TWI808190B - Polymerizable composition, inkjet ink, heat-resistant soluble member, three-dimensional structure with support, and method for producing three-dimensional shaped object - Google Patents

Abstract

The present invention provides a polymerizable composition capable of forming a cured product (heat-resistant soluble member) that appropriately maintains solubility in an aqueous solution even after heat treatment. A polymerizable composition characterized by containing: a monofunctional acrylic compound, including one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound; a monofunctional N-vinyl compound; and a polymerization initiator that generates free radicals by irradiation with ionizing radiation.

Description

Polymerizable composition, inkjet ink, heat-resistant soluble member, three-dimensional structure with support, and method for producing three-dimensional shaped object

The present invention relates to a polymerizable composition, an inkjet ink comprising the polymerizable composition, a heat-resistant soluble member comprising an ionizing radiation-cured product of the polymerizable composition, a three-dimensional structure with a support including the heat-resistant soluble member as a support, and a method for manufacturing a three-dimensional shape using the polymerizable composition.

In recent years, as a method of manufacturing a three-dimensional structure, an optical three-dimensional modeling method called a layered modeling method has been proposed, which creates metadata such as overlapping thin plates obtained by slicing three-dimensional computer-aided design (CAD) data of a product, and repeats the step of irradiating and curing a film containing a photocurable resin composition using a radically polymerizable compound or a cationic polymerizable compound multiple times, thereby manufacturing a three-dimensional structure of a desired shape. As a device for manufacturing a three-dimensional structure by the above-mentioned optical three-dimensional modeling method, cheaper devices have appeared on the market, and the expansion of applications not only for industrial purposes such as prototype production but also for ordinary households is expected. For example, by using a specific radically polymerizable compound in such a build-up method, the dimensional accuracy and productivity of a molded object can be improved (Patent Document 1).

Here, if the shape of the three-dimensional structure (three-dimensional object) finally produced by optical three-dimensional modeling is complex, it may experience a state in which it is difficult to bear its own weight at the stage of the structure (main body) produced by optical three-dimensional modeling. In such a case, from the viewpoint of maintaining the shape of the main body, a supporting portion for supporting the main body may be formed together with the main body by optical three-dimensional modeling. The three-dimensional structure with the support including the main body and the support obtained in this way can be obtained by removing the three-dimensional structure with the support as the final step to obtain a photosculpture. In such a production method, as a composition capable of forming a support portion, for example, Patent Document 2 discloses a photocurable liquid resin composition having good solubility in an aqueous solution after curing.

On the other hand, in order to use a three-dimensional object manufactured by a manufacturing method including optical three-dimensional modeling as a working model, the three-dimensional object is required to have sufficient mechanical strength or heat resistance to withstand usage conditions. For this purpose, there are cases where post curing (post cure) such as heating or light irradiation is performed on the structure (main body) produced by the optical three-dimensional modeling method (for example, Patent Document 3), and a photosensitive resin composition based on the implementation of post curing by heating (post bake) has also been proposed (for example, Patent Document 4). [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-189782 [Patent Document 2] Japanese Patent Laid-Open No. 2010-155889 [Patent Document 3] Japanese Patent Laid-Open No. 2013-023574 [Patent Document 4] Japanese Patent Laid-Open No. 2013-194205

[Problems to be Solved by the Invention] Even when the main body is formed using a composition that presupposes post-baking as disclosed in Patent Document 4, it may be necessary to form a support as described in Patent Document 2 by optical stereolithography. At this time, if the support portion is removed from the three-dimensional structure with the support portion formed by the optical three-dimensional modeling method before post-baking, the main body may not be able to bear its own weight and be damaged. Therefore, in the case of forming a three-dimensional structure with a support part including a body part formed of a composition premised on post-baking, the support part is also post-baked when formed by optical stereolithography. This post-baking may affect the solubility of the support part, but sufficient studies have not been conducted on this point.

In this way, when the treatment (heat treatment) of raising the temperature of the ionizing radiation-cured product obtained by irradiating the polymerizable composition with ionizing radiation is performed, the ionizing radiation-cured product after the heat treatment may also be required to have appropriate solubility in an aqueous solution. This heat treatment may not be performed for the purpose of actively heating the ionizing radiation cured product. As a specific example of such a case, the case where the entire substrate is heated for the purpose of heating members (solder, etc.) provided in other parts of the substrate on which the ionizing radiation hardened product is formed. In addition, as another example, when film formation is performed by a dry process on a substrate on which an ionizing radiation-cured product is formed, the deposited material (metal, etc.) contacts the ionizing radiation-cured product at a high temperature, and thus the temperature of the ionized radiation-cured product rises. Furthermore, in this specification, the so-called "ionizing radiation" refers to electromagnetic waves such as γ-rays, X-rays, ultraviolet rays, and visible light, and electrons, protons, or ions, etc., which can generate free radicals by being irradiated to or colliding with a polymerization initiator.

