JP7415357B2 - Active energy ray-curable composition, storage container, two-dimensional or three-dimensional image forming device, two-dimensional or three-dimensional image forming method, cured product, molded product, and method for producing a three-dimensional object - Google Patents

Description

The present invention relates to an active energy ray-curable composition, a storage container, a two-dimensional or three-dimensional image forming device, a two-dimensional or three-dimensional image forming method, a cured product, a molded product, and a method for producing a three-dimensional object. .

In recent years, there has been a demand for active energy ray-curable inkjet ink compositions with excellent color development, particularly in the field of sign graphics.

Such active energy ray-curable inkjet ink compositions usually contain a surfactant in order to improve wetting and spreading properties on the media and ejection stability. There is a problem in that the color development in the density region is reduced.
On the other hand, in a composition that does not contain a surfactant, the dispersibility of the pigment decreases, and problems in ejection stability may occur, especially in the case of magenta pigment.

In order to solve the problem of ink dispersion stability, for example, an actinic light-curable inkjet ink containing a dispersant that has both an acid value and an amine value and whose acid value is larger than the amine value has been proposed. (For example, see Patent Document 1).

In addition, for example, the amine value is 20 mgKOH/g or less, the acid value is 10 mgKOH/g or less, a repeating unit derived from styrene, a repeating unit derived from an unsaturated fatty acid having 12 or more carbon atoms, and an ethylenically unsaturated and a repeating unit derived from polyalkylene oxide having a double bond, and the number of repeating units derived from styrene is 1 to 10 moles per mole of repeating units derived from an unsaturated fatty acid having 12 or more carbon atoms, Actinic radiation-curable inkjet inks containing a dispersant containing a copolymer having 10 to 60 moles of repeating units derived from polyalkylene oxide having ethylenically unsaturated double bonds have been proposed (for example, Patent Document (see 2).

Further, for example, at least one of the acid value and amine value of the pigment dispersant is 10 mgKOH/g or more, the water content is 0.05% by mass or more and 1.0% by mass or less based on the total amount of the ink composition, and the radical A radically polymerizable ultraviolet curable inkjet composition containing a radically polymerizable compound having a vinyl ether group and a (meth)acrylate group as a polymerizable compound has been proposed (see, for example, Patent Document 3).

An object of the present invention is to provide an active energy ray-curable composition that is excellent in color development, substrate adhesion, and ejection stability in a high concentration region.

The active energy ray-curable composition of the present invention as a means for solving the above problems is made of a polymerizable monomer that does not substantially contain a surfactant and has a static surface tension of 40 mN/m or more at 25°C. The content is 15% by mass or less based on the total amount of the active energy ray curable composition, contains an organic pigment as a coloring material at 2% by mass or more based on the total amount of the active energy ray curable composition, and as a dispersant. A dispersant having an amine value of 5 mgKOH/g or more and 35 mgKOH/g or less, and amine value>acid value, containing the dispersant in an amount of 15% by mass or more and 70% by mass or less based on the mass of the organic pigment, and having an active The amount of water contained in the energy beam curable composition is 500 mass ppm or more and 3,000 mass ppm or less.

According to the present invention, it is possible to provide an active energy ray-curable composition that is excellent in color development, substrate adhesion, and ejection stability in a high concentration region.

FIG. 1 is a schematic diagram showing an example of a three-dimensional object manufacturing apparatus used in the three-dimensional object manufacturing method of the present invention. FIG. 2 is a schematic diagram showing another example of the three-dimensional object manufacturing apparatus used in the three-dimensional object manufacturing method of the present invention. FIG. 3 is a schematic diagram illustrating an example of a method for producing a three-dimensional object using the active energy ray-curable composition of the present invention.

(Active energy ray-curable composition)
The active energy ray curable composition of the present invention substantially does not contain a surfactant and has a static surface tension of 40 mN/m or more at 25°C. It contains 15% by mass or less based on the total amount of the composition, contains an organic pigment as a coloring material of 2% by mass or more based on the total amount of the active energy ray-curable composition, and has an amine value of 5 mgKOH/g or more and 35 mgKOH/g as a dispersant. and the active energy ray-curable composition contains a dispersant whose amine value>acid value is 15% by mass or more and 70% by mass or less based on the mass of the organic pigment; The amount is 500 mass ppm or more and 3,000 mass ppm or less, and further contains other components as necessary.

The conventional technique described in Patent Document 1 has a problem in that the stability of the ink during heating is poor.
The conventional technique described in Patent Document 2 has a problem in that when moisture in the air is incorporated into the ink during the production of the ink, the dispersion stability deteriorates and agglomerated foreign substances are generated.
In the conventional technology described in Patent Document 3, it is essential to contain a radically polymerizable compound having a vinyl ether group and a (meth)acrylate group as a radically polymerizable compound, and in addition to poor adhesion to the substrate, it is difficult to implement. In view of the examples, the effect is exhibited by containing the dispersant in an amount of 50% by mass or more based on the pigment. If the content of the dispersant is high, poor adhesion to the base material and high viscosity of the ink will occur.
In this way, in the conventional technology, active energy ray-curable compositions that have excellent dispersibility of organic pigments, color development in high concentration areas, and discharge stability are secured even when they do not substantially contain surfactants. things are not provided.

