JP2017214523A - Active energy ray-curable composition, active energy ray-curable ink, composition storage container, two-dimensional or three-dimensional image, apparatus and method for forming the same, structure and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition capable of improving yellow discoloration and odor without causing a problem in skin sensitivity.SOLUTION: An active energy ray-curable composition contains (A) (meth)acrylate and/or (meth)acrylamide of which skin sensitivity is negative, (B) vinyl ether and/or t-butyl methacrylate and/or n-pentyl methacrylate and/or n-hexyl methacrylate of which skin sensitivity is negative, and (C) benzoin isobutyl ether.SELECTED DRAWING: Figure 4

Description

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

Since the active energy ray curable ink has less odor and quick drying than the solvent-based ink, there is an advantage that it can be suitably recorded on a recording medium that does not absorb the ink.
Photopolymerizable inkjet inks that use (meth) acrylic acid esters and photopolymerizable inkjet inks that use vinyl ethers in combination are well known (Patent Document 1, etc.).
In addition, many of the monomers used in conventional photopolymerizable inkjet inks are toxic. Especially, (meth) acrylic acid esters that are inexpensive and can be procured easily have skin sensitivities that cause allergies when touching the skin. Most had high toxicity. However, a solution has been found by the photopolymerizable inkjet ink disclosed in Patent Document 2 and the like.
However, not only the monomer but also the initiator contained in the ink has high safety, and no white ink or clear ink that can satisfy whiteness and odor has been found so far.
Further, in the case of white ink or clear ink, there is a problem that yellowing easily occurs due to curing, and whiteness and transparency are impaired. In addition, the reduction of odor after printing has become one of the problems, and no ink has been found so far that can satisfy all of skin sensitivity, yellowing and odor.

On the other hand, the active energy ray curable ink binds the monomers in the active energy ray curable ink using several kinds of polymerization initiators having different absorption wavelengths according to the type of light source such as a mercury lamp or a metal halide lamp. And let it harden.
In recent years, ultraviolet light emitting diodes having a peak emission wavelength at 365 nm or 385 nm, which consume less power, are often used from the viewpoint of power saving. In addition, practical application of LEDs having a wavelength range of 255 to 350 nm (peak 285 nm) having a wavelength shorter than 365 nm (deep ultraviolet rays) is also under consideration, and inks that can also be used for these LEDs are desired.
A white ink and a clear ink that are compatible with LEDs of 255 to 350 nm and can achieve both safety, yellowing and odor have not been found so far.

  An object of this invention is to provide the active energy ray hardening-type composition which can improve yellowing and an odor, without a problem about skin sensitivity.

The above problem is solved by the following configuration 1).
1) (A) (meth) acrylic acid ester and / or (meth) acrylamide having negative skin sensitivity, and (B) vinyl ether and / or t-butyl methacrylate having negative skin sensitivity and / or An active energy ray-curable composition comprising n-pentyl methacrylate and / or n-hexyl methacrylate and (C) benzoin isobutyl ether. (However, the (meth) acrylic acid ester does not include t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate.)

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type composition which can improve yellowing and an odor without a problem regarding skin sensitivity is provided.

1 is a schematic diagram illustrating an example of an image forming apparatus according to the present invention. It is the schematic which shows an example of another image forming apparatus in this invention. It is the schematic which shows an example of another image forming apparatus in this invention. It is a figure which shows the light absorbency of benzoin isobutyl ether. It is a bluff showing an example of a yellowing situation when Irgacure 379 or benzoin isobutyl ether is used as a polymerization initiator.

  The active energy ray-curable composition of the present invention includes (A) (meth) acrylic acid ester and / or (meth) acrylamide having negative skin sensitivity, and (B) vinyl ether having negative skin sensitivity. And / or t-butyl methacrylate and / or n-pentyl methacrylate and / or n-hexyl methacrylate, and (C) benzoin isobutyl ether. However, the (meth) acrylic acid ester does not include t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate.

The component (A) is a photopolymerizable monomer having negative skin sensitivity, and the component (B) is a photopolymerizable monomer having low viscosity and negative skin sensitivity, Component C) is a polymerization initiator that has negative skin sensitivity and can solve the problems of yellowing and odor.
By combining these components, it is possible to provide an active energy ray-curable composition that can improve yellowing and odor without causing problems with skin sensitivity.

  The (C) component benzoin isobutyl ether has a structure represented by the following general formula (1) and is negative in skin sensitivity.

As shown in FIG. 4, the absorption characteristics of benzoin isobutyl ether have absorption near 250 nm, so that it does not overlap with the absorption peak of titanium oxide (230 nm or less), and white ink using a titanium oxide pigment has good curability. Can be obtained.
In particular, when a deep UV LED having a short wavelength of 255 nm to 350 nm is used, good curability is obtained due to the light absorption characteristics of benzoin isobutyl ether.

5-30 mass% is preferable with respect to all the monomers, and, as for the usage-amount of the benzoin isobutyl ether which is (C) component, 10-15 mass% is more preferable.
When 5% by mass or more is used, curability is improved, and when 30% by mass or less is used, problems such as reduced solubility, reduced strength of the cured film, and generation of odors are less likely to occur.
In the present invention, a polymerization initiator other than benzoin isobutyl ether may be used as long as the effects of the present invention are not impaired.
In addition, all the monomers said by this invention mean the sum total of (A) and (B) component demonstrated below, and the photopolymerizable monomer other than these used as needed.

  Benzoin isobutyl ether is disclosed as an initiator in, for example, Japanese Patent No. 5564788, Japanese Patent No. 5663899, Japanese Patent Application Laid-Open No. 2015-221908, and the like. However, there is no technical idea in the prior art that attempts to improve skin sensitivity, yellowing and odor by using benzoin isobutyl ether together with a monomer having no skin sensitivity.