In view of the above circumstances, the present invention aims to provide a polymerizable composition capable of forming a cured product (heat-resistant soluble member) that appropriately maintains solubility in an aqueous solution even after heat treatment such as post-baking. An object of the present invention is to provide an inkjet ink comprising the polymerizable composition, a heat-resistant soluble member comprising a hardened product of the polymerizable composition, a three-dimensional structure with supports including a support comprising the heat-resistant soluble member, and a method for producing a three-dimensional shape using the polymerizable composition. [Means to solve the problem]

The present invention provided to solve the above-mentioned problems is as follows. [1] A polymerizable composition for forming a heat-resistant soluble member, characterized by containing: a monofunctional acrylic compound, including one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound; a monofunctional N-vinyl compound; and a polymerization initiator that generates radicals by irradiation with ionizing radiation. [2] The polymerizable composition according to [1], wherein the monofunctional N-vinyl compound is a monofunctional N-vinylamide compound. [3] The polymerizable composition according to [2], wherein the monofunctional N-vinylamide compound contains one or two or more compounds selected from N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam. [4] The polymerizable composition according to any one of the above [1] to the above [3], which has a viscosity at 60°C of 15 mPa･s or less. [5] The polymerizable composition according to any one of the above [1] to the above [4], which contains 30% by mass or less of a volatile solvent relative to the entire polymerizable composition. [6] An inkjet ink comprising the polymerizable composition according to any one of [1] to [5]. [7] A heat-resistant soluble member comprising an ionizing radiation-cured product of the polymerizable composition according to any one of [1] to [5], wherein the heat-resistant soluble member can be dissolved in an aqueous solution even after being heated at 150° C. for 2 hours in the air. [8] The heat-resistant soluble member according to [7], wherein the aqueous solution is a water-alcohol mixed solution. The alcohol is preferably an alcohol having miscibility with water, more preferably an alcohol having 4 or less carbon atoms. [9] The heat-resistant soluble member according to [7] or [8], wherein the aqueous solution has a pH of 8 or less. [10] A three-dimensional structure with a support part, characterized by comprising: a body part providing a three-dimensional shape; and a support part carrying the body part, and the support part includes the heat-resistant soluble member as described in any one of [7] to [9]. [11] A method for manufacturing a three-dimensional figure, characterized by comprising: a forming step of using a first liquid composition for forming a main body and a second liquid composition for forming a support, and forming a three-dimensional structure with a support in a state where the main body is supported by the support by a layered molding method, the body provides the three-dimensional figure, and the support supports the main body; and a removing step of dissolving and removing the support of the three-dimensional structure with the support using an aqueous solution to obtain the three-dimensional structure. A molded object, wherein the second liquid composition comprises the polymerizable composition according to any one of [1] to [5], and the support part contains the heat-resistant soluble member according to any one of [7] to [9]. [12] The method for manufacturing a three-dimensional structure according to [11], further comprising a heating step after the forming step and before starting the removing step, wherein the heating step heats the three-dimensional structure with support parts to change the physical properties of the main body. [Effect of the invention]

According to the present invention, there is provided a polymerizable composition capable of forming a cured product (heat-resistant soluble member) that appropriately maintains solubility in an aqueous solution even through a heating step. In addition, according to the present invention, there are provided an inkjet ink comprising the polymerizable composition, a heat-resistant soluble member comprising an ionizing radiation-cured product of the polymerizable composition, a three-dimensional structure with a support including a support comprising the heat-resistant soluble member, and a method for producing a three-dimensional shaped object.

Hereinafter, methods for producing the polymerizable composition, inkjet ink, heat-resistant soluble member, three-dimensional structure with support parts, and three-dimensional shaped object according to the embodiment of the present invention will be described.

A polymerizable composition according to an embodiment of the present invention is used to form a heat-resistant soluble member, and contains: a monofunctional acrylic compound, one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound; a monofunctional N-vinyl compound; and a polymerization initiator that generates radicals by irradiation with ionizing radiation.

The monofunctional acrylic compound includes one or two or more compounds selected from the group consisting of monofunctional acrylate compounds and monofunctional acrylamide compounds. The monofunctional acrylate compound is a compound having a (meth)acrylate or (meth)acrylate-based partial structure and having one ethylenic double bond in the molecule. In addition, in this specification, in order to show one or both of "acrylic acid" and "methacrylic acid", it may express as "(meth)acrylic acid." Terms related to (meth)acrylic acid, such as "(meth)acrylate" and "(meth)acryloxy" also have the same meaning.

The monofunctional acrylate compound preferably has a hydroxyl group (—OH) from the viewpoint of ensuring solubility in an aqueous solution of an ionizing radiation-cured product obtained by irradiating a polymerizable composition with ionizing radiation. Specific examples of such a hydroxyl group (—OH)-containing monofunctional acrylate compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, N-hydroxyethyl (meth)acrylamide, and polyoxyethylene monoacrylate. Among them, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are preferable from the viewpoint of relatively less volatilization and therefore easy to ensure the compositional stability of the polymerizable composition, and 4-hydroxybutyl acrylate is particularly preferable from the viewpoint of the ease of dissolution of the obtained ionizing radiation-cured product in an aqueous solution.

