JP6878766B2 - Image forming apparatus and image forming method using an active energy ray-curable composition, an active energy ray-curable ink, an ink container, and an active energy ray-curable composition. - Google Patents

Description

The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink composed of the composition, an ink storage container containing the ink, and a two-dimensional or three-dimensional image forming apparatus using the composition. And the image formation method.

Conventionally, photopolymerizable inks have been used for offsets, silk screens, topcoating agents, etc., but in recent years, they have been used due to merits such as cost reduction by simplifying the drying process and reduction of the amount of solvent volatilized as an environmental measure. The amount is increasing.
Water-based inks and solvent-based inks are often used as inkjet inks, and they are used properly according to their respective characteristics. However, water-based and solvent-based inkjet inks have restrictions on the receiving base material (member to which the ink is applied, recording medium) that can be used for industrial purposes, and the water resistance of the ink itself is relatively poor. It has problems such as high drying energy of ink and ink components adhering to the head due to drying. Therefore, it has been studied to replace water-based and solvent-based inkjet inks with photopolymerizable inks having relatively low volatility.

Recently, there are increasing demands for performing molding processing (post-processing) after printing a photopolymerizable inkjet ink on a base material. Since the printed portion covers the outermost surface of the molded product, scratch resistance, dent resistance, and the like are required, and it is also important that the printed portion has high adhesion to the base material. It is necessary to have high hardness to ensure scratch resistance and dent resistance. Generally, a polymerizable monofunctional monomer is used for the inkjet ink, but simply blending the monofunctional monomer does not show sufficient hardness. Further, it is generally well known that the hardness is expected to increase by blending a polymerizable polyfunctional monomer, but the rigidity of the printed portion increases as the hardness increases, and it is difficult to follow the substrate. Therefore, the adhesion is lost.
As described above, hardness and adhesion are always in a trade-off relationship, and it has not been possible to achieve a high degree of compatibility between these with conventional techniques.
For example, Patent Document 1 describes an invention relating to an ultraviolet curable ink containing a monofunctional acrylic monomer having a Tg of less than 20 ° C., with the problems of ejection property, curability, and flexibility. Although inventions in which a Tg and a high Tg monomer are used in combination have been disclosed, both hardness and stretchability have not been achieved.

An object of the present invention is to provide an active energy ray-curable composition which solves the above-mentioned problems of the prior art and can obtain a cured product having both high hardness, adhesion and heat stretchability.

The above problem is solved by the invention of 1) below.
1) It contains a monofunctional monomer having one ethylenically unsaturated double bond and inorganic fine particles having an amphipathic functional group, and the monofunctional monomer is 80% by mass or more based on the content of the total polymerizable compound. An active energy ray-curable composition.

According to the present invention, it is possible to provide an active energy ray-curable composition capable of obtaining a cured product having both high hardness, adhesion and heat stretchability.

It is the schematic which shows an example of the image forming apparatus in this 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 still another image forming apparatus in this invention.

Hereinafter, the present invention 1) will be described in detail, but the following 2) to 8) are also included in the embodiment thereof, and these will also be described.
2) The active energy ray-curable composition according to 1), wherein the inorganic fine particles having an amphipathic functional group are silica fine particles, and a hydrophilic group-containing compound is chemically bonded to the surface thereof. ..
3) The hydrophilic groups of the hydrophilic group-containing compound are hydroxyl groups, silanol groups, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, alkali metal salts of these groups, polyalkylene oxide groups, quaternary ammonium bases and The active energy ray-curable composition according to 2), which is at least one selected from the group consisting of a quaternary phosphonium base.
4) An active energy ray-curable ink comprising the active energy ray-curable composition according to any one of 1) to 3).
5) The active energy ray-curable ink according to 4), which can be ejected to the surface of the recording medium by an inkjet recording method.
6) An ink container containing the active energy ray-curable ink according to 4) or 5).
7) A two-dimensional or three-dimensional image forming apparatus including an accommodating portion accommodating the active energy ray-curable composition according to any one of 1) to 3) and an irradiation means for irradiating the active energy ray.
8) A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating the active energy ray-curable composition according to any one of 1) to 3) with active energy rays.

The active energy ray-curable composition of the present invention (hereinafter, also referred to as a composition) contains a monofunctional monomer having one ethylenically unsaturated double bond and inorganic fine particles having an amphoteric functional group. Further, if necessary, a polymerization initiator, a polymerization accelerator, a coloring material, an organic solvent, and other components may be contained.

<Monofunctional monomer>
Examples of the monofunctional monomer having one ethylenically unsaturated double bond used in the present invention include the following. Phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobolonyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethylacrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, ethyldiglycol acrylate, cyclic trimethylpropanformal monoacrylate, imide acrylate, isoamyl acrylate, ethoxylated succinic acid. Acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, benzyl acrylate, methylphenoxyethyl acrylate, cyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, tribromo ethoxylated Phenyl acrylate, 2-phenoxyethyl acrylate, acryloylmorpholine, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, Diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nonylphenol acrylate, methoxypolyethylene glycol (350) Monoacrylate, methoxypolyethylene glycol (550) monoacrylate, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone and the like can be mentioned, but the present invention is not limited thereto. If necessary, two or more of these monomers may be used in combination.
These monofunctional monomers can be selected and used according to the structure of the inorganic fine particles having an amphipathic functional group.
Further, the blending amount of the monofunctional monomer needs to be 80% by mass or more with respect to the total polymerizable compound. If it is less than 80% by mass, a cured film having excellent stretchability cannot be obtained.