“Skin sensitivity is negative” refers to a compound corresponding to at least one of the following (1) to (3).
(1) In the skin sensitivity test by the LLNA method (Local Lymph Node Assay), a compound having a Stimulation Index (SI value) of less than 3 indicating the degree of sensitivity (2) MSDS (Chemical Safety Data Sheet) A compound evaluated as “negative skin sensibility” or “no skin sensibility” (3) “Skin sensibility negative” or “skin in literature [eg Contact Dermatitis 8 223-235 (1982)] Regarding the compound (1) evaluated as “no sensitivity”, for example, “Functional Materials”, September 2005, Vol. 25, no. 9, as shown in P55, when the SI value is less than 3, it is determined that the skin sensitivity is negative. The lower the SI value, the lower the skin sensitivity. Therefore, in the present invention, it is preferable to use a monomer or oligomer having an SI value as low as possible, preferably less than 3, preferably 2 or less, more preferably 1.6 or less. Use things.

Examples of (A) (meth) acrylic acid ester or (meth) acrylamide having negative skin sensitivity include, for example, γ-butyrolactone methacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol dimethacrylate, caprolactone-modified diester. pentaerythritol hexaacrylate, polypropylene glycol diacrylate _{[CH 2 = CH-CO- (OC} 3 H 6) n-OCOCH = CH 2 (n ≒ 12) ], caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, polyethoxylated Tetramethylol methane tetraacrylate, ethylene oxide modified bisphenol A diacrylate, neopentyl glycol dimethacrylate, hydroxyethyl acrylamide, stearyl alcohol Examples include chlorate.
Among these, caprolactone-modified dipentaerythritol hexaacrylate is preferable from the viewpoint of improving the effect of the present invention. Moreover, 2 or more types can also be used together for (A) component.
10-90 mass% is preferable with respect to all the monomers, and, as for the usage-amount of these (A) components, it is more preferable that it is 40-60 mass%.

(B) Examples of vinyl ethers with negative skin sensitivity include triethylene glycol divinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, etc., but they are sufficiently low in viscosity and have a boiling point that is not too low. Triethylene glycol divinyl ether is preferable because it is easy to handle.
As mentioned above, vinyl ether, t-butyl methacrylate, n-pentyl methacrylate, and n-hexyl methacrylate have a sufficiently low viscosity, so that the skin sensitivity is more negative than when these are not used together. From this viewpoint, t-butyl methacrylate, n-pentyl methacrylate, and n-hexyl methacrylate are preferable.
10-90 mass% is preferable with respect to all the monomers, and, as for the usage-amount of the monomer of these (B) components, 40-60 mass% is more preferable. Moreover, 2 or more types can also be used together for (B) component.

In addition, there are some problems with the skin sensation alone, and even if a compound whose skin sensibility is unconfirmed, the following (meth) acrylate, (meth) acrylamide, Vinyl ether can also be used in combination.
Ethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, γ-butyrolactone acrylate, isobornyl (meth) acrylate, formalized trimethylolpropane mono (meth) acrylate, polytetramethylene glycol di (meth) Acrylate, trimethylolpropane (meth) acrylic acid benzoate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate [CH ₂ ═CH—CO— (OC ₂ H ₄ ) n-OCOCH = CH ₂ (n≈4)], (n≈9), (n≈14), (n≈23)], dipropylene glycol di (meth) acrylate, tripropylene glycol Distearate (meth) acrylate, polypropylene glycol di methacrylate _{[CH 2 = C (CH 3)} -CO- (OC 3 H 6) n-OCOC (CH 3) = CH 2 (n ≒ 7) ], 1,3 Butanediol di (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol diacrylate, tricyclode Candimethanol diacrylate, propylene oxide modified bisphenol A di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acryloylmorpholine, 2-hydroxypropyl (meth) acrylamide, propylene Oxide modified tetramethylol methane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, caprolactone modified dipentaerythritol hydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, Trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-Hydroxyethyl) isocyanurate tri (meth) acrylate , Neopentyl glycol diacrylate, ethoxylated neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, propylene oxide modified glyceryl tri (meth) acrylate, polyester di (meth) acrylate, polyester tri ( (Meth) acrylate, polyester tetra (meth) acrylate, polyester penta (meth) acrylate, polyester poly (meth) acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, polyurethane di (meth) acrylate, polyurethane tri ( (Meth) acrylate, polyurethane tetra (meth) acrylate, polyurethane penta (meth) acrylate, polyurethane poly (meth) ) Acrylate, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, dicyclopentadiene vinyl ether, tricyclodecane vinyl ether, benzyl vinyl ether, ethyl oxetane methyl vinyl ether and the like.

The active energy ray-curable composition of the present invention can be used as an active energy ray-curable ink, and is particularly useful for white ink or clear ink.
In the case of white ink, examples of preferable pigments include inorganic pigments, for example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, and synthetic silica. Examples thereof include silicas such as acid salts, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, and clay. Among these, titanium oxide is preferable from the point of concealability.
Examples of the crystal structure of titanium oxide include an anatase structure and a rutile structure. Among these, a rutile structure is preferable because of its low photocatalytic activity.
The pigment is preferably surface-treated, and more preferably a surface treatment that can make the surface of the pigment hydrophilic. By making the surface of the pigment hydrophilic, the dispersibility of the pigment can be improved and the curability can be improved.
Examples of the treatment agent used for the surface treatment include Al ₂ O ₃ , SiO ₂ , and ZrO ₂ . Among these, Al ₂ O ₃ is preferable from the viewpoint of dispersibility. In addition to improving dispersibility, SiO ₂ and ZrO ₂ have the effect of preventing the photocatalytic activity of titanium oxide, and can improve the light resistance of the resulting cured film.
The surface treatment method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include known methods such as pigment derivative treatment, resin modification, oxidation treatment, and plasma treatment.