Specific examples of monofunctional acrylamide compounds include N-isopropylacrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, and (methyl) Acryloylmorpholine. Among these, (meth)acryloylmorpholine is preferred from the viewpoint of being relatively less volatile and thus easily ensuring the compositional stability of the polymerizable composition.

The monofunctional N-vinyl compound is a compound having an ethylenically unsaturated group bonded to an amine group, and the amine group can also form a carbonyl group and an amide bond. In this specification, such a monofunctional compound in which an amine group bonded to an ethylenically unsaturated group constitutes an amide bond is also referred to as a "monofunctional N-vinylamide compound". The monofunctional N-vinylamide compound is a preferable example of the monofunctional N-vinyl compound. Specific examples of monofunctional N-vinylamide compounds include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam, etc. Specific examples of monofunctional N-vinyl compounds other than monofunctional N-vinylamide compounds include 1-vinylimidazole and 9-vinylcarbazole. Among these compounds, N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam, and 1-vinylimidazole are preferred from the viewpoint of ease of dissolution of the obtained ionizing radiation-cured product in an aqueous solution, and N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam are particularly preferred from the viewpoint of restrictions on product transportation.

The type of the polymerization initiator is not limited as long as it can generate radicals by irradiation with ionizing radiation and can initiate the polymerization reaction of the monofunctional acrylic compound and the monofunctional N-vinyl compound. The content of the polymerization initiator is also appropriately set according to the type and content of the monofunctional acrylic compound and the monofunctional N-vinyl compound, and the type of the polymerization initiator. Without limitation, the content of the polymerization initiator is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and most preferably 0.1 to 4 parts by weight relative to the entire amount of the polymerizable composition.

作為聚合起始劑的具體例，可列舉：二苯甲酮、米其勒酮（Michler's ketone）、4,4'-雙(二乙基胺基)二苯甲酮、氧雜蒽酮、硫雜蒽酮、異丙基氧雜蒽酮、2,4-二乙基硫雜蒽酮、2-乙基蒽醌、苯乙酮、2-羥基-2-甲基苯丙酮、2-羥基-2-甲基-4'-異丙基苯丙酮、1-羥基環己基苯基酮、異丙基安息香醚、異丁基安息香醚、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、樟腦醌、苯並蒽酮、2-羥基-1-[4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基]-2-甲基-丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-1-丁酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-嗎啉基苯基)-1-丁酮、氧基-苯基-乙酸2-(2-氧代-2-苯基-乙醯氧基-乙氧基)-乙基酯、氧基-苯基-乙酸2-(2-羥基-乙氧基)-乙基酯、氧基-苯基-乙酸2-(2-氧代-2-苯基-乙醯氧基-乙氧基)-乙基酯與氧基-苯基-乙酸2-(2-羥基-乙氧基)-乙基酯的混合物、苯基乙醛酸甲基酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4,4'-二(第三丁基過氧羰基)二苯甲酮、3,4,4'-三(第三丁基過氧羰基)二苯甲酮、3,3',4,4'-四(第三丁基過氧羰基)二苯甲酮、3,3',4,4'-四(第三己基過氧羰基)二苯甲酮、3,3'-二(甲氧羰基)-4,4'-二(第三丁基過氧羰基)二苯甲酮、3,4'-二(甲氧羰基)-4,3'-二(第三丁基過氧羰基)二苯甲酮、4,4'-二(甲氧羰基)-3,3'-二(第三丁基過氧羰基)二苯甲酮、2-(4'-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(3',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(2',4'-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(2'-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、2-(4'-戊氧基苯乙烯基)-4,6-雙(三氯甲基)-均三嗪、4-[對-N,N-二(乙氧基羰基甲基)]-2,6-二(三氯甲基)-均三嗪、1,3-雙(三氯甲基)-5-(2'-氯苯基)-均三嗪、1,3-雙(三氯甲基)-5-(4'-甲氧基苯基)-均三嗪、2-(對-二甲基胺基苯乙烯基)苯並噁唑、2-(對-二甲基胺基苯乙烯基)苯並噻唑、2-巰基苯並噻唑、3,3'-羰基雙(7-二乙基胺基香豆素)、2-(鄰氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(4-乙氧基羰基苯基)-1,2'-聯咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4-二溴苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、3-(2-甲基-2-二甲基胺基丙醯基)咔唑、3,6-雙(2-甲基-2-嗎啉基丙醯基)-9-正十二烷基咔唑、1-羥基環己基苯基酮、雙(η ⁵ -2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1Η-吡咯-1-基)-苯基)鈦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦及2,4,6-三甲基苯甲醯基二苯基氧化膦。 These compounds may be used alone, or two or more of them may be used in combination. Among them, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-[4-(methylthio) are preferred from the standpoint of high sensitivity to an ultraviolet-light emitting diode (UV-LED) light source and photocurability. Phenyl]-2-morpholinyl-1-propanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