<Inorganic fine particles with amphipathic functional groups>
Examples of the inorganic material constituting the inorganic fine particles having an amphoteric functional group include silica, titanium oxide, potassium titanate, wollastonite, zonotrite, gypsum, aluminum borate, and various fibers such as aramid fiber and glass fiber. Although it can be mentioned, silica is preferable from the viewpoint of hardness, transparency and discharge performance.
Silica fine particles can be used as they are because they usually have a hydrophilic group such as a silanol group or an alkali metal salt thereof on the surface, but the hydrophilic group is introduced for the purpose of improving the affinity with the organic component. It is preferable to do so.
When the surface of silica fine particles is chemically bonded with an organic hydrophilic group such as a polyalkylene oxide group or a semi-organic / semi-inorganic hydrophilic group such as silicate having a high concentration of hydroxyl groups to protect the surface, active energy is obtained. The affinity with the linear curable organic component and the organic solvent is increased, and at the same time, it becomes easier to increase the surface concentration of the colloidal silica component at the time of forming the coating film. As a result, at the time of forming the coating film, the concentration of hydrophilic groups such as polyalkylene oxide groups and hydroxyl groups and the concentration of hydrophilic groups such as silanol groups and alkali metal salts thereof on the silica surface are increased, and the water absorption and moisture content of silica are increased. Retention functions can be concentrated on the surface. Further, in some cases, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or an alkali metal base thereof can be introduced at the same time.

To introduce a hydrophilic group, a hydrophilic group-containing compound is chemically bonded to the surface of the silica fine particles. Preferred hydrophilic groups include hydroxyl groups, silanol groups, carboxylic acid groups, sulfonic acid groups, phosphate groups and alkali metal salts thereof, polyalkylene oxide groups and additions / inclusions with the alkali metal compounds, and quaternary groups. Examples thereof include an ammonium base and a quaternary phosphonium base.
Among these, a polyalkylene oxide group and a silicate group having a high concentration of a hydroxyl group or a silanol group are particularly preferable, and these hydrophilic groups are chemically bonded to the silica surface via an appropriate functional group and introduced. To do.

Preferred compounds having the hydrophilic group include, for example, (1) a polyoxyalkylene compound having an alkoxysilyl group, (2) a silicate compound having a polyoxyalkylene group, (3) a hydroxyl group and a silanol group at high concentrations. Examples thereof include silicate compounds having. Hereinafter, they will be described in order.

(1) Polyoxyalkylene compound having an alkoxysilyl group Examples of typical compounds having such a structure include, but are not limited to, the following compounds (i) to (iii).
(I) A compound obtained by reacting an isocyanate having an alkoxysilyl group with a polyoxyalkylene compound having a hydroxyl group (ii) By reacting a mercaptan having an alkoxysilyl group with a polyoxyalkylene compound having a (meth) acryloyl group Compounds obtained (iii) Compounds obtained by reacting an epoxide having an alkoxysilyl group with a polyoxyalkylene compound having a hydroxyl group.

Regarding (i) Examples of the isocyanate having an alkoxysilyl group include triethoxysilylpropyl isocyanate (KBE9007 manufactured by Shin-Etsu Chemical Co., Ltd.), trimethoxysilylpropyl isocyanate, or trimethoxysilylpropyl mercaptan (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., Toray Dow Corning). Examples thereof include compounds in which a trialkoxysilylalkyl mercaptan such as SH6062 manufactured by Silicon Co., Ltd. and one NCO group of diisocyanate (for example, isophorone diisocyanate, hexamethylene diisocyanate, MDI, TDI, etc.) are bonded by a thiourethane bond.

Examples of the polyoxyalkylene compound having a hydroxyl group include polyethylene glycol monoalkyl ether (polyethylene glycol monomethyl ether, polyethylene glycol monolauryl ether, etc.) and polyethylene glycol monoalkylphenyl ether (polyethylene glycol nonylphenyl ether, polyethylene glycol). Ether-type polyalkylene glycol such as octylphenyl ether), monocarboxylic acid ester of polyethylene glycol (polyethylene glycol monolaurate, polyethylene glycol monooleate, etc.), monoalkyl ether of polyalkylene glycol block copolymer, polyalkylene glycol random copolymer Monoalkyl ether, or mono (meth) acrylic acid ester compound of α, ω-hydroxy-terminated polyalkylene glycol [polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate , Poly (ethylene / propylene) glycol mono (meth) acrylate, poly (ethylene / tetramethylene) glycol mono (meth) acrylate, etc.]. Of these, polyethylene glycol monoalkyl ether or polyoxyethylene glycol mono (meth) acrylate is preferable.

In order to generate a urethane bond from a hydroxyl group and an isocyanate group, for example, each compound may be blended at a ratio of NCO group / OH group ≤ 1 and usually mixed and stirred at 60 to 100 ° C. for 1 to 20 hours. In this reaction, in order to prevent polymerization by acryloyl groups during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, and the amount thereof is a reaction mixture. On the other hand, it is usually 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass.
Further, in order to promote the reaction, known reaction catalysts such as di-n-butyltin dilaurate and diazabicyclooctane (DABCO) may be added. In addition, this reaction involves, for example, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ether solvent such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, a carboxylic acid ester solvent such as ethyl acetate and butyl acetate, and aromatics such as xylene and toluene. It can be carried out in a solvent that does not contain a group capable of reacting with an isocyanate group, such as a hydrocarbon solvent, or in the presence of an active energy ray-curable compound having a (meth) acryloyl group or a (meth) acrylamide group. .. Further, it may be carried out in the solvent and in the presence of an active energy ray-curable compound.

Regarding (ii) Examples of the mercaptan having an alkoxysilyl group include trimethoxysilylpropyl mercaptan (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., SH6062 manufactured by Toray Dow Corning Silicon Co., Ltd., etc.).
Examples of the polyoxyalkylene compound having a (meth) acryloyl group include a mono (meth) acrylic acid ester compound of α, ω-hydroxy-terminated polyalkylene glycol [polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth). Acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene / propylene) glycol mono (meth) acrylate, poly (ethylene / tetramethylene) glycol mono (meth) acrylate, etc.] can be mentioned.
The conditions of the reaction, commonly known as the Michael addition reaction, are applied to both reactions. Although this reaction proceeds at room temperature without a catalyst, it is practically preferable to add a catalyst to allow the reaction to proceed rapidly. Examples of the catalyst that can be used in the reaction include metal alkoxides, cyclic amines, quaternary ammonium salts, and tertiary phosphines. Among these, tertiary phosphines are preferable from the viewpoint of catalytic activity and handleability, and triphenylphosphine is particularly preferable.

