09 to 0.22, and the amount of the dispersant adsorbed on the carbon black is 50 to 180 mg per 1 g of carbon black.

  According to the present invention, there is provided an active energy ray-curable composition having high dispersibility and dischargeability, and excellent in hiding property, curability and liquid permeability.

It is a schematic diagram showing an example (manufacturing apparatus of a two-dimensional stereoscopic image) of an image forming apparatus provided with an inkjet ejection means. FIG. 3 is a schematic diagram showing an example of an image forming apparatus (an apparatus for producing a three-dimensional stereoscopic image) including an inkjet ejection unit. It is a schematic diagram showing another example (manufacturing device of a three-dimensional solid image) of an image forming device. It is an example of the ultraviolet spectrum of a mercury lamp. It is an example of the ultraviolet spectrum of a metal halide lamp. It is an example of the ultraviolet spectrum of UV-LED.

(Active energy ray curable composition)
The active energy ray-curable composition of the present invention contains carbon black, a dispersant and a polymerizable compound, and further contains a polymerization initiator, a polymerization accelerator and other components, if necessary.

In the present invention, since the pigment is carbon black, the hiding power is high, and since the amount of the adsorbing component adsorbed on the pigment is 50 to 180 mg per 1 g of carbon black, excellent dispersibility and efficient dispersion are achieved. The agent is adsorbed, and the dischargeability, hiding power, curability, and liquid permeability are compatible. Hereinafter, carbon black may be simply referred to as a pigment.
When the amount of the adsorbing component is less than 50 mg, the affinity between the pigment and the dispersion medium cannot be maintained and the pigment dispersibility is reduced, and when it is more than 180 mg, the viscosity of the dispersion liquid itself becomes high and the curability and adhesion are improved. , The strength of the cured film is reduced. Further, especially in the step of removing coarse particles through a filter of 1 μm or less, liquid permeability is lowered and productivity is lowered.

In the present invention, the adsorbent component adsorbed on the pigment is a dispersant, and the amount adsorbed on the pigment (dispersant adsorbed amount) is more preferably 70 to 130 mg per 1 g of the pigment. Hereinafter, the case where the adsorbing component is a dispersant will be described as an example.
Further, the amount of the dispersant not adsorbed on the pigment is more preferably 10 to 50% of the adsorbed amount of the dispersant. By maintaining this ratio, the balance with the amount of the dispersant adsorbed is maintained, and the effect of the present invention is further enhanced.
When the amount of the dispersant not adsorbed on the pigment is less than 10% of the adsorbed amount of the dispersant, the dispersant adsorbed on the pigment is likely to move to the dispersion medium side, and the adsorbed amount of the dispersant is reduced. If the amount of the dispersant not adsorbed on the pigment exceeds 50% of the amount of the dispersant adsorbed, the effect of maintaining the above balance is not exerted, but rather the viscosity of the dispersion is increased or the liquid permeability is decreased. Or the side effect of decreasing the curability and adhesiveness becomes large.

  Further, the amount of the dispersant adsorbed when the active energy ray-curable composition of the present invention is stored at 70° C. for 2 weeks is preferably in the range of 80% to 120% of the amount of the dispersant adsorbed before the storage. Even if the dispersant is adsorbed on the pigment, if the adsorptive power is weak, the dispersant is desorbed from the pigment when stored at 70° C. for 2 weeks, and the dispersibility is impaired. If the above ratio is less than 80%, the adsorption force is weak and the dispersed state becomes unstable. On the other hand, if it exceeds 120%, the viscosity of the dispersion changes greatly, which is not preferable.

The dispersant adsorption amount can be measured, for example, by the following method. Weigh 1.5 g of the active energy ray-curable composition into a 1 ml sample holder for centrifugation. This is centrifuged at 10,000 rpm for 1 hour to remove the supernatant. Almost the same amount of acetone as the removed amount is added to this, the mixture is stirred with a spatula, and similarly centrifuged, and a total of 4 times. This is completely dried in a vacuum dryer.
Accurately measure about 100 mg of the above dried sample in an aluminum cup, heat at 400° C. for 2 hours and measure the remaining amount (remaining amount after heating), and calculate the difference in mass of the dried sample before and after heating (weight reduction after heating) , The dispersant adsorption amount is calculated from the following formula.

[Amount of dispersant adsorbed on 1 g of pigment=(1000 (mg)/remaining amount after heating (mg))×(weight loss after heating (mg)-carbon weight loss (mg)]
The carbon weight loss is the weight loss (mg) when 1000 mg of carbon black alone is heated alone at 400° C. for 2 hours.

The amount of dispersant not adsorbed to the pigment is (dispersant prescription amount/pigment prescription amount)×1000 (mg)-dispersant amount adsorbed on 1 g of pigment (mg) when the input amount is known. Required by.
When the input amount is unknown, the input amount can be determined, for example, by collecting the supernatant of the above method and measuring it by liquid chromatography or the like.

  The volume average particle diameter of the active energy ray-curable composition of the present invention is preferably 100 nm or more and 150 nm or less, more preferably 110 nm or more and 140 nm or less. If the volume average particle size is less than 100 nm, the print density may decrease, and if it is more than 150 nm, head clogging tends to occur when recording is performed using an inkjet system, and ejection stability may decrease. is there. As the volume average particle size, the active energy ray-curable composition is diluted about 100 times with phenoxyethyl acrylate, and a particle size distribution meter (device name: UPA150, manufactured by Nikkiso Co., Ltd.) is used. It can be determined by measuring the volume average particle diameter of the linear curable composition. The volume average particle diameter of the active energy ray-curable composition means the volume average particle diameter obtained by subjecting the active energy ray-curable composition itself to measurement, and Corresponds to the particle size of the particulate object (specifically, a pigment dispersion containing a pigment).

  Further, in the active energy ray-curable composition of the present invention, it is preferable that 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. According to this aspect, there is an effect that the printing density is high and the ejection stability is improved.

The active energy ray-curable composition was used to irradiate and cure an active energy ray having an illuminance of 1 W/cm ² and an irradiation amount of 500 mJ/cm ² on a transparent substrate, and the average thickness was The print density of the cured product of 10 μm is preferably 1.4 or more, more preferably 1.5 or more.
The average thickness is measured using, for example, a contact (pointer type) to an eddy current type film thickness meter, for example, an electronic micrometer (manufactured by Anritsu Co., Ltd.), and calculated from an average value of film thicknesses at 10 points. be able to.

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

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

The number average primary particle diameter of the carbon black used in the present invention is preferably 35 nm or more and 60 nm or less, and more preferably 40 nm or more and 55 nm or less.
When the number average primary particle diameter is 35 nm or more and 60 nm or less, the print density is easily 1.4 or more, and the dispersibility can be improved.

