JP2019059101A - Ink composition for three-dimensional molding, ink cartridge for three-dimensional molding, and three-dimensional molding apparatus - Google Patents

Abstract

To provide a three-dimensional molding ink composition which can obtain a cured product of an odor-suppressed ink as compared to a case where a perfume having no ring structure is contained.SOLUTION: An ink composition for three-dimensional molding comprises a polymerizable compound having a ring structure, and a perfume having a ring structure. It is preferable that the ring structure contained in the polymerizable compound and the ring structure contained in the perfume be the same ring structure or a ring structure having a stereoisomer relationship with each other.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an ink composition for three-dimensional shaping, an ink cartridge for three-dimensional shaping, and a three-dimensional shaping apparatus.

  The three-dimensional modeling apparatus is also called a 3D printer. As a three-dimensional modeling apparatus, for example, an ink composition for three-dimensional modeling is disposed using an inkjet method according to three-dimensional cross-sectional shape data, and curing with ultraviolet light is repeated to three-dimensionally model (for example, industrial products An apparatus for producing parts such as a toy, a toy such as a doll, etc.) is known.

In the three-dimensional structure, for example, a curable ink such as an ultraviolet curable ink is used.
Here, in the curable ink used for forming a conventional flat image, the odor of the ink derived from the polymerizable compound (monomer) used for the effect can be reduced by using a compound such as a fragrance together. It is being considered.

  For example, Patent Document 1 discloses “ink for inkjet recording characterized by the addition of a perfume”.

  Patent Document 2 is characterized in that “an actinic radiation curable composition containing a photopolymerizable compound and a photopolymerization initiator, contains at least one selected from a deodorant, a fragrance and an antioxidant. Actinic radiation curable compositions are disclosed.

  Patent Document 3 discloses "an ink composition characterized by containing a) a polymerizable compound, b) a polymerization initiator, c) a colorant, and d) a perfume.

JP-A-59-145263 Patent 2006-124636 gazette JP, 2006-316115, A

In the ink composition for three-dimensional formation (hereinafter, also simply referred to as "ink"), a three-dimensional object is obtained by laminating a cured product of the ink.
At the time of manufacturing a three-dimensional structure, a method of curing (provisionally curing) each layer laminated by irradiation with light (for example, ultraviolet light (UV)) and laminating, and performing complete curing by heat etc. after the lamination is finished, etc. Has been done.
Here, in the production of a three-dimensional structure, the layer of the cured ink has a thickness rather than a planar image, and the thickness of each layer is increased from the viewpoint of improving the formation speed of the structure. Is required.
However, as the thickness of the layer increases, the amount of monomer remaining without polymerization at the time of temporary curing increases, and odor derived from the monomer is more likely to be generated compared to the case of forming a flat image.
Therefore, even if a compound such as a perfume is added as described in Patent Documents 1 to 3, the odor is more likely to be generated in a three-dimensional structure than a plane image in a three-dimensional structure, and therefore the odor of the cured product obtained by temporary curing There were cases where suppression was insufficient.

  Therefore, the object of the present invention is to provide a cured product of an ink in which the odor is suppressed when light is temporarily cured, as compared to the case where only a fragrance having no ring structure is contained as a fragrance. An ink composition is provided.

  The above-mentioned subject is solved by the following means. That is,

The invention according to claim 1 is a polymerizable compound having a ring structure,
And a perfume having a ring structure.

The invention according to claim 2 is characterized in that the ring structure contained in the polymerizable compound and the ring structure contained in the perfume have the same ring structure or have a stereoisomer relationship with each other. The ink composition for three-dimensional modeling according to claim 1, which is

The invention according to claim 3 is the three-dimensional structure according to claim 2, wherein each of the ring structure contained in the polymerizable compound and the ring structure contained in the perfume is an alicyclic structure. Ink composition.

The invention according to claim 4 is the ink according to claim 3, wherein at least one of the ring structure contained in the polymerizable compound and the ring structure contained in the perfume is an isobornyl ring structure. Composition.

The invention according to claim 5 is that the polymerizable compound is an ester compound of (meth) acrylic acid and an alcohol compound having a ring structure, and the perfume is a carboxylic acid compound and an alcohol compound having a ring structure. The ink composition for three-dimensional modeling according to any one of claims 1 to 4, which is an ester compound.

The invention according to claim 6 is the ink composition for three-dimensional modeling according to claim 5, wherein the polymerizable compound is isobornyl (meth) acrylate, and the perfume is isobornyl acetate.

In the invention according to claim 7, the content of the perfume is 0.7% by mass or more and 2.5% by mass or less with respect to the total mass of the ink composition. The ink composition for three-dimensional modeling as described in 4.

The invention according to claim 8 is an ink cartridge for three-dimensional formation containing the ink composition for three-dimensional formation according to any one of claims 1 to 7.

The invention according to claim 9 is a discharge part that accommodates the ink composition for three-dimensional formation according to any one of claims 1 to 7 and discharges the ink composition for three-dimensional formation;
A light irradiator that emits light for curing the discharged three-dimensional modeling ink composition;
3D modeling device equipped with

  According to the invention as set forth in claim 1 or 5, the cured product of the ink in which the odor is suppressed can be obtained when it is temporarily cured by light as compared with the case where only the perfume having no ring structure is contained as the perfume. An ink composition for three-dimensional shaping is provided.

  According to the invention as set forth in claim 2 or 3, the temporary curing is carried out by light as compared with the case where the ring structure contained in the polymerizable compound is an isobornyl ring and the ring structure contained in the perfume is a benzene ring. In this case, there is provided a three-dimensional shaping ink composition which can obtain a cured product of the ink in which the odor is suppressed.

  According to the invention of claim 4, compared with the case where one of the ring structure contained in the polymerizable compound and the ring structure contained in the fragrance does not contain the isobornyl ring, the odor is temporarily cured by light. Provided is a three-dimensional shaping ink composition which can obtain a cured product of suppressed ink.

  According to the invention as set forth in claim 6, when the ring structure contained in the polymerizable compound is an isobornyl ring and the ring structure contained in the perfume is a bornyl ring, the case is temporarily cured with light Further, there is provided a three-dimensional shaping ink composition capable of obtaining a cured product of the ink in which the odor is suppressed.

  According to the invention as set forth in claim 7, a cured product of the ink in which the odor is suppressed can