JP7383960B2 - Curable composition, curable ink, curable inkjet ink, storage container, two-dimensional or three-dimensional image forming device, two-dimensional or three-dimensional image forming method, and cured product - Google Patents

Description

The present invention relates to a curable composition, a curable ink, a curable inkjet ink, a container, a two-dimensional or three-dimensional image forming apparatus, a two-dimensional or three-dimensional image forming method, and a cured product.

A curable composition such as an active energy ray curable composition forms a cured product by curing. At this time, since active energy ray irradiation means or the like is used as a curing means, the drying means can be simplified or omitted. Therefore, it can be used for thick substrates with low thermal conductivity, has high substrate compatibility, and is used in various image forming methods such as inkjet printing and screen printing.

One of the properties required for a cured product of a curable composition is antifouling properties. Stain resistance refers to the property of preventing water-based and oil-based stains. As a method for improving the stain resistance on the surface of a cured product, for example, by using a curable composition containing a surfactant having a fluorine element in its molecular structure and orienting the fluorine atoms on the surface of the cured product. A method of developing stain resistance is known.

Patent Document 1 discloses an antifouling film that includes a polymer layer that is a cured product of a perfluoropolyether-based fluorine-containing monomer having a reactive group and a curable resin.

Patent Document 2 discloses a fingerprint-resistant hard coat paint containing an ultraviolet curable composition and a fluorine-based surfactant having an ultraviolet-reactive group.

However, if the surface of the cured product of the curable composition is not sufficiently cured, there is a problem in that the development of antifouling properties is suppressed.

The invention according to claim 1 is a curable composition containing a polysilane compound , a polymerizable compound , and a polymerizable surfactant.

The curable composition of the present invention exhibits the effect that the cured product has excellent antifouling properties.

FIG. 1 is a schematic diagram showing an example of an image forming apparatus. FIG. 3 is a schematic diagram showing an example of another image forming apparatus. FIG. 7 is a schematic diagram showing an example of yet another image forming apparatus.

An example of an embodiment of the present invention will be described below. Note that the present invention is not limited to the embodiments shown below, and may be modified within the scope of those skilled in the art, such as other embodiments, additions, modifications, deletions, etc. These are also included within the scope of the present invention as long as they exhibit the functions and effects of the present invention.

<<Curable composition>>
A curable composition is a liquid composition that can form a cured product. The curable composition contains a polysilane compound and a polymerizable surfactant, and if necessary, a polymerizable compound, a polymerization initiator, a coloring material, an organic solvent, and other components. Examples of the curable composition include active energy ray curable compositions that can form a cured product by irradiation with active energy rays.

<Polysilane compound>
The curable composition contains a polysilane compound. The polysilane compound may be a homopolymer or a copolymer having repeating units, or may be a copolymer with other repeating units. By containing a polysilane compound, the cured product obtained by curing the curable liquid composition by irradiating it with active energy rays, etc., improves the surface curability and coating hardness expressed by pencil hardness, etc. can be improved. It is thought that the above effect is obtained because the polysilane compound functions as a polymerization initiator and suppresses curing inhibition caused by oxygen. That is, in the sense that the curable composition of the present embodiment can more effectively solve the problem, it is preferable to use it in an environment where curing inhibition by oxygen is likely to occur. For example, the curable composition is cured in the atmosphere. Although it is preferable to use it in cases, it is not limited thereto. The mechanism of action of the polysilane compound will be explained. For example, in radical polymerization, it is known that when peroxy radicals (R-O-O.) are generated, the reactivity decreases and the radical reaction stops. Even if radicals are generated, it is presumed that by extracting hydrogen, there is an effect of regenerating the radicals.

As the polysilane compound, for example, a compound synthesized by the method described in Japanese Patent No. 3,883,453 can be used. Specifically, it is preferable to use a polysilane compound containing a phenyl group in its repeating unit, such as polyphenylsilane and poly(methylphenyl)silane. These may be used alone or in combination of two or more.