From the viewpoint of simplifying the formation steps of the ionizing radiation-cured product, the polymerizable composition of this embodiment may not contain a volatile solvent substantially, but may contain a volatile solvent from the viewpoint of adjusting the viscosity of the polymerizable composition. When used, the volatile solvent can be mixed with other components to form a polymerizable composition. When the polymerizable composition contains a volatile solvent, the volatile solvent can start to volatilize when the polymerizable composition is not hardened, and it is preferable to volatilize at least in the stage where the ionizing radiation-cured product is formed by appropriately heating before, during, and/or after irradiation of ionizing radiation. If the unvolatilized solvent remains excessively in the state where the polymerizable composition is cured to some extent, the final cured product (ionizing radiation cured product) has a porous structure, and the mechanical strength may decrease. Therefore, the content of the volatile solvent is preferably 30% by mass or less with respect to the entire polymerizable composition.

Specific examples of volatile solvents include diethyl ether, tetrahydrofuran, diphenyl ether, dimethoxybenzene, acetone, methanol, ethanol, isopropanol, butanol, tertiary butanol, benzyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, benzonitrile, ethylene carbonate, propylene carbonate, ethyl acetate, isobutyl acetate, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, oxyethyl acetate Ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2 -Propyl oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, acetone Propyl Acetate, Methyl Acetate, Ethyl Acetate, Methyl 2-Oxobutyrate, Ethyl 2-Oxobutyrate, Methyl 2-Hydroxyisobutyrate, Dioxane, Ethylene Glycol, Ethylene Glycol Monomethyl Ether, Ethylene Glycol Monoethyl Ether, Diethylene Glycol, Triethylene Glycol, Propylene Glycol, Dipropylene Glycol, Tripropylene Glycol, 1,4-Butanediol, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Monobutyl Ether , propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylimidazolinone, etc. These compounds may be used alone, or two or more of them may be used in combination.

The polymerizable composition of this embodiment may contain components other than the above-mentioned components as other additives. Specific examples of other additives include surfactants, polymerization inhibitors, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, fillers, pigments, dyes, etc., but are not particularly limited as long as they can be uniformly mixed with other components and can be properly cured without departing from the scope of the present invention. As a specific example, a filler containing light-transmitting particles such as silicon oxide particles may be mentioned. Such a filler can improve the mechanical strength of the ionizing radiation-cured product without hindering the curing of the polymerizable composition.

The polymerizable composition of this embodiment is supplied onto the substrate by coating, dripping, etc. during use, whereby the polymerizable composition has a film-like shape or a predetermined pattern on the substrate. In some cases, the viscosity at 25° C. of the polymerizable composition of the present embodiment is preferably 100 mPa·s or less from the viewpoint of improving the ease of supplying the polymerizable composition onto the substrate in this way. In particular, when the polymerizable composition is supplied onto the substrate using an inkjet printer, it is preferable to satisfy the above viscosity range. Furthermore, the inkjet ink containing the polymerizable composition of the present embodiment has a viscosity at a discharge temperature (for example, 60° C.) of preferably 15 mPa·s or less, particularly preferably 10 mPa·s or less.

The polymerizable composition of this embodiment is cured by irradiation with ionizing radiation to become an ionizing radiation cured product. The ionizing radiation-cured product is soluble in an aqueous solution even after being heated at 150° C. for 2 hours in the air. The aqueous solution is a solution containing water and may be composed of water, but is preferably a mixed solvent with a polar solvent, more preferably a mixed solution of a protic polar solvent such as alcohol and water. From the viewpoint of improving the uniformity of the mixed solution, etc., the alcohol preferably has a high solubility in water, that is, has miscibility with water. The content of water in the aqueous solution is appropriately set according to the types of components other than water contained in the aqueous solution or the composition of the ionizing radiation-cured product. When the water-based solution contains a mixture of water and alcohol, that is, a water-alcohol mixture, when the alcohol contained in the water-alcohol mixture contains a substance with a carbon number of 4 or less such as ethanol or isopropanol, the alcohol content is sometimes preferably 25% by volume or more and 90% by volume or less, sometimes more preferably 50% by volume or more and 85% by volume or less, and sometimes preferably 70% by volume or more and 80% by volume or less.

The aqueous solution may contain organic solvents other than alcohol. Examples of such organic solvents include aprotic organic solvents such as N-methylpyrrolidone, acetone, acetonitrile, and dimethylsulfoxide. From the viewpoint of reducing the environmental load, the content of organic solvents other than alcohol in the aqueous solution is preferably 20% by volume or less of the entire aqueous solution.