The present inventors have determined that the content of a polymerizable monomer that does not substantially contain a surfactant and has a static surface tension of 40 mN/m or more at 25°C is based on the total amount of the active energy ray-curable composition. 15% by mass or less, contains an organic pigment as a coloring material of 2% by mass or more based on the total amount of the active energy ray-curable composition, has an amine value of 5 mgKOH/g or more and 35 mgKOH/g or less as a dispersant, and contains an amine The active energy ray-curable composition contains a dispersant whose value>acid value is 15% by mass or more and 70% by mass or less based on the mass of the organic pigment, and the active energy ray-curable composition contains a water content of 500 mass ppm. It has been discovered that a composition having a concentration of 3,000 mass ppm or less has excellent dispersibility of organic pigments even when it does not contain a surfactant, and can achieve both high color development and ejection stability in a high concentration region, and the present invention I was able to complete it.

The active energy ray-curable composition of the present invention does not substantially contain a surfactant. In the present invention, a surfactant refers to a compound having surface-active ability, excluding so-called "pigment dispersants."

The amount of water contained in the active energy ray-curable composition of the present invention is 500 mass ppm or more and 3,000 mass ppm or less, preferably 500 mass ppm or more and 2,000 mass ppm or less.
The moisture content can be measured using, for example, a Karl Fischer moisture meter.

The active energy ray-curable composition of the present invention contains a polymerizable monomer having a static surface tension of 40 mN/m or more at 25°C, and has a static surface tension of 30 mN/m or more and 35 mN/m or less at 25°C. It is preferable to contain a certain polymerizable monomer and a polymerizable monomer whose static surface tension at 25° C. is less than 30 mN/m. The content of these polymerizable monomers is preferably 50% by mass or more and 90% by mass or less based on the total amount of the active energy ray-curable composition.

<<Polymerizable monomer having a static surface tension of 40 mN/m or more at 25°C>>
Examples of the polymerizable monomer having a static surface tension at 25° C. of 40 mN/m or more include (meth)acryloylmorpholine, N-vinylcaprolactam, and the like. These may be used alone or in combination of two or more.
The content of the polymerizable monomer having a static surface tension of 40 mN/m or more at 25°C is 15% by mass or less, and 5% by mass or more and 15% by mass or less, based on the total amount of the active energy ray-curable composition. is preferable, and more preferably 10% by mass or more and 15% by mass or less.
When the content of the polymerizable monomer having a static surface tension of 40 mN/m or more at 25° C. is 15% by mass or less, the active energy ray-curable composition has excellent color development in a high concentration region and discharge stability. You can get things.
The static surface tension can be measured at 25° C. using a static surface tension measuring device, for example.

<<Polymerizable monomer whose static surface tension at 25°C is 30 mN/m or more and 35 mN/m or less>>
Examples of the polymerizable monomer having a static surface tension at 25° C. of 30 mN/m or more and 35 mN/m or less include isobornyl (meth)acrylate and lauryl (meth)acrylate. These may be used alone or in combination of two or more.
The content of the polymerizable monomer having a static surface tension of 30 mN/m or more and 35 mN/m or less at 25° C. is preferably 15% by mass or more, and 15% by mass or more based on the total amount of the active energy ray-curable composition. It is more preferably 40% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less.
When the content of the polymerizable monomer whose static surface tension at 25° C. is 30 mN/m or more and 35 mN/m or less is 15% by mass or more, the active energy has excellent color development and ejection stability in a high concentration region. A line-curable composition is obtained.
The static surface tension can be measured at 25° C. using a static surface tension measuring device, for example.

<<Polymerizable monomer whose static surface tension at 25°C is less than 30 mN/m>>
Examples of polymerizable monomers having a static surface tension of less than 30 mN/m at 25°C include isodecyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-octyl (meth)acrylate, Examples include isobutyl (meth)acrylate, isononyl (meth)acrylate, octyl/decyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.
The content of the polymerizable monomer having a static surface tension of less than 30 mN/m at 25°C is preferably 3% by mass or less, and 1% by mass or more and 3% by mass or less based on the total amount of the active energy ray-curable composition. is more preferable.
When the content of the polymerizable monomer having a static surface tension of less than 30 mN/m at 25° C. is 3% by mass or less, the active energy ray-curable composition has excellent color development in a high concentration region and discharge stability. You can get things.
The static surface tension can be measured at 25° C. using a static surface tension measuring device, for example.