As the titanium oxide, can be a commercially available product, The commercially available product, trade name: TCR-52 (number-average primary particle diameter: 230 nm, surface _treatment: Al _{2 O} 3), trade name: S3618 ( Number average primary particle size: 230 nm, surface treatment: Al ₂ O ₃ (above, manufactured by Sakai Chemical Industry Co., Ltd.), trade name: JR403 (number average primary particle size: 250 nm, manufactured by Teika Corporation, surface treatment: Al ₂ O ₃ , SiO ₂ ) are preferred. These may be used alone or in combination of two or more. Product name: JR (number average primary particle size: 270 nm, manufactured by Teika Co., Ltd., surface treatment: none), product name: JR301 (number average primary particle size: 300 nm, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O) ₃ ), trade name: R45M (number average primary particle size: 290 nm, manufactured by Sakai Chemical Industry Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ ) and the like can be partially contained.

Among these titanium oxides, those having a number average primary particle diameter of 200 nm to 260 nm are particularly preferable. When it is smaller than 200 nm, the concealing property is lowered, and when it is larger than 260 nm, the yellowing level is lowered or the sedimentation property is deteriorated.
Moreover, as said titanium oxide, what is described in Unexamined-Japanese-Patent No. 2012-214534 and Unexamined-Japanese-Patent No. 2014-185235 can be used conveniently, for example.

  The volume average particle size of the active energy ray-curable composition of the present invention is preferably 200 nm or more and 280 nm or less, and more preferably 210 nm or more and 260 nm or less. When the volume average particle size is 200 nm or more, concealment and printing density can be improved. When the volume average particle size is 280 nm or less, the concealability is improved and head clogging is suppressed when recording using an inkjet system. Discharge stability can be improved. The volume average particle size is obtained by diluting the active energy ray-curable composition with the monomer about 100 times and using a particle size distribution meter (device name: UPA150, manufactured by Nikkiso Co., Ltd.) to cure the active energy ray. It can be determined by measuring the volume average particle size of the mold composition. The volume average particle size of the active energy ray curable composition means a volume average particle size obtained by subjecting the active energy ray curable composition itself to measurement, and the active energy ray curable composition contains This corresponds to the particle size of a particulate object (specifically, a pigment dispersion containing a pigment).

In the active energy ray-curable composition of the present invention, the content of an object having a volume particle size of 160 nm or less is preferably 10% by volume or less based on the total amount of the active energy ray-curable composition. When the content is 10% by volume or less, concealability and concentration can be improved.
In the active energy ray-curable composition of the present invention, the content of an object having a volume particle size of 370 nm or more is preferably 10% by volume or less based on the total amount of the active energy ray-curable composition. When the content is 10% by volume or less, yellowing and inkjet discharge stability are improved.

The active energy ray-curable composition of the present invention can be used as inks other than white ink, and for example, inorganic pigments, organic pigments, dyes and the like can be used.
Examples of inorganic pigments that can be used include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, titanium oxide, and the like.
Examples of the organic pigment 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 quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, A daylight fluorescent pigment is mentioned.
Moreover, in order to make the dispersibility of a pigment more favorable, you may further contain a dispersing agent. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent conventionally used for preparing pigment dispersions, such as a polymer dispersing agent, is mentioned.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used. One kind may be used alone, or two or more kinds may be used in combination.

  In the active energy ray-curable composition of the present invention, the proportion of the pigment or dye used is, for example, from 1% by mass to 20% by mass with respect to the entire active energy ray-curable composition, and in the case of an organic pigment, 2% by mass or more. It is preferably 5% by mass or less, and preferably 8% by mass or more and 15% by mass or less for inorganic pigments.

The active energy ray-curable composition of the present invention uses a polymerization inhibitor such as 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, and methoquinone as necessary. be able to.
As content of a polymerization inhibitor, 0.005 mass% or more and 3 mass% or less are preferable with respect to the polymerization initiator whole quantity. When the content is 0.005% by mass or more, storage stability can be improved, an increase in viscosity can be suppressed under a high temperature environment, and when it is 3% by mass or less, curability can be improved.

  Moreover, the following various components can also be used for the active energy ray hardening-type composition of this invention as needed.

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

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

<Manufacturing method>
As a method for producing the active energy ray-curable composition, a pigment, and if necessary, a dispersant and a polymerizable unsaturated monomer are charged into a dispersing machine using a medium such as a ball mill, a disk mill, a pin mill, or a dyno mill. It can be obtained by dispersing and kneading to prepare a pigment dispersion, and further mixing the components (A) to (C) and other various components. Further, a medialess dispersion device such as a disper or a homogenizer may be used.

<Active energy rays>
Active energy rays used for curing the active energy ray-curable composition of the present invention include polymerizable components in the composition such as electron rays, α rays, β rays, γ rays, and X rays in addition to ultraviolet rays. There is no particular limitation as long as it can provide the energy necessary for proceeding the polymerization reaction.
There is no restriction | limiting in particular as a light source of the said active energy ray, Although it can select suitably, For example, a mercury lamp, a metal halide lamp, UV-LED lamp etc. are mentioned.
The mercury lamp is a quartz glass arc tube filled with high-purity mercury (Hg) and a small amount of rare gas. The main wavelength is 365 nm, and ultraviolet rays of 254 nm, 303 nm, and 313 nm are efficiently used. It is characterized by high radiation and short wavelength UV output.
The metal halide lamp is a lamp in which a metal is enclosed in the form of a halide in addition to mercury in an arc tube, and emits an active energy ray spectrum over a wide range from 200 nm to 450 nm. Compared to a mercury lamp, it is 300 nm to 450 nm. It is characterized by high output of long wavelength ultraviolet rays.
The UV-LED lamp has a feature that the environmental load can be reduced by the LED system with a long life and low power consumption, and there is no generation of ozone, and the apparatus can be made compact, and the active energy ray curable composition of the present invention is used. It is preferable as a lamp used for curing. The active energy ray-curable composition of the present invention has a wavelength range shorter than 365 nm (because of its ability to absorb deep ultraviolet rays, and is particularly suitable for application to LED lamps having emission peaks in the wavelength range of 250 nm to 400 nm. It will be advantageous.

