KR20210020871A - Polymerizable composition, inkjet ink, heat-resistant soluble member, three-dimensional structure with support, and method for producing three-dimensional sculpture - Google Patents

Abstract

A polymerizable composition capable of forming a cured product (a heat-resistant soluble member) that properly maintains solubility in an aqueous solution even after heat treatment, comprising a monofunctional acrylic acid ester compound and a monofunctional acrylamide compound A polymerization characterized by containing a monofunctional acrylic compound consisting of one or two or more compounds selected from the group, a monofunctional N-vinyl compound, and a polymerization initiator that generates radicals by irradiation with ionizing radiation. Sex compositions are provided.

Description

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

The present invention uses a polymerizable composition, an inkjet ink composed of the polymerizable composition, a heat-resistant soluble member composed of an ionizing radiation cured product of the polymerizable composition, and the aforementioned heat-resistant soluble member as a support part. It relates to a three-dimensional structure provided with a support, and a method for producing a three-dimensional structure using the polymerizable composition.

In recent years, as a method of manufacturing a three-dimensional structure, raw data obtained by slicing three-dimensional CAD data of a product called lamination molding method and overlapping thin plates are created, and radical polymerizable compounds or cationic polymerizable compounds are used. An optical three-dimensional shaping method has been proposed in which a three-dimensional structure having a desired shape is produced by repeating the step of irradiating light and curing a thin film made of the used photocurable resin composition a plurality of times. As a device for manufacturing three-dimensional structures by the optical three-dimensional modeling method, cheaper ones are appearing on the market. For example, it is expected that the use can be expanded so that it can be used not only in industrial applications such as the manufacture of prototypes, but also in general homes. Has become. For example, in such a lamination molding method, by using a specific radically polymerizable compound, the dimensional accuracy and productivity of the molding can be improved (Patent Document 1).

Here, if the shape of the three-dimensional structure (stereoscopic object) finally manufactured using the optical three-dimensional modeling method is complicated, it is difficult to support the self-weight at the stage of the structure (body part) produced by the optical three-dimensional modeling method. There is a case of going through the state. In such a case, from the viewpoint of maintaining the shape of the body portion, the support portion for supporting the body portion may be formed by an optical three-dimensional shaping method together with the body portion. The three-dimensional structure with a support, which is formed of a body portion and a support, thus obtained, can be obtained as a final step by removing the support from the three-dimensional structure with a support. As a composition capable of forming a support in such a manufacturing method, a photocurable liquid resin composition having good solubility in an aqueous solution after curing is disclosed, for example, in Patent Document 2.

On the other hand, in order to use a three-dimensional sculpture produced by a manufacturing method including an optical three-dimensional sculpture as a working model, it is required to have sufficient mechanical strength and heat resistance to withstand the conditions of use. For this purpose, post-cure, such as heating or light irradiation, is sometimes performed on a structure (body part) created by an optical three-dimensional shaping method (for example, Patent Document 3), and post-baking, which is a post-cure by heating, is performed. A photosensitive resin composition has also been proposed (for example, Patent Document 4).

Japanese Laid-Open Patent No. 2008-189782 Japanese Laid-Open Patent No. 2010-155889 Japanese Patent Laid-Open Publication No. 2013-023574 Japanese Laid-Open Patent No. 2013-194205

Even in the case of forming the body portion using a composition based on post-baking as shown in Patent Literature 4, it may be necessary to form a support as described in Patent Literature 2 by an optical three-dimensional shaping method. At this time, if the support portion is removed from the three-dimensional structure with the support portion formed by the optical three-dimensional shaping method before post-baking, the body portion may not be able to withstand its own weight and may be damaged. Therefore, when a three-dimensional structure with a support portion having a body portion formed from a composition on the premise of post-baking is formed by an optical three-dimensional shaping method, the support portion is also post-baked. This post-baking may have an effect on the solubility of the support portion, but sufficient studies on this point have not been made.