<<Other polymerizable monomers>>
The composition of the present invention comprises a polymerizable monomer having a static surface tension of 40 mN/m or more at 25°C, a polymerizable monomer having a static surface tension of 30 mN/m to 35 mN/m at 25°C, and a polymerizable monomer having a static surface tension of 30 mN/m to 35 mN/m at 25°C. In addition to the polymerizable monomer having a static surface tension of less than 30 mN/m, other polymerizable monomers may be contained.
As other polymerizable monomers, known polymerizable monomers such as (meth)acrylic acid esters can be used. For example, methyl (meth)acrylate, ethyl (meth)acrylate, allyl (meth)acrylate, glycidyl ( meth)acrylate, 2-(dimethylamino)ethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-butoxyethyl(meth)acrylate, ethyl carbitol(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofur Furyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate , tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neo Examples include pentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate. These may be used alone or in combination of two or more.

<Color material>
As the coloring material, glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold, silver, etc. are applied depending on the purpose and required characteristics of the active energy ray-curable composition of the present invention. Various pigments can be used.
As the pigment, an organic pigment is 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, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalones. Polycyclic pigments such as pigments, dye chelates (e.g., basic dye type chelates, acidic dye type chelates, etc.), dyeing lakes (e.g., basic dye type lakes, acidic dye type lakes, etc.), nitro pigments, nitroso pigments, Examples include aniline black and daylight fluorescent pigments. These may be used alone or in combination of two or more.
Examples of the organic pigment include Pigment Red122 (PR122) and Pigment Violes19 (PV19).
The content of the organic pigment is 2% by mass or more, preferably 2% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 10% by mass or less, based on the total amount of the active energy ray-curable composition. More preferably 2% by mass or more and 5% by mass or less.

<Dispersant>
In order to improve the dispersibility of the organic pigment as a coloring material, the active energy ray-curable composition of the present invention contains a dispersant.
As the dispersant, a dispersant having an amine value of 5 mgKOH/g or more and 35 mgKOH/g or less, and in which the amine value>acid value is used. By using a dispersant having an amine value of 5 mgKOH/g or more and 35 mgKOH/g or less, and in which the amine value is greater than the acid value, there is an advantage that the dispersibility of the pigment is improved.
A dispersant having an amine value of 13 mgKOH/g or more and 35 mgKOH/g or less and amine value>acid value is preferable, and a dispersant having an amine value of 17 mgKOH/g or more and 30 mgKOH/g or less and amine value>acid value. A dispersant having an amine value of 6 mgKOH/g or more and 16 mgKOH/g or less, and in which the amine value is greater than the acid value, is more preferable.

The dispersant is preferably at least one of a maleimide-styrene copolymer and an ammonium salt of a maleimide-styrene copolymer.
As the dispersant, commercially available products can be used, and examples of the commercially available products include BYK JET-9150, BYK JET-9151, BYK JET-9152 (manufactured by BYK), Solsperse 32000 (manufactured by Lubrirose), etc. can be mentioned.
The content of the dispersant is 15% by mass or more and 70% by mass or less, preferably 15% by mass or more and 50% by mass or less, and more preferably 30% by mass or more and 50% by mass or less, based on the mass of the organic pigment.

<Polymerization initiator>
The active energy ray-curable composition of the present invention may contain a polymerization initiator. Note that the polymerization initiator may also be simply referred to as an initiator. A photopolymerization initiator is used as the polymerization initiator.
Any photopolymerization initiator may be used as long as it can generate active species such as radicals and cations with the energy of active energy rays and initiate polymerization of polymerizable compounds (monomers and oligomers). As the photopolymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be used alone or in combination of two or more types, and among them, radical polymerization initiators are preferred.
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, Examples include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

In order to obtain a sufficient curing rate, the content of the polymerization initiator is preferably 1% by mass or more and 20% by mass or less, and 3% by mass or more and 15% by mass or less, based on the total amount of the active energy ray-curable composition. More preferably, it is 5% by mass or more and 10% by mass or less.

In addition to the above polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited and can be appropriately selected depending on the purpose, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p- Examples include amine compounds such as 2-ethylhexyl dimethylaminobenzoate, N,N-dimethylbenzylamine, 4,4'-bis(diethylamino)benzophenone, and the like.
The content of the polymerization accelerator is not particularly limited and may be appropriately set depending on the polymerization initiator used and its amount.

<Other ingredients>
The active energy ray-curable composition of the present invention may contain other components as necessary. Other ingredients are not particularly limited and can be selected as appropriate depending on the purpose, such as polymerization inhibitors, leveling agents, antifoaming agents, optical brighteners, penetration enhancers, wetting agents (humectants). , a fixing agent, a viscosity stabilizer, an antifungal agent, a preservative, an antioxidant, an ultraviolet absorber, a chelating agent, a pH adjuster, a thickener, and the like.

Note that for each component in the active energy ray-curable composition, low molecular weight components such as polymerizable monomers and polymerization initiators can be identified by gas chromatogram mass spectrometry or the like.