The content of the polysilane compound is preferably more than 1.0% by mass and less than 8.0% by mass, and 1.5% by mass or more and 7.5% by mass or less, based on the mass of the curable composition. It is more preferably 1.5% by mass or more and 6.0% by mass or less, and particularly preferably 2.0% by mass or more and 5.0% by mass or less. When the content exceeds 1.0% by mass, the curability of the surface of the cured product and the hardness of the coating film are improved. Furthermore, when the content is less than 8.0% by mass, the solubility of the polysilane compound is improved, and the storage stability and ejection stability of the curable composition are improved.

<Polymerizable surfactant>
The curable composition contains a polymerizable surfactant. A polymerizable surfactant is a surfactant whose structure includes a functional group such as a (meth)acryloyl group that has polymerization reactivity when irradiated with active energy rays. The polymerizable surfactant present on the surface of the curable composition undergoes a polymerization reaction with polymerizable compounds such as polymerizable monomers, and is fixed and oriented, resulting in water and oil repellency appearing on the surface of the cured product. , antifouling properties are improved. At this time, the higher the curability of the surface of the cured product, the more the polymerizable surfactant can be fixed and oriented on the surface of the cured product. Examples of methods for increasing the curability of the surface of the cured product include a method of reducing the effect of oxygen on curing inhibition by purging with nitrogen or the like during curing. However, existing equipment for curing polymerizable surfactants generally has a means for curing in the atmosphere, and even if means such as nitrogen purging are added, the problem is that the equipment space will increase. there were. Therefore, the curable composition contains a polysilane compound to improve the curability of the surface of the cured product, and the polymerizable surfactant is immobilized and oriented on the surface of the cured product to exhibit antifouling properties. That is, the curable composition of this embodiment is preferably used in an apparatus that does not have a means for nitrogen purging or the like when curing the curable composition, in the sense that the problem can be solved more effectively. However, it is not limited to this.

The polymerizable surfactant is not particularly limited as long as it can exhibit antifouling properties, but includes, for example, a polymerizable surfactant having a fluorine atom in its molecular structure (hereinafter also referred to as a "fluorine-based polymerizable surfactant"), and silicone-containing polymerizable surfactants (hereinafter also referred to as "silicone-based polymerizable surfactants"), and fluorine-based polymerizable surfactants are more preferred. When a fluorine-based polymerizable surfactant is used, fluorine atoms are fixed and oriented on the surface of the cured product, improving stain resistance. Furthermore, when a silicone-based polymerizable surfactant is used, silicone is fixed and oriented on the surface of the cured product, improving antifouling properties.

The fluorine-based polymerizable surfactant is not particularly limited as long as it can exhibit antifouling properties, but examples include KY-1200, X-71-1203M (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Megafac RS- Examples include Megafac RS-72-K, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, and Megafac RS-77 (all of the above are trade names, manufactured by DIC). These may be used alone or in combination of two or more.

The silicone-based polymerizable surfactant is not particularly limited as long as it can exhibit antifouling properties, but examples include X-22-164A/B and X-22-2445 (all trade names, manufactured by Shin-Etsu Silicone). Can be mentioned. These may be used alone or in combination of two or more.

The content of the polymerizable surfactant is preferably more than 0.01% by mass and less than 2.0% by mass, and 0.02% by mass or more and 1.9% by mass, based on the mass of the curable composition. The content is more preferably 0.05% by mass or more and 1.5% by mass or less, and particularly preferably 0.1% by mass or more and 1.0% by mass or less. When the content is less than 2.0% by mass, antifouling properties and discharge stability are improved.

<Polymerizable compound>
The curable composition may contain a polymerizable compound. The polymerizable compound is a compound whose structure includes a functional group that exhibits polymerization reactivity when irradiated with active energy rays, and does not include the above-mentioned polymerizable surfactant. Examples of the polymerizable compound include polymerizable monomers and polymerizable oligomers.

The polymerizable monomer is not particularly limited as long as it is polymerizable, and examples include (meth)acrylate, (meth)acrylamide, vinyl ether, etc. More specifically, 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)acrylate, ) 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)], same (n≒9), same (n≒14), same (n≒23), dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol dimethacrylate [ 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, tricyclodecane dimethanol diacrylate, propylene oxide modified bisphenol A di( meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (meth)acryloylmorpholine, propylene oxide modified tetramethylolmethanetetra(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 triacrylate Methylolpropane 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 Acrylate, polyester penta(meth)acrylate, polyester poly(meth)acrylate, polyurethane di(meth)acrylate, polyurethane tri(meth)acrylate, polyurethane tetra(meth)acrylate, polyurethane penta(meth)acrylate, polyurethane poly(meth)acrylate , 2-hydroxypropyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, Examples include cyclopentadiene vinyl ether, tricyclodecane vinyl ether, benzyl vinyl ether, and ethyloxetane methyl vinyl ether. These may be used alone or in combination of two or more.