In this way, even when a treatment (heat treatment) to increase the temperature of the cured ionizing radiation obtained by irradiating the polymerizable composition with ionizing radiation is performed, appropriate solubility in an aqueous solution is required for the cured ionizing radiation after the heat treatment. There is. This heat treatment is sometimes performed without the purpose of actively heating the ionizing radiation cured product. As a specific example of such a case, for the purpose of heating members (solder, etc.) provided in other portions of the substrate on which the cured ionizing radiation is formed, the entire substrate is heated. In addition, when the film formation by the dry process is performed on the substrate on which the cured ionizing radiation product is formed, the temperature of the cured ionizing radiation product is increased because the deposited material (metal, etc.) comes into contact with the cured ionizing radiation at a high temperature. Can be lifted. In the present specification, the term "ionizing radiation" refers to electromagnetic waves such as γ-rays, X-rays, ultraviolet rays, and visible light, and energy that can generate radicals by irradiating or colliding with a polymerization initiator such as electrons and protons and ions. It means the generic term of the circle.

In view of these current circumstances, an object of the present invention is to provide a polymerizable composition capable of forming a cured product (heat-resistant soluble member) that adequately maintains solubility in an aqueous solution even through heat treatment such as post-baking. . The present invention provides an inkjet ink comprising the above polymerizable composition, a heat-resistant soluble member comprising a cured product of the polymerizable composition, a three-dimensional structure with a support having a support comprising the heat-resistant soluble member, and the polymerizable It is an object of the present invention to provide a method for producing a three-dimensional sculpture using a composition.

In order to solve the above problems, the present invention provided is as follows.

[1] A polymerizable composition for forming a heat-resistant soluble member, comprising a monofunctional acrylic compound consisting of one or two or more compounds selected from the group consisting of a monofunctional acrylic ester compound and a monofunctional acrylamide compound, and a monofunctional N -A polymerizable composition comprising a 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 above [2], wherein the monofunctional N-vinylamide compound is composed of one or two or more compounds selected from N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam. The polymerizable composition described in.

[4] The polymerizable composition according to any one of [1] to [3], wherein the viscosity at 60°C is 15 mPa·s or less.

[5] The polymerizable composition according to any one of [1] to [4], containing 30 mass% or less of a volatile solvent with respect to the entire polymerizable composition.

[6] An ink jet 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], which is soluble in an aqueous solution even after being heated at 150°C for 2 hours in air. Absence of availability.

[8] The heat-resistant soluble member according to [7], wherein the aqueous solution is a water-alcohol mixture. The above-described alcohol is preferably an alcohol having miscibility with water, and 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 support portion comprising a body portion for providing a three-dimensional sculpture and a support portion for supporting the body portion, wherein the support portion is made of the heat-resistant soluble member according to any one of [7] to [9] above. Attachment three-dimensional structure.

[11] A method of manufacturing a three-dimensional sculpture, comprising: a first liquid composition for forming a body portion providing the three-dimensional sculpture and a second liquid composition for forming a support portion supporting the body portion, wherein the body portion is A shaping step of forming a three-dimensional structure with a support in a state supported by a laminated molding method, and a removal step of dissolving and removing the support of the three-dimensional structure with a support with an aqueous solution to obtain the three-dimensional sculpture, The second liquid composition is composed of the polymerizable composition according to any one of [1] to [5], and the support portion is a heat-resistant soluble member according to any one of [7] to [9]. A method for producing a three-dimensional sculpture, characterized in that consisting of.

[12] The method for producing a three-dimensional sculpture according to [11], further comprising a heating step of heating the three-dimensional structure with a support to change physical properties of the main body after the molding step and before the start of the removal step.

According to the present invention, there is provided a polymerizable composition capable of forming a cured product (heat-resistant soluble member) that adequately maintains solubility in an aqueous solution even through a heating step. Further, according to the present invention, a three-dimensional structure with a support having a support made of an inkjet ink made of the polymerizable composition, an ionizing radiation cured product of the polymerizable composition, and a support made of the heat resistant soluble member, And a method of manufacturing a three-dimensional sculpture.

Hereinafter, a method of manufacturing a polymerizable composition, inkjet ink, heat-resistant soluble member, a three-dimensional structure with a support, and a three-dimensional sculpture according to an embodiment of the present invention will be described.

The polymerizable composition according to an embodiment of the present invention is for forming a heat-resistant soluble member, and is a monofunctional acrylic type consisting of one or two or more compounds selected from the group consisting of a monofunctional acrylic acid ester compound and a monofunctional acrylamide compound. It contains a compound, a monofunctional N-vinyl compound, and a polymerization initiator that generates radicals by irradiation with ionizing radiation.