<Preparation of active energy ray curable composition>
The active energy ray-curable composition of the present invention can be prepared using the various components described above, and the preparation means and conditions are not particularly limited. For example, polymerizable monomers, organic pigments, dispersants, etc. , Kitty Mill, Disc Mill, Pin Mill, Dyno Mill, etc., and disperse to prepare a pigment dispersion, and further mix a polymerization initiator, a polymerization inhibitor, a surfactant, etc. with the pigment dispersion. It can be prepared by:

<Viscosity>
The viscosity of the active energy ray-curable composition of the present invention may be adjusted as appropriate depending on the purpose and the means of application, and is not particularly limited, but for example, when applying a discharge means such as discharging the composition from a nozzle. The viscosity in the range of 20°C to 65°C, preferably 60 mPa·s or less at 25°C, preferably 3 mPa·s or more and 40 mPa·s or less, more preferably 5 mPa·s or more and 30 mPa·s or less, It is more preferably 5 mPa·s or more and 15 mPa·s or less, and particularly preferably 6 mPa·s or more and 12 mPa·s or less.
Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. The above viscosity was measured using a cone plate rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd. using a cone rotor (1°34' x R24) at a rotation speed of 50 rpm and a constant temperature circulating water temperature of 20°C. The temperature can be set and measured as appropriate in the range of ~65°C. VISCOMATE VM-150III can be used to adjust the temperature of circulating water.

<Curing means>
As a curing means for curing the active energy ray-curable composition of the present invention, curing with active energy rays can be mentioned.
The active energy rays used to cure the active energy ray-curable composition include, in addition to ultraviolet rays, electron beams, α rays, β rays, γ rays, and X-rays that can be used to cure the active energy ray curable composition. It is not particularly limited as long as it can provide the energy necessary to proceed with the polymerization reaction of the chemical component. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Furthermore, in the case of ultraviolet irradiation, mercury-free devices are strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are compact, long-life, highly efficient, and low-cost, and are preferred as ultraviolet light sources.

<Application>
The use of the active energy ray-curable composition of the present invention is not particularly limited as long as it is a field in which active energy ray-curable materials are generally used, and can be appropriately selected depending on the purpose. Fields include molding resins, paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, and various optical materials.
Furthermore, the active energy ray-curable composition of the present invention can be used as an ink to not only form two-dimensional characters and images and design coatings on various substrates, but also to form three-dimensional three-dimensional images (three-dimensional objects). It can also be used as a material for three-dimensional modeling. This material for three-dimensional modeling may be used, for example, as a binder between powder particles used in a powder layering method in which three-dimensional modeling is performed by repeating curing and lamination of powder layers. It may be used as a three-dimensional constituent material (model material) or a support member (support material) used in such a layered manufacturing method (stereolithography method). Note that FIG. 2 shows a method for three-dimensional modeling in which the composition of the present invention is discharged onto a predetermined area and cured by irradiation with active energy rays, and the compositions are sequentially laminated (details will be described later). A method in which a storage pool (accommodating part) 1 of the composition 5 of the present invention is irradiated with active energy rays 4 to form a hardened layer 6 of a predetermined shape on a movable stage 3, and this is sequentially laminated to perform three-dimensional modeling. be.

The present invention also includes a cured product obtained by curing the active energy ray-curable composition of the present invention, and a molded product obtained by stretching the cured product.
After applying the composition onto a plastic substrate and curing it, it is preferable that the cured product can be continuously stretched in a range of 100% or more and 1,000% or less during heat treatment of the plastic substrate.
The molded product is, for example, a cured product formed in the form of a sheet or film, which is subjected to molding processing such as heating stretching or punching, and is used, for example, in automobiles, OA equipment, electric/electronic equipment, etc. It is suitably used in applications where the surface needs to be molded after decoration, such as meters for cameras and operation panels.
The above-mentioned base material is not particularly limited and can be selected as appropriate depending on the purpose, such as paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, or composite materials thereof. can be mentioned. Among these, plastic base materials are preferred from the viewpoint of processability.

<<Storage container>>
The housing container of the present invention refers to a container in which the active energy ray-curable composition of the present invention is housed, and is suitable for use as described above. For example, when the composition of the present invention is used as an ink, the container containing the ink can be used as an ink cartridge or an ink bottle. This eliminates the need for direct contact with the body and prevents stains on hands and clothes. Further, it is possible to prevent foreign matter such as dust from entering the ink. In addition, the shape, size, material, etc. of the container itself may be suitable for the purpose and usage, and are not particularly limited, but the material may be a light-blocking material that does not transmit light, or the container may be light-blocking. It is desirable that it be covered with a plastic sheet, etc.

(Two-dimensional or three-dimensional image forming method and two-dimensional or three-dimensional image forming apparatus)
The two-dimensional or three-dimensional image forming method of the present invention comprises: a housing section that accommodates the active energy ray-curable composition of the present invention; a applying means that applies the composition; and a curing means that hardens the composition. , and further includes other means as necessary.
The two-dimensional or three-dimensional image forming apparatus of the present invention includes a applying step of applying the active energy ray-curable composition of the present invention, a curing step of curing the composition, and further includes other steps as necessary. Including the process of

The two-dimensional or three-dimensional image forming method of the present invention may use active energy rays or heating. In order to cure the active energy ray-curable composition of the present invention with active energy rays, there is an irradiation step of irradiating active energy rays. The container may be provided with an irradiation means for irradiating the composition of the present invention, and a housing section for housing the composition of the present invention, and the container may be housed in the housing section. Furthermore, it may have a discharging step and a discharging means for discharging the composition of the present invention. The method of discharging is not particularly limited, but examples include continuous injection type and on-demand type. On-demand types include piezo type, thermal type, electrostatic type, etc.