(Use)
The use of the active energy ray-curable composition of the present invention is not particularly limited as long as it is a field where an active energy ray-curable material is generally used, and can be appropriately selected according to the purpose. It can be applied to resins, paints, adhesives, insulating materials, release agents, coating materials, sealing materials, various resists, various optical materials, and the like.
Furthermore, the active energy ray-curable composition of the present invention is not only used as an ink to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional model). Can also be used.

As the three-dimensional modeling material, for example, as a binder of powder particles used in a powder lamination method which is one of 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 ejected to a predetermined area and irradiated with active energy rays and cured, and an active energy ray-curable composition. A solid object in an optical modeling method or the like in which a storage pool (container) 1 of 5 is irradiated with active energy rays 4 to form a hardened layer 6 having a predetermined shape on the movable stage 3, and this is sequentially laminated to perform three-dimensional modeling. It can be used as a constituent material.
A three-dimensional modeling apparatus for modeling a three-dimensional modeled object using such an active energy ray-curable composition can use a known one, and is not particularly limited. A thing provided with a supply means, a discharge means, an active energy ray irradiation means, etc. can be used.

  The present invention also includes a cured product obtained by curing the active energy ray-curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate such as a recording medium. . The molded product is obtained by subjecting a cured product or structure formed in a sheet shape or a film shape to a molding process such as heat stretching or punching, for example, an automobile, an OA device, an electric -It is suitably used for applications that require the surface to be molded after decorating, such as meters for electronic devices and cameras, and panels for operation units. The substrate is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include paper, plastic, metal, ceramic, glass, and composite materials thereof. From the viewpoint of workability, plastic is preferable. A substrate is preferred. In addition, the stretchability of the cured product in the present invention is expressed as a stretchability at 180 ° C. as a ratio of (length after tensile test−length before tensile test) / (length before tensile test). It is preferably 50% or more, and more preferably 100% or more.

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

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

(Image Forming Method and Image Forming Apparatus)
The image forming method in the present invention has an irradiation step of irradiating active energy rays in order to cure at least the active energy ray curable composition, and the image forming apparatus in the present invention is an active energy ray curable type. The container may be housed with a housing part containing the composition and an irradiation means for irradiating the active energy ray-curable composition with active energy rays. Furthermore, you may have the discharge process and discharge means which discharge an active energy ray hardening-type composition. A method for discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.
FIG. 1 is an example of an image forming apparatus provided with an ink jet ejection unit. Ink is ejected to the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d including ink cartridges and discharge heads of active energy ray curable inks of yellow, magenta, cyan, and black. Is done. Thereafter, the light is cured by irradiating active energy rays from the light sources 24a, 24b, 24c, and 24d for curing the ink, thereby forming a color image. Thereafter, the recording medium 22 is conveyed to the processing unit 25 and the printed matter winding roll 26. Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied by the ink discharge unit. If necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. In addition, for a recording medium that moves intermittently according to the ejection head width, a serial method in which ink is ejected onto the recording medium by moving the head, or the recording medium is moved continuously and held at a fixed position. Any ink jet recording apparatus of a line system in which ink is ejected from a head onto a recording medium can be applied.

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

  The recorded matter recorded by the ink of the present invention is not only printed on a smooth surface such as ordinary paper or resin film, but also printed on a surface to be printed having irregularities, such as metal or ceramic. It includes those printed on a printing surface made of various materials. Further, by stacking two-dimensional images, it is possible to form an image having a stereoscopic effect (an image composed of two and three dimensions) or a three-dimensional object.

  FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) used in the present invention. The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to transfer the first active energy ray-curable composition from the molded article ejection head unit 30 to the support. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is discharged from the discharge head units 31 and 32, and these respective compositions are discharged by the adjacent ultraviolet irradiation means 33 and 34. It is laminated while curing. More specifically, for example, the second active energy ray-curable composition is ejected from the support ejection head units 31 and 32 on the model support substrate 37 and solidified by irradiation with active energy rays. After forming the first support layer having the reservoir, the first active energy ray-curable composition is discharged from the ejection head unit 30 for a molded article into the reservoir and is solidified by irradiation with active energy rays. Then, the step of forming the first modeled object layer is repeated a plurality of times while lowering the stage 38 movable in the vertical direction in accordance with the number of stacking, thereby stacking the support layer and the modeled object layer to form the three-dimensional modeled object 35. Is produced. Thereafter, the support laminate 36 is removed as necessary. In FIG. 2, only one shaped article discharge head unit 30 is provided, but two or more shaped article discharge head units 30 may be provided.

(2D or 3D image)
The two-dimensional or three-dimensional image of the present invention is formed by applying and curing either the active energy ray-curable composition of the present invention or the active energy ray-curable ink of the present invention on a substrate. .
The two-dimensional or three-dimensional image recorded by the active energy ray-curable ink of the present invention is not only recorded on a smooth surface such as ordinary paper or resin film, but also recorded on a recording surface having irregularities. And those recorded on a recording surface made of various materials such as metal and ceramics.
Examples of the two-dimensional image include characters, symbols, figures, combinations thereof, and solid images.
Examples of the three-dimensional image include a three-dimensional model.
There is no restriction | limiting in particular as average thickness of the said three-dimensional molded item, According to the objective, it can select suitably, 10 micrometers or more are preferable.

Since the two-dimensional or three-dimensional image uses either the active energy ray-curable composition of the present invention or the active energy ray-curable ink of the present invention, 2 is formed on a non-permeable substrate. A three-dimensional or three-dimensional image has excellent water resistance such that good adhesion can be maintained even after being immersed in water.
The two-dimensional or three-dimensional image is preferably cured using light-emitting diode light.

