JP2023008529A - Active energy ray-curable composition, active energy ray-curable ink composition, active energy ray-curable inkjet ink composition, image forming device body, and image forming method - Google Patents

Abstract

To provide an active energy ray-curable composition that has high adhesion to substrates while having high blocking resistance.SOLUTION: An active energy ray-curable composition contains a trifunctional adduct urethane acrylate oligomer, a monofunctional monomer and a polyfunctional monomer. Relative to the whole composition, the content of the monofunctional monomer is larger than the total content of the trifunctional adduct urethane acrylate oligomer and the polyfunctional monomer.SELECTED DRAWING: Figure 1

Description

The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink composition, an active energy ray-curable ink composition for inkjet, an image forming apparatus and an image forming method.

Since active energy ray-curable compositions are cured by irradiation with active energy rays, they are superior to solvent-based ink compositions in drying properties and are widely used.

On the other hand, when an active energy ray-curable composition is used, it is required to improve adhesion to substrates, for example, to improve adhesion to plastic substrates such as acrylic. . For example, the following techniques have been proposed as conventional techniques.

Patent Literature 1 proposes an inkjet ink composition containing a colorant, a tri- or more functional urethane acrylate oligomer, and a photopolymerization initiator. According to Patent Document 1, good print quality can be obtained even on a non-absorbent recording medium, and in particular, the adhesiveness to the recording medium substrate is excellent.

Patent Document 2 discloses an inkjet recording method in which a first undercoat layer and a second undercoat layer are formed on an aluminum foil base material, an ink composition is discharged onto the second undercoat layer, and cured by ultraviolet irradiation. disclosed that the ink composition comprises a radically polymerizable monomer, a radical polymerization initiator, and a colorant. According to Patent Document 2, it is said that the resulting printed material has excellent heat-resistant adhesion.

Patent Document 3 discloses an active energy ray-curable urethane (meth)acrylate characterized by having a long-chain alkyl group having 13 to 25 carbon atoms and an active energy ray-curable functional group and modified with polycaprolactone. It is According to Patent Document 3, it can be suitably used as a paint or coating agent in fields where scratch resistance and lubricity are required.

However, when attempting to achieve the required level of adhesion to the substrate, there is a problem that the strength of the coating film is lowered and the anti-blocking property of the coating film is lowered. On the other hand, if, for example, a cross-linking component is added to the composition in order to improve the blocking resistance, the internal stress of the coating film will increase and the adhesion to the substrate will decrease. Thus, there is a trade-off problem between the adhesion to the substrate and the blocking resistance.

Accordingly, an object of the present invention is to provide an active energy ray-curable composition that achieves both adhesion to a substrate and blocking resistance.

In order to solve the above problems, the active energy ray-curable composition of the present invention is an active energy ray-curable composition containing a trifunctional adduct urethane acrylate oligomer, a monofunctional monomer and a multifunctional monomer, the composition The content of the monofunctional monomer in the entire composition is characterized by being greater than the total content of the trifunctional adduct urethane acrylate oligomer and the polyfunctional monomer in the entire composition.

ADVANTAGE OF THE INVENTION According to this invention, the active-energy-ray-curable composition which can be compatible with adhesiveness with respect to a base material and blocking resistance can be provided.

1 is a schematic diagram showing an example of an image forming apparatus according to the present invention; FIG. FIG. 3 is a schematic diagram showing an example of another image forming apparatus according to the present invention; FIG. 10 is a schematic diagram showing an example of still another image forming apparatus according to the present invention; It is a schematic diagram showing an example of a structure obtained by the present invention.

Hereinafter, the active energy ray-curable composition, active energy ray-curable ink composition, active energy ray-curable inkjet ink composition, composition container, image forming apparatus, image forming method, cured product, The decorative body will be described with reference to the drawings. In addition, the present invention is not limited to the embodiments shown below, and can be changed within the scope of those skilled in the art, such as other embodiments, additions, modifications, deletions, etc. is also included in the scope of the present invention as long as the functions and effects of the present invention are exhibited.

(Active energy ray-curable composition)
The active energy ray-curable composition of the present invention contains a trifunctional adduct urethane acrylate oligomer, a monofunctional monomer and a multifunctional monomer, and if necessary, a polymerization initiator, a coloring material, an organic solvent, other components, etc. include.