The content of the polymerizable compound is preferably 30.0% by mass or more, more preferably 40% by mass or more, and 50.0% by mass or more based on the mass of the curable composition. is more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more. Further, the content of the polymerizable compound is preferably 99.0% by mass or less based on the mass of the curable composition.

<Polymerization initiator>
The curable composition may contain a polymerization initiator. The polymerization initiator may be any initiator as long as it can generate active species such as radicals and cations using energy such as active energy rays and initiate polymerization of the polymerizable compound. As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators, etc. can be used alone or in combination of two or more types, and among them, radical polymerization initiators are used. It is preferable. Compared to cationic polymerization initiators, base generators, and the like, radical polymerization initiators are superior in wettability to application means for applying curable compositions, such as inkjet heads, and in storage stability of curable compositions. On the other hand, it is known that in the step of irradiating active energy rays such as ultraviolet rays, if the curing is inhibited by oxygen, the hardenability of the surface of the cured product decreases.

Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds. Among these, acylphosphine oxide compounds (also referred to as "acylphosphine oxide polymerization initiators") are preferred, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and 2,4, More preferably, it is at least one selected from 6-trimethylbenzoyl-diphenyl-phosphine oxide. When an acylphosphine oxide polymerization initiator is used as a polymerization initiator, yellowing of the cured product can be suppressed.

In addition to the polymerization initiator, a polymerization accelerator (sensitizer) can also 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 can be appropriately set depending on the polymerization initiator used and its amount.

<Color material>
The curable composition may contain a coloring material. As the coloring material, various pigments and dyes that impart glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold, and silver are used depending on the purpose and required characteristics of the curable composition. be able to. The content of the coloring material may be appropriately determined in consideration of the desired color density, dispersibility in the curable composition, etc., and is not particularly limited; Preferably, it is 20% by mass. Note that the curable composition may be colorless and transparent without containing a coloring material, and in that case, it is suitable to use it as an overcoat layer for protecting an image, for example.

As the pigment, inorganic pigments or organic pigments can be used, and one type may be used alone, or two or more types may be used in combination.
As the inorganic pigment, for example, carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalones. Polycyclic pigments such as pigments, dye chelates (e.g. basic dye type chelates, acidic dye type chelates, etc.), dyeing lakes (basic dye type lakes, acidic dye type lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments may be mentioned.
In addition, in order to improve the dispersibility of the pigment, a dispersant may be further included. The dispersant is not particularly limited, but includes, for example, dispersants commonly used for preparing pigment dispersions such as polymer dispersants.

As the dye, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.

<Organic solvent>
The curable composition may contain an organic solvent, but 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 will be further improved, and it will also be possible to prevent environmental pollution. . Note that "organic solvent" refers to general non-reactive organic solvents such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from reactive monomers. be. Moreover, "not containing" an organic solvent means substantially not containing it, and preferably less than 0.1% by mass.

<Other ingredients>
The curable composition may contain other components. Other ingredients include, but are not particularly limited to, conventionally known polymerization inhibitors, leveling agents, antifoaming agents, optical brighteners, penetration enhancers, wetting agents (humectants), fixing agents, and viscosity stabilizers. , a fungicide, a preservative, an antioxidant, an ultraviolet absorber, a chelating agent, a pH adjuster, and a thickener.

<Active energy rays>
Active energy rays as an example of external energy applied to cure the curable composition include ultraviolet rays as well as electron beams, α rays, β rays, γ rays, X rays, etc. It is not particularly limited as long as it can provide the energy necessary to proceed with the polymerization reaction of the components. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Furthermore, in the case of ultraviolet irradiation, mercury-free devices are strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are compact, long-life, highly efficient, and low-cost, and are preferred as ultraviolet light sources. Note that active energy rays include applying energy necessary for advancing the polymerization reaction of the polymerizable component in the composition by heating.