The water-based solution may preferably be non-alkali, that is, non-alkali. When the aqueous solution contains an inorganic alkaline substance such as sodium hydroxide or an organic alkaline substance such as tetramethylammonium hydroxide in order to make the aqueous solution alkaline, the handling properties of the aqueous solution may also decrease. Furthermore, the pH of a general alkali-based solution is 9 or more, so in this specification, the so-called non-alkali water-based solution means a pH of less than 9. The pH of the aqueous solution is preferably at most 8, more preferably at most 7.5, from the viewpoint of being more reliably alkali-free.

The ionizing radiation cured product of this embodiment is less likely to change in shape even when heated. As a specific example, when the ionizing radiation cured product of this embodiment has a film shape with a thickness of 13 μm to 18 μm formed on a glass substrate, even if it is heated at 150° C. for 2 hours in the air, the residual film ratio defined by (thickness after heat treatment)/(thickness before heat treatment) is 80% or more, in a preferable example, it is 85% or more, and in a more preferable example, it is 90% or more. Therefore, even in the case where the soluble member including the ionizing radiation cured product is heated, the shape of the soluble member is less likely to change.

Hereinafter, a method for producing a three-dimensional shaped object using the polymerizable composition of this embodiment will be described. As described above, the ionizing radiation-cured product obtained by irradiating the polymerizable composition of this embodiment with ionizing radiation can properly maintain solubility in an aqueous solution even when heated at about 150° C. for 2 hours, so it can be used as a heat-resistant soluble member. Therefore, when three-dimensional modeling is performed using a polymerizable composition to form a three-dimensional structure, a heat-resistant soluble member including the ionizing radiation-cured product of this embodiment is preferable as a support portion for supporting the structure during manufacture.

Specifically, the manufacturing method of the three-dimensional structure includes the following forming steps and removing steps, and further includes a heating step if necessary.

First, in the shaping step, using the first liquid composition for forming the body part and the second liquid composition for forming the support part, a three-dimensional structure with a support part in a state where the body part is supported by the support part is formed by a build-up molding method, the body part provides a three-dimensional shape finally obtained by three-dimensional modeling, and the support part carries the body part.

The first liquid composition contains: a polyfunctional polymerizable substance having a plurality of ethylenically unsaturated bonds generally used in a build-up method, and a polymerization initiator having appropriate sensitivity to ionizing radiation used for curing (for example, light from an LED lamp). The first liquid composition may contain a filler as necessary (specific examples include inorganic particles such as silicon oxide and titanium dioxide), and may be colored by containing a paint or a pigment. The second liquid composition contains the polymerizable composition of the present embodiment described above.

From the viewpoint of simplification of the manufacturing process, it is preferable that both the pattern of the first liquid composition and the pattern of the second liquid composition are formed by an inkjet printer. By irradiating the pattern of the first liquid composition and the pattern of the second liquid composition with ionizing radiation, the pattern of the first liquid composition becomes a cured product forming the body portion, and the pattern of the second liquid composition becomes a cured product (heat-resistant soluble member) forming the support portion.

After obtaining a three-dimensional structure with a support including a main body and a support for supporting the main body by the build-up method in this way, a heating step is performed to change the physical properties of the main body by heating the three-dimensional structure with a support. Specific examples of physical properties in this case include mechanical properties such as bending rigidity. As described above, the first liquid composition for forming the main body has a polymerizable substance. Therefore, by heating the cured product obtained by irradiation with ionizing radiation, the degree of polymerization can be further advanced, thereby improving the mechanical properties. In this way, the mechanical properties of the main body portion are improved by heating, and as a result, the rigidity of the main body portion can be increased to such an extent that no support by the support portion is required. By performing such post-hardening of the body portion by, for example, batch processing, the work time required for the build-up method can be shortened, and the productivity of three-dimensional shaped objects may be improved.

Finally, a removal step is carried out. The removal step uses an aqueous solution to dissolve and remove the support portion of the three-dimensional structure with the support portion to obtain a three-dimensional shape based on the main body. In the removal step, the aqueous solution is brought into contact with the three-dimensional structure with the support (specifically, the three-dimensional structure with the support is immersed in a container containing the aqueous solution; or the three-dimensional structure with the support is sprayed with the aqueous solution), whereby only the support is selectively dissolved, and the three-dimensional structure based on the main body is obtained as a three-dimensional shape.

Although the present invention has been described with reference to the above-mentioned embodiments, the present invention is not limited to the above-mentioned embodiments, and may be improved or changed for the purpose of improvement or within the scope of the idea of the present invention. For example, in the case where the main body includes a hollow portion having an opening, if the ionizing radiation-cured product (heat-resistant soluble member) of the polymerizable composition of the present invention is disposed so as to fill at least a part of the hollow portion to protect the wall constituting the hollow portion from damage, then the heat-resistant soluble member is a support portion in one embodiment of the present invention.