In conventional active energy ray-curable compositions, if the coating film is softened in order to increase the adhesion to the substrate, the blocking resistance may decrease. When the crosslinking component is added, there is a problem that the adhesion to the substrate is lowered.

In view of the above problems, the present inventors conducted intensive studies and arrived at the present invention.
The active energy ray-curable composition of the present invention is an active energy ray-curable composition containing a trifunctional adduct urethane acrylate oligomer, a monofunctional monomer and a multifunctional monomer, and the composition as a whole contains the monofunctional monomer. The amount is characterized by being greater than the total amount of the content of the trifunctional adduct urethane acrylate oligomer and the polyfunctional monomer relative to the entire composition.
According to the present invention, both adhesion to a substrate and blocking resistance can be achieved. In addition, the ejection stability is excellent when the composition is ejected by inkjet.

A cured product obtained from the active energy ray-curable composition of the present invention is referred to as a cured product, a coating film, a cured ink product, or the like.

<Trifunctional adduct urethane acrylate oligomer>
The functional urethane acrylate oligomer used in the present invention must be an adduct. Since the cross-linking point of the adduct is composed of C—C bonds with little steric hindrance, it is highly effective as a chemical cross-linking point. can get.

The trifunctional adduct urethane acrylate oligomer used in the present invention can be appropriately selected, and can be produced, for example, by the method described in Patent Document 3 (JP-A-2002-256053).

The content of the trifunctional adduct urethane acrylate oligomer is preferably 1.0% by mass or more and 5.0% by mass or less relative to the entire composition. When the content of the trifunctional adduct urethane acrylate oligomer is 1.0% by mass or more and 5.0% by mass or less, continuous ejection stability during ejection of the composition can be improved.

<Monofunctional monomer>
Examples of monofunctional monomers used in the present invention include phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate and isooctyl acrylate. , 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyldiglycol acrylate, cyclic triethylene glycol acrylate methylolpropane formal monoacrylate, imide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, N-vinylformamide, cyclohexyl acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t -butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, acryloylmorpholine, phenoxydiethylene glycol acrylate, vinylcaprolactam, vinylpyrrolidone, 2-hydroxy-3-phenoxy Propyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, iso Octyl acrylate, octyl/decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nonylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene glycol (550) monoacrylate, isobornyl acrylate, and the like. It can be, but is not limited to.

The content of the monofunctional monomer is preferably 60.0% by mass or more and 80.0% by mass or less with respect to the total amount of the composition.

<Polyfunctional monomer>
The active energy ray-curable composition of the present invention contains a polyfunctional monomer. By including the polyfunctional monomer, a coating film having a strong crosslinked structure can be obtained. Polyfunctional monomers that contain, for example, unsaturated bonds derived from (meth)acryloyl groups as functional groups can be used.

Examples of polyfunctional monomers include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tetramethylolmethane tetra(meth)acrylate. , trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, bis(4-(meth)acryloxypolyethoxyphenyl)propane, diallyl phthalate, triallyl trimellitate, 1,6-hexanediol diol (meth) acrylate, 1,9-nonanediol di(meth) acrylate, 1,3-butylene glycol di(meth) acrylate, 1,10-decanediol di(meth) acrylate, neopentyl glycol hydroxypivalate di(meth) ) acrylate, tetramethylolmethane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, modified glycerin tri(meth)acrylate, bisphenol A diglycidyl ether (meth)acrylic acid adduct, modified bisphenol A di(meth) ) acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate tolylene diisocyanate urethane prepolymer, pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer, ditrimethylolpropane tetra(meth)acrylate, penta Examples include, but are not limited to, erythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer. Incidentally, (meth)acrylic acid ester refers to acrylic acid ester or methacrylic acid ester, and (meth)acrylate has the same meaning.

The content of the polyfunctional monomer is preferably 3.0% by mass or more and 15.0% by mass or less with respect to the total amount of the composition. When the content of the polyfunctional monomer is 3.0% by mass or more, sufficient anti-blocking property is obtained, and when it is 15.0% by mass or less, the adhesion to the substrate is less likely to decrease.

The number of functional groups of the polyfunctional monomer is preferably three. When the number of functional groups is 3, a coating film having a relatively excellent balance between blocking resistance and adhesion to a substrate can be obtained.