The monofunctional acrylic compound is composed of one or two or more compounds selected from the group consisting of a monofunctional acrylic acid ester compound and a monofunctional acrylamide compound. The monofunctional acrylic acid ester compound is a compound having a partial structure based on (meth)acrylic acid ester or (meth)acrylic acid ester, and having one ethylenic double bond in a molecule. And in this specification, in order to represent one or both of "acrylic acid" and "methacrylic acid", it may express like "(meth)acrylic acid". Terms related to (meth)acrylic acid, for example, "(meth)acrylate" and "(meth)acryloxy" also have the above meanings.

From the viewpoint of securing the solubility of the cured ionizing radiation obtained by irradiating the polymerizable composition with an aqueous solution of an ionizing radiation, the monofunctional acrylic acid ester compound preferably has a hydroxyl group (-OH). As specific examples of such a hydroxyl group (-OH)-containing monofunctional acrylic acid ester compound, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylic Rate, 1,4-cyclohexanedimethanol mono (meth)acrylate, N-hydroxyethyl (meth)acrylamide, and polyoxyethylene monoacrylate. Among these, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are preferable from the viewpoint of being relatively difficult to volatilize, and thus ensuring composition stability of the polymerizable composition, and the resulting cured ionizing radiation From the viewpoint of the ease of dissolution in an aqueous solution, 4-hydroxybutyl acrylate is particularly preferred.

As specific examples of monofunctional acrylamide compounds, N-isopropylacrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethyl (meth) Acrylamide, N,N-diethylaminoethyl (meth)acrylamide, and N,N-dimethylaminopropyl (meth)acrylamide and (meth)acryloylmorpholine. Among these, (meth)acryloylmorpholine is preferred from the viewpoint of being relatively difficult to volatilize, and therefore, easily securing composition stability of the polymerizable composition.

The monofunctional N-vinyl compound is a compound having a structure in which an ethylenic unsaturated group is bonded to an amino group, and the amino group may constitute a carbonyl group and an amide bond. In the present specification, a monofunctional compound in which the amino group to which such an ethylenically unsaturated group is bonded constitutes an amide bond is also referred to as a "monofunctional N-vinylamide compound". The monofunctional N-vinylamide compound is a preferred example of a monofunctional N-vinyl compound. Specific examples of the monofunctional N-vinylamide compound include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam, and the like, and single tubes other than monofunctional N-vinylamide compounds Specific examples of the rhomboid N-vinyl compound include 1-vinylimidazole and 9-vinyl carbazole. Among these compounds, N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam and 1-vinylimidazole from the viewpoint of the ease of dissolution of the obtained ionizing radiation cured product in an aqueous solution. It is preferred, and from the viewpoint of restriction on transport of the product, N-vinylformamide, N-vinylacetamide and N-vinyl-ε-caprolactam are particularly preferred.

The polymerization initiator can generate radicals by irradiation with ionizing radiation, and the type is not limited as long as it 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. For a non-limiting example, the content of the curing agent is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and particularly preferably 0.1 to 4 parts by weight based on the total amount of the polymerizable composition.

As specific examples of the polymerization initiator, benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethyl thioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropyl Benzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one , Camphorquinone, benzanthrone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- 1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, oxy-phenyl-acetic acid 2-(2-oxo-2 -Phenyl-acetoxy-ethoxy)-ethyl ester, oxy-phenyl-acetic acid 2-(2-hydroxy-ethoxy)-ethyl ester, oxy-phenyl-acetic acid 2-(2-oxo-2 -Phenyl-acetoxy-ethoxy)-ethyl ester and oxy-phenyl-acetic acid 2-(2-hydroxy-ethoxy)-ethyl ester mixture, phenylglyoxylic acid methyl ester, 4-dimethylaminobenzoic acid Ethyl, 4-dimethylaminobenzoic acid isoamyl, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 3, 3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-di (Methoxycarbonyl)-4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(tert-butylperoxy) Carbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(tert-butylperoxycarbonyl)benzophenone, 2-(4'-methoxystyrene Reel)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(triclo Romethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-di(ethoxycarbonyl) Methyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3- Bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole , 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole , 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-di Bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropi) O'Nyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3- (1H-pyrrol-1-yl)-phenyl) titanium, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These compounds may be used alone or in combination of two or more. Among them, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino Phenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine Oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, has high sensitivity to a UV-LED light source, and is preferable from the viewpoint of photocurability.