<Preparation of curable composition>
The curable composition can be prepared using the various components mentioned above, and the preparation means and conditions are not particularly limited. For example, the polymerizable compound, coloring material, dispersant, etc. , into a dispersing machine such as a pin mill or a dyno mill, and disperse to prepare a colorant dispersion, and then further mix a polymerizable compound, an initiator, a polymerization inhibitor, a surfactant, etc. with the colorant dispersion. It can be prepared.

<Viscosity>
The viscosity of the curable composition may be adjusted as appropriate depending on the purpose and the means of application, and is not particularly limited. The viscosity at 25° C. is preferably 3 to 40 mPa·s, more preferably 5 to 15 mPa·s, and particularly preferably 6 to 12 mPa·s. Further, it is particularly preferable that the viscosity range is satisfied without including the above-mentioned organic solvent. The above viscosity was measured using a cone plate rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd. using a cone rotor (1°34' x R24) at a rotation speed of 50 rpm and a constant temperature circulating water temperature of 20 to 20. The temperature can be appropriately set and measured within the range of 65°C. VISCOMATE VM-150III can be used to adjust the temperature of circulating water.

<Application>
The use of the curable composition is not particularly limited as long as it is a field in which curable materials are generally used, and can be appropriately selected depending on the purpose.For example, it can be used in molding resins, paints, adhesives, and insulation materials. , mold release agents, coating materials, sealing materials, various resists, and various optical materials.
Furthermore, the curable composition can be used not only as a curable ink, more preferably as a curable inkjet ink, to form two-dimensional characters, images, and design coatings on various substrates, but also to form three-dimensional three-dimensional images. It can also be used as a material for three-dimensional modeling (three-dimensional modeling). This material for three-dimensional modeling may be used, for example, as a binder between powder particles used in a powder layering method in which three-dimensional modeling is performed by repeating curing and lamination of powder layers. It may be used as a three-dimensional constituent material (model material) or a support member (support material) used in such a layered manufacturing method (stereolithography method). In addition, FIG. 2 shows a method of three-dimensional modeling by discharging a curable composition onto a predetermined area, irradiating active energy rays to cure the composition, and sequentially stacking the compositions (details will be described later). In this method, active energy rays 4 are irradiated onto a storage pool (accommodating part) 1 of mold composition 5 to form a cured layer 6 of a predetermined shape on a movable stage 3, and this is sequentially laminated to perform three-dimensional modeling.
As a three-dimensional modeling device for modeling a three-dimensional object using a curable composition, a known device can be used, and is not particularly limited. a container), a supply means for supplying the curable composition from the storage means, an application means for applying the curable composition supplied from the storage means, an irradiation means for irradiating the applied curable composition with active energy rays, etc. Here are some things to prepare.
Furthermore, the cured product obtained by curing the curable composition (in other words, the cured product derived from the curable composition) also includes molded products obtained by processing the cured product formed on the base material. . A molded product is, for example, a cured product or structure formed in the form of a sheet or film, which is subjected to molding processes such as heating stretching or punching. It is suitably used in applications where the surface needs to be molded after decoration, such as meters and operation panels for electronic devices, cameras, etc. Note that in this application, the cured product formed on the base material is referred to as a decorative portion.
The base material is not particularly limited and can be selected as appropriate depending on the purpose, such as paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, or composite materials thereof. Plastic base materials are preferred from the viewpoint of processability.

<<Curable ink, Curable inkjet ink>>
Curable ink is an ink containing the above-mentioned curable composition, and is used, for example, for forming two-dimensional characters and images, for forming design coatings on various substrates, and for three-dimensional purposes. It is used for purposes such as forming three-dimensional images (three-dimensional objects).
The curable inkjet ink is a curable ink that is discharged and used by an inkjet method.