(Method for manufacturing a three-dimensional object)
The method for producing a three-dimensional object of the present invention includes a modeling step of modeling a three-dimensional object using the active energy ray-curable composition of the present invention, and further includes other steps as necessary.
The modeling process is preferably performed using a three-dimensional printer, but can also be performed using a mold.
There is no particular restriction on the manufacturing apparatus for three-dimensional objects for modeling three-dimensional objects using the active energy ray-curable composition of the present invention, and it can be appropriately selected depending on the purpose. Examples include those that are equipped with a storage part that accommodates the energy beam curable composition, a discharge means that discharges the composition, a curing means that hardens the composition, and the like.

Here, FIG. 1 is a schematic diagram showing an example of a three-dimensional structure manufacturing apparatus including an inkjet discharge means. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d, which is equipped with an ink cartridge and ejection head for active energy ray-curable ink of yellow, magenta, cyan, and black. Ru. Thereafter, active energy rays are irradiated from the light sources 24a, 24b, 24c, and 24d for curing the ink to form a color image. Thereafter, the recording medium 22 is conveyed to a processing unit 25 and a print take-up 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 at the ink ejection portion. Further, if necessary, a mechanism may be provided to cool the recording medium to about room temperature by contact or non-contact. Inkjet recording methods include a serial method in which ink is ejected onto the recording medium by moving the head while the recording medium is moved intermittently according to the width of the ejection head, and a serial method in which the recording medium is moved continuously. Any line method in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
The recording medium 22 is not particularly limited and can be appropriately selected depending on the purpose, and examples include paper, film, metal, or a composite material thereof, and may be in the form of a sheet. Further, the configuration may be such that only one-sided printing is possible, or the configuration may be such that double-sided printing is also possible.
Furthermore, the 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 emitted from the light source 24d. This makes it possible to save energy and reduce costs.
The recorded materials recorded with the ink used in the present invention include not only those printed on smooth surfaces such as ordinary paper and resin films, but also those printed on uneven printing surfaces, and those printed on metals and ceramics. It also includes those printed on printing surfaces made of various materials such as. Further, by stacking two-dimensional images, it is also possible to form an image with a three-dimensional effect (an image consisting of two-dimensional and three-dimensional images) or a three-dimensional object.

FIG. 2 is a schematic diagram showing an example of a three-dimensional structure manufacturing apparatus according to 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 inject the first composition from the ejection head unit 30 for the shaped object to the ejection head units 31 and 32 for the support. The step of discharging the first composition from the discharge head unit 30 for a modeled object and solidifying it by irradiating active energy rays to form a first modeled object layer is performed by moving the composition up and down in accordance with the number of times of lamination. By repeating this multiple times while lowering the stage 38, the support layer and the object layer are laminated to produce the three-dimensional object 35. Thereafter, the support stack 36 is removed if necessary. In FIG. 2, only one ejection head unit 30 is provided, but two or more ejection head units 30 may be provided.

Examples of the present invention will be described below, but the present invention is not limited to these Examples in any way.

<Measurement of static surface tension of polymerizable monomer>
The static surface tension of the polymerizable monomer was measured by the plate method using CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.

<Measurement of amine value of dispersant>
The amine value of the dispersant can be determined by dissolving 1 g of the dispersant in 100 mL of methyl isobutyl ketone, and using an automatic titration device (device name: GT-200, Mitsubishi Chemical Analytic Co., Ltd.) with a 0.01 mol/L methyl isobutyl ketone chlorate solution. The amine value was measured by performing potentiometric titration using a commercially available product (manufactured by Kawasaki, Ltd.), measuring the potential difference, and calculating the amine value based on the obtained potential difference.
<Measurement of acid value of dispersant>
The acid value of the dispersant is determined by dissolving 1 g of the dispersant in 100 mL of methyl isobutyl ketone, and using an automatic titration device (device name: GT-200, Mitsubishi Chemical Analytic Co., Ltd.) with a 0.01 mol/L methyl isobutyl ketone chlorate solution. The acid value was measured by performing potentiometric titration using a commercially available product (manufactured by J.D. Co., Ltd.), measuring the potential difference, and calculating the acid value based on the obtained potential difference.

<Measurement of moisture content>
The moisture content of the active energy ray-curable composition was measured using a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd.).

(Examples 1 to 17 and Comparative Examples 1 to 10)
Active energy ray-curable compositions of Examples 1 to 17 and Comparative Examples 1 to 10 were prepared according to the compositions and contents listed in Tables 1 to 3 by conventional methods.
Next, various properties of each of the obtained active energy ray-curable compositions were evaluated as follows. The results are shown in Tables 1 to 3.