The polymerizable composition according to the present embodiment does not need to contain a volatile solvent substantially from the viewpoint of simplifying the formation process of the cured ionizing product, but may contain a volatile solvent from the viewpoint of adjusting the viscosity of the polymerizable composition, etc. . When used, the volatile solvent may be mixed with other compositions to form a polymerizable composition. In the case where the polymerizable composition contains a volatile solvent, the volatile solvent may initiate volatilization in a state in which the polymerizable composition is uncured, and at least by heating appropriately before, during, and/or after irradiation of ionizing radiation. It is preferable to volatilize at the stage where the radiation cured product is formed. If the non-volatile solvent remains excessively even 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 mechanical strength may decrease. Therefore, it is preferable that the content of the volatile solvent is 30 mass% or less with respect to the whole polymerizable composition.

As specific examples of the volatile solvent, diethyl ether, tetrahydrofuran, diphenyl ether, dimethoxybenzene, acetone, methanol, ethanol, isopropanol, butyl alcohol, tert-butyl alcohol, 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, 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, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2 -Ethyl methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 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 mono Butyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol Colmonomethyl 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, di Ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, tetraethylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, N- And methyl-2-pyrrolidone and dimethylimidazolidinone. These compounds may be used alone or in combination of two or more.

The polymerizable composition according to the present embodiment may contain other additives other than the above-described components. As specific examples of other additives, surfactants, polymerization inhibitors, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, fillers, pigments, dyes, etc. may be mentioned, but the scope does not depart from the spirit of the present invention. In the inside, it is possible to uniformly mix with other components, and it is not particularly limited as long as it can be properly cured. As a specific example, a filler made of light-transmitting particles such as silica particles may be mentioned. Such a filler can increase the mechanical strength of an ionizing radiation cured product without interfering with the curing of the polymerizable composition.

The polymerizable composition according to the present embodiment is supplied on a substrate by application, dropping, etc. during use, so that the polymerizable composition has a film-like shape or a predetermined pattern on the substrate. do. From the viewpoint of enhancing the ease of supply of the polymerization composition onto such a substrate, the viscosity at 25°C of the polymerizable composition according to the present embodiment may be preferably 100 mPa·s or less. Particularly, in the case where the polymerization composition is supplied onto the substrate by an ink jet printer, it is preferable to satisfy the above viscosity range. In addition, the inkjet ink made of the resin composition according to the present embodiment preferably has a viscosity of 15 mPa·s or less at a discharge temperature (eg, 60° C.), and particularly preferably 10 mPa·s or less.

The polymerizable composition according to the present embodiment is cured by irradiation with ionizing radiation to become an ionizing radiation cured product. Such an 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, and more preferably a mixed solution of a protonic polar solvent such as alcohol and water. From the viewpoint of enhancing the uniformity of the liquid mixture, it is preferable that the alcohol has high solubility in water, that is, miscibility with water. The content of water in the aqueous solution is appropriately set depending on the kind of components other than water contained in the aqueous solution and the composition of the cured ionizing radiation. When the aqueous solution consists of a water-alcohol mixture that is a mixture of water and alcohol, and the alcohol contained in the water-alcohol mixture is made of a substance having 4 or less carbon atoms such as ethanol or isopropanol, the content of alcohol is 25 In some cases, it is preferable to be at least 90% by volume, in some cases, it is more preferable to be at least 50% by volume and not more than 85% by volume, and in some cases, it is particularly preferable that it is 70% by volume or more and 80% by volume or less.

The aqueous solution may contain an organic solvent other than alcohol. As such an organic solvent, an aprotic organic solvent such as N-methylpyrrolidone, acetone, acetonitrile, and dimethyl sulfoxide is exemplified. From the viewpoint of reducing the environmental load, the content of the organic solvent other than alcohol in the aqueous solution is preferably contained in an amount of 20% by volume or less of the total amount of the aqueous solution.

In some cases, the aqueous solution is preferably alkali-free, that is, non-alkali. In order to make the aqueous solution alkaline, when the aqueous solution contains an inorganic alkaline substance such as sodium hydroxide or an organic alkaline substance such as tetramethylammonium hydroxide, the handleability of the aqueous solution may decrease. In addition, since a general alkali-based solution has a pH of 9 or more, the aqueous solution that is alkali-free in the present specification means that the pH is less than 9. From the viewpoint of making it more reliably alkali-free, the pH of the aqueous solution is preferably 8 or less, and more preferably 7.5 or less.