Further, the DBP oil absorption of the carbon black used in the present invention is preferably 35 g/100 g or more and 55 g/100 g or less, and more preferably 40 g/100 g or more and 50 g/100 g or less. By using such carbon black, the print density can easily be 1.4% or more and the dispersibility can be improved.
The carbon black used in the present invention is preferably an oxidized carbon black having a pH of 3.5 or less. pH 3.5 or less Oxidized carbon black has many functional groups such as quinone, carboxyl, aldehyde, lactone, and phenol, and has high dispersant adsorption. When such an oxidized carbon black having a pH of 3.5 or less is used, the print density can easily be 1.4 or more and the dispersibility can be improved.

  The number average primary particle size of the active energy ray-curable composition is 200 or more and 500 or more primary particles in a visual field of 10,000 times using a scanning electron microscope (device name: SU3500, manufactured by Hitachi High-Technology Co., Ltd.). It is possible to obtain the average diameter of the cumulative distribution by measuring the unidirectional diameters at intervals between two parallel lines in a certain direction sandwiching not more than one primary particle. The DBP oil absorption can be measured using the method described in JIS K6217-4. The pH of the oxidation-treated carbon black is obtained by making carbon black into an aqueous suspension and measuring the pH.

  The volume average particle diameter (Dv) of the active energy ray-curable composition of the present invention and the particle diameter ratio (Dv/Dn) of the number average primary particle diameter (Dn) of the pigment are 1.5 or more and 3. It is preferably 0 or less, more preferably 1.8 or more and 2.5 or less. According to this mode, the effect of dispersion stability is exhibited.

  Although carbon black is used as a pigment in the present invention, for example, a cyan pigment or a cyan pigment derivative may be contained as a complementary color.

  The cyan pigment is C.I. I. Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:5, 15:6 and the like phthalocyanine pigments and Pigment Blue 18, 56 and the like alkali blue pigments are preferable. As the cyan pigment derivative, an acidic type having a carboxyl group, a sulfone group or a nitro group at the terminal group, or a basic type having an amino group or an acid amide group is used.

Examples of carbon black suitable for the present invention include Special Black 250 manufactured by Orion (Degussa) and MOGUL-E manufactured by Cabot.
The Special Black 250 is described as an example of carbon black that can be used in JP 2012-144681 A or the like, and is used in Examples in JP 2012-31254 A.

  However, even if the carbon blacks described in JP2012-144681A and JP2012-31254A are used, the dispersion in the present invention may occur due to a combination with other materials, a prescribed amount, a difference in a construction method, and the like. The adsorbed amount of the dispersant in the present invention is not satisfied, and the adsorbed amount of the dispersant in the present invention is obtained only by adjusting and optimizing these materials, prescription amounts, and construction methods. As an example, in order to satisfy the amount of the dispersant adsorbed in the present invention, a high pigment concentration of about 35% pigment concentration, kneading than crushing force at a viscosity of about 200 ~ 700 mPas viscosities, dispersion method to increase the shear shear force, Examples include dispersion conditions, a method of optimizing the pigment and the dispersant, and dispersing.

  The carbon black can be used as a mixture of two or more kinds within a range in which the amount of the dispersant adsorbed can be maintained.

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

  The content of carbon black is preferably 1% by mass or more and 10% by mass or less based on the total amount of the active energy ray-curable composition. 2 mass% or more and 5 mass% or less are more preferable. When the content is 1% by mass or more, the printing density can be improved, and when the content is 10% by mass or less, the increase in viscosity can be suppressed and the ejection property can be improved.

<Polymerizable compound>
The polymerizable compound is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a polymerizable unsaturated monomer compound and a polymerizable oligomer.

<<Polymeric unsaturated monomer compound>>
The polymerizable unsaturated monomer compound is not particularly limited and may be appropriately selected depending on the purpose. For example, a monofunctional polymerizable unsaturated monomer compound, a bifunctional polymerizable unsaturated monomer compound, and a trifunctional compound. And the polymerizable unsaturated monomer compound having four or more functional groups. 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 thereof include phenyl glycol monoacrylate, cyclohexyl acrylate, acryloylmorpholine, 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 thereof 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, and tris(2-hydroxyethyl)isocyanurate triacrylate. 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.
Each of the polymerizable unsaturated monomer compounds may be used alone or in combination of two or more kinds, or two or more kinds of different kinds of polymerizable unsaturated monomer compounds may be used in combination.

  As the polymerizable unsaturated monomer compound, a polyfunctional polymerizable unsaturated monomer compound can accelerate the curing speed more than a monofunctional polymerizable unsaturated monomer compound, but when the viscosity of the composition increases. Alternatively, volume shrinkage may increase. Therefore, it is preferable to use a polymerizable unsaturated monomer compound that can make the viscosity as low as possible.

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

  The skin irritation (P.I.I.) of the polymerizable unsaturated monomer compound is appropriately selected depending on the intended purpose without any limitation, but it is preferably 1.0 or less. When the skin irritation is 1.0 or less, irritation to the skin can be reduced and safety can be improved.

  The hue of the polymerizable unsaturated monomer compound is preferably 2 or less on the Gardner gray scale, and more preferably colorless and transparent. When the Gardner gray scale is 2 or less, it is possible to prevent the color of the image portion from changing. The Gardner gray scale can be measured according to JIS-0071-2 Chemical Product Color Test Method-Gardner Color Number Test Method.

  The content of the polymerizable unsaturated monomer compound is preferably 50% by mass or more and 90% by mass or less, more preferably 65% by mass or more and 85% by mass or less with respect to the total amount of the active energy ray-curable composition.

<<Polymerizable Oligomer>>
The polymerizable oligomer preferably has at least one ethylenically unsaturated double bond. The term “oligomer” means a polymer in which the number of repeating monomer structural units is 2 or more and 20 or less.

  The weight average molecular weight of the polymerizable oligomer is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1,000 or more and 30,000 or less in terms of polystyrene, and 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 acryl oligomers (for example, aromatic urethane acryl oligomers, aliphatic urethane acryl oligomers, etc.), epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers. These may be used alone or in combination of two or more. Among these, oligomers having 2 to 5 unsaturated carbon-carbon bonds are preferable, and oligomers having 2 unsaturated carbon-carbon bonds are more preferable. When the number of unsaturated carbon-carbon bonds is 2 or more and 5 or less, good curability can be obtained.