<<Storage container>>
The storage container refers to a container in which the curable composition is stored, and is suitable for use as described above. For example, when the curable composition is used as an ink or an inkjet ink, the container containing these inks can be used as an ink cartridge or an ink bottle, making it easy to transport the ink, replace the ink, etc. There is no need to directly touch the ink during work, which prevents stains on hands, fingers, and clothing. Further, it is possible to prevent foreign matter such as dust from entering the ink. In addition, the shape, size, material, etc. of the container itself may be suitable for the purpose and usage, and are not particularly limited, but the material may be a light-blocking material that does not transmit light, or the container may be light-blocking. It is desirable that it be covered with a plastic sheet, etc.

<<Image forming method, image forming apparatus>>
The image forming method includes a step of applying a curable composition, a curable ink, or a curable inkjet ink (hereinafter referred to as a "curable composition, etc."), and a step of applying a curable composition, etc. to the applied curable composition, etc. The method includes an irradiation step of irradiating active energy rays, and may include other steps as necessary.
The image forming apparatus includes a storage means containing a curable composition, an application means for applying the stored curable composition, and an irradiation means for irradiating the applied curable composition with active energy rays. and may have other means as necessary.
Examples of the above-mentioned application step and application means include a discharge step and a discharge means.The method of discharge is not particularly limited, and includes continuous injection type, on-demand type, and the like. On-demand types include piezo type, thermal type, electrostatic type, etc.

FIG. 1 shows an example of an image forming apparatus equipped with an inkjet discharge means. Inks are ejected onto the recording medium 22 supplied from the supply roll 21 by color printing units 23a, 23b, 23c, and 23d each including ink cartridges and ejection heads for yellow, magenta, cyan, and black curable inks. Thereafter, active energy rays are irradiated from the light sources 24a, 24b, 24c, and 24d for curing the ink to form a color image. Thereafter, the recording medium 22 is conveyed to a processing unit 25 and a print take-up roll 26. Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism may be provided to cool the recording medium to about room temperature by contact or non-contact. Inkjet recording methods include a serial method in which ink is ejected onto the recording medium by moving the head while the recording medium is moved intermittently according to the width of the ejection head, and a serial method in which the recording medium is moved continuously. Any line method in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, but includes paper, film, ceramics, glass, metal, composite materials thereof, and may be in the form of a sheet. It may also be cardboard, building materials such as wallpaper and flooring materials, concrete, cloth for clothing such as T-shirts, textiles, leather, and the like. Further, the configuration may be such that only one-sided printing is possible, or the configuration may be such that double-sided printing is also possible.
Furthermore, the active energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the active energy rays may be emitted from the light source 24d. This makes it possible to save energy and reduce costs.
Recorded materials recorded with ink include not only those printed on smooth surfaces such as ordinary paper and resin films, but also those printed on uneven printing surfaces, and various materials such as metals and ceramics. This includes those printed on a printing surface consisting of. Further, by stacking two-dimensional images, it is also possible to form an image with a three-dimensional effect (an image consisting of two-dimensional and three-dimensional images) or a three-dimensional object.

FIG. 2 is a schematic diagram showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus). The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to inject the first curable composition from the ejection head unit 30 for a shaped object to the ejection head unit 31 for a support. , 32, a second curable composition having a different composition from the first curable composition is discharged, and these compositions are laminated while being cured by adjacent ultraviolet irradiation means 33, 34. More specifically, for example, the second curable composition is discharged from the support discharge head units 31 and 32 onto the shaped object support substrate 37, and is solidified by irradiation with active energy rays to form a reservoir. After forming the first support layer, the first curable composition is discharged from the shaped object discharge head unit 30 into the reservoir, and is solidified by irradiation with active energy rays to form the first shaped object. By repeating the step of forming layers multiple times while lowering the vertically movable stage 38 in accordance with the number of times of lamination, the support layer and the molded object layer are laminated to produce the three-dimensional molded object 35. Thereafter, the support stack 36 is removed if necessary. In FIG. 2, only one ejection head unit 30 is provided, but two or more ejection head units 30 may be provided.

<<Cured product>>
The cured product is a structure derived from an active curable composition or the like, and in other words, it is a structure formed by curing the curable composition or the like by irradiating it with active energy rays or the like.

<<Molded products>>
The molded product is a structure that includes a base material and the above-mentioned cured product formed on the base material, and is subjected to stretching processing, etc., as necessary.