The ionizing radiation cured product according to the present embodiment is hardly changed in shape even when heated. For example, in the case where the cured ionizing radiation according to the present embodiment has a film shape having a thickness of 13 to 18 μm formed on a glass substrate, even when heated at 150° C. for 2 hours in air, (thickness after heat treatment)/ The residual film ratio defined by (thickness after heat treatment) is 80% or more, 85% or more in a preferred example, and 90% or more in a more preferred example. Therefore, even when a soluble member made of an ionizing radiation cured product is heated, it is difficult to change the shape of the soluble member.

Hereinafter, a method of producing a three-dimensional object using the polymerizable composition according to the present embodiment will be described. The cured ionizing radiation obtained by irradiating the polymerizable composition according to the present embodiment with ionizing radiation, as described above, can adequately maintain the solubility in an aqueous solution even when heated for 2 hours at about 150°C. It can be used as a fusible member. Therefore, when performing three-dimensional shaping to form a three-dimensional structure using a polymerizable composition, a heat-resistant soluble member made of the cured ionizing radiation according to the present embodiment is preferable as a support for supporting the structure in the manufacturing process.

Specifically, the manufacturing method of the three-dimensional structure includes the following shaping process and removal process, and further includes a heating process if necessary.

First, in the shaping process, a first liquid composition for forming a body portion providing a three-dimensional sculpture finally obtained by three-dimensional shaping and a second liquid composition for forming a support portion supporting the body portion are used, and the body portion is The three-dimensional structure with the support in the state supported by is formed by the lamination method.

The first liquid composition is a polyfunctional polymerizable material having a plurality of ethylenically unsaturated bonds, which is generally used in a lamination method, and against ionizing radiation (e.g., light from an LED lamp) used for curing. It contains a polymerization initiator with adequate sensitivity. The 1st liquid composition may contain a filler (inorganic particles, such as silica and titanium dioxide, as a specific example), as needed, and may contain paint, pigment, etc., and may be colored. The second liquid composition is made of the polymerizable composition according to the present embodiment described above.

It is preferable from the viewpoint of simplification of the manufacturing process 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 that becomes the body part, and the pattern of the second liquid composition becomes a cured product (heat resistance Available member).

In this way, when a three-dimensional structure with a support comprising a body portion and a support portion holding the body portion is obtained by the lamination molding method, the three-dimensional structure with the support portion is heated to perform a heating step of changing the physical properties of the body portion. Specific examples of the physical properties in this case include mechanical properties such as bending stiffness. As described above, since the first liquid composition for forming the body portion has a polymerizable material, the degree of polymerization can be further advanced by heating the cured product obtained by irradiation with ionizing radiation, thereby enhancing the mechanical properties described above. . As a result of improving the mechanical properties of the body portion by heating in this way, the rigidity of the body portion may be increased to the extent that support by the support portion is not required. By performing such a postcure of the main body by, for example, a patch treatment, it is possible to shorten the working time for the lamination molding method, thereby increasing the productivity of the three-dimensional sculpture in some cases.

Finally, a removal step of dissolving and removing the support portion of the three-dimensional structure with the support portion with an aqueous solution to obtain a three-dimensional object based on the body portion is performed. In the removal process, the above-described 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 with an aqueous solution. By spraying), only the support portion is selectively dissolved, and a three-dimensional structure based on the body portion is obtained as a three-dimensional sculpture.

Although the present invention has been described with reference to the above embodiments, the present invention is not limited to the above embodiments, and can be improved or changed within the scope of the purpose of improvement or the spirit of the present invention. For example, when the body portion has a hollow portion having an opening, an ionizing radiation cured product (heat-resistant fusible member) of the polymerizable composition according to the present invention is positioned to fill at least a part of the hollow portion When used to protect the wall portion constituting the hollow portion, the heat-resistant soluble member is a support portion according to an embodiment of the present invention.

Alternatively, the heat-resistant soluble member according to the present embodiment can also be used as a protective material or a temporary fixing material. For example, by providing a heat-resistant soluble member according to the present embodiment as a protective material on the surface of a member that is concerned about occurrence of defects such as cracks and fruits due to collision with other members, the member can be protected from defects. In addition, as another example, for a member having a portion that is easily displaced when an external force is applied and is likely to collide with another portion of the member (specific examples, such as a tongue or diaphragm), the displacement of that portion is suppressed. As much as possible, by temporarily fixing the portion using the heat-resistant soluble member according to the present embodiment, the member is not easily damaged even when an external force such as transport is applied. In this way, when protection or temporary fixing is not required, the member to be protected/temporarily fixed can perform its original function properly by dissolving and removing the heat-resistant soluble member according to the present embodiment.