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

(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.
In addition, the two-dimensional or three-dimensional image of the present invention, the structure of the present invention, and the molded product of the present invention have no problem in skin sensitivity even if an uncured monomer component remains. Even if it touches, since it does not cause skin feeling, a safe article can be provided.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Moreover, 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 were determined as follows.

<Volume average particle diameter of active energy ray-curable composition>
As the volume average particle size of the active energy ray-curable composition, the obtained active energy ray-curable composition was diluted about 100 times with a monomer, and a particle size distribution meter (device name: UPA150, manufactured by Nikkiso Co., Ltd.) ) Was used to measure the volume particle size and volume average particle size of the active energy ray-curable composition. From the obtained volume particle size, the content of the object having a volume particle size of 160 nm or less in the active energy ray-curable composition and the content of the object having a volume particle size of 370 nm or more in the active energy ray-curable composition Was calculated.

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

(Preparation of pigment dispersion)
<Preparation of Pigment Dispersion A>
Titanium oxide A (trade name: TCR-52, manufactured by Sakai Chemical Industry Co., Ltd., surface treatment: Al ₂ O ₃ , number average primary particle size: 230 nm) 110 parts by mass, amine group-containing acrylic block copolymer (dispersant, product) Name: BYKJET-9151, manufactured by BYK Japan Japan Co., Ltd.) 10 parts by mass and triethylene glycol divinyl ether (manufactured by BASF) 100 parts by mass, filled with 2 mm diameter zirconia beads (filling rate: 45% by volume) 500 mL ball mill And dispersed for 48 hours at a dispersion temperature of 25 ° C. at 70 rpm. Then, it was placed in a 1 L sand mill filled with zirconia beads having a diameter of 0.1 mm (filling rate: 80% by volume) and dispersed at a peripheral speed of 8 m / second and a dispersion temperature of 25 ° C. for 3 hours to prepare Pigment Dispersion A. .

<Preparation of Pigment Dispersion B>
Titanium oxide B (trade name: JR403, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ , number average primary particle size: 250 nm) 110 parts by mass, amine group-containing acrylic block copolymer (dispersant, product) Name: BYKJET-9151, manufactured by BYK Japan Japan Co., Ltd. 10 parts by mass, and t-butyl methacrylate “Light Ester TB” (manufactured by Kyoeisha Chemical Co., Ltd.) 100 parts by mass using a homogenizer at 5,000 revolutions and a dispersion temperature. After dispersion at 35 ° C. for 20 minutes, the mixture is placed in a 1 L sand mill filled with zirconia beads having a diameter of 0.3 mm (filling rate: 90% by volume) and dispersed at a peripheral speed of 10 m / second and at a dispersion temperature of 30 ° C. for 1 hour. Dispersion B was prepared.

<Preparation of Pigment Dispersion C>
Titanium oxide C (trade name: R21, manufactured by Sakai Chemical Industry Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ , number average primary particle size: 200 nm) 110 parts by mass, fatty acid amine comb having polyethyleneimine as the main skeleton 15 parts by mass of a resin dispersant (dispersant, trade name: Solsperse 39000, manufactured by Nihon Ruble Resor Co., Ltd.) and 105 parts by mass of n-pentyl methacrylate (manufactured by Toyo Science Co., Ltd.) are filled with zirconia beads having a diameter of 2 mm (filling ratio: 43 Pigment Dispersion C was prepared by placing it in a 500 mL ball mill with a volume%) and a dispersion temperature of 25 ° C. and 70 revolutions / minute for 150 hours.

<Preparation of Pigment Dispersion D>
Titanium oxide D (trade name: JR405, manufactured by Teika Co., Ltd., surface treatment: Al ₂ O ₃ , number average primary particle size: 210 nm) 110 parts by mass, amine group-containing acrylic block copolymer (dispersant, trade name: BYKJET) -9151, manufactured by Big Chemie Japan Co., Ltd.) 7 parts by mass and 103 parts by mass of n-hexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 500 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling rate: 45 vol%) The dispersion temperature was 25 ° C. and 70 rotations / minute for 180 hours to prepare Pigment Dispersion D.

<Preparation of Pigment Dispersion E>
Titanium oxide E (trade name: R45M, manufactured by Sakai Chemical Industry Co., Ltd., surface treatment: Al ₂ O ₃ , SiO ₂ , number average primary particle size: 290 nm) 110 parts by mass, fatty acid amine comb having polyethyleneimine as a main skeleton 12 parts by weight of a resin dispersant (dispersant, trade name: Solsperse 39000, manufactured by Nihon Ruble Resor Co., Ltd.) and 108 parts by mass of n-pentyl methacrylate (manufactured by Toyo Science Co., Ltd.) were dispersed at a temperature of 35 ° C. using a homogenizer. After dispersion at 8,000 rpm for 15 minutes, the mixture is 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 / second. Dispersion E was produced.

<Preparation of Pigment Dispersion F>
44 parts by mass of dimethylquinacridone A (trade name: PR122RGT, manufactured by DIC), comb-type resin dispersant of fatty acid amine having polyethyleneimine as a main skeleton (dispersant, trade name: Solsperse 39000, manufactured by Nippon Louvre Rizole, acid value) : 33 mgKOH / g, amine value: 0 mgKOH / g) 26 parts by mass and n-pentyl methacrylate (manufactured by Toyo Science Co., Ltd.) 150 parts by mass using a homogenizer at a dispersion temperature of 35 ° C. and 8,000 rpm for 15 minutes After dispersion, pigment dispersion F was prepared by placing in a sand mill filled with zirconia beads having a diameter of 0.3 mm (filling rate: 80% by volume) and dispersing for 1 hour at a dispersion temperature of 30 ° C. and a peripheral speed of 8 m / sec.

  The compositions of the obtained pigment dispersions A to F are shown in Table 1.