<Relationship between content>
In the present invention, the content of the monofunctional monomer in the composition as a whole is required to be greater than the total content of the trifunctional adduct urethane acrylate oligomer and the multifunctional monomer in the composition as a whole. By increasing the content of the monofunctional monomer in this manner, good adhesion to the substrate can be obtained. In addition, it is possible to improve the continuous ejection stability when ejecting the composition.

The difference in content relative to the entire composition, that is, content of monofunctional monomer-(total content of trifunctional adduct urethane acrylate oligomer and polyfunctional monomer) is preferably, for example, 10% by mass or more. , more preferably 20% by mass or more, and even more preferably 30% by mass or more. Moreover, the difference in content with respect to the entire composition is preferably 80% by mass or less.

<Polymerization initiator>
The active energy ray-curable composition of the present invention may contain a polymerization initiator.
Any polymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays to initiate polymerization of polymerizable compounds (monomers and oligomers). As such polymerization initiators, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more. Among them, radical polymerization initiators are used. is preferred.

In order to obtain a sufficient curing speed, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the composition.

Examples of radical polymerization initiators 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 ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

Moreover, in addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. Examples of the polymerization accelerator include, but are not limited to, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N, Amine compounds such as N-dimethylbenzylamine and 4,4'-bis(diethylamino)benzophenone are preferred, and the content thereof may be appropriately set according to the polymerization initiator to be used and its amount.

<Color material>
The active energy ray-curable composition of the present invention may contain a coloring material.
As the coloring material, various pigments and dyes imparting glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold and silver can be used depending on the purpose and required properties of the composition of the present invention. can be used.

The content of the coloring material may be appropriately determined in consideration of the desired color density, dispersibility in the composition, etc., and is not particularly limited. It is preferably 1 to 20% by mass.

In addition, the active energy ray-curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, it is suitable as an overcoat layer for protecting images, for example.

As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone, or two or more kinds may be used in combination.

Examples of inorganic pigments that can be used include carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

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 quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye chelates, acid dye chelates, etc.), dyeing lakes (basic dye lakes, acid dye lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments may be mentioned.

In addition, a dispersant may be further included in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, but includes, for example, dispersants commonly used for preparing pigment dispersions such as polymeric dispersants.

As dyes, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and they may be used singly or in combination of two or more.

<Organic solvent>
Although the active energy ray-curable composition of the present invention may contain an organic solvent, it is preferable not to contain it if possible. If the composition does not contain organic solvents, especially volatile organic solvents (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further increased, and it is possible to prevent environmental pollution. . The term "organic solvent" means general non-reactive organic solvents such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from reactive monomers. be. In addition, "not including" an organic solvent means not including substantially an organic solvent, and it is preferably less than 0.1% by mass.

<Other ingredients>
The active energy ray-curable composition of the present invention may optionally contain other known components. Other components include, but are not particularly limited to, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration accelerators, humectants (humectants), fixing agents, Viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, thickeners, and the like.

<Preparation of active energy ray-curable composition>
The active energy ray-curable composition of the present invention can be produced using the various components described above, and the preparation means and conditions are not particularly limited. For example, a polymerizable compound, a pigment, a dispersant, etc. are put into a dispersing machine such as a ball mill, Kitty mill, disk mill, pin mill, or Dyno mill, dispersed to prepare a pigment dispersion, and the pigment dispersion is further added with a polymerizable compound. , an initiator, a polymerization inhibitor, a surfactant, and the like.

<Viscosity>
The viscosity of the active energy ray-curable composition of the present invention is not particularly limited, and may be appropriately adjusted depending on the application and means of application. For example, when a discharge means for discharging the composition from a nozzle is used, the viscosity at 20° C. to 65° C., desirably at 25° C., is preferably 3 to 40 mPa·s, preferably 5 to 15 mPa·s. s is more preferred, and 6 to 12 mPa·s is particularly preferred. 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 rotary viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34′×R24), rotating at 50 rpm, and constant temperature circulating water at 20°C. Measurement can be performed by appropriately setting the temperature in the range of ~65°C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

(Active energy ray-curable ink composition, active energy ray-curable inkjet ink composition)
The active energy ray-curable composition of the present invention achieves both adhesion to a substrate and blocking resistance, and is excellent in jetting stability by inkjet. It is particularly suitable for use in an active energy ray-curable inkjet ink composition.