As the polymerizable oligomer, a commercially available product can be used, and examples of the commercially available product 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; CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, manufactured by Sartomer. 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, CN982B88, CN982CN, CN982CN, CN982, CN982, CN982, CN985, CN985B, CN985B, CN983. CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011, CN9013, CN9018, CN9019, CN9024, CN9025, CN9026, CN9028, CN9029, CN9030, CN9060, CN9165, 78911, CN9167. CN9290, CN9782, CN9783, CN9788, CN9893; EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KRM8200, EBECRYL manufactured by Daicel Cytec Co., Ltd. 5129, EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYLEC83L, EBECRYB01R8370, EBECRYL8370, EBECRYL8170, EBECRYBLYL8370, EBECRYLE9270, EBECRYLE9270, EBECRYLE9270, EBECRYLE9270. These may be used alone or in combination of two or more.
Further, instead of a commercial product, a synthetic product obtained by synthesis may be used, or a synthetic product and a commercial product may be used in combination.

  The skin irritation (P.I.I.) of the polymerizable oligomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.0 or less. When the skin irritation is 1.0 or less, irritation to the skin can be reduced and safety can be improved.

  The hue of the polymerizable oligomer is preferably 2 or less on the Gardner gray scale, and more preferably colorless and transparent. When the Gardner gray scale is 2 or less, it is possible to prevent the color of the image portion from changing. The Gardner gray scale can be measured according to JIS-0071-2 Chemical Product Color Test Method-Gardner Color Number Test Method.

  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 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.

<Dispersant>
The dispersant is preferably contained to disperse the pigment.

The acid value of the dispersant is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more.
The amine value of the dispersant is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more.

The dispersant is preferably a polymer dispersant.
Examples of the polymer dispersants include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers and the like. These may be used alone or in combination of two or more. Among these, acrylic polymers and copolymers are preferable, and acrylic block copolymers having an acid value of 5 mgKOH/g or more and an amine value of 10 mgKOH/g or more are more preferable from the viewpoint of adsorption to the pigment.

As the polymer dispersant, a commercially available product may be used, and as the commercially available product, for example, Ajinomoto Fine Techno Co., Ltd., Addisper series, Japan Ruble Resol Co., Ltd. (Avecia Co., Noveon Co.) Spurs series (Product name: Solsperse 32000 (acid value: 15.5 mgKOH/g, amine value: 31.2 mgKOH/g), product name: Solsperse 39000 (acid value: 33 mgKOH/g, amine value: 0 mgKOH/g), etc.) , DISK BYK Japan manufactured by DISPERBYK series ((trade name: DISPERBYK-168, acid value: 0 mgKOH/g, amine value: 11 mgKOH/g), (trade name: DISPERBYK-167, acid value: 0 mgKOH/g, amine Value: 13 mgKOH/g) etc.), BYKJET series, Disparlon series manufactured by Kusumoto Kasei Co., Ltd., and the like. These may be used alone or in combination of two or more.
As the acrylic block copolymer, a commercially available product may be used, and examples of the commercially available product include: BYKJET-9151 (manufactured by BYK Chemie Japan, Inc., acid value: 8 mgKOH/g, amine value: 18 mg KOH/g) is preferred.

  Since the dispersant can coat the pigment with the dispersant adsorption amount of the present invention without excess or deficiency, aggregation can be prevented, dispersibility can be improved, and excess dispersant can be dissolved in the monomer to increase the viscosity. Can be suppressed and the dischargeability can be improved.

<Polymerization initiator>
The polymerization initiator may be any one that can generate active species such as radicals and cations by the energy of the active energy ray to initiate the polymerization of the polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators or cationic polymerization initiators can be used alone or in combination of two or more, and it is preferable to use the radical polymerization initiator. The content of the polymerization initiator is preferably 5% by mass or more and 20% by mass or less with respect to the total amount of the active energy ray-curable composition in order to obtain a sufficient curing rate.

Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds. , 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 in accordance with 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, and a thioxanthone compound is preferable because it is less susceptible to oxygen inhibition during thin film formation. (Thioxanthone type polymerization initiator) is more preferable.

  As the polymerization initiator, a commercially available product may be used, and examples of the commercially available product include Irgacure 819, Irgacure 369, Irgacure 907, DarocurITX, Lucilin TPO, manufactured by BASF, and Vicure 10 manufactured by Stauffer Chemical. 30 and the like. These may be used alone or in combination of two or more.

  A commercially available product can be used as the thioxanthone-based polymerization initiator, and examples of the commercially available product include Speedcure DETX (2,4-diethylthioxanthone) and Speedcure ITX (2-isopropylthioxanthone) (above, Lambson Corporation). Manufactured); KAYACURE DETX-S (2,4-diethylthioxanthone) (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  Further, as the polymerization initiator, (i) high absorption efficiency of active energy rays, (ii) high solubility in the polymerizable unsaturated monomer compound, (iii) odor, yellowing, and low toxicity , (Iv) those which do not cause a dark reaction are preferable.

Further, in addition to the polymerization initiator, a polymerization accelerator can be used together.
The polymerization accelerator is not particularly limited, and examples thereof include ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. Examples thereof include 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), for example, the polymerization initiator has the following formulas (I) and (II). Generate radicals. The radical causes an addition reaction to the polymerizable double bond of the polymerizable unsaturated monomer compound or the polymerizable oligomer. A radical is further 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-based polymerization initiator of the above formula (I) is used, the reaction may be delayed only by the polymerization initiator. Therefore, by using an amine-based sensitizer together, the reactivity is enhanced. It is preferable. By including an amine compound as a polymerization accelerator, it has an effect of supplying hydrogen to the polymerization initiator by a hydrogen abstraction action and an effect of preventing reaction inhibition by 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>
Other components are not particularly limited, but include, for example, other conventionally known coloring materials, organic solvents, polymerization inhibitors, slip agents (surfactants), penetration accelerators, wetting agents (humectants), fixing agents. , Antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, thickeners and the like.

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

  The content of the polymerization inhibitor is preferably 0.005% by mass or more and 3% by mass or less based on the total amount of the polymerization initiator. When the content is 0.005 mass% or more, storage stability can be improved, an increase in viscosity can be suppressed in a high temperature environment, and when it is 3 mass% or less, curability can be improved.

<< Surfactant >>
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include higher fatty acid surfactants, silicone surfactants, and fluorine surfactants.

  The content of the surfactant is preferably 0.1% by mass or more and 3% by mass or less, and more preferably 0.2% by mass or more and 1% by mass or less, based on the total amount of the active energy ray-curable composition. When the content is 0.1% by mass or more, wettability can be improved, and when the content is 3% by mass or less, curability can be improved. When the content is within a more preferable range, wettability and leveling property 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 include it if possible. By not containing organic solvent (for example, VOC (Volatile Organic Compounds) free), volatile organic solvent does not remain in the cured film, and printing site safety can be obtained and environmental pollution can be prevented. Becomes The “organic solvent” means one generally called a volatile organic compound (VOC), and examples thereof include ether, ketone, xylene, ethyl acetate, cyclohexanone, toluene, and the like. It is to be distinguished from the functional monomer. In addition, the phrase "does not include" the organic solvent means that the organic solvent is not substantially contained, and the content thereof is preferably less than 0.1% by mass.