Examples 1-16
Using the pigment dispersions A to F, the following materials (A) to (C) were mixed at the blending ratios (numerical values are parts by mass) shown in the respective columns of the examples in Table 4 to obtain inks.
(A) (meth) acrylic acid ester and / or (meth) acrylamide having negative skin sensitivity (B) triethylene glycol divinyl ether, t-butyl methacrylate, n-pentyl methacrylate having negative skin sensitivity , N-hexyl methacrylate (C) radical photopolymerization initiator having negative skin sensitivity

Details of monomers A1 to A14, monomers B1 to B4, and C1 to C4 in Table 4 are as follows. The numerical value in the parenthesis at the end is the “SI value” in the LLNA test of (1), “Negative” or “None” is the MSDS (chemical safety data sheet) of (2), or (3) Are evaluated as “negative skin sensation” or “no skin sensation”.
Details of the SI value evaluation method will be described later.

A1: Caprolactone-modified dipentaerythritol hexaacrylate Nippon Kayaku Co., Ltd. “DPCA-60” (negative) MSDS evaluation (test method: OECD test guideline 406)
A2: Polyethoxylated tetramethylolmethane tetraacrylate “NTM-35E” (1.7) manufactured by Shin-Nakamura Chemical Co., Ltd.
A3: “BPE-10” (1.2) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ethylene oxide-modified bisphenol A diacrylate
A4: Caprolactone modified hydroxypivalate neopentyl glycol diacrylate Nippon Kayaku Co., Ltd. “HX-620” (0.9)
A5: “HEAA” produced by hydroxyethyl acrylamide Kojinsha (none) (test method: OECD test guideline 429)
A6: Polypropylene glycol diacrylate polypropylene glycol diacrylate _{[CH 2 = CH-CO- (OC} 3 H 6) n-OCOCH = CH 2 (n ≒ 12) ]
“M-270” manufactured by Toagosei Co., Ltd. (1.5)
A7: Tricyclodecane dimethanol dimethacrylate “DCP” (1.3) manufactured by Shin-Nakamura Chemical Co., Ltd.
A8: Polyethylene glycol dimethacrylate represented by formula (1) (n≈14)]
Kyoeisha Chemical Company "Light Ester 14EG" (1.6)
A9: Polyethylene glycol dimethacrylate represented by formula (1) (n≈9)]
"Light Ester 9EG" manufactured by Kyoeisha Chemical Co., Ltd. (1.3)
_{CH 2 = C (CH 3)} -CO- (OC 2 H 4) n-OCOC (CH 3) = CH 2 (1)
A10: “SR350” (1.9) manufactured by trimethylolpropane trimethacrylate Sartomer
A11: γ-butyrolactone methacrylate “GBLMA” (2.1) manufactured by Osaka Organic Chemical Co., Ltd.
A12: “SYA” (2.7) manufactured by Stearyl Acrylate Osaka Organic Chemical Co., Ltd.
A13: Neopentyl glycol dimethacrylate “NPG” (2.0) manufactured by Shin-Nakamura Chemical Co., Ltd.
A14: “SR214” (2.6) manufactured by 1,4-butanediol dimethacrylate Sartomer

B1: Triethylene glycol divinyl ether Evaluation by BASF (negative) MSDS (Test method: OECD test guideline 406)
B2: Evaluation in literature of “Light Ester TB” (negative) made by t-butyl methacrylate Kyoeisha Chemicals (test method: maximization method)
B3: n-Pentylmethacrylate Toyo Science Co., Ltd. “n-AmylMethacrylate” (negative) evaluation in literature (test method: maximization method)
B4: n-Hexyl Methacrylate “Hexyl Methacrylate” (Negative) Evaluation by Tokyo Chemical Industry Co., Ltd. (Test Method: Maximization Method)

<SI value evaluation method>
The SI value was measured as follows according to a skin sensitivity test by the LLNA method (Local Lymph Node Assay).
[Test material]
《Positive control substance》
Α-hexylcinnamaldehyde (HCA; manufactured by Wako Pure Chemical Industries, Ltd.) was used as a positive control substance.
《Medium》
As a medium, a mixed solution in which the following acetone and olive oil were mixed at a volume ratio of 4: 1 was used.
・ Acetone (Wako Pure Chemical Industries)
・ Olive oil (Fujimi Pharmaceutical)
《Animals used》
For each of the test substance, the positive control, and the vehicle control, female mice were acclimated for 8 days including 6 days of quarantine. During quarantine and habituation, no abnormalities were observed in all animals. Using the body weight measured 2 days before the start of sensation, the group was divided into 2 groups (4 animals / group) so that the body weight of the individual was within ± 20% of the total body weight by random sampling by weight . The age of the animals at the start of sensation was 8-9 weeks of age. Animals that were excluded by grouping were excluded from the study.
The animals used were identified by applying oil-based ink to the tail throughout the test period, and the cages were identified by labeling.
《Creation environment》
Animals are used throughout the entire breeding period including quarantine and acclimatization period, temperature 21 to 25 ° C., relative humidity 40 to 70%, ventilation rate 10 to 15 times / hour, light / dark cycle 12 hours sense (lights from 7 o'clock to 19 o'clock) Breeding in the breeding room of the barrier system set to “off”.
The cage made of polycarbonate was used as the breeding cage. The animals used were kept at 4 / cage.
The feed used was a solid feed MF for experimental animals (manufactured by Oriental Yeast Co., Ltd.), and was used freely by the animals used. The drinking water was allowed to be freely consumed by the animals using a water supply bottle with tap water added with sodium hypochlorite (Purelux, Oyalax) so that the chlorine concentration was about 5 ppm. Sun flakes (fir, electric planer shavings, manufactured by Charles River Japan) were used for the flooring. The feed and breeding equipment were each autoclaved (121 ° C., 30 minutes).
Cages and bedding were exchanged at the time of grouping and the auricular lymph node intake day (at the time of removal from the breeding room), and the water bottles and racks were exchanged at the time of grouping.