The active energy ray-curable ink composition of the present invention is characterized by containing the active energy ray-curable composition of the present invention. Further, the active energy ray-curable ink composition for inkjet of the present invention is characterized by including the active energy ray-curable ink composition of the present invention.

(active energy ray)
Examples of the active energy ray used for curing the active energy ray-curable composition of the present invention include ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, and other polymerizable components in the composition. It is not particularly limited as long as it can impart the energy necessary for proceeding with the polymerization reaction. Especially when using a high-energy light source, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, there is a strong desire to eliminate mercury 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, have a long life, are highly efficient, and are low in cost, and are preferred as ultraviolet light sources.

(Composition container)
The composition storage container of the present invention stores the active energy ray-curable composition of the present invention, the active energy ray-curable ink composition of the present invention, or the active energy ray-curable inkjet ink composition of the present invention. A composition container characterized by:

The composition storage container of the present invention means a container in which an active energy ray-curable composition or the like is stored, and is suitable for applications such as those described below. For example, when the active energy ray-curable 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. When used in this way, there is no need to directly touch the ink during operations such as ink transfer and ink replacement, and it is possible to prevent stains on fingers and clothes. In addition, it is possible to prevent foreign matter such as dust from entering the ink.

The shape, size, material, etc. of the container itself are not particularly limited as long as they are suitable for the application and usage. etc. is preferably covered.

(Image forming apparatus, image forming method)
The image forming apparatus of the present invention includes a storage section in which the active energy ray-curable composition of the present invention, the active energy ray-curable ink composition of the present invention, or the active energy ray-curable inkjet ink composition of the present invention is stored. and an irradiation unit for irradiating active energy rays. If necessary, it may have a means for applying the composition to the substrate, or the like.
The base material is also called a recording medium, a recording medium, a medium, or the like.

The containing portion may contain the composition containing container. In this case, for example, the composition contained in the containing portion may be supplied to the applying means, and the composition may be applied from the applying means to the substrate. . Also, as will be described later, a storage pool or the like may be used as the storage unit.

In the image forming method of the present invention, the active energy ray-curable composition of the present invention, the active energy ray-curable ink composition of the present invention, or the active energy ray-curable ink composition of the present invention is irradiated with an active energy ray. A two-dimensional or three-dimensional imaging method, characterized in that it includes a step of irradiating the light. It may have a step of applying the composition to the substrate, etc., if necessary.

In the present invention, an active energy ray may be used, or heating may be used. The active energy ray-curable composition of the present invention can be cured by the irradiation part for irradiating the active energy ray and the irradiation process.

The image forming apparatus and the image forming method of the present invention may have applying means and applying step, and the applying means and applying step are ejecting means and ejecting step for ejecting the active energy ray-curable composition. good too. The method of discharging is not particularly limited, but examples include a continuous injection type, an on-demand type, and the like. The on-demand type includes a piezo system, a thermal system, an electrostatic system, and the like.

FIG. 1 shows an example of an image forming apparatus equipped with an inkjet ejection means. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by the respective color printing units 23a, 23b, 23c, and 23d, which are provided with ink cartridges and ejection heads for active energy ray-curable inks of yellow, magenta, cyan, and black. be done. After that, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, thereby forming a color image. After that, the recording medium 22 is conveyed to the processing unit 25 and the print take-up roll 26 . A heating mechanism may be provided in each of the printing units 23a, 23b, 23c, and 23d so that the ink is liquefied at the ink discharge section. Further, if necessary, a mechanism may be provided for cooling the recording medium to about room temperature by contact or non-contact. Inkjet recording methods include a serial method in which a head is moved to eject ink onto a recording medium that moves intermittently according to the width of an ejection head, and a serial method in which ink is ejected onto a recording medium by moving the recording medium continuously. Any line system 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, but includes paper, film, ceramics, glass, metal, composite materials thereof, and the like, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or that double-sided printing is also possible. Not limited to those used as general recording media, corrugated cardboard, building materials such as wallpaper and flooring, concrete, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate.

Furthermore, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the active energy ray may be irradiated from the light source 24d. Thereby, energy saving and cost reduction can be achieved.

The recorded matter to be recorded with the ink of the present invention includes not only those printed on smooth surfaces such as ordinary paper and resin films, but also those printed on uneven surfaces to be printed, and those printed on metals, ceramics, and the like. It also includes those printed on a printing surface made of various materials. In addition, by layering two-dimensional images, it is possible to form an image (an image consisting of two-dimensional and three-dimensional images) or a three-dimensional object with a partial three-dimensional effect.