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

<Example of preparation of curable composition>
(Examples 1 to 18 and Comparative Examples 1 to 6)
The curable compositions of Examples 1 to 18 and Comparative Examples 1 to 6 were obtained by adding each material shown in Tables 1 to 3 in the content shown in Tables 1 to 3 by a conventional method and then mixing. was created. Note that the unit of content shown in Tables 1 to 3 is "mass %".

In Table 1, the product names and manufacturing company names of the compounds used are as follows.

<Polymerizable compound>
・ACMO: Acryloylmorpholine, manufactured by KJ Chemicals Co., Ltd. ・NVC: N-vinylcaprolactam, manufactured by Tokyo Kasei Kogyo Co., Ltd. ・IBXA: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ・PEA: Phenoxyethyl acrylate, manufactured by Osaka Organic Co., Ltd. Manufactured by Kagaku Kogyo Co., Ltd. ・DPGDA: Dipropylene glycol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

<Polymerizable surfactant>
・Megafac RS-76-NS: Manufactured by DIC, active ingredient concentration 20% by mass
・X-22-2445: Manufactured by Shin-Etsu Silicone Co., Ltd., active ingredient concentration 100% by mass
Note that the numerical values of the content of polymerizable surfactant shown in Tables 1 to 3 represent the mass equivalent to the total amount of polymerizable surfactant. For example, Megafac RS-76-NS has an active ingredient concentration of 20% by mass, so if 5.0% by mass is written in Table 1, the amount of active ingredient added is 1.0% by mass.

<Surfactant>
・TEGO WET270 (manufactured by EVONIK)

<Polymerization initiator>
・Irg 819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by BASF ・Irg TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF ・Ir369: 2-( dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, manufactured by BASF ・Ir379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]-1-butanone, manufactured by BASF

<Sensitizer>
・DETX: 2,4-diethylthioxanthene-9-one, manufactured by Daido Kasei Kogyo Co., Ltd.

<Polysilane compound>
・OGSOL SI-10-10: Polysilane compound having a phenyl group, Mw 1100, manufactured by Osaka Gas Chemical Company ・OGSOL SI-10-20: Polysilane compound having a phenyl group, Mw 1800, manufactured by Osaka Gas Chemical Company ・OGSOL SI-20- 10: Polysilane compound having phenyl group, Mw1200, manufactured by Osaka Gas Chemical Co., Ltd.

Note that OGSOL SI-10-10 and OGSOL SI-10-20 are polysilane compounds having the structure shown below.

Furthermore, OGSOL SI-20-10 is a polysilane compound having the structure shown below.

Using each of the curable compositions of Examples 1 to 18 and Comparative Examples 1 to 6, curability, stain resistance (water-based stains), stain resistance (oil-based stains), yellowing, and solubility were evaluated. , was evaluated as follows. The results are shown in Tables 1 to 3 below.

<Curability>
First, a curable composition was applied onto a commercially available PET film using bar coater #12, and the curable composition was cured by irradiation with ultraviolet rays according to the following curing conditions. The formed coating film (cured product) had an average thickness of 7 μm.
Next, the curability of the prepared cured product was confirmed by tack evaluation. Tack evaluation was performed in accordance with JIS Z0273 and evaluated based on the following evaluation criteria.
[Curing conditions]
Ultraviolet irradiation was carried out using a D bulb of Light Hammer 6 manufactured by Heraus, in a wavelength range corresponding to the UV-A region (wavelength of 350 nm or more and 400 nm or less) at an integrated light amount of 500 mJ/cm ² to 4000 mJ/cm ² .
〔Evaluation criteria〕
A: There is no tack and no liquid component remains on the surface of the cured product.
B: There is no tack, but a liquid component remains on the surface of the cured product.
C: There is a tack.

<Stain resistance (water-based stains)>
First, a cured product was prepared in the same manner as the cured product used for evaluation of curability.
Next, write on the prepared cured product with a water-based marker (White Board Marker-B, red, blue, black, manufactured by Monami), leave it for 3 days, and then wipe it off with a 2 cm square piece of cotton (Kanakin No. 3). went. At this time, the presence or absence of a marker remaining on the cured product was used as an index of stain resistance against water-based stains, and evaluation was made based on the following evaluation criteria.
〔Evaluation criteria〕
A: All markers on the cured product can be wiped off.
B: The concentration of the marker is diluted, but it remains on the cured product.
C: Marker cannot be wiped off.