Regarding (iii) Examples of the epoxide having an alkoxysilyl group include γ-glycidoxypropyltrimethoxysilane (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) and γ-glycidoxypropyltriethoxysilane (KBE402 manufactured by Shin-Etsu Chemical Co., Ltd.). ), Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd., etc.) and the like.
Examples of the polyoxyalkylene compound having a hydroxyl group include the same compounds as in the case of (i) described above.
Known conditions for the reaction of the epoxy group and the hydroxy group are applied to both reactions.

(2) Silicate compound having a polyoxyalkylene group The silicate compound having a polyoxyalkylene group includes a polyoxyalkylene compound having a hydroxyl group (particularly a polyoxyalkylene compound having a hydroxyl group at one end) and 1 to 4 carbon atoms. It is obtained by a dealcohol / ester exchange reaction with a silicate having an alkyl group or an oligomer thereof. Examples of the polyoxyalkylene compound having a hydroxyl group include the same compounds as in the case of (i) of (1) described above.
Examples of the silicate having an alkyl group having 1 to 4 carbon atoms include methyl silicate (tetramethoxysilane), its oligomer (MS51, MS56, etc. manufactured by Mitsubishi Chemical Corporation), ethyl silicate (tetraethoxysilane), or an oligomer thereof, and the like. , Tetrapropoxysilane, co-modified oligomer with tetrabutoxysilane, and the like. In particular, a methyl silicate oligomer or an oligomer having a methyl silicate oligomer as a main component and co-modified with silicates having an alkyl group having 2 to 4 carbon atoms is preferable from the viewpoint of reactivity and performance.

Examples of catalysts for the dealcohol-ester exchange reaction include hydrogen chloride solution, phosphoric acid solution, inorganic acids such as boric acid, inorganic acid esters such as methyl phosphate and methyl borate, citric acid, and maleic acid as acid catalysts. Organic acids such as acetic acid and paratoluene sulfonic acid, heterocyclic amines such as alcoholic potassium hydroxide, ammonia, trialkylamines and dimethylaminopyridine as alkali catalysts, and metal acetylacetone complexes such as aluminum triacetylacetonate can be mentioned. Be done.
The de-alcohol / transesterification reaction is usually carried out at room temperature to 100 ° C. for 1 to 100 hours, preferably at room temperature for 4 hours or more, and then heated at room temperature to 70 ° C. for 1 to 10 hours to proceed with the reaction. Further, in order to promote the reaction, alcohol produced as a by-product may be distilled off or removed from the system. Further, the reaction system may be diluted with a solvent. The solvent is preferably a hydrolyzate silane alkoxide, water, or a solvent compatible with a catalyst. For example, alcohols such as methanol, ethanol, isopropanol and isobutanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone are used. , Ethers such as THF and dioxane, carboxylic acid esters such as ethyl acetate and butyl acetate, and hydroxy group-containing ethers such as propylene glycol monomethyl ether.

(3) A silicate compound having a high concentration of a hydroxyl group and a silanol group The silicate compound having a high concentration of a hydroxyl group and a silanol group is a desorption of a fluoroalcohol and a silicate having an alkyl group having 1 to 4 carbon atoms or an oligomer thereof. It is obtained by partial hydrolysis after an alcohol ester exchange reaction. It can also be obtained by hydrolyzing and condensing a silicate compound containing tetramethoxysilane or an oligomer thereof as a main component with a large amount of water.
As the fluorinated alcohol, a fluorinated alcohol having 2 to 5 carbon atoms is preferable from the viewpoint of affinity with other hydrophilic groups and easiness of volatilization removal. Typical examples are 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3-hexafluoroisopropanol, 3,3,4. , 4,4-Pentafluorobutanol, 2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,3,4,5,5,5-nonafluoropentanol And so on.
As the silicate having an alkyl group having 1 to 4 carbon atoms, the same silicates as those listed in (2) above can be used.
The catalyst, reaction conditions, solvent, etc. for the dealcohol / transesterification reaction are the same as those for the dealcohol / transesterification reaction (2).

The hydrolysis reaction may be carried out in advance before the reaction with the silica fine particles, but the fluorine-containing alkoxy group is efficiently removed at the same time as the reaction with the silica fine particles, and a hydroxyl group or a silanol group is generated at a high concentration. Therefore, it is preferable from the viewpoint of efficiency.
The reaction of hydrolyzing and condensing a silicate compound containing tetramethoxysilane or an oligomer thereof as a main component with a large amount of water is usually 1 to 10 times the stoichiometric amount required to decompose all methoxy groups. Preferably, 1.05 to 5 times the amount of water is added (however, even if more than the stoichiometric amount of water required to decompose all the methoxy groups is used, not all the methoxy groups are decomposed. , Usually the methoxy group remains).
This reaction can also be carried out in a medium under the same conditions as in the case of (2) above.