Alternatively, the heat-resistant soluble member of this embodiment can also be used as a protective material or a temporary fixing material. For example, by providing the heat-resistant soluble member of the present embodiment as a protective material on the surface of a member that may be damaged by a collision with another member, the member can be protected from damage. In addition, as another example, for a member having a part that is likely to be displaced when an external force is applied and collides with other parts of the member (as a specific example, a tongue or a partition can be mentioned), the heat-resistant soluble member of this embodiment is used to temporarily fix the part to suppress the displacement of the part, whereby the member is less likely to be damaged even if it is placed in a state where an external force is applied such as transportation. If the member thus protected and temporarily fixed no longer needs protection or temporary fixation, it can properly perform its original function by dissolving and removing the heat-resistant soluble member of this embodiment. [Example]

Hereinafter, although an Example etc. demonstrate this invention more concretely, the scope of the present invention is not limited to these Examples etc.

(Example 1) Prepare 7.06 parts by mass of acryloylmorpholine (ACMO), which is a monofunctional acrylamide compound as a monofunctional acrylic compound, 3.55 parts by mass of N-vinyl formamide (NVF) as a monofunctional N-vinyl compound, and IRGACURE 379EG (manufactured by BASF) as a polymerization initiator. , hereinafter referred to as “IRG379”) 1.27 parts by mass, and BYK 342 (manufactured by BYK Chemie Japan) as a surfactant 0.0053 parts by mass of the resin composition. In the resin composition, the monofunctional acrylic compound and the monofunctional N-vinyl compound are equimolar (the molar ratio is 1:1). In the following other examples and comparative examples, the content of each compound in the resin composition was set so that the number of ethylenically unsaturated bonds in the respective compounds of the two compounds having ethylenically unsaturated bonds contained in the resin composition were equal to each other (equimolar in terms of the number of functional groups). In the resin composition, the polymerization initiator is an amount corresponding to 12% of the total parts by mass of the monofunctional acrylic compound and the monofunctional N-vinyl compound, and the surfactant is an amount corresponding to 500 ppm of the total parts by mass of the monofunctional acrylic compound and the monofunctional N-vinyl compound. In the following other examples and comparative examples, the content of the polymerization initiator and the content of the surfactant were respectively set so as to satisfy the relationship of the total parts by mass described above. The viscosity of the obtained resin composition was 10.4 mPa·s at 25°C and 8.8 mPa·s at 30°C. Therefore, if the resin composition of Example 1 is 30 degreeC or more, it is especially preferable as the ink for inkjet.

(Example 2) Prepare 7.06 parts by mass of acrylylmorpholine (ACMO) which is a monofunctional acrylamide compound as a monofunctional acrylic compound, 6.96 parts by mass of N-vinyl-ε-caprolactam (NVC) as a monofunctional N-vinyl compound, 1.68 parts by mass of IRG379 as a polymerization initiator, and BYK 34 as a surfactant 2 0.0070 parts by mass of the resin composition. The viscosity of the obtained resin composition was 10.8 mPa·s at 25°C and 9.0 mPa·s at 30°C. Therefore, if the resin composition of Example 2 is 30 degreeC or more, it is especially preferable as the ink for inkjet.

(Example 3) Prepare 7.06 parts by mass of acryl morpholine (ACMO), which is a monofunctional acrylamide compound as a monofunctional acrylic compound, 4.26 parts by mass of N-vinyl acetamide (NVAc) as a monofunctional N-vinyl compound, 1.36 parts by mass of IRG379 as a polymerization initiator, and BYK 342 0. 0057 parts by mass of the resin composition. The viscosity at 25° C. of the obtained resin composition was 6.8 mPa·s. Therefore, if the resin composition of Example 3 is 25 degreeC or more, it is especially preferable as the ink for inkjet.

(Example 4) Prepare 7.06 parts by mass of acryl morpholine (ACMO) which is a monofunctional acrylamide compound as a monofunctional acrylic compound, 4.71 parts by mass of N-vinyl imidazole (N-vinyl imidazole, NVIM) as a monofunctional N-vinyl compound, 1.41 parts by mass of IRG379 as a polymerization initiator, and BYK 342 0.005 as a surfactant 9 parts by mass of the resin composition. The viscosity at 25° C. of the obtained resin composition was 7.5 mPa·s. Therefore, if the resin composition of Example 4 is 25 degreeC or more, it is especially preferable as the ink for inkjet.

(Example 5) A resin composition containing 7.21 parts by mass of 4-hydroxybutyl acrylate (4HBA) as a monofunctional acrylic compound, 3.55 parts by mass of N-vinylformamide (NVF) as a monofunctional N-vinyl compound, 1.29 parts by mass of IRG379 as a polymerization initiator, and 0.0054 parts by mass of BYK 342 as a surfactant thing. The viscosity at 25° C. of the obtained resin composition was 9.0 mPa·s. Therefore, if the resin composition of Example 5 is 25 degreeC or more, it is especially preferable as the ink for inkjet.