FIG. 2 is a schematic diagram showing an example of another image forming apparatus (three-dimensional stereoscopic image forming 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, and ejects the first active energy ray-curable composition from the ejection head unit 30 for a modeled object. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is ejected from the head units 31 and 32, and these compositions are cured by adjacent ultraviolet irradiation means 33 and 34. It is laminated while doing so.

More specifically, for example, the second active energy ray-curable composition is ejected from the support ejection head units 31 and 32 onto the shaped object support substrate 37, and is irradiated with an active energy ray to be solidified. After forming the first support layer having a reservoir, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object into the reservoir, and is irradiated with an active energy ray to be solidified. By repeating the step of forming the first model layer by pressing the support layer and the model layer a plurality of times while lowering the vertically movable stage 38 according to the number of layers, the support layer and the model layer are laminated to form the three-dimensional model 35 . to manufacture. After that, the support laminate 36 is removed as needed.
In FIG. 2, only one ejection head unit 30 for a modeled object is provided, but two or more may be provided.

(Application)
The application of the active energy ray-curable composition of the present invention is not particularly limited as long as it is a field where active energy ray-curable materials are generally used, and can be appropriately selected according to the purpose. Examples include resins, paints, adhesives, insulating materials, 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 not only as an ink to form two-dimensional characters and images, and to form a design coating film on various substrates, but also to form three-dimensional images (three-dimensional objects). It can also be used as a three-dimensional modeling material for forming. This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder lamination method in which three-dimensional modeling is performed by repeating curing and lamination of powder layers. ) to (D) may be used as a three-dimensional structural material (model material) or a supporting member (supporting material) used in the laminate molding method (stereolithography method).

As described above, FIG. 2 shows a method in which the active energy ray-curable composition of the present invention is discharged to a predetermined region, and the compositions cured by irradiating the active energy ray are successively laminated to perform three-dimensional modeling. be. 3(A) to 3(D), a storage pool (accommodating portion) 1 of the active energy ray-curable composition 5 of the present invention is irradiated with an active energy ray 4 to form a cured layer 6 of a predetermined shape on a movable stage 3. It is a method of forming three-dimensionally by forming on top and stacking them one by one.

First, in FIG. 3(A), the active energy ray 4 is irradiated to the storage pool (storage part) 1 of the active energy ray-curable composition 5 of the present invention. Subsequently, in FIG. 3B, a hardened layer 6 having a predetermined shape is formed on the movable stage 3 by irradiation with the active energy ray 4 . Subsequently, in FIG. 3C, the movable stage 3 is lowered. Subsequently, in FIG. 3D, a cured layer 6 is further formed on the obtained cured layer 6 by irradiation with active energy rays 4 .

As a stereolithography apparatus for molding a three-dimensional object using the active energy ray-curable composition of the present invention, a known apparatus can be used, and is not particularly limited. For example, means for containing the composition , a supply means, a discharge means, an active energy ray irradiation means, and the like.

The present invention also includes a molded article obtained by processing a cured product obtained by curing an active energy ray-curable composition and a structure in which the cured product is formed on a substrate. The molded article is, for example, a sheet-shaped or film-shaped cured product or structure subjected to molding such as heat stretching or punching.・It is suitable for applications that require molding after surface decoration, such as electronic equipment, meters for cameras, and operation panels.

The base material is not particularly limited and can be appropriately selected according to the purpose. Examples include paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, composite materials thereof, and the like. and a plastic substrate is preferable from the viewpoint of workability.

Moreover, the present invention is applicable to the following uses, for example.
After providing electronic components on a substrate selected from glass, polyimide, anodized aluminum, polycarbonate, etc., the active energy ray-curable composition of the present invention is applied. Moreover, an active energy ray is appropriately irradiated. As a result, it is possible to manufacture a structure in which the electronic components are not easily peeled off and the electronic components are protected. For example, the active energy ray-curable composition of the present invention can be used to produce chip protective layers to be printed on wearable products.

The base material here is not particularly limited, but for example, a base material having a thickness of less than 0.1 mm can be used.
Further, the electronic component here is not particularly limited, but includes, for example, conductive ink and the like.
In addition, the application method may be an inkjet method, a screen method, or any other method.