The bonding reaction between the silica fine particles and the hydrophilic group-containing compound can be carried out by various methods generally used in the production of this type of compound. Basically, a method is generally used in which an alkoxysilyl group is hydrolyzed to generate a silanol group, and a condensation reaction is carried out with an alkoxy group and / or a hydroxyl group on the surface of the inorganic oxide to bond them.
Therefore, usually, a hydrophilic group-containing compound having an alkoxysilyl group is subjected to a condensation reaction on the surface of silica fine particles under hydrolysis conditions, so that the hydrophilic group-containing compound can be chemically bonded to the surface. Water should be used within a range that does not impair the performance of the coating film and the stability of the coating liquid. The amount of water is 1 mol% or more, preferably 30 mol% or more, based on the alkoxysilyl group. If it is less than 1 mol%, hydrolysis and condensation reactions are unlikely to occur. In addition, when a functional group that is easily hydrolyzed is contained, a side reaction is likely to occur if an excessive amount of water is present. In such a case, it is necessary to suppress the amount of water to 400 mol% or less. Examples of the water used include distilled water, ion-exchanged water, industrial water, soft water and the like.
Further, in order to promote the hydrolysis and condensation reactions, an acid, alkali or other suitable compound may be added as a catalyst as long as the performance of the coating film and the performance of the coating liquid are not impaired. Examples of the acid catalyst include hydrogen chloride solution, phosphoric acid solution, inorganic acids such as boric acid, and organic acids such as citric acid, maleic acid, acetic acid, and paratoluenesulfonic acid. Examples of alkaline catalysts include alcoholic potassium hydroxide, ammonia, trialkylamines, heterocyclic amines such as dimethylaminopyridine, and the like. In addition, examples of other catalysts include acetylacetone metal complexes such as acetylacetone aluminum.

The mass ratio of the silica fine particles to the hydrophilic group-containing compound is silica fine particles / hydrophilic group-containing compound = 95/5 to 10/90, preferably 85/15 to 30/70. If there are more silica fine particles than the above range, the surface protection of the silica fine particles tends to be insufficient, while if there are more hydrophilic group-containing compounds than the above range, the dispersion state is destabilized by polymerization and cross-linking of the alkoxysilane itself. Also, it is likely to cause a significant increase in viscosity.
The binding reaction is usually carried out from room temperature at 100 ° C. for 1 to 100 hours, preferably 0 to 30 ° C. for 4 hours or more, and then continuously allowed to proceed at 20 to 70 ° C. for 1 to 30 hours. Further, the reaction system may be diluted with a solvent in order to suppress side reactions. The solvent is preferably a hydrolyzate silane alkoxide, water, or a solvent compatible with a catalyst. For example, alcohols such as methanol, ethanol, isopropanol and isobutanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone are used. , Ethers such as THF and dioxane, hydroxy group-containing ethers such as propylene glycol monomethyl ether, and carboxylic acid esters such as ethyl acetate and butyl acetate.

Apart from the method of reacting the hydrophilic group-containing compound described in (1), (2) and (3) above with the silica fine particles, the trialkoxysilane compound having a mercapto group is reacted with the silica fine particles in advance, and then (meth). There is also a method of adding a mercapto group to the acryloyl group of a polyalkylene oxide having an acryloyl group and introducing a similar hydrophilic group.
Further, a trialkoxysilane having a mercapto group is reacted with silica fine particles, then the mercapto group is reacted with a diisocyanate compound, one of the isocyanate groups is used to bond with a thiourethane bond, and the remaining isocyanate group has a hydroxyl group. There is also a method of introducing a similar hydrophilic group by a method of reacting a polyalkylene oxide compound to bond with a urethane bond.

<Polyfunctional monomer>
In the present invention, a polyfunctional monomer having two or more ethylenically unsaturated double bonds can be used in addition to the monofunctional monomer. Examples include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol triacrylate, and polypropylene. Glycoldiacrylate, neopentyl glycol diacrylate, bispentaerythritol hexaacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated-1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, 1,9-Nonandiol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl glycol diacrylate hydroxypivalate, trimethylolpropane triacrylate hydroxypivalate, 1,3- Butylene glycol di (meth) acrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, tetramethylolmethane triacrylate, tetramethylolmethane Tetraacrylate, tetramethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryltriacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, Dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentylglycoldi (meth) ) Acrylic, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated tri Examples thereof include, but are not limited to, methylolpropane triacrylate.
If necessary, two or more kinds of these polyfunctional monomers may be used in combination.

<Oligomer>
In the present invention, in addition to the monofunctional monomer, an oligomer having an ethylenically unsaturated double bond can be used. Examples thereof include aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate ligomers, polyester acrylate ligomers, and other special oligomers.
The commercially available products include UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, UV-3700B, UV-6640B, UV-8630B, UV- of Nippon Chemical Synthesis Co., Ltd. 7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, UT-5454, CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963A80, CN963E80, CN963E80 CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN968, CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972, CN973, CN973A80, CN973H85, CN973J75, CN CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN983, CN984, CN985, CN985B88, CN986, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN900 CN9010, CN9011, CN9013, CN9018, CN9019, CN9024, CN9025, CN9026, CN9028, CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, CN9788, CN9893, EBECRY2 EBECRYL230, EBECRYL270, KRM8200, EBECRYL5129, EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL8311, EBECRYL8701 and the like can be used in combination.
It is also possible to use the oligomers obtained by synthesis alone or in combination.
Among the oligomers, those having 2 to 5 unsaturated carbon-carbon bonds are preferable, and those having 2 unsaturated carbon-carbon bonds are most preferable because good stretchability can be obtained.