<Viscosity>
Each active energy ray-curable composition was measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., VISCOMETER TVE-22L, cone rotor: 1°34' x R24) at a sample temperature of 40°C and a rotation speed of 50 rpm. The viscosity was evaluated based on the following criteria.
[Evaluation criteria]
S: Viscosity at 40°C is 10 mPa·s or more and less than 11 mPa·s A: Viscosity at 40°C is 10 mPa·s or more and less than 13 mPa·s B: Viscosity at 40°C is 8 mPa·s or more and less than 10 mPa·s, or 13 mPa・s or more and less than 14 mPa・s C: Viscosity at 40°C is less than 8 mPa・s, or 14 mPa・s or more

<Color development in high concentration area>
For each active energy ray-curable composition, a solid image was printed using an inkjet printing device with a GEN5 head manufactured by Ricoh Co., Ltd. at a resolution of 600 dpi x 1200 dpi and an ink adhesion amount of 1.7 mg/cm ² using X Rite extract. Regarding the saturation c* calculated from the values of a* and b* measured using (manufactured by X Rite) using the formula c*=√{(a*) ² + (b*) ² }, Color development in the high concentration region was evaluated based on the following criteria.
[Evaluation criteria]
-In the case of cyan-
SS: Saturation c* is 60 or more S: Saturation c* is 55 or more and less than 60 A: Saturation c* is 50 or more and less than 55 B: Saturation c* is 45 or more and less than 50 C: Saturation c* is 45 Less than - for magenta -
SS: Saturation c* is 75 or more S: Saturation c* is 70 or more and less than 75 A: Saturation c* is 65 or more and less than 70 B: Saturation c* is 60 or more and less than 65 C: Saturation c* is 60 Less than - in the case of yellow -
SS: Saturation c* is 95 or more S: Saturation c* is 90 or more and less than 95 A: Saturation c* is 85 or more and less than 90 B: Saturation c* is 80 or more and less than 85 C: Saturation c* is 80 less than

<Discharge stability>
When each active energy ray-curable composition was continuously ejected for 1 minute at a frequency of 20 kHz using an inkjet ejection device having a GEN5 head manufactured by Ricoh Co., Ltd. under conditions such that the flight speed of each active energy ray-curable composition was 7 m/s ± 1 m/s. The number of nozzles that failed to eject was measured, and the ejection stability was evaluated using the following criteria.
[Evaluation criteria]
S: The number of non-discharging nozzles is 0. A: The number of non-discharging nozzles is 1 or more and less than 3. B: The number of non-discharging nozzles is 3 or more and less than 10. C: The number of non-discharging nozzles is 10. That's all

<Substrate adhesion>
For each active energy ray-curable composition, a solid image was printed at a resolution of 600 dpi x 1200 dpi and an ink adhesion amount of 1.7 mg/cm ² using an inkjet printing device with a GEN5 head manufactured by Ricoh Co., Ltd. according to JIS-K5600. Evaluation was made according to the following criteria using the cross-cut test method described in -5-6.
[Evaluation criteria]
A: Classification 0 or 1
B: Classification 2
C: Classification 3, 4 or 5

Details of each component in Tables 1 to 3 are as follows.
<Polymerizable monomer having a static surface tension of 40 mN/m or more at 25°C>
・NVC: N-vinyl caprolactam (manufactured by Ashland, static surface tension 40 mN/m at 25°C)
・ACMO: Acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd., static surface tension 45 mN/m at 25°C)

<Polymerizable monomer whose static surface tension at 25°C is 30 mN/m or more and 35 mN/m or less>
・IBXA: Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., static surface tension 30 mN/m at 25°C)
・LA: Lauryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., static surface tension at 25°C 30 mN/m

Isodecyl (meth)acrylate, isooctyl (meth)acrylate <Polymerizable monomer whose static surface tension at 25°C is less than 30 mN/m>
・ODA-N: Octyl/decyl acrylate (manufactured by Daicel Corporation, static surface tension 29 mN/m at 25°C)
・IDA: Isodecyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., static surface tension at 25°C 28 mN/m
・IOA: Isononyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., static surface tension at 25°C 28 mN/m

<Other polymerizable monomers>
・PEA: Phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・CTFA: Cyclic trimethylolpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・THFA: Tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・DPGDA: Dipropylene glycol diacrylate (manufactured by Sartomer)
・DCPDA: Dicyclopentanyl diacrylate (manufactured by Nippon Kayaku Co., Ltd.)

<Polymerization inhibitor>
・TBH: 2-tert-butylhydroquinone (manufactured by Seiko Kagaku Co., Ltd.)
・MEHQ: 4-methoxyphenol (manufactured by Seiko Kagaku Co., Ltd.)