<Manufacturing method>
As a method for producing the active energy ray-curable composition, a pigment, a dispersant and a polymerizable compound are charged into a disperser using media such as a ball mill, a kitty mill, a disc mill, a pin mill and a dyno mill, and dispersed and kneaded. It can be obtained by preparing a pigment dispersion liquid by further mixing it with a polymerization initiator, a polymerization inhibitor, a surfactant and the like. Alternatively, a medialess dispersion device such as a disper or a homogenizer may be used.

<Active energy ray>
Examples of the active energy ray used for curing the active energy ray-curable composition of the present invention include ultraviolet rays, electron rays, α rays, β rays, γ rays, X rays, and other polymerizable components in the composition. There is no particular limitation as long as it can provide the energy required for advancing the polymerization reaction. Especially when a high energy light source is used, the polymerization reaction can proceed without using a polymerization initiator.

The light source of the active energy ray is not particularly limited and may be appropriately selected, and examples thereof include a mercury lamp, a metal halide lamp, and a UV-LED lamp.
As the mercury lamp, a high-purity mercury (Hg) and a small amount of rare gas are enclosed in a quartz glass arc tube, and the main wavelength is 365 nm, and ultraviolet rays of 254 nm, 303 nm, and 313 nm are efficiently emitted. The feature is that it radiates and the output of short wavelength ultraviolet rays is high.
As the metal halide lamp, in addition to mercury, a metal is enclosed in the form of a halide in an arc tube, which emits an active energy ray spectrum over a wide range from 200 nm to 450 nm, and is 300 nm or more and 450 nm or less as compared with a mercury lamp. It is characterized by high output of long-wavelength ultraviolet light.
The UV-LED lamp is characterized by a long life and low power consumption LED system that can reduce the environmental load, can generate a compact ozone-free device, and can provide the active energy ray-curable composition of the present invention. It is preferable as a lamp used for curing.
FIG. 4 shows an example of the ultraviolet spectrum of a mercury lamp, FIG. 5 shows an example of the ultraviolet spectrum of a metal halide lamp, and FIG. 6 shows an example of the ultraviolet spectrum of a UV-LED.

(Use)
The active energy ray-curable composition of the present invention is not particularly limited as long as it is a field in which an active energy ray-curable material is generally used, and can be appropriately selected according to the purpose. For example, a molding resin, It can be applied to 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 used as an ink to form not only two-dimensional characters and images, but also a three-dimensional object (three-dimensional object) for forming a three-dimensional object. Can also be used as

As the three-dimensional modeling material, for example, as a binder between powder particles used in the powder lamination method which is one of the three-dimensional modeling methods, and as shown in FIG. 2, an active energy ray-curable composition is used. As shown in FIG. 3, a material jet method (stereolithography method) in which three-dimensional modeling is performed by sequentially stacking materials that have been discharged to a predetermined area and irradiated with active energy rays and cured, and an active energy ray-curable composition A storage pool (accommodation part) 5 of 5 is irradiated with active energy rays 4 to form a hardened layer 6 of a predetermined shape on a movable stage 3, and the solid layers are sequentially laminated to perform three-dimensional modeling. It can be used as a constituent material.
The three-dimensional modeling device for modeling a three-dimensional model using such an active energy ray-curable composition may be a known one, and is not particularly limited, but for example, a means for accommodating the composition, It is possible to use those provided with a supply means, a discharge means, an active energy ray irradiation means, and the like.

  The present invention also includes a cured product obtained by curing an active energy ray-curable composition, and a molded product obtained by processing a structure formed on a base material such as a recording medium. .. The molded product is, for example, a cured product or structure formed in a sheet shape or a film shape, which has been subjected to molding processing such as heat drawing and punching processing. -It is suitable for use in applications where it is necessary to mold the surface after decorating it, such as electronic devices, meters for cameras, panels for operating parts, etc. The base material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper, plastic, metal, ceramics, glass, and composite materials thereof. Substrates are preferred. Further, the stretchability of the cured product in the present invention is expressed as the stretchability at 180° C. by the 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”) comprises the active energy ray-curable composition of the present invention and is preferably for inkjet.

The static surface tension of the active energy ray-curable ink at 25° C. 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 tensiometer (CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd.). The static surface tension is based on the specifications of a commercially available inkjet ejection head such as GEN4 manufactured by Ricoh Printing Systems Co., Ltd.

(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 containing the ink can be used as an ink cartridge or an ink bottle, whereby ink transport, ink exchange, etc. In the above work, it is not necessary to directly touch the ink, and it is possible to prevent stains on fingers and clothes. Further, it is possible to prevent foreign matter such as dust from entering the ink. Further, the shape, size, material, etc. of the container itself may be those suitable for the intended 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 light-shielding. It is desirable to be covered with a property sheet.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an irradiation step of irradiating an active energy ray in order to cure the active energy ray-curable composition, and the image forming apparatus of the present invention irradiates the active energy ray. The container may be accommodated in the accommodating section, and an accommodating section for accommodating the active energy ray-curable composition. Further, a discharging step and a discharging means for discharging the active energy ray-curable composition may be provided. The method of discharging is not particularly limited, and examples thereof include a continuous jet type and an on-demand type. Examples of the on-demand type include piezo type, thermal type and electrostatic type.

  FIG. 1 is an example of an image forming apparatus provided with an inkjet ejection unit. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d including an ink cartridge of active energy ray curable ink of each color of yellow, magenta, cyan, and black and an ejection head. To be done. Then, an active energy ray is irradiated from the light sources 24a, 24b, 24c, and 24d for curing the ink to cure the ink to form a color image. Then, 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, 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejecting portion. Further, 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 width of the ejection head, the head is moved to eject ink on the recording medium, or the recording medium is continuously moved and held at a fixed position. Any line type ink jet recording apparatus in which ink is ejected from the head onto the recording medium is applicable.

The recording medium 22 is not particularly limited, and may be paper, film, metal, a composite material of these, or the like, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible or double-sided printing is possible.
Furthermore, the irradiation of active energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the active energy rays may be irradiated from the light source 24d. As a result, energy saving and cost reduction can be achieved.