(Non-polymerizable resin)
In the present invention, a non-polymerizable resin having no polymerizable ethylenically unsaturated double bond may be used. Examples thereof include acrylic resins, polyester resins, polyurethane resins, PVC resins, ketone resins, epoxy resins, nitrocellulose resins, phenoxy resins, or mixtures thereof.
Specifically, as an acrylic resin, John Krill (manufactured by Johnson Polymer Co., Ltd.), Eslek P (manufactured by Sekisui Chemical Co., Ltd.), Elvacite 4026, Elvacite 2028 (Lucite International, Inc), etc.; ), Byron (manufactured by Toyo Boseki), etc .; As polyurethane resins, Byron UR (manufactured by Toyo Boseki), NT-Hyramic (manufactured by Dainichi Seika), Chris Bonn (manufactured by Dainippon Ink and Chemicals), Nippon (Nippon Polyurethane) SOLBIN (manufactured by Nissin Chemical Co., Ltd.), Viniblanc (manufactured by Nisshin Chemical Co., Ltd.), Saran Latex (manufactured by Asahi Kasei Chemicals Co., Ltd.), Sumi Elite (manufactured by Sumitomo Chemical Co., Ltd.) Chemicals), UCAR (Dow Chemical), etc .; Hirac (Hitachi Kasei), SK (Degza), etc. as ketone resins; EPPN-201 (Nippon Kayakusha) as epoxy resins ), HP-7200 (manufactured by DIC), etc .; as nitrocellulose resin, HIG, LIGHT, SL, VX (manufactured by Asahi Kasei), industrial nitrocellulose RS, SS (manufactured by Daicel Chemical Co., Ltd.); Examples thereof include YP-50 and YP-50S (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.).
Further, a non-polymerizable resin obtained by synthesis may be used, or may be used in combination with the commercially available product. When synthesizing a non-polymerizable resin, a material having a polymerizable ethylenically unsaturated double bond may be used as a raw material.

<Active energy ray>
The 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 beams, α rays, β rays, γ rays, and X rays in addition to ultraviolet rays. It is not particularly limited as long as it can impart the energy required for advancing the polymerization reaction of. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

<Polymerization initiator>
The active energy ray-curable composition of the present invention may contain a polymerization initiator. The polymerization initiator may be one that can generate active species such as radicals and cations by the energy of the active energy ray and initiate the polymerization of the polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used alone or in combination of two or more, and among them, a radical polymerization initiator is used. Is preferable. Further, in order to obtain a sufficient curing rate, 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 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, and the like. Examples thereof include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Further, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited, but for example, 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 preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

<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 that impart glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold and silver are used according to the purpose and required characteristics of the composition in the present invention. Can be used. The content of the coloring material may be appropriately determined in consideration of the desired color concentration, dispersibility in the composition, etc., and is not particularly limited, but is 0.1 with respect to the total mass (100% by mass) of the composition. It is preferably ~ 20% by mass. 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, for example, an overcoat layer for protecting an image.
As the pigment, an inorganic pigment or an organic pigment 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 black (CI 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, azolakes 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 chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing lake (basic dye type lake, acidic dye type lake), nitro pigment, nitroso pigment, aniline black, Daylight fluorescent pigments can be mentioned.
Further, in order to improve the dispersibility of the pigment, a dispersant may be further contained. The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used, and one type may be used alone or two or more types may be used in combination.

<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. If the composition does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further enhanced, and it is possible to prevent environmental pollution. .. The "organic solvent" means, for example, a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. is there. Further, "not containing" the organic solvent means that it is substantially not contained, and it is preferably less than 0.1% by mass.

<Other ingredients>
The active energy ray-curable composition of the present invention may contain other known components, if necessary. The other components are not particularly limited, but for example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration promoters, wetting agents (moisturizing agents), and fixing agents. Agents, viscosity stabilizers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like.

<Preparation of active energy ray-curable composition>
The active energy ray-curable composition of the present invention can be prepared by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like are used in a ball mill. A pigment dispersion is prepared by charging it into a disperser such as a kitty mill, a disc mill, a pin mill, or a dyno mill and dispersing it, and the pigment dispersion is further mixed with a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, and the like. Can be prepared by

<Viscosity>
The viscosity of the active energy ray-curable composition of the present invention may be appropriately adjusted according to the application and application means, and is not particularly limited. For example, when a discharge means for discharging the composition from a nozzle is applied. The viscosity in the range of 20 ° C. to 65 ° C., preferably 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 containing the organic solvent. For the above viscosity, a cone rotor (1 ° 34'x R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Use>
The application of the active energy ray-curable composition of the present invention is not particularly limited as long as it is in a field in which an active energy ray-curable material is generally used, and can be appropriately selected depending on the intended purpose, for example, for molding. Examples thereof include resins, paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, and various optical materials.
Further, the active energy ray-curable composition of the present invention can be used as an ink to not only form two-dimensional characters and images and design coatings on various substrates, but also to form a three-dimensional three-dimensional image (three-dimensional model). 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 repeatedly curing and laminating a powder layer, and is also shown in FIGS. 2 and 3. It may be used as a three-dimensional constituent material (model material) or a support member (support material) used in such a laminated modeling method (stereolithography). In addition, FIG. 2 is a method in which the active energy ray-curable composition of the present invention is discharged into a predetermined region, and the ones cured by irradiating with active energy rays are sequentially laminated to perform three-dimensional modeling (details will be described later). ), FIG. 3 shows that the storage pool (accommodation portion) 1 of the active energy ray-curable composition 5 of the present invention is irradiated with the active energy ray 4 to form a cured layer 6 having a predetermined shape on the movable stage 3. This is a method of sequentially laminating and performing three-dimensional modeling.
A known three-dimensional modeling device for modeling a three-dimensional model using the active energy ray-curable composition of the present invention can be used, and is not particularly limited, but for example, a means for accommodating the composition. Those provided with a supply means, a discharge means, an active energy ray irradiation means, and the like can be mentioned.
The present invention also includes a cured product obtained by curing an active energy ray-curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate. The molded product is, for example, a cured product or structure formed in the form of a sheet or a film, which has been subjected to molding processing such as heat stretching or punching. For example, automobiles, OA equipment, and electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, panels for operation units, and the like.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paper, thread, fiber, cloth, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof and the like. From the viewpoint of processability, a plastic base material is preferable.