[Example]

Hereinafter, the present invention will be described more specifically by examples and the like, but the scope of the present invention is not limited to these examples.

(Example 1)

Acryloylmorpholine (ACMO) is 7.06 parts by mass as a monofunctional acrylamide compound, a kind of monofunctional acrylic compound, N-vinylformamide (NVF) is 3.55 parts by mass as a monofunctional N-vinyl compound, and IRGACURE as a polymerization initiator A resin composition containing 1.27 parts by mass of 379EG (manufactured by BASF, hereinafter abbreviated as “IRG379”) and 0.0053 parts by mass of BYK342 (manufactured by Bicchemi Japan) as a surfactant was prepared. In the resin composition, the monofunctional acrylic compound and the monofunctional N-vinyl compound were equimolar (molar ratio of 1:1). In the following other Examples and Comparative Examples as well, the two types of compounds having ethylenically unsaturated bonds contained in the resin composition may have the same number of ethylenically unsaturated bonds of each compound (equal moles as the number of functional groups). , The content of each compound in the resin composition was set. In the resin composition, the polymerization initiator is an amount equivalent to 12% of the total mass part of the monofunctional acrylic compound and the monofunctional N-vinyl compound, and the surfactant is the total mass of the monofunctional acrylic compound and the monofunctional N-vinyl compound It was an amount equivalent to 500 ppm of negative. Also in the following other Examples and Comparative Examples, the content of the polymerization initiator and the content of the surfactant were set so as to satisfy the relationship of the total mass parts described above, respectively. The viscosity of the obtained resin composition at 25°C was 10.4 mPa·s, and at 30°C, it was 8.8 mPa·s. Therefore, the resin composition according to Example 1 was particularly preferable as an ink jet ink when it was 30°C or higher.

(Example 2)

7.06 parts by mass of acryloylmorpholine (ACMO) as a monofunctional acrylamide compound, which is a kind of monofunctional acrylic compound, 6.96 parts by mass of N-vinyl-ε-caprolactam (NVC) as a monofunctional N-vinyl compound, A resin composition containing 1.68 parts by mass of IRG379 as a polymerization initiator and 0.0070 parts by mass of BYK342 as a surfactant was prepared. The viscosity of the obtained resin composition at 25°C was 10.8 mPa·s, and at 30°C, it was 9.0 mPa·s. Therefore, the resin composition according to Example 2 was particularly preferable as an ink jet ink when it was 30°C or higher.

(Example 3)

Acryloylmorpholine (ACMO) is 7.06 parts by mass as a monofunctional acrylamide compound, a kind of monofunctional acrylic compound, N-vinylacetamide (NVAc) is 4.26 parts by mass as a monofunctional N-vinyl compound, and IRG379 as a polymerization initiator A resin composition containing 1.36 parts by mass and 0.0057 parts by mass of BYK342 as a surfactant was prepared. The viscosity at 25° C. of the obtained resin composition was 6.8 mPa·s. Therefore, the resin composition according to Example 3 was particularly preferable as an ink jet ink when it was 25°C or higher.

(Example 4)

Acryloylmorpholine (ACMO) is 7.06 parts by mass as a monofunctional acrylamide compound, a kind of monofunctional acrylic compound, N-vinylimidazole (NVIM) is 4.71 parts by mass as a monofunctional N-vinyl compound, and as a polymerization initiator A resin composition containing 1.41 parts by mass of IRG379 and 0.0059 parts by mass of BYK342 as a surfactant was prepared. The viscosity at 25°C of the obtained resin composition was 7.5 mPa·s. Therefore, the resin composition according to Example 4 was particularly preferable as an ink jet ink when it was 25°C or higher.

(Example 5)

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, interface A resin composition containing 0.0054 parts by mass of BYK342 as an activator was prepared. The viscosity at 25°C of the obtained resin composition was 9.0 mPa·s. Therefore, when the resin composition according to Example 5 was 25°C or higher, it was particularly preferable as an ink jet ink.

(Example 6)

6.36 parts by mass of diethylacrylamide (DEAA) as a monofunctional acrylamide compound, which is a kind of monofunctional acrylic compound, 3.55 parts by mass of N-vinylformamide (NVF) as a monofunctional N-vinyl compound, and IRG379 as a polymerization initiator. A resin composition containing 1.19 parts by mass and 0.0050 parts by mass of BYK342 as a surfactant was prepared. The viscosity of the obtained resin composition at 25°C was 3.7 mPa·s. Therefore, when the resin composition according to Example 6 was 25°C or higher, it was particularly preferable as an ink jet ink.