  The recorded matter to be recorded by the ink of the present invention is not only those printed on a smooth surface such as ordinary paper and resin film, but also those printed on a printed surface having irregularities, such as metal and ceramics. It also includes those printed on the printing surface made of various materials. Further, by stacking two-dimensional images, it is possible to form a partially stereoscopic image (two-dimensional and three-dimensional image) 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 of FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged, and transfers the first active energy ray-curable composition from the ejection head unit 30 for a model to a support. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is ejected from the ejection head units 31, 32, and these compositions are adjoined by the adjacent ultraviolet irradiation means 33, 34. It is laminated while curing. More specifically, for example, the second active energy ray-curable composition is ejected from the ejection head units 31 and 32 for the support onto the molded article supporting substrate 37, and the active energy ray is irradiated to be solidified. After forming the first support layer having a reservoir, the first active energy ray-curable composition is ejected from the ejection head unit 30 for a molded article to the reservoir and irradiated with active energy rays to be solidified. The step of forming the first modeling object layer by repeating the above process a plurality of times while lowering the vertically movable stage 38 in accordance with the number of times of stacking, thereby stacking the support layer and the modeling object layer to form the three-dimensional modeling object 35. To produce. After that, the support laminated portion 36 is removed if necessary. In addition, in FIG. 2, only one ejection head unit 30 for a molded object is provided, but two or more ejection 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 ink of the present invention is not only an ordinary one printed on a smooth surface such as paper or a resin film, but also recorded on an uneven recording surface. And those recorded on recording surfaces made of various materials such as metals and ceramics.

Examples of the two-dimensional image include a character, a symbol, a figure or a combination thereof, and a solid image.
Examples of the three-dimensional image include a three-dimensional object.
The average thickness of the three-dimensional model is not particularly limited and may be appropriately selected depending on the intended purpose, and is preferably 10 μm or more.

The two-dimensional or three-dimensional image is formed on a non-permeable substrate because either the active energy ray-curable composition of the present invention or the active energy ray-curable ink of the present invention is used. A three-dimensional or three-dimensional image has excellent water resistance that can maintain good adhesion even after immersion in water.
The two-dimensional or three-dimensional image is preferably cured using light emitting diode light.

(Structure)
The structure of the present invention has a base material and the two-dimensional or three-dimensional image of the present invention on the base material.
The base material is not particularly limited and can be appropriately selected depending on the purpose.

(Molded product)
The molded product of the present invention is formed by stretching either the two-dimensional or three-dimensional image of the present invention and the structure of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
Further, the adsorbed amount of the dispersant, the amount of the dispersant not adsorbed on the pigment (non-adsorbed amount of the dispersant), the volume average particle diameter of the active energy ray-curable composition, the volume particle diameter, and the number average primary particle diameter of the pigment are , Was obtained as follows. The measurement results are shown in Tables 6 and 7 together with the composition stored at 70° C. for 2 weeks.

<Dispersant adsorption amount>
1.5 g of the active energy ray-curable composition was weighed in a 1 ml sample holder for centrifugation, centrifuged at 10,000 rpm for 1 hour to remove the supernatant, and the amount of the removed solution was almost the same. Acetone was added, the mixture was stirred with a spatula, and the mixture was centrifuged in the same manner, and a total of 4 times. This is completely dried with a vacuum dryer, about 100 mg of the above dried sample is accurately weighed in an aluminum cup, heated at 400° C. for 2 hours, and the remaining amount is measured (remaining amount after heating). The mass difference was calculated (weight reduction after heating), and the dispersant adsorption amount was calculated from the following formula.
[Amount of dispersant adsorbed on 1 g of pigment=(1000 (mg)/remaining amount after heating (mg))×(weight loss after heating (mg)-carbon weight loss (mg)]
The carbon weight loss is the weight loss (mg) when 1000 mg of carbon black alone is heated alone at 400° C. for 2 hours.
<Amount of unadsorbed dispersant>
(Dispersant formulation amount/pigment formulation amount)×1000 (mg)−Dispersant amount adsorbed on 1 g of pigment (mg).

<Volume average particle size of active energy ray-curable composition>
As the volume average particle diameter of the active energy ray-curable composition, the obtained active energy ray-curable composition is diluted about 100 times with phenoxyethyl acrylate, and a particle size distribution meter (device name: UPA150, Nikkiso Co., Ltd.) is used. (Manufactured by the company) was used to measure the volume particle diameter and volume average particle diameter of the active energy ray-curable composition. From the obtained volume particle diameter, the content of the active energy ray-curable composition having a volume particle diameter of 50 nm or less and the content of the active energy ray-curable composition having a volume particle diameter of 230 nm or more were calculated.

<Number average primary particle size of pigment>
As the number average primary particle diameter of the pigment, the obtained active energy ray-curable composition was observed with a scanning electron microscope (apparatus name: SU3500, manufactured by Hitachi High-Technology Co., Ltd.) in a field of view of 10,000 times. The unidirectional diameter in the interval between two parallel lines in a fixed direction sandwiching 200 or more and 500 or less primary particles was measured, and the average diameter of the cumulative distribution was calculated.

(Preparation of pigment dispersion)
<Preparation of Pigment Dispersion A>
45 parts by mass of carbon black A (trade name: Special Black 250: manufactured by Orion), amine group-containing acrylic block copolymer (dispersant, BYKJET-9151, manufactured by BYK Japan KK, acid value: 8 mgKOH/g , Amine value: 18 mg KOH/g) and 100 parts by mass of phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) were placed in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling ratio: 45% by volume). After dispersing at 70 rpm for 96 hours at a dispersion temperature of 25° C., 72 parts by mass of phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added and dispersed for 30 minutes, and then zirconia beads having a diameter of 0.1 mm were used. It was placed in a filled 1 L sand mill (filling rate: 80% by volume) and dispersed at a peripheral speed of 8 m/sec at a dispersion temperature of 25° C. for 3 hours to prepare a pigment dispersion A.

<Preparation of Pigment Dispersion B>
45 parts by mass of carbon black A (trade name: Special Black 250: manufactured by Orion), amine group-containing acrylic block copolymer (dispersant, BYKJET-9151, manufactured by BYK Japan KK, acid value: 8 mgKOH/g) , Amine value: 18 mg KOH/g) 6 parts by mass, and phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 80 parts by mass were dispersed at a dispersion temperature of 35° C. for 20 minutes at 5,000 rotations using a homogenizer. , 1 mm sand mill filled with 0.3 mm diameter zirconia beads (filling rate: 90% by volume), the peripheral speed was 10 m/sec and the dispersion temperature was 30° C. for 1 hour, and then phenoxyethyl acrylate (Osaka Organic (Manufactured by Kagaku Kogyo Co., Ltd.) 94 parts by mass was added and dispersed for 20 minutes to prepare a pigment dispersion B.

<Preparation of Pigment Dispersion C>
45 parts by mass of carbon black B (trade name: Special Black 350: manufactured by Orion Co., Ltd.), a comb resin dispersant of a fatty acid amine having polyethyleneimine as a main skeleton (dispersant, trade name: Sols Perth 39000, manufactured by Nippon Ruble Resol Co., acid Value: 33 mgKOH/g, amine value: 0 mgKOH/g) 4 parts by mass, and acryloylmorpholine (manufactured by Kojin Co., Ltd.) 83 parts by mass in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling ratio: 43% by volume). The mixture was put therein and the dispersion temperature was 70° C./minute at 25° C. for 180 hours, and then 93 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) was added to prepare a pigment dispersion C.