<Composition container>
The composition container of the present invention means a container in which an active energy ray-curable composition is contained, and is suitable for use in the above-mentioned applications. For example, when the active energy ray-curable composition of the present invention is used for ink, the container containing the ink can be used as an ink cartridge or an ink bottle, whereby ink transfer, ink replacement, etc. It is not necessary to directly touch the ink in the work, and it is possible to prevent the fingers and clothes from getting dirty. In addition, it is possible to prevent foreign substances such as dust from being mixed into the ink. The shape, size, material, etc. of the container itself are not particularly limited as long as they are suitable for the intended use and usage, but the material is a light-shielding material that does not transmit light, or the container has a light-shielding property. It is desirable that it is covered with a sheet or the like.

<Image formation method, forming device>
The method for forming an image of the present invention includes, at least, an irradiation step of irradiating an active energy ray to cure the active energy ray-curable composition of the present invention, and the image forming apparatus of the present invention has an active energy. An irradiation means for irradiating the rays and an accommodating portion for accommodating the active energy ray-curable composition of the present invention may be provided, and the container may be accommodated in the accommodating portion. Further, it may have a discharge step and a discharge means for discharging the active energy ray-curable composition. The method of 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 inkjet ejection means. Ink is ejected to the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d provided with an ink cartridge for each color active energy ray-curable ink of yellow, magenta, cyan, and black and an ejection head. Will be done. Then, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, and a color image is formed. After that, the recording medium 22 is conveyed to the processing unit 25 and the printed matter take-up roll 26. Each printing unit 23a, 23b, 23c, 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. Further, as an inkjet recording method, a serial method in which the head is moved to eject ink onto the recording medium or a recording medium is continuously moved with respect to a recording medium that moves intermittently according to the width of the ejection head. Any of the line methods of ejecting ink onto the recording medium from the head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, and examples thereof include paper, film, metal, and composite materials thereof, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or double-sided printing is also possible.
Further, the activation energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the activation energy rays may be irradiated from the light source 24d. As a result, energy saving and cost reduction can be achieved.
The recorded material recorded by the ink of the present invention includes not only those printed on a smooth surface such as ordinary paper or resin film, but also those printed on an uneven surface to be printed, metal, ceramic, and the like. It also includes those printed on the surface to be printed made of various materials. Further, by superimposing two-dimensional images, it is possible to form a partially three-dimensional image (an image composed of two-dimensional and three-dimensional) 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) according to the present invention. The image forming apparatus 39 of FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to discharge the first active energy ray-curable composition from the discharge head unit 30 for a modeled object for a support. The second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is discharged from the head units 31 and 32, and each of these compositions is cured by the adjacent ultraviolet irradiation means 33 and 34. While stacking. More specifically, for example, the second active energy ray-curable composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, and is irradiated with active energy rays to be solidified. After forming the first support layer having the reservoir portion, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object to the reservoir portion, and is solidified by irradiating the reservoir portion with the active energy ray. By repeating the process of forming the first modeled object layer a plurality of times while lowering the vertically movable stage 38 according to the number of times of stacking, the support layer and the modeled object layer are laminated to form the three-dimensional modeled object 35. To make. After that, the support laminated portion 36 is removed as needed. Although only one discharge head unit 30 for a modeled object is provided in FIG. 2, two or more discharge head units 30 can be provided.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "%" in the example is used.
It is "mass%".
The materials used in the examples and comparative examples are as follows. In addition, the types and blending amounts (parts by mass) of these materials are shown in the respective columns of Examples in Table 1-1, Table 1-2, and Comparative Examples in Table 2.

(Monofunctional monomer)
-Tetrahydrofurfuryl acrylate (THFA: manufactured by Osaka Organic Industry Co., Ltd.)
-Phenoxyethyl acrylate (PEA) (SR339: manufactured by Sartmer)
-Phenoxydiethylene glycol acrylate (PHE-2D: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-Methoxyglycol acrylate (ME-3: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

(Polyfunctional monomer)
・ 1,3-butylene glycol diacrylate: SR212 (manufactured by Sartmer)

(Oligomer)
-Polyester urethane acrylate oligomer: Shikou UV-3010B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

(Non-polymerizable resin)
-Byron: GA-1310, Mn: 20 x 103 (manufactured by Toyobo Co., Ltd.)

(Polymerization initiator)
1-Hydroxycyclohexylphenyl ketone: Irgacure 184 (manufactured by BASF)
2-Hyrodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one: LUCIRIN TPO (manufactured by BASF)
-2,4-Diethylthioxanthone: KAYACURE-DETX-S (manufactured by Nippon Kayaku Co., Ltd.)

(Color material)
Cyan pigment A mixture of phthalocyanine blue manufactured by Sanyo Pigment Co., Ltd. and polymer dispersant S32000 manufactured by Japan Lubrizol Co., Ltd. in a mass ratio of 3: 1.

(Inorganic fine particles)
Silane Fine Particles [Production Example 1] Preparation of Silane Coupling Agent (S1) 350 g of polyethylene glycol having an average molecular weight of 350 at one end and 247 g of triethoxysilylpropyl isocyanate (KBE9007 manufactured by Shinetsu Chemical Co., Ltd.) are diluted with 597 g of methyl ethyl ketone. Then, 0.2 g of dibutyltin dilaurate was added as a condensation catalyst and reacted at room temperature to 80 ° C. for 5 hours to obtain a silane coupling agent (S1) having a polyethylene glycol chain (solid content: 50%).

[Production Example 2] Preparation of silane coupling agent (S2) 400 g of polyethylene glycol (Blemmer AE-400, manufactured by Nippon Yushi Co., Ltd.) and triethoxysilylpropyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.), which are single-ended acrylic acid esters having an average molecular weight of 400 , KBE9007) 247 g is diluted with 650 g of methyl ethyl ketone, 0.4 g of p-methoxyphenol as a polymerization inhibitor and 0.2 g of dibutyltin dilaurate as a condensation catalyst are added, and the mixture is reacted at room temperature to 80 ° C. for 5 hours to form a polyethylene glycol chain. A silane coupling agent (S2) having a silane coupling agent (S2) was obtained (solid content 50%).