The configuration of this example is shown in FIG. An electronic component 52 is formed on a substrate 51 , and a coating 53 made of an active energy ray-curable composition is formed on the electronic component 52 . In the composition of this example, the electronic components are protected and adhesion can be improved.

(cured product)
The cured product obtained by the present invention (also referred to as a coating film, cured ink, etc.) includes the active energy ray-curable composition, the active energy ray-curable ink composition, and the active energy ray-curable inkjet ink of the present invention. It is formed by curing by irradiating at least one of the compositions with an active energy ray. As these compositions, the same compositions as those described above can be used.

(decorative body)
As the decorative body selected according to the present invention, the surface decoration made of a cured product is applied to a base material, and the same cured product as described above can be used.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, hereinafter, "parts" means "parts by mass" unless otherwise specified.

(Synthesis example 1)
33 parts of toluene and 4.8 parts of stearyl alcohol (NAA-46) were placed in a 500 ml flask equipped with a stirrer, thermometer and condenser, and the temperature was raised to 40°C. After confirming that the stearyl alcohol was completely dissolved, hexamethylene diisocyanate trimethylolpropane adduct-modified type (Barnock DN-950; manufactured by Dainippon Ink and Chemicals, Inc., non-volatile content (NV): 75%, NCO: 12 %) was charged and the temperature was raised to 70°C. After reacting at the same temperature for 30 minutes, 0.02 part of dibutyltin laurate was added and the mixture was kept at the same temperature for 3 hours. After that, 63.9 parts of polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA3; manufactured by Daicel Chemical Industries, hydroxyl value: 122 mgKOH/g), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethyl ether were added and heated at 70°C. After holding for 3 hours to complete the reaction, 60.7 parts of toluene was added to obtain urethane acrylate A (trifunctional adduct) having a solid content of 50% by weight.

(Synthesis example 2)
60.8 parts of toluene and 8.4 parts of stearyl alcohol (NAA-46) were placed in a 500 ml flask equipped with a stirrer, thermometer and condenser, and the temperature was raised to 40°C. After confirming that the stearyl alcohol was completely dissolved, 50 parts of isocyanurate-modified hexamethylene diisocyanate (Takenate D-170N; manufactured by Takeda Pharmaceutical Co., Ltd., NCO%: 20.9%) was charged and the temperature was raised to 70°C. warmed up. After reacting at the same temperature for 30 minutes, 0.02 part of dibutyltin laurate was added and the mixture was kept at the same temperature for 3 hours. Then, 83.5 parts of polycaprolactone-modified hydroxyethyl acrylate (PLAXEL FA2D), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethyl ether were added, and the reaction was completed by holding at 70°C for 3 hours. .1 part was added to obtain urethane acrylate B (trifunctional isocyanurate) having a solid content of 50% by weight.

(Synthesis Example 3)
78.3 parts of toluene and 8.5 parts of stearyl alcohol (NAA-46) were placed in a 500 ml flask equipped with a stirrer, thermometer and condenser, and the temperature was raised to 40°C. After confirming that the stearyl alcohol was completely dissolved, hexamethylene diisocyanate biuret-modified type (Duranate 24A-90CX; manufactured by Asahi Kasei Corporation, non-volatile content (NV): 90%, NCO%: 21.2) 50 parts was charged and heated to 70°C. After reacting at the same temperature for 30 minutes, 0.02 part of dibutyltin laurate was added and the mixture was kept at the same temperature for 3 hours. After that, 140.8 parts of polycaprolactone-modified hydroxyethyl acrylate (PLAXEL FA4; manufactured by Daicel Chemical Industries, Ltd., hydroxyl value: 98 mgKOH/g), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethyl ether were charged, C. for 3 hours to terminate the reaction, and 111 parts of toluene was added to obtain urethane acrylate C (trifunctional biuret) having a solid content of 50% by weight.

(Examples 1 to 18 and Comparative Examples 1 to 8)
<Materials used>
Materials other than the urethane acrylate oligomer include polyfunctional monomers shown in Table 1 and monofunctional monomers shown in Table 2, TPO (product name: Omnirad TPO, manufactured by IGM) as a polymerization initiator, and MEHQ (product name: methoquinone) as a polymerization inhibitor. , manufactured by Seiko Chemical Co., Ltd.) was used.