<Preparation of Pigment Dispersion D>
45 parts by mass of carbon black C (trade name: MOGUL-L: manufactured by Cabot Corp.), amine group-containing acrylic block copolymer (dispersant, BYKJET-9151, manufactured by BYK Japan KK, acid value: 8 mgKOH/ g, amine value: 18 mgKOH/g) 10 parts by mass, and 67 parts by mass of 2-vinyloxyethoxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) filled with zirconia beads having a diameter of 2 mm (filling ratio: 45% by volume), 500 mL ball mill. Then, the dispersion temperature was set to 25° C. and the rotation speed was 70 rotations/minute for 200 hours.

<Preparation of Pigment Dispersion E>
45 parts by mass of carbon black B (trade name: Special Black 350: manufactured by Orion Co., Ltd.), a comb resin dispersant of a fatty acid amine having polyethyleneimine as a main skeleton (dispersant, trade name: Sols Perth 39000, manufactured by Nippon Ruble Resol Co., acid Value: 33 mgKOH/g, amine value: 0 mgKOH/g) 9 parts by mass, and 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 79 parts by mass at a dispersion temperature of 35° C. using a homogenizer. After dispersing at 000 rpm for 15 minutes, the mixture was placed in a sand mill filled with zirconia beads having a diameter of 0.3 mm (filling rate: 80% by volume) and dispersed for 1 hour at a dispersion temperature of 30° C. and a peripheral speed of 8 m/sec. -72 parts by weight of hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added to prepare a pigment dispersion E.

<Preparation of Pigment Dispersion F>
Preparation of Pigment Dispersion A, except that Carbon Black A (trade name: Special Black 250, manufactured by Orion) was changed to Carbon Black D (Product Name: Special Black 550, manufactured by Orion) in the preparation of Pigment Dispersion A A pigment dispersion F was prepared in the same manner as in.

<Preparation of Pigment Dispersion G>
In the preparation of the pigment dispersion B, except that the carbon black A (trade name: Special Black 250, manufactured by Orion Co., Ltd.) was changed to carbon black E (trade name: MOGUL-E, manufactured by Cabot Corporation). Pigment Dispersion G was prepared in the same manner as the preparation.

<Preparation of Pigment Dispersion H>
45 parts by mass of carbon black F (trade name: MA14, manufactured by Mitsubishi Chemical Co., Ltd.), carboxylic acid ester-containing acrylic block copolymer (dispersant, trade name: DISPERBYK-168, BYK Japan KK, acid value: 0 mgKOH/ g, amine value: 11 mg KOH/g) 5 parts by mass, and 105 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) at a dispersion temperature of 35° C. using a homogenizer at 15 rpm at 8,000 rpm. After being dispersed for 70 minutes, 70 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added, and the mixture was placed in a sand mill filled with zirconia beads having a diameter of 0.5 mm (filling ratio: 75% by volume) and the dispersion temperature was 25°C. A pigment dispersion H was prepared by dispersing at a peripheral speed of 8 m/sec for 1 hour.

<Preparation of Pigment Dispersion I> (Comparative Example 1 Dispersion)
In the production of the pigment dispersion D, an amine group-containing acrylic block copolymer (dispersant, BYKJET-9151, manufactured by BYK Japan KK, acid value: 8 mgKOH/g, amine value: 18 mgKOH/g) was used. Pigment Dispersion D except that it was changed to a dicarboxylic acid ester-containing acrylic block copolymer (dispersant, trade name: DISPERBYK-168, BYK Japan KK, acid value: 0 mgKOH/g, amine value: 11 mgKOH/g). Pigment Dispersion I was prepared in the same manner as in 1.

<Preparation of Pigment Dispersion J> (Comparative Example 2 Dispersion)
Carbon black G (trade name: trade name: #850, manufactured by Mitsubishi Chemical Co., Ltd.) 45 parts by mass, amine group-containing acrylic block copolymer (dispersing agent, trade name: BYKJET-9151, manufactured by BYK Japan KK, acid) Value: 8 mgKOH/g, amine value: 18 mgKOH/g) 15 parts by mass, and acryloylmorpholine (manufactured by Kojin Co., Ltd.) 165 parts by mass in a 500 mL ball mill filled with 1 mm diameter zirconia beads (filling ratio: 48% by volume). Pigment Dispersion J was prepared by putting the mixture in a dispersion temperature of 35° C. and 70 rotations/minute for 240 hours.

<Preparation of Pigment Dispersion K> (Comparative Example 3 dispersion)
Carbon black H (trade name: #5, manufactured by Mitsubishi Chemical Co., Ltd.) 45 parts by mass, comb resin dispersant of fatty acid amine having polyethyleneimine as a main skeleton (dispersant, trade name: Sols Perth 39000, manufactured by Japan Louvre Resor Co., Ltd. , Acid value: 33 mgKOH/g, amine value: 0 mgKOH/g) 20 parts by mass, and 160 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.) were filled with 1 mm diameter zirconia beads (filling ratio: 46% by volume) 500 mL. The mixture was placed in a ball mill and dispersed at a temperature of 35° C. for 70 rotations/minute for 280 hours to prepare a pigment dispersion K.

<Production of Pigment Dispersion L> (Comparative Example 4 Dispersion)
Carbon black I (trade name: #7350/F, manufactured by Tokai Carbon Co., Ltd.) 45 parts by mass, butyl acetate-containing acrylic block copolymer ((trade name: DISPERBYK-167 dispersant, BYK Japan KK, acid value: 0 mgKOH/g, amine value: 13 mgKOH/g) 14 parts by mass, and phenoxyethyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) 166 parts by mass in a 500 mL ball mill filled with zirconia beads having a diameter of 3 mm (filling ratio: 40% by volume). The mixture was put in the dispersion temperature of 25° C. and 70 rpm for 72 hours to prepare a pigment dispersion L.
The compositions of the obtained pigment dispersions A to L are shown in Tables 1 and 2.

(Example 1)
Pigment Dispersion A 15 parts by mass, benzyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) 60 parts by mass, tripropylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) 5 parts by mass, pentaerythritol triacrylate (Shin Nakamura Chemical Co., Ltd. stock) (Manufactured by the company) 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 (manufactured by Nippon Kayaku Co., Ltd.) ) 0.2 parts by mass and polyether modified polydimethylsiloxane (trade name: BYK3510, manufactured by BYK Japan KK) 0.3 parts by mass were mixed to obtain an active energy ray-curable composition 1.