[Production Example 3] Preparation of silicate (S3) 152 g of tetramethoxysilane oligomer (MKC silicate MS51 manufactured by Mitsubishi Chemical Corporation) and 350 g of polyethylene glycol monomethyl ether having an average molecular weight of 350 are dissolved in 520 g of methyl ethyl ketone, and 1 g of aluminum triacetylacetonate is dissolved. , 0.3 g of tributyl borate was added and reacted at 20 to 70 ° C. for 8 hours while removing methanol to obtain a silicate (S3) having a polyethylene glycol chain (solid content 50%).

[Production Example 4] Preparation of silicate (S4) 152 g of tetramethoxysilane oligomer (MKC silicate MS51 manufactured by Mitsubishi Chemical Corporation) and 400 g of polyethylene glycol monoacrylate (Blemmer AE-400 manufactured by Nippon Oil & Fats Co., Ltd.) having an average molecular weight of 400 are 570 g. Dissolve in methyl ethyl ketone, add 1 g of aluminum triacetylacetonate, 0.3 g of tributyl borate, and 0.2 g of the polymerization inhibitor p-methoxyphenol, and react at 20 to 70 ° C. for 8 hours while removing methanol to carry out polyethylene glycol. A silicate (S4) having a chain was obtained (solid content 50%).

[Production Example 5] Preparation of silicate (S5) 152 g of tetramethoxysilane oligomer (MKC silicate MS51 manufactured by Mitsubishi Chemical Corporation) and 1100 g of polyethylene glycol monolauryl ether having an average molecular weight of 1100 are dissolved in 1300 g of methyl ethyl ketone to dissolve aluminum triacetylacetonate. 1 g and 0.3 g of tributyl borate were added and reacted at 20 to 70 ° C. for 8 hours while removing methanol to obtain a silicate (S5) having a polyethylene glycol chain (solid content 50%).

[Production Example 6] Preparation of silicate (S6) 152 g of tetramethoxysilane oligomer (MKC silicate MS51 manufactured by Mitsubishi Chemical Corporation) and 100 g of trifluoroethanol were dissolved in 250 g of methyl ethyl ketone to dissolve 1 g of aluminum triacetylacetonate and 0. 3 g was added and reacted at 20 to 70 ° C. for 8 hours while removing methanol to obtain a silicate having a trifluoroethoxy group. Next, 1.5 g of water was added to this silicate solution, and the mixture was reacted at 20 to 70 ° C. for 8 hours while removing trifluoroethanol to obtain a silicate (S6) having a high concentration of hydroxyl groups and silanol groups. (Solid content 50%).

[Production Example 7] Preparation of silicate (S7) 100 g of tetramethoxysilane oligomer (MKC silicate MS51 manufactured by Mitsubishi Chemical Corporation) is dissolved in 105 g of ethanol, 1 g of aluminum triacetylacetonate and 20 g of water are added, and the temperature is 20 to 30 ° C. The reaction was carried out for 4 hours to obtain a silicate (S7) (partially hydrolyzed condensate) having a high concentration of silanol groups (solid content 50%).

[Manufacturing Example 8]
100 g of silica fine particle SFP-20M (manufactured by Denki Kagaku Kogyo Co., Ltd.) was solvent-substituted with propylene glycol monomethyl ether (PGM), water was removed, and the concentration was adjusted to 15% with PGM. Next, after adding 100 g of PGM, 10 g of a silane coupling agent (S1), 0.2 g of aluminum triacetylacetonate, and 0.4 g of water were added and reacted at 20 to 30 ° C. for 24 hours to obtain a hydrophilic group. Silane fine particles (A-01) having a methoxy-terminated polyethylene oxide group were obtained.

[Manufacturing Example 9]
After replacing 100 g of silica fine particles SFP-20M (manufactured by Denki Kagaku Kogyo Co., Ltd.) with PGM to adjust the solid content to 15%, 100 g of PGM, 10 g of silane coupling agent (S2), 0.2 g of p-methoxyphenol, and aluminum. 0.2 g of triacetylacetonate and 0.4 g of water were added and reacted at 20 to 30 ° C. for 24 hours to obtain silica fine particles (A-02) having an acrylate-terminated polyethylene oxide group as a hydrophilic group.

[Manufacturing Example 10]
After replacing 100 g of silica fine particles SFP-20M (manufactured by Denki Kagaku Kogyo Co., Ltd.) with PGM to adjust the solid content to 15%, PGM 100 g, silicate (S3) 10 g, aluminum triacetylacetonate 0.2 g, and water 0. 8 g was added and reacted at 20 to 50 ° C. for 24 hours to obtain silica fine particles (A-03) having a silicate group having a methoxy-terminated polyethylene oxide group as a hydrophilic group.

[Manufacturing Example 11]
After replacing 100 g of silica fine particles SFP-20M (manufactured by Denki Kagaku Kogyo Co., Ltd.) with PGM to adjust the solid content to 15%, 100 g of PGM, 10 g of silicate (S4), 0.2 g of p-methoxyphenol, and aluminum triacetylacetate. 0.2 g of nalto was added and reacted at 20 to 70 ° C. for 10 hours to obtain silica fine particles (A-04) having a silicate group having an acrylate-terminated polyethylene oxide group as a hydrophilic group.

[Manufacturing Example 12]
After replacing 100 g of silica fine particles SFP-20M (manufactured by Denki Kagaku Kogyo Co., Ltd.) with PGM to adjust the solid content to 15%, 100 g of PGM, 10 g of silicate (S5), and 0.2 g of aluminum triacetylacetonate were added, and 20 The reaction was carried out at ~ 70 ° C. for 10 hours to obtain silica fine particles (A-05) having a silicate group having a lauryl ether-terminated polyethylene oxide group as a hydrophilic group.