(Comparative Example 1)

Acryloylmorpholine (ACMO) is 7.06 parts by mass as a monofunctional acrylamide compound, which is a kind of monofunctional acrylic compound, and 4-hydroxybutyl acrylate (4HBA) is 7.21 parts by mass as a monofunctional acrylic compound, and IRG379 as a polymerization initiator. A resin composition containing 1.71 parts by mass and 0.0071 parts by mass of BYK342 as a surfactant was prepared. The viscosity of the obtained resin composition at 25°C was 12.8 mPa·s, and at 40°C, it was 7.9 mPa·s. Therefore, the resin composition according to Comparative Example 1 is particularly preferable as an ink jet ink when it is 40°C or higher.

(Comparative Example 2)

As a monofunctional acrylamide compound, which is a kind of monofunctional acrylic compound, 7.06 parts by mass of acryloylmorpholine (ACMO), 6.53 parts by mass of polyethylene glycol #400 diacrylate (9EG-A) as a bifunctional acrylic compound, polymerization A resin composition containing 1.21 parts by mass of IRG379 as an initiator and 0.0071 parts by mass of BYK342 as a surfactant was prepared. The molar ratio of the monofunctional acrylic compound and the bifunctional acrylic compound in the resin composition was 1:0.5 so that the number of functional groups was the same. The viscosity of the obtained resin composition at 25°C was 52.8 mPa·s, and at 60°C, it was 14.9 mPa·s. Therefore, the resin composition according to Comparative Example 2 is preferably 60°C or higher as an ink jet ink.

(Comparative Example 3)

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, and 1.00 mass of IRG379 as a polymerization initiator A resin composition containing 0.0042 parts by mass of BYK342 as part and 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 was the same. The viscosity of the obtained resin composition at 25°C was 52.8 mPa·s, and at 60°C, it was 14.6 mPa·s. Therefore, the resin composition according to Comparative Example 3 is preferably 60°C or higher as an ink jet ink.

(Evaluation Example 1) Evaluation of photocurability

Each of the resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 was applied on a glass substrate by spin coating for 10 seconds to obtain a coating film. The coating film of the obtained resin composition was cured under the following conditions to obtain an ionizing radiation cured product.

UV irradiation device: "ASM1503NM-UV-LED" manufactured by Asumi Kiken

Lamp wavelength: 365nm

Exposure ^{dose: 500mJ / cm 2, 1000mJ /} cm 2, 1500mJ / cm 2, 2000mJ / cm 2

Intensity: 700mW / cm ²

For the measurement of UV light, a UV monitor ("UV-Pad" manufactured by Opsytec) measuring UVA (315 to 400 nm) was used.

The resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 3 were applied and exposed to form a film of an ionizing radiation cured product on a glass substrate. After that, the surface of the cured film was touched with a finger, and the exposure amount to be completely non-sticky was investigated. Table 1 shows the results.

[Table 1]

As shown in Table 1, in Examples 1 to 6 and Comparative Examples 2 and 3, the exposure amount in the non-sticky state is 1500 mJ/cm ² or less, and in particular, Examples 1, 3, 4 and 6 and comparison Examples 2 and 3 were particularly good as ^{500 mJ/cm 2.} In contrast, in Comparative Example 1, ^{even when the exposure amount was 2000 mJ/cm 2} , the state of no stickiness was not reached, and the curing of the resin composition was not completed.

(Evaluation Example 2) Evaluation of residual film rate after heat treatment

Each of the resin compositions according to Examples 1 to 6 and Comparative Examples 2 and 3 was applied and cured under the same conditions as in Evaluation Example 1 to obtain a film of an ionizing radiation cured product. As the photocuring condition, exposure was performed with the exposure amount confirmed in Evaluation Example 1 and in a state where there was no stickiness. Thereafter, the obtained ionizing radiation cured film was further subjected to heat treatment under the following conditions. In addition, in Comparative Example 1 ^{, even if the exposure amount was 2000 mJ/cm 2} , the state of no stickiness was not reached, so that it was not subject to evaluation, and no additional heat treatment was performed.