(Example 2)
Pigment Dispersion A 15 parts by mass, tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 40 parts by mass, acryloylmorpholine (manufactured by Kojin Co., Ltd.) 35 parts by mass, urethane acrylate oligomer (trade name: EBECRYL8402, Daicel Cytec stock) (Manufactured by the company) 6 parts by mass, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: IRGACURE369, manufactured by BASF) 3.5 parts by mass, p-methoxyphenol ( 0.2 parts by mass of Nippon Kayaku Co., Ltd. and 0.3 parts by mass of an acrylic functional group-containing modified polydimethylsiloxane 1 (trade name: BYK-3576, manufactured by Big Chemie Japan Co., Ltd.) are mixed, and active energy rays are mixed. Curable composition 2 was obtained.

(Example 3)
An active energy ray-curable composition 3 was obtained in the same manner as in Example 1 except that the pigment dispersion A was changed to the pigment dispersion B.

(Example 4)
Pigment Dispersion C 15 parts by mass, benzyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) 40 parts by mass, tripropylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) 26 parts by mass, pentaerythritol triacrylate (Shin Nakamura Chemical Co., Ltd. stock) (Manufactured by the company) 7 parts by mass, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: IRGACURE819, 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 (manufactured by Nippon Kayaku Co., Ltd.) ) 0.2 parts by mass and 0.3 part by mass of polyether-modified polydimethylsiloxane (trade name: BYK3510, manufactured by BYK Japan KK) were mixed to obtain an active energy ray-curable composition 4.

(Example 5)
Pigment Dispersion D 15 parts by mass, isobornyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) 35 parts by mass, 2-methyl-2-ethyl-1,3-dioxolan-4-ylmethyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) 25 parts by mass, dimethylol tricyclodecane diacrylate (manufactured by Nippon Kayaku Co., Ltd.), 20 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Osaka Organic 4.5 parts by mass of Chemical Industry Co., Ltd., 0.2 parts by mass of p-methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.), and 0.3 parts by mass of modified polyether containing a crosslinkable functional group are mixed to obtain active energy. A linear curable composition 5 was obtained.

(Example 6)
An active energy ray-curable composition 6 was obtained in the same manner as in Example 4 except that the pigment dispersion C was changed to the pigment dispersion E.

(Example 7)
Pigment Dispersion F 15 parts by mass, tetrahydrofurfuryl acrylate (manufactured by Hitachi Chemical Co., Ltd.) 67 parts by mass, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF) 5 parts by mass Parts, 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 polydimethylsiloxane ( (Product name: BYK3510, manufactured by BYK Japan KK) 0.3 parts by mass were mixed to obtain an active energy ray-curable composition 7.

(Example 8)
15 parts by mass of pigment dispersion G, 38 parts by mass of acryloylmorpholine (manufactured by Kojin Co., Ltd.), 20 parts by mass of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 15 parts by mass of dipentaerythritol pentaacrylate (manufactured by Satomer). , Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: IRGACURE819, 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-isopropylthioxanthone (trade name: SpeedcureITX, manufactured by Lambson) 3.5 parts by mass, 2,6-di-tert-butyl-p-cresol (manufactured by Nippon Kayaku Co., Ltd.) ) 0.2 parts by mass, and acrylic functional group-containing modified polydimethylsiloxane 2 (trade name: BYK-3575, manufactured by BYK Japan KK) 0.3 parts by mass are mixed to prepare an active energy ray-curable composition 8. Obtained.

(Example 9)
Pigment Dispersion H 15 parts by mass, tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by mass, pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 parts by mass, 4-hydroxybutyl acrylate (Osaka Organic) Chemical Industry Co., Ltd.) 38 parts by mass, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: IRGACURE819, 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 of polyether modified polydimethylsiloxane (trade name: BYK-3510, manufactured by Big Chemie Japan Co., Ltd.) are mixed to prepare an active energy ray curable composition 9. Obtained.

(Comparative Example 1)
An active energy ray-curable composition 10 was obtained in the same manner as in Example 4, except that the pigment dispersion C was changed to the pigment dispersion I.

(Comparative example 2)
An active energy ray-curable composition 11 was obtained in the same manner as in Example 4, except that the pigment dispersion C was changed to the pigment dispersion J.

(Comparative example 3)
An active energy ray-curable composition 12 was obtained in the same manner as in Example 4 except that the pigment dispersion C was changed to the pigment dispersion K.

(Comparative example 4)
An active energy ray-curable composition 13 was obtained in the same manner as in Example 4, except that the pigment dispersion C was changed to the pigment dispersion L.

  Regarding the obtained active energy ray-curable compositions 1 to 13 of Examples 1 to 9 and Comparative Examples 1 to 4, "ejection property", "liquid permeability", "printing density", " "Curability" and "adhesion" were evaluated. The evaluation results are shown in Table 7.

<Dischargeability>
Stability was evaluated by a discharge test at 2 KHz using a discharge tester equipped with a Ricoh GEN5 head.
Droplet fluctuation of 5% or less: ◎, Droplet fluctuation of more than 5% and 10% or less: ○, Droplet fluctuation of more than 10% and 20% or less: △, Droplet fluctuation of more than 20%: ×

<Liquid permeability>
Liquid permeability when 100 g of ink was passed through a 10 μm filter at a pressure of 50 Kpa with a Ricoh liquid permeability evaluation device was evaluated.
Finished flow rate/initial flow rate 0.8 or more: ◎, Finished flow rate/initial flow rate 0.5 to less than 0.8: ○, Finished flow rate/initial flow rate 0.1 to less than 0.5: △, Pass Stopping liquid flow in the middle of liquid volume, less than 0.1: ×

<Print density>
The obtained active energy ray-curable composition was applied to a recording medium (trade name: Cosmoshine A4300 coated PET film, manufactured by Toyobo Co., Ltd., average thickness: 100 μm, color: transparent), and a printer (device name: SG7100, Inc.). A 10 cm×10 cm solid image was obtained using an evaluation printer modified from Ricoh). The obtained solid image was subjected to an illuminance of 1 W/cm ² and an irradiation amount of 500 mJ/ by using a UV-LED device for an inkjet printer (device name: UV-LED module (single-pass water cooling, manufactured by Ushio Inc.)). Curing treatment was performed so that the thickness became cm ^2, and an image (cured product) of 10 cm×10 cm having an average thickness of 10 μm was obtained.
For the measurement of the irradiation dose, an ultraviolet intensity meter (device name: UM-10) and a light receiving part (device name: UM-400) (above, manufactured by Konica Minolta Co., Ltd.) were used. As a method of measuring the average thickness, an electronic micrometer (manufactured by Anritsu Corporation) was used to measure the thickness, and the average value of the thicknesses at 10 points was calculated. In addition, the evaluation printer was changed to an MH2620 head (manufactured by Ricoh Co., Ltd.) capable of heating and ejecting the head part using a transporting and driving part of a device name: SG7100 (manufactured by Ricoh Co., Ltd.). Is.
The obtained image (cured product) of the recording medium was measured for the density of the image (cured product) with respect to black by using a reflection spectral densitometer (device name: X-Rite 939, manufactured by X-Rite Co.) to obtain the print density. did.