[Manufacturing Example 13]
100 g of silica fine particles SFP-20M (manufactured by Denki Kagaku Kogyo Co., Ltd.), 100 g of isopropanol, 10 g of silicate (S6), and 0.2 g of aluminum triacetylacetonate are added and reacted at 20 to 70 ° C. for 10 hours to hydroxylate as a hydrophilic group. Silica fine particles (A-06) having a silicate group having a high concentration of a group and a silanol group were obtained.

[Manufacturing Example 14]
100 g of silica fine particles SFP-20M (manufactured by Denki Kagaku Kogyo Co., Ltd.), 100 g of isopropanol, 10 g of silicate (S7), and 0.2 g of aluminum triacetylacetonate are added and reacted at 20 to 70 ° C. for 10 hours to hydroxylate as a hydrophilic group. Silica fine particles (A-07) having a silicate group having a high concentration of a group and a silanol group were obtained.

[Manufacturing Example 15]
To 10 g of zirconia fine particles (TZ-3Y-E, manufactured by Tosoh Corporation), 5 g of a silane coupling agent AY43-048 (manufactured by Tosoh Silicone Co., Ltd.) was added as a surface modifier and mixed dry, and the surface of the zirconia fine particles was surface-modified. (B-01) modified by

[Example 1]
The materials shown in the column of Example 1 in Table 1-1 are added and mixed in order from the top of the table with stirring, and after stirring for 1 hour, it is confirmed that there is no undissolved residue, and the material is filtered with a membrane filter to cause head clogging. The causative coarse particles were removed to prepare an ink.
This ink was ejected onto a polycarbonate film so as to have a film thickness of 10 μm using an inkjet ejection device mounted on a GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.). Immediately after the discharge, a cured product was obtained by irradiating ultraviolet rays with a ^{light intensity of 1500 mJ / cm 2} by a UV irradiator LH6 manufactured by Fusion Systems Japan.

[Examples 2 to 15, Comparative Examples 1 to 10]
Inks were prepared and cured in the same manner as in Example 1 except that the materials shown in the columns of Examples 2 to 15 in Table 1-1 and Table 1-2 and Comparative Examples 1 to 10 in Table 2 were used. I got something.

The characteristics (hardness, stretchability, adhesion) of each of the obtained cured products were evaluated as follows. The results are shown in Table 3-1 and 3-2 and Table 4.

<Hardness>
The pencil hardness (before stretching) of the cured product was measured according to JIS K5600-5-4 scratch hardness (pencil method), and evaluated according to the following criteria.

(Devices and appliances)
・ Equipment: COTEC scratch pencil hardness TQC WW tester (for load 750g only)
-Pencil: Pencil set for wooden drawing with the following hardness (Mitsubishi UNI)
6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H
-Pencil scraper: A special scraper that scrapes only the wood part, leaving the cylindrical core of the pencil as it is.
-Abrasive paper: 3M-P1000

[Evaluation criteria]
◯: Pencil hardness H or higher Δ: Pencil hardness HB, F
×: Pencil hardness B or less

<Stretchability>
A tensile test of the cured product was carried out under the following equipment and conditions to determine the elongation at break at 180 ° C., which was evaluated according to the following criteria.
・ Tensile tester; Autograph AGS-5kNX (manufactured by Shimadzu Corporation)
-Tensile speed: 20 mm / min
・ Temperature: 180 ℃
-Sample; JIS K6251 dumbbell-shaped (No. 6)

Break elongation = (length after tensile test-length before tensile test) / (length before tensile test)
× 100

[Evaluation criteria]
◯: 100% or more Δ: 50% or more, less than 100% ×: less than 50%

<Adhesion>
The adhesion of the cured product was examined according to the grid test (old standard) of JIS K5400, and evaluated according to the following criteria.
The numerical value of the adhesiveness is 100 when there is no peeling in the grid portion cut into 100 pieces, and when the adhesiveness is 80, the area of the non-peeled portion is 80%. Means the state.

[Evaluation criteria]
◯: Adhesion is 90 or more Δ: Adhesion is 80 or more and less than 90 ×: Adhesion is less than 80

1 Storage pool (accommodation)
3 Movable stage 4 Active energy ray 5 Active energy ray Curing type composition 6 Curing layer 21 Supply roll 22 Recording medium 23 Printing unit 23a, 23b, 23c, 23d Each color printing unit 24a, 24b, 24c, 24d Curing light source 25 Processing Unit 26 Printed matter take-up roll 30 Discharge head unit for modeled object 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional modeled object 36 Support laminated part 37 Modeled object support substrate 38 Stage movable in the vertical direction 39 Image forming device A Movable direction B Movable direction

Japanese Patent No. 4335955 Japanese Patent No. 5689614

Claims (6)

A monofunctional monomer having one ethylenically unsaturated double bond and
Containing a silane coupling agent containing a hydrophilic group or silica or zirconium surface-treated with a silicate containing a hydrophilic group .
The hydrophilic group consists of a group consisting of a hydroxyl group, a silanol group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an alkali metal salt of these groups, a polyalkylene oxide group, a quaternary ammonium base and a quaternary phosphonium base. At least one of the chosen
The silane coupling agent containing the hydrophilic group and the silicate containing the hydrophilic group do not have fluorine,
The monofunctional monomer is at least one of tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, and methoxyglycol acrylate.
Wherein Ri der 80 wt% or more based on the content of the monofunctional monomer is the total polymerizable compounds,
An active energy ray-curable composition, wherein the silica or zirconium is 5% by mass or more and 10% by mass or less with respect to the content of the total polymerizable compound. 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 2, which can be ejected to the surface of a recording medium by an inkjet recording method. An ink container containing the active energy ray-curable ink according to claim 2 or 3. A two-dimensional or three-dimensional image forming apparatus including an accommodating portion accommodating the active energy ray-curable composition according to claim 1 and an irradiation means for irradiating the active energy ray. A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating the active energy ray-curable composition according to claim 1 with active energy rays.

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