[Test method]
<< Group composition >>
Table 2 shows the group structure used in the SI value measurement test.

[Preparation]
<Test substance>
Table 3 shows the weighing conditions of the test substance. The test substance was weighed into a volumetric flask, and the volume was adjusted to 1 mL while adding the medium. The preparation liquid was put in a light-tight airtight container (made of glass).

《Positive control substance》
Approximately 0.25 g of HCA was accurately weighed, and a 25.0 w / v% solution was prepared as 1 mL while adding the medium. The preparation was placed in a light-tight airtight container (made of glass).
<< BrdU >>
200 mg of 5-bromo-2'-deoxyuridine (BrdU, manufactured by Nacalai Tesque) was accurately weighed into a volumetric flask, physiological saline (manufactured by Otsuka Pharmaceutical Co., Ltd.) was added, and ultrasonic irradiation was performed to dissolve. Thereafter, the volume was adjusted to 20 mL to prepare a 10 mg / mL solution (BrdU preparation solution). The preparation solution was sterilized by filtration using a sterilized filtration filter and placed in a sterilized container.
《Preparation time and storage period》
The positive control substance preparation solution was prepared the day before the start of sensation, and stored in a cold place except when used. Media and test substance preparations were prepared on the day of each sensation. BrdU solution was prepared 2 days before administration and stored in a cold place until the day of administration.

[Sensitivity and BrdU administration]
《Sense》
25 μL of each test substance and positive control substance preparation and medium were applied to both ears of the animal. A micro pipettor was used for coating. This operation was performed once a day for 3 consecutive days.
Administration of BrdU
About 48 hours after the final feeling, the BrdU preparation solution was intraperitoneally administered 0.5 mL per animal.

[Observation and inspection]
《General condition》
All animals used in the test were observed at least once a day from the day when the sensation started until the day when the auricular lymph nodes were collected (the date of removal from the breeding room). In addition, in the calculation method of the observation date, the feeling start date was set to Day1.
<< Weighing >>
The body weight was measured on the day when the sensation started and the day when the auricular lymph nodes were collected (the date of removal from the breeding room). Moreover, the average value and standard error of the body weight for every group were calculated.
《Auricular lymph node collection and weight measurement》
Approximately 24 hours after BrdU administration, animals were euthanized and auricular lymph nodes were collected. The surrounding tissues were removed and the bilateral auricular lymph nodes were weighed together. Moreover, the average value and standard error of the auricular lymph node weight for each group were calculated. After weighing, each individual was stored frozen in a biomedical freezer set at -20 ° C.
<Measurement of BrdU incorporation>
After returning the auricular lymph node to room temperature, it was ground and suspended while adding physiological saline. After filtering this suspension, 3 wells of each individual were dispensed into 96-well microplates, and the BrdU incorporation was measured by ELISA. Each reagent was obtained from a multi-plate reader (FLUOstar OPTIMA, BMG LABTECH) using a commercially available kit (Cell Proliferation ELISA, BrdU colorimetric, Cat. No. 1647229, manufactured by Roche Diagnostics). With respect to the absorbance (OD 370 nm to 492 nm, BrdU incorporation amount) of individuals, the average value of 3 wells was used as the BrdU measurement value of each individual.

[Evaluation of results]
<< Calculation of Stimulation Index (SI) >>
As shown by the following formula, the measured value of BrdU of each individual was gradually decreased by the average value of BrdU measured values of the vehicle control group, and the SI value of each individual was calculated. The SI value of each test group was the average value of SI of each individual. The standard error of SI for each test group was also calculated. The SI value was rounded off to the first decimal place by rounding off the second decimal place.

Comparative Examples 1-4
An ink was obtained by mixing at a blending ratio (numerical value is parts by mass) shown in each column of the comparative example in Table 5 below.
Here, Irgacure 379 is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, and Irgacure 184 is 1-hydroxy- Cyclohexyl-phenyl-ketone.

<Curing sample>
For the inks of Examples 1 to 6, 8, 9, 11, 14, 15 and Comparative Examples, the ink was ejected onto a commercially available PET film as a recording medium by a UV irradiation machine LH6 manufactured by Fusion Systems Japan, Inc. Irradiated and carried out.
Examples 7, 10, 12, 13, and 16 were cured by light irradiation in the same manner using Nikkiso's deep ultraviolet LED (255 to 350 nm).
In handling the ink, the ink is sealed so that air bubbles do not enter the aluminum pouch bag, the above-mentioned pouch bag in which the ink is sealed is stored in a plastic cartridge, and the housing that can store this cartridge is, The ink flow path was installed from the cartridge until it reached the GEN5 head manufactured by Ricoh Printing Systems, and this produced a solid printed coating film by inkjet discharge.
The produced solid printed coating film was cured in order that it was in a non-sticky state by touching it with 1000 (mJ / cm ² ) irradiation in the wavelength range corresponding to the UVA region and changing the integrated light quantity. As a result, a cured sample was prepared.
It is desirable that the physical properties of the ink meet the required specifications of the inkjet discharge head to be used. Various ejection heads are commercially available from many manufacturers, and some of them have a wide range of temperature control functions. In consideration of such a situation, the viscosity of the ink is preferably 5 to 20 mPa · s at 25 ° C., and more preferably 5 to 18 mPa · s in consideration of discharging at 25 ° C. However, it is possible to use the temperature control function of the discharge head. If the viscosity is too high at 25 ° C., the head may be heated as necessary to reduce the viscosity of the ink. Assuming that the heating condition is 60 ° C., the viscosity at 60 ° C. is desirably 2 to 15 mPa · s, and more preferably 7 to 12 mPa · s.