<Curability>
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 in the evaluation of the print density. The obtained image (cured product) was rubbed 10 reciprocations under a load of 50 g/cm ² with a white cotton cloth attached to a clock meter (device name: NO416, manufactured by Yasuda Seiki Co., Ltd.). 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 is measured, and the density after the reciprocating friction is measured before the reciprocating friction. A value obtained by subtracting the concentration was calculated, and "curability" was evaluated based on the following evaluation criteria.
-Evaluation criteria-
◎: 0.001 or less ○: 0.001 or more and 0.005 or less △: 0.005 or more and 0.009 or less ×: 0.009 or more

<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 in the same manner as in the evaluation of the print density. The solid part of the obtained image (cured product) is cut with a cutter knife into 100 squares in a grid pattern at 1 mm intervals according to JIS K5400, and cellophane adhesive tape (trade name: Scotch Mending Tape (18 mm), 3M Japan Co., Ltd.) Peeling off with a company), counting the mass that did not peel off while looking with a magnifying glass (trade name: PEAK No. 1961 (×10), manufactured by Tokai Sangyo Co., Ltd.), and based on the following evaluation criteria, "adhesion" evaluated.
-Evaluation criteria-
⊚: 100 pieces out of 100 pieces that did not peel off ○: 80 pieces or more and 99 pieces or less in 100 pieces that did not come off △: 40 pieces or more and 79 pieces or less in 100 pieces that did not peel off The number of cells that did not exist was 39 or less out of 100.

As is clear from the results in Table 7, the active energy ray-curable composition (active energy ray-curable ink) of the present invention is capable of satisfying both ejection property, liquid permeability, print density, curability and adhesion.
When the amount of the dispersant adsorbed is within the range of the present invention, since the dispersibility is good, the aggregation of the pigment does not occur and the print density is improved. Further, since there is no excess dispersant, the dischargeability and liquid permeability are improved. Further, since the dispersant becomes a factor that hinders the curability, it can be seen that the curability and the adhesion are improved by the absence of the extra dispersant.
From the above results, the dispersant adsorption amount of the present invention may or may not be obtained even if the same material is used, and the dispersant adsorption amount characteristic of the present invention cannot be obtained until the material, prescription and preparation method are optimized. It can be seen that it is possible to obtain an ink holding

1 Storage pool (accommodation section)
3 Movable stage 4 Active energy ray 5 Active energy ray curable composition 6 Cured layer 21 Supply roll 22 Recording medium 23a, 23b, 23c, 23d Each color printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Printed material winding Roll 30 Ejection head unit 31, 32 for support Ejection head unit 33, 34 for support UV irradiation means 35 Three-dimensional object 36 Support laminate part 37 Object support substrate 38 Stage 39 Image forming apparatus

JP, 2009-57546, A JP, 2011-53094, A JP, 2013-112169, A JP, 2009-108213, A JP, 2009-52010, A JP, 2005-263898, A JP, 2006-342201, A

Claims (20)

It contains carbon black, a dispersant and a polymerizable compound, and the content ratio of the dispersant to the carbon black is 0.09 to 0.22 when the carbon black is 1 (mass basis), and the carbon black. The active energy ray-curable composition is characterized in that the amount of the dispersant adsorbed on is 50 to 180 mg per 1 g of carbon black. The dispersion amount of the previous SL amount of the dispersant adsorbed on the carbon black is 70~130mg per carbon black 1g, and the dispersing agent that is not adsorbed on the carbon black is adsorbed on the carbon black The active energy ray-curable composition according to claim 1, which is 10 to 50% of the amount of the agent. The amount of the dispersant adsorbed on the carbon black when the active energy ray-curable composition is stored at 70° C. for 2 weeks is equal to the amount of the dispersant adsorbed on the carbon black before storage. The active energy ray-curable composition according to claim 1 or 2, wherein the composition is in the range of 80% to 120%.   The carbon black is an oxidation-treated carbon black having a number average primary particle diameter of 35 nm or more and 60 nm or less, a DBP oil absorption amount of 35 g/100 g or more and 55 g/100 g or less, and a pH of 3.5 or less. The active energy ray-curable composition according to any one of 1 to 3.   5. The dispersant is an acrylic block copolymer, and the acrylic block copolymer has an acid value of 5 mgKOH/g or more and an amine value of 10 mgKOH/g or more. The active energy ray-curable composition according to any one of 1.   The volume average particle diameter is 100 nm or more and 150 nm or less, the proportion of the particle diameter 50 nm or less is 10% by volume or less, and the proportion of the particle diameter 230 nm or more is 10% by volume or less. The active energy ray-curable composition according to any one of 1.   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 carbon black is 1.5 or more and 3.0 or less. The active energy ray-curable composition according to any one of claims 1 to 6, wherein   It is a three-dimensional modeling material, The active energy ray curable composition in any one of Claims 1-7 characterized by the above-mentioned.   The active energy ray-curable composition according to any one of claims 1 to 8, which has sensitivity to a light emitting diode light having an emission peak in a wavelength range of 360 nm or more and 400 nm or less.   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 10, which is for inkjet.   A composition storage container, characterized in that the active energy ray-curable composition according to any one of claims 1 to 9 is stored in the container.   At least an accommodating part for accommodating the active energy ray-curable composition according to any one of claims 1 to 9, and an irradiation unit for irradiating the active energy ray-curable composition with an active energy ray. An apparatus for forming a two-dimensional or three-dimensional image, comprising:   The two-dimensional or three-dimensional image forming apparatus according to claim 13, further comprising a discharging unit that discharges the active energy ray-curable composition by an inkjet recording method.   A method for forming a two-dimensional or three-dimensional image, comprising a step of irradiating the active energy ray-curable composition according to any one of claims 1 to 9 with an active energy ray.   The method for forming a two-dimensional or three-dimensional image according to claim 15, further comprising a discharging step of discharging the active energy ray-curable composition by an inkjet recording method.   The method for forming a two-dimensional or three-dimensional image according to claim 15 or 16, wherein the active energy ray is light from a light emitting diode.   A two-dimensional or three-dimensional image obtained by irradiating the active energy ray-curable composition according to any one of claims 1 to 9 with an active energy ray to cure the composition.   A structure comprising a base material and the two-dimensional or three-dimensional image according to claim 18 on the base material.   A molded product, which is obtained by stretching the two-dimensional or three-dimensional image according to claim 18 or the structure according to claim 19.