<Surfactant>
・BYK3500: Manufactured by BYK

<Pigment>
・PR122: Manufactured by Clariant ・PV19: Manufactured by Clariant

<Dispersant>
・BYK JET-9151: Manufactured by BYK (acid value = 7 mgKOH/g, amine value = 17 mgKOH/g)
・BYK JET-9150: Manufactured by BYK (acid value = 5mgKOH/g, amine value = 12mgKOH/g)
・Solsperse 32000: manufactured by Lubrizol (acid value = 15 mgKOH/g, amine value = 31 mgKOH/g)
・Solsperse 24000: manufactured by Lubrizol (acid value = 25 mgKOH/g, amine value = 42 mgKOH/g)
・PB821: Manufactured by Ajinomoto Fine Techno Co., Ltd. (Acid value = 13mgKOH/g, Amine value = 9mgKOH/g)

Examples of aspects of the present invention are as follows.
<1> Substantially does not contain surfactant,
The content of the polymerizable monomer having a static surface tension at 25° C. of 40 mN/m or more is 15% by mass or less based on the total amount of the active energy ray-curable composition,
Containing an organic pigment as a coloring material at 2% by mass or more based on the total amount of the active energy ray-curable composition,
The dispersant has an amine value of 5 mgKOH/g or more and 35 mgKOH/g or less, and contains a dispersant whose amine value is greater than acid value,
The dispersant is contained in an amount of 15% by mass or more and 70% by mass or less based on the mass of the organic pigment,
The active energy ray curable composition is characterized in that the amount of water contained in the active energy ray curable composition is 500 mass ppm or more and 3,000 mass ppm or less.
<2> The active energy ray-curable composition according to <1>, which contains the dispersant in an amount of 15% by mass or more and less than 50% by mass based on the mass of the organic pigment.
<3> The active energy ray-curable composition according to any one of <1> to <2>, which contains the dispersant in an amount of 30% by mass or more and less than 50% by mass based on the mass of the organic pigment.
<4> The active energy according to any one of <1> to <3>, wherein the dispersant has an amine value of 13 mgKOH/g or more and 35 mgKOH/g or less, and the amine value>acid value. It is a line curable composition.
<5> The active energy according to any one of <1> to <4>, wherein the dispersant has an amine value of 17 mgKOH/g or more and 30 mgKOH/g or less, and the amine value>acid value. It is a line curable composition.
<6> The active energy according to any one of <1> to <5>, wherein the dispersant has an acid value of 6 mgKOH/g or more and 16 mgKOH/g or less, and the amine value>acid value. It is a line curable composition.
<7> The active energy ray-curable composition according to any one of <1> to <6>, wherein the dispersant is at least one of a maleimide-styrene copolymer and an ammonium salt of a maleimide-styrene copolymer. It is a thing.
<8> The active energy ray-curable composition according to any one of <1> to <7>, containing a polymerizable monomer having a static surface tension of 30 mN/m or more and 35 mN/m or less at 25°C. .
<9> The content of the polymerizable monomer having a static surface tension of 30 mN/m or more and 35 mN/m or less at 25° C. is 15% by mass or more based on the total amount of the active energy ray-curable composition. The active energy ray-curable composition according to any one of items 1 to 8.
<10> Contains a polymerizable monomer having a static surface tension of less than 30 mN/m at 25°C, and the content of the polymerizable monomer is 1% by mass or more based on the total amount of the active energy ray-curable composition3. The active energy ray-curable composition according to any one of <1> to <9> above, wherein the active energy ray-curable composition is at most % by mass.
<11> The polymerizable monomer having a static surface tension of 40 mN/m or more at 25°C is at least one selected from (meth)acryloylmorpholine and N-vinylcaprolactam from <1> to <10>. The active energy ray-curable composition according to any one of the above.
<12> The polymerizable monomer having a static surface tension of 30 mN/m or more and 35 mN/m or less at 25° C. is at least one selected from isobornyl (meth)acrylate and lauryl (meth)acrylate. The active energy ray-curable composition according to any one of items 1> to <11>.
<13> The polymerizable monomer having a static surface tension at 25°C of less than 30 mN/m is isodecyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-octyl (meth)acrylate. The active energy ray-curable composition according to any one of <1> to <12>, which is at least one selected from , isobutyl (meth)acrylate, and isononyl (meth)acrylate.
<14> The active energy ray-curable composition according to any one of <1> to <13>, wherein the organic pigment is Pigment Red122 (PR122).
<15> The active energy ray-curable composition according to any one of <1> to <14>, which is an inkjet ink.
<16> A container characterized in that the active energy ray-curable composition according to any one of <1> to <15> is housed in the container.
<17> A housing section that houses the active energy ray-curable composition according to any one of <1> to <15>;
a applying means for applying the active energy ray-curable composition;
A curing means for curing the active energy ray-curable composition;
A two-dimensional or three-dimensional image forming apparatus is characterized in that it has:
<18> A step of applying the active energy ray-curable composition according to any one of <1> to <15>;
A two-dimensional or three-dimensional image forming method is characterized in that it includes a curing step of curing the active energy ray-curable composition.
<19> A cured product characterized by being formed using the active energy ray-curable composition according to any one of <1> to <15>.
<20> A molded product obtained by stretching the cured product according to <19> above.
<21> A method for producing a three-dimensional object, comprising a modeling step of forming a three-dimensional object using the active energy ray-curable composition according to any one of <1> to <15>. .