<Preparation of active energy ray-curable composition>
Based on the materials and contents (% by mass) shown in Tables 3 to 5, active energy ray-curable compositions of Examples and Comparative Examples were prepared by a conventional method.
For the active energy ray-curable composition of each example and comparative example, a 10 μm film was prepared on the acrylic substrate, and the film was cured with an LED lamp (peak wavelength 395 nm, 3000 mJ/cm ² ) manufactured by Ushio Inc. and applied. A membrane was obtained.

<Evaluation>
Next, various properties of the obtained coating film were evaluated as follows. The results are shown in Tables 3-5.

<<Blocking resistance>>
Blocking resistance was evaluated as follows.
A load of 5 kg per A4 size was applied to the surface of the cured coating film and the acrylic substrate, and the laminate was allowed to stand at room temperature for 24 hours. After standing, evaluation was made based on the following criteria based on the presence or absence of sticking between the coating film and the substrate and the degree of change in the coating film (visual change rate).

[Evaluation criteria]
◎: No sticking, no change in coating film ○: Sticking, but no change in coating film △: Sticking, change rate of coating film less than 10% ×: Sticking, Change rate of coating film is 10% or more

<<Adhesion>>
Adhesion was evaluated based on the following criteria according to the evaluation method of the cross-cut method of adhesion test JIS K5600-5-6.

[Evaluation criteria]
◎: No peeling at all ○: Peeling along the cut of the cutter, but the squares are not peeled △: Less than 50% of the squares are peeled ×: More than 50% of the squares are peeled off

<<Ejection stability by inkjet>>
Each inkjet ink prepared based on the materials and contents (% by mass) shown in Tables 3 to 5 was loaded into an inkjet ejection device (manufactured by Ricoh Co., Ltd., head: GEN5 manufactured by Ricoh Printing Systems), and continuously for 30 minutes. was discharged. After continuous ejection, the state of ejection from the nozzle was observed with a camera and evaluated according to the following criteria.

[Evaluation criteria]
○: Ejection from all nozzles △: Non-ejection observed from less than 30 nozzles ×: Non-ejection observed from 30 nozzles or more

1 storage pool 3 movable stage 4 active energy ray 5 active energy ray-curable composition 6 hardening 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 Take-up roll 30 Discharge head unit for model 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional model 36 Support laminate 37 Model support substrate 38 Movable stage 39 Image forming device 51 Base material 52 electronic components 53 coating

JP 2006-257155 A Japanese Patent Application Laid-Open No. 2020-1189 JP-A-2002-256053

Claims (9)

An active energy ray-curable composition comprising a trifunctional adduct urethane acrylate oligomer, a monofunctional monomer and a multifunctional monomer,
The active energy ray-curable composition, wherein the content of the monofunctional monomer in the entire composition is greater than the total content of the trifunctional adduct urethane acrylate oligomer and the polyfunctional monomer in the entire composition. thing. 2. The active energy ray-curable composition according to claim 1, wherein the content of said trifunctional adduct urethane acrylate oligomer relative to the entire composition is 1.0% by mass or more and 5.0% by mass or less. 3. The active energy ray-curable composition according to claim 1, wherein the content of said polyfunctional monomer with respect to the entire composition is 3.0% by mass or more and 15.0% by mass or less. 4. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the polyfunctional monomer has 3 functional groups. An active energy ray-curable ink composition comprising the active energy ray-curable composition according to any one of claims 1 to 4. An active energy ray-curable inkjet ink composition comprising the active energy ray-curable ink composition according to claim 5 . The active energy ray-curable composition according to any one of claims 1 to 4, the active energy ray-curable ink composition according to claim 5, or the active energy ray-curable ink composition for inkjet according to claim 6. A composition container, characterized in that it contains a The active energy ray-curable composition according to any one of claims 1 to 4, the active energy ray-curable ink composition according to claim 5, or the active energy ray-curable ink composition for inkjet according to claim 6. a containment unit containing
and an irradiation unit for irradiating active energy rays. The active energy ray-curable composition according to any one of claims 1 to 4, the active energy ray-curable ink composition according to claim 5, or the active energy ray-curable ink composition for inkjet according to claim 6. A two-dimensional or three-dimensional image forming method, comprising an irradiation step of irradiating an active energy ray onto the surface.

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