(Example 6) Prepared are 6.36 parts by mass of diethylacrylamide (diethyl acetoacetamide, DEAA) which is a monofunctional acrylamide compound as a monofunctional acrylic compound, 3.55 parts by mass of N-vinylformamide (NVF) as a monofunctional N-vinyl compound, 1.19 parts by mass of IRG379 as a polymerization initiator, and Surfactant BYK (BYK) 342 0.0050 parts by mass of the resin composition. The viscosity at 25° C. of the obtained resin composition was 3.7 mPa·s. Therefore, if the resin composition of Example 6 is 25 degreeC or more, it is especially preferable as the ink for inkjet.

(comparative example 1) A resin composition was prepared containing 7.06 parts by mass of acrylmorpholine (ACMO) which is a monofunctional acrylamide compound which is a monofunctional acrylic compound, 7.21 parts by mass of 4-hydroxybutyl acrylate (4HBA) which is a monofunctional acrylic compound, 1.71 parts by mass of IRG379 as a polymerization initiator, and 0.0071 parts by mass of BYK 342 as a surfactant. The viscosity of the obtained resin composition was 12.8 mPa·s at 25°C and 7.9 mPa·s at 40°C. Therefore, the resin composition of Comparative Example 1 is particularly preferable as an inkjet ink if the temperature is 40° C. or higher.

(comparative example 2) Prepared a resin composition containing 7.06 parts by mass of acryl morpholine (ACMO) which is a monofunctional acrylamide compound as a monofunctional acrylic compound, 6.53 parts by mass of polyethylene glycol #400 diacrylate (9EG-A) as a difunctional acrylic compound, 1.21 parts by mass of IRG379 as a polymerization initiator, and 0.0071 parts by mass of BYK 342 as a surfactant things. The molar ratio of the monofunctional type acrylic compound and the bifunctional type acrylic compound in a resin composition was set to 1:0.5 so that the number of functional groups might become equal. The viscosity of the obtained resin composition was 52.8 mPa·s at 25°C and 14.9 mPa·s at 60°C. Therefore, the resin composition of Comparative Example 2 is particularly preferable as an inkjet ink if the temperature is 60° C. or higher.

(comparative example 3) A resin composition containing 6.53 parts by mass of polyethylene glycol #400 diacrylate (9EG-A) as a bifunctional acrylic compound, 1.78 parts by mass of N-vinylformamide (NVF) as a monofunctional N-vinyl compound, 1.00 parts by mass of IRG379 as a polymerization initiator, and 0.0042 parts by mass of BYK 342 as a surfactant was prepared. The molar ratio of the bifunctional acrylic compound and the monofunctional N-vinyl compound in the resin composition was set to 0.5:1 so that the number of functional groups became equal. The viscosity of the obtained resin composition was 52.8 mPa·s at 25°C and 14.6 mPa·s at 60°C. Therefore, the resin composition of Comparative Example 3 is particularly preferable as an inkjet ink if the temperature is 60° C. or higher.

(Evaluation Example 1) Evaluation of Photocurability The resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were each applied on a glass substrate by spin coating for 10 seconds to obtain coating films. The coating film of the obtained resin composition was cured under the following conditions to obtain an ionizing radiation cured product. UV irradiation device: "ASM1503 NM-UV-LED" manufactured by Asumi Giken Inc. Lamp wavelength: 365 nm Exposure amount: 500 mJ/cm ² , 1000 mJ/cm ² , 1500 mJ/cm ² , 2000 mJ/cm ² Illuminance: 700 mW/cm ² 400 nm) UV monitor ("UV-Pad" manufactured by Opsytec). The resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were coated and exposed to form a film of an ionizing radiation cured product on a glass substrate. Then, the cured film surface was touched with a finger, and the exposure amount at the time of completely becoming a non-adhesive state was checked. The results are shown in Table 1.

[Table 1]

As shown in Table 1, in Examples 1 to 6, and Comparative Examples 2 and 3, the non-adhesive exposure amount was 1500 mJ/cm ² or less, and especially 500 mJ/cm 2 in Examples 1, 3, 4, and 6, and Comparative Examples 2 and ³ were particularly good. In contrast, in Comparative Example 1, even when the exposure amount was set to 2000 mJ/cm ² , the non-tacky state was not achieved, and the curing of the resin composition was not completed.

(Evaluation Example 2) Evaluation of Residual Film Ratio after Heat Treatment The resin compositions of Examples 1 to 6 and Comparative Examples 2 and 3 were applied and cured under the same conditions as in Evaluation Example 1 to obtain ionizing radiation-cured films. Exposure was performed with the exposure amount being the non-tack exposure amount confirmed in Evaluation Example 1 as photocuring conditions. Thereafter, the obtained film of the ionizing radiation cured product was further heat-treated under the following conditions. In addition, in Comparative Example 1, even if the exposure amount was 2000 mJ/cm ² , the non-tacky state was not achieved, so it was not evaluated, and additional heat treatment was not performed. Clean oven: "DT610" manufactured by Yamato Scientific, Inc. Temperature: 150°C Heating time: 2 hours The film thickness (unit: μm) of the ionizing radiation cured product was measured before and after heat treatment, and the remaining film rate (unit: %) defined by (thickness after heat treatment)/(thickness before heat treatment) was calculated. Table 2 shows the film thickness and residual film ratio before and after heat treatment.

[Table 2]

As shown in Table 2, in Example 1 to Example 6 and Comparative Example 2 and Comparative Example 3, the remaining film rate is more than 80%, and especially the remaining film rate of Example 1 and Example 5 and Comparative Example 2 and Comparative Example 3 is more than 90%, which is particularly good.

(Evaluation Example 3) Evaluation of Solubility The resin compositions of Examples 1 to 6 and Comparative Examples 2 and 3 were applied and cured under the same conditions as in Evaluation Example 2 to obtain ionizing radiation cured products. In addition, thereafter, heat treatment was performed on the obtained ionizing radiation cured product under the same conditions as those in Evaluation Example 2. In addition, in Comparative Example 1, even if the exposure amount was set to 2000 mJ/cm ² , the non-viscous state was not achieved, so it was not used as an evaluation object, and the solubility evaluation was not performed. Next, a mixed solution of water and ethanol (EtOH) (mixing ratio: water/EtOH=25/75) was prepared as a solution, and the heat-treated ionizing radiation-cured product was immersed in the solution at 25° C. to observe the dissolved state of the ionizing radiation-cured product. The evaluation criteria are as follows. A: Dissolved within 5 minutes B: Dissolved within 5 minutes to 15 minutes C: Not dissolved after 15 minutes

[table 3]

In the ionizing radiation-cured products of Examples 1 to 6, the ionizing radiation-cured products after heat treatment were dissolved within 5 minutes and were good. On the other hand, in the ionizing radiation-cured products of Comparative Example 2 and Comparative Example 3, the ionizing radiation-cured products after heat treatment were not dissolved even after 15 minutes after immersion.

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Claims (12)

A polymeric composition, characterized in that it is used to form a heat-resistant soluble member, and contains: a monofunctional acrylic compound selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, N-hydroxyethyl (meth)acrylamide, polyoxyethylene monoacrylate, N-isopropylacrylamide, N,N-dimethyl One or more compounds from the group consisting of (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide and (meth)acrylmorpholine; monofunctional N-vinyl compounds, wherein the monofunctional N - Vinyl compounds excluding N-vinyl-2-pyrrolidone; and polymerization initiators that generate radicals by irradiation with ionizing radiation. The polymerizable composition as described in claim 1 of the patent application, wherein the monofunctional N-vinyl compound is a monofunctional N-vinylamide compound. The polymerizable composition as described in item 2 of the patent application, wherein the monofunctional N-vinylamide compound comprises one or more compounds selected from N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam. The polymerizable composition described in any one of the first to third items of the scope of the patent application has a viscosity of 15mPa at 60°C. below s. Polymerization as described in any one of item 1 to item 3 of the scope of application A composition containing 30% by mass or less of a volatile solvent relative to the entire polymerizable composition. An inkjet ink, comprising the polymerizable composition described in any one of the first to fifth items of the patent application. A heat-resistant soluble member comprising an ionizing radiation-cured product of the polymerizable composition described in any one of claims 1 to 5, wherein the heat-resistant soluble member can be dissolved in an aqueous solution even after being heated at 150°C for 2 hours in the atmosphere. The heat-resistant soluble member as described in claim 7 of the patent application, wherein the water-based solution is a water-alcohol mixture. The heat-resistant soluble member according to claim 7 or claim 8, wherein the pH of the aqueous solution is 8 or less. A three-dimensional structure with a support part, characterized in that it includes: a body part providing a three-dimensional shape; and a support part carrying the body part, and the support part includes the heat-resistant soluble member according to any one of items 7 to 9 in the scope of the patent application. A method for manufacturing a three-dimensional figure, comprising: a forming step of using a first liquid composition for forming a body part and a second liquid composition for forming a support part, and forming a three-dimensional structure with a support part in a state in which the body part is supported by the support part by a build-up method, the body part provides the three-dimensional figure, and the support part carries the body part; In the removing step, the supporting part of the three-dimensional structure with a supporting part is dissolved and removed by using an aqueous solution to obtain the three-dimensional shape, the second liquid composition includes the polymerizable composition described in any one of the 1st to 5th items of the patent application, and the support part contains the heat-resistant soluble member described in any one of the 7th to 9th items of the patent application. The method for manufacturing a three-dimensional shape as described in claim 11 of the patent application, which further includes a heating step after the shaping step and before the removal step, and the heating step heats the three-dimensional structure with a support portion to change the physical properties of the main body.