The active energy ray-curable composition according to any one of <1> to <15>, the container according to <16>, the two-dimensional or three-dimensional image forming apparatus according to <17>, the The two-dimensional or three-dimensional image forming method according to <18>, the cured product according to <19>, the molded product according to <20>, and the production of a three-dimensional object according to <21> According to the method, problems in the prior art can be solved and the objectives of the present invention can be achieved.

1 Storage pool (storage area)
3 Movable stage 4 Active energy ray 5 Composition 6 Cured layer 21 Supply roll 22 Recording medium 23a, 23b, 23c, 23d Printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Printed matter winding roll 30 Discharge head for modeled object Units 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional object 36 Support stack 37 Structure support substrate

Patent No. 4748063 Patent No. 5649674 Patent No. 6281391

Claims (20)

Contains no surfactants,
The content of the polymerizable monomer having a static surface tension at 25° C. of 40 mN/m or more is 15% by mass or less based on the total amount of the active energy ray-curable composition,
Containing Pigment Red 122 (PR122), which is an organic pigment, as a coloring material in an amount of 2% by mass or more based on the total amount of the active energy ray-curable composition,
The dispersant has an amine value of 5 mgKOH/g or more and 35 mgKOH/g or less, and contains a dispersant whose amine value is greater than acid value,
The dispersant is contained in an amount of 15% by mass or more and 70% by mass or less based on the mass of Pigment Red122 (PR122),
An active energy ray curable composition characterized in that the amount of water contained in the active energy ray curable composition is 500 mass ppm or more and 3,000 mass ppm or less. The active energy ray-curable composition according to claim 1, which contains the dispersant in an amount of 15% by mass or more and less than 50% by mass based on the mass of the Pigment Red122 (PR122). The active energy ray-curable composition according to any one of claims 1 to 2, which contains the dispersant in an amount of 30% by mass or more and less than 50% by mass based on the mass of the Pigment Red122 (PR122). The active energy ray-curable composition according to any one of claims 1 to 3, wherein the dispersant has an amine value of 13 mgKOH/g or more and 35 mgKOH/g or less, and the amine value>acid value. The active energy ray-curable composition according to any one of claims 1 to 4, wherein the dispersant has an amine value of 17 mgKOH/g or more and 30 mgKOH/g or less, and the amine value>acid value. The active energy ray-curable composition according to any one of claims 1 to 5, wherein the dispersant has an acid value of 6 mgKOH/g or more and 16 mgKOH/g or less, and the amine value>acid value. The active energy ray-curable composition according to any one of claims 1 to 6, wherein the dispersant is at least one of a maleimide-styrene copolymer and an ammonium salt of a maleimide-styrene copolymer. The active energy ray-curable composition according to any one of claims 1 to 7, containing a polymerizable monomer having a static surface tension of 30 mN/m or more and 35 mN/m or less at 25°C. 9. The content of the polymerizable monomer having a static surface tension of 30 mN/m or more and 35 mN/m or less at 25° C. is 15% by mass or more based on the total amount of the active energy ray-curable composition. active energy ray curable composition. The active energy ray-curable composition contains a polymerizable monomer having a static surface tension of less than 30 mN/m at 25°C, and the content of the polymerizable monomer having a static surface tension of less than 30 mN/m at 25° C The active energy ray-curable composition according to any one of claims 1 to 9, wherein the active energy ray-curable composition is 1% by mass or more and 3% by mass or less based on the total amount of the composition. Any one of claims 1 to 10, wherein the polymerizable monomer having a static surface tension of 40 mN/m or more at 25°C is at least one selected from (meth)acryloylmorpholine and N-vinylcaprolactam. active energy ray curable composition. 9. The polymerizable monomer having a static surface tension at 25° C. of 30 mN/m or more and 35 mN/m or less is at least one selected from isobornyl (meth)acrylate and lauryl (meth)acrylate. active energy ray curable composition. The polymerizable monomer having a static surface tension of less than 30 mN/m at 25°C is isodecyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-octyl (meth)acrylate, isobutyl ( The active energy ray-curable composition according to claim 10 , which is at least one selected from meth)acrylate and isononyl (meth)acrylate. The active energy ray-curable composition according to any one of claims 1 to 13, which is an inkjet ink. A container containing the active energy ray-curable composition according to any one of claims 1 to 14. A housing section that houses the active energy ray-curable composition according to any one of claims 1 to 14;
a applying means for applying the active energy ray-curable composition;
A curing means for curing the active energy ray-curable composition;
A two-dimensional or three-dimensional image forming device comprising: A step of applying the active energy ray-curable composition according to any one of claims 1 to 14;
A two-dimensional or three-dimensional image forming method, comprising a curing step of curing the active energy ray-curable composition. A cured product formed using the active energy ray-curable composition according to any one of claims 1 to 14. A molded product obtained by stretching the cured product according to claim 18. A method for producing a three-dimensional object, the method comprising the step of modeling a three-dimensional object using the active energy ray-curable composition according to any one of claims 1 to 14.

Images