<Stain resistance (oil-based stains)>
First, a cured product was prepared in the same manner as the cured product used for evaluation of curability.
Next, writing was performed on each of the cured product immediately after production and the cured product left for one day after production using an oil marker (Mackie, red/black, manufactured by Zebra). At this time, the oil repellency on the cured product was used as an index of the stain resistance against oily stains, and evaluation was made based on the following evaluation criteria.
〔Evaluation criteria〕
A: The cured product repels the marker immediately after it is produced.
B: The cured product immediately after preparation does not repel the marker, but the cured product after being left for one day does repel the marker.
C: None of the cured products repels markers.

<Yellowing>
First, a cured product was prepared in the same manner as the cured product used for evaluation of curability.
Next, the color of the produced cured product was visually observed and evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
A: No yellowing occurred in the cured product.
B: Yellowing has occurred in the cured product.

<Solubility>
Examples 1 to 18 and Comparative Examples 1 to 6 were cured by adding materials other than polysilane compounds among the materials shown in Tables 1 to 3 in the content ratio shown in Tables 1 to 3 and then mixing. 5 g of the liquid mixture before the mold composition was prepared was obtained. Next, polysilane compounds were added so that the content ratios shown in Tables 1 to 3 were obtained, and the mixture was stirred for 3 hours in a 9 mL sample bottle at 25° C. and 40% RH. The solubility of the polysilane compound in the curable composition after stirring was visually confirmed. The evaluation criteria for solubility are as follows.
〔Evaluation criteria〕
A: The curable composition after stirring is transparent.
B: The curable composition is opaque after stirring.

<Other evaluations>
Each of the curable compositions of Examples 1 to 18 and Comparative Examples 1 to 6 can be ejected by an inkjet ejection device equipped with an inkjet head (product name: MH5421, manufactured by Ricoh Co., Ltd.). It has been separately confirmed that the produced cured product has the same evaluation results as the cured product produced by coating using bar coater #12.

39 Image forming device

Patent No. 6080154 Patent No. 6345902

Claims (16)

A curable composition comprising a polysilane compound , a polymerizable compound , and a polymerizable surfactant. The curable composition according to claim 1, wherein the content of the polysilane compound is 1.5% by mass or more and 7.5% by mass or less based on the mass of the curable composition. The curable composition according to claim 1, wherein the content of the polysilane compound is 2.0% by mass or more and 5.0% by mass or less based on the mass of the curable composition. The curable composition according to any one of claims 1 to 3, wherein the polysilane compound has a phenyl group in a repeating unit. The curable type according to any one of claims 1 to 4, wherein the content of the polymerizable surfactant is 0.02% by mass or more and 1.9% by mass or less based on the mass of the curable composition. Composition. The curable type according to any one of claims 1 to 4, wherein the content of the polymerizable surfactant is 0.1% by mass or more and 1.0% by mass or less based on the mass of the curable composition. Composition. The curable composition according to any one of claims 1 to 6, wherein the polymerizable surfactant has a fluorine atom in its molecular structure. The curable composition according to any one of claims 1 to 7, further comprising a radical polymerization initiator. The curable composition according to any one of claims 1 to 8, further comprising an acylphosphine oxide polymerization initiator. A curable ink containing the curable composition according to any one of claims 1 to 9. A curable inkjet ink comprising the curable composition according to any one of claims 1 to 9. A storage container containing the curable composition according to any one of claims 1 to 9. A storage means containing the curable composition according to any one of claims 1 to 9;
applying means for applying the contained curable composition;
A two-dimensional or three-dimensional image forming apparatus comprising: an irradiation means for irradiating the applied curable composition with active energy rays. A applying step of applying the curable composition according to any one of claims 1 to 9,
A two-dimensional or three-dimensional image forming method comprising the step of irradiating the applied curable composition with active energy rays. 15. The two-dimensional or three-dimensional image forming method according to claim 14, wherein the irradiation step is performed in the atmosphere. A cured product derived from the curable composition according to any one of claims 1 to 9.