<Yellowing>
A white paper is placed on the side of the recording medium opposite to the side on which the obtained image (cured product) is formed, and a reflection spectrodensitometer (device name: X-Rite 939, manufactured by X-Rite) is used, and b * Was used as a measure of yellowing. The smaller | b * |, the better the yellowing.
: | B * | <1
○: 1 ≦ | b * | <2
Δ: 2 ≦ | b * | ≦ 3
×: | b * |> 3

<Odor>
The odor of the cured sample was determined by an odor test. The panel was set at 10 people, and the evaluation was based on the percentage of people who judged that there was an odor.
◎: 0 out of 10 ○: 1 out of 10 △: 2-5 out of 10 ×: 6 or more out of 10

  The results are shown in Table 6.

  * Since Example 6 is not white ink or clear ink, the volume particle size of the ink is not measured.

As can be seen from the above results, the compositions of the examples have (A) (meth) acrylic acid ester and / or (meth) acrylamide having negative skin sensitivity, and (B) negative skin sensitivity. Since it contains certain vinyl ether and / or t-butyl methacrylate and / or n-pentyl methacrylate and / or n-hexyl methacrylate and (C) benzoin isobutyl ether, safety is confirmed without any problem with respect to skin sensitivity. Yellowing and odor are also improved. On the other hand, since the composition of a comparative example did not satisfy | fill all the requirements of said (A)-(C) component, it was not able to improve safety | security, yellowing, and an odor simultaneously.
FIG. 5 is a bluff showing an example of a yellowing situation when Irgacure 379 or benzoin isobutyl ether is used as a polymerization initiator. In the present invention, since benzoin isobutyl ether is used as the polymerization initiator, it is confirmed that the yellowing level is greatly improved.
In Example 6, the color is magenta and the yellowing level is unknown, but a bright magenta color is obtained.
In Examples 5 and 16, since the volume particle size of the composition is large and the ratio of particles of 370 nm or more is large, the yellowing level tends to slightly decrease.

1 Reservation pool (container)
DESCRIPTION OF SYMBOLS 3 Movable stage 4 Active energy ray 5 Active energy ray hardening-type composition 6 Hardened 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 Print winding Roll 30 Model ejection head unit 31, 32 Support body ejection head unit 33, 34 Ultraviolet irradiation means 35 Three-dimensional model 36 Support layer stacking unit 37 Model object support substrate 38 Stage 39 Image forming apparatus

JP-T-2004-526820 Japanese Patent No. 5803582

Claims (19)

(A) (meth) acrylic acid ester and / or (meth) acrylamide having negative skin sensitivity,
(B) vinyl ether and / or t-butyl methacrylate and / or n-pentyl methacrylate and / or n-hexyl methacrylate having negative skin sensitivity,
(C) An active energy ray-curable composition comprising benzoin isobutyl ether.
(However, the (meth) acrylic acid ester does not include t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate.)   2. The active energy ray-curable composition according to claim 1, which is used for white ink or clear ink. (A) (meth) acrylic acid ester and / or (meth) acrylamide is γ-butyrolactone methacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol dimethacrylate, caprolactone-modified dipentaerythritol hexaacrylate, polypropylene glycol diacrylate _{[CH 2 = CH-CO- (OC} 3 H 6) n-OCOCH = CH 2 (n ≒ 12) ], caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, polyethoxylated tetramethylolmethane tetraacrylate, ethylene oxide-modified Selected from bisphenol A diacrylate, neopentyl glycol dimethacrylate, hydroxyethyl acrylamide, and stearyl acrylate The active energy ray-curable composition according to claim 1 or 2, which is at least one kind.   The (A) (meth) acrylic acid ester includes caprolactone-modified dipentaerythritol hexaacrylate and (B) t-butyl methacrylate and / or n-pentyl methacrylate and / or n-hexyl methacrylate. The active energy ray hardening-type composition in any one of 1-3.   The content of the (A) (meth) acrylic acid ester and / or (meth) acrylamide with respect to the total monomers is 40 to 60% by mass, and the (B) vinyl ether and / or t-butyl methacrylate and / or n- The active energy ray-curable composition according to any one of claims 1 to 4, wherein the content of pentyl methacrylate and / or n-hexyl methacrylate is 40 to 60 mass% with respect to all monomers.   The pigment contains titanium oxide having a number average primary particle size of 200 nm or more and 260 nm or less, a volume average particle size of 200 nm or more and 280 nm or less, and a content of an object having a volume particle size of 160 nm or less is 10% by volume or less. The active energy ray-curable composition according to claim 2, wherein the content of an object having a volume particle size of 370 nm or more is 10% by volume or less.   The active energy ray-curable composition according to claim 1, which is a three-dimensional modeling material.   The active energy ray-curable composition according to any one of claims 1 to 7, which is sensitive to light-emitting diode light having an emission peak in a wavelength range of 250 nm to 400 nm.   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 9, which is used for inkjet.   A composition storage container comprising the active energy ray-curable composition according to claim 1 in a container.   A two-dimensional or three-dimensional image obtained by irradiating the active energy ray-curable composition according to any one of claims 1 to 8 with an active energy ray and curing the composition.   At least a housing part that houses the active energy ray-curable composition according to any one of claims 1 to 8, and an irradiation means for irradiating the active energy ray-curable composition with active energy rays. An apparatus for forming a two-dimensional or three-dimensional image, comprising:   The two-dimensional or three-dimensional image forming apparatus according to claim 13, further comprising ejection means for ejecting the active energy ray-curable composition by an ink jet recording method.   A two-dimensional or three-dimensional image forming method including an irradiation step of irradiating the active energy ray-curable composition according to any one of claims 1 to 8 with an active energy ray.   The method for forming a two-dimensional or three-dimensional image according to claim 15, further comprising a discharge step of discharging the active energy ray-curable composition by an ink jet recording method.   The method for forming a two-dimensional or three-dimensional image according to claim 15 or 16, wherein the active energy ray is light-emitting diode light.   A structure having a base material and the two-dimensional or three-dimensional image according to claim 12 on the base material. A molded product obtained by stretching one of the two-dimensional or three-dimensional image according to claim 12 or the structure according to claim 18.