Clean oven: ``DT610'' manufactured by Yamato Science Corporation

Temperature: 150℃

Heating time: 2 hours

Before and after the heat treatment, the film thickness (unit: µm) of the ionizing radiation cured product was measured, and the residual film rate (unit: %) defined by (thickness after heat treatment)/thickness after heat treatment) was calculated. The film thickness and residual film ratio before and after heat treatment are shown in Table 2.

[Table 2]

As shown in Table 2, in Examples 1 to 6 and Comparative Examples 2 and 3, the residual film ratio is 80% or more, and in particular, in Examples 1 and 5 and Comparative Examples 2 and 3, the residual film ratio is 90% or more. It was particularly good.

(Evaluation Example 3) Evaluation of solubility

Each of the resin compositions according to Examples 1 to 6 and Comparative Examples 2 and 3 was applied and cured under the same conditions as in Evaluation Example 2 to obtain an ionizing radiation cured product. Further, after that, the obtained cured ionizing radiation was subjected to heat treatment under the same conditions as in Evaluation Example 2. In addition, in Comparative Example 1 ^{, even when the exposure amount was 2000 mJ/cm 2} , the state of no stickiness was not reached, and the evaluation was made out of the evaluation object, and solubility was not evaluated.

Next, a mixed solution of water and ethanol (EtOH) (mixing ratio: water/EtOH = 25/75) was prepared as a dissolving solution, and the cured ionizing radiation product after heat treatment was immersed in the solution at 25° C. Observed.

The evaluation criteria are as follows.

A: dissolved within 5 minutes

B: Dissolved in the period up to 15 minutes after the lapse of 5 minutes

C: did not dissolve even after 15 minutes

[Table 3]

In the ionizing radiation cured product according to Examples 1 to 6, the ionizing radiation cured product after the heat treatment dissolved within 5 minutes and was good. In contrast, in the cured ionizing radiation according to Comparative Examples 2 and 3, the cured ionizing radiation after heat treatment did not dissolve even after 15 minutes elapsed after immersion.

Claims (12)

As a polymerizable composition for forming a heat-resistant soluble member,
A monofunctional acrylic compound consisting of one or two or more compounds selected from the group consisting of a monofunctional acrylic acid ester compound and a monofunctional acrylamide compound,
Monofunctional N-vinyl compound, and
Polymerization initiator that generates radicals by irradiation with ionizing radiation
Containing, the polymerizable composition. The method of claim 1,
The polymerizable composition, wherein the monofunctional N-vinyl compound is a monofunctional N-vinylamide compound. The method of claim 2,
The polymerizable composition, wherein the monofunctional N-vinylamide compound is composed of one or two or more compounds selected from N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam. The method according to any one of claims 1 to 3,
The polymerizable composition, wherein the viscosity at 60°C is 15 mPa·s or less. The method according to any one of claims 1 to 4,
A polymerizable composition containing 30% by mass or less of a volatile solvent with respect to the entire polymerizable composition. An ink jet ink comprising the polymerizable composition according to any one of claims 1 to 5. As a heat-resistant soluble member comprising an ionizing radiation cured product of the polymerizable composition according to any one of claims 1 to 5,
A heat-resistant soluble member that is soluble in an aqueous solution even after being heated at 150°C for 2 hours in the air. The method of claim 7,
The aqueous solution is a water-alcohol mixture, heat-resistant soluble member. The method according to claim 7 or 8,
The aqueous solution has a pH of 8 or less, a heat-resistant soluble member. A body portion for providing a three-dimensional sculpture and a support portion for supporting the body portion,
The three-dimensional structure with a support, wherein the support is made of the heat-resistant soluble member according to any one of claims 7 to 9. As a method of manufacturing a three-dimensional sculpture,
Using a first liquid composition for forming a body portion providing the three-dimensional sculpture and a second liquid composition for forming a support portion supporting the body portion, wherein the body portion is supported by the support portion. A molding step of forming a three-dimensional structure with a support by a lamination molding method, and
A removal step of dissolving and removing the support portion of the three-dimensional structure with a support portion with an aqueous solution to obtain the three-dimensional structure,
The second liquid composition is made of the polymerizable composition according to any one of claims 1 to 5, and the support part is made of the heat-resistant soluble member according to any one of claims 7 to 9, Method of manufacturing three-dimensional sculpture The method of claim 11,
After the molding process and before the start of the removal process, the method of manufacturing a three-dimensional sculpture further comprising a heating step of heating the three-dimensional structure with the support to change physical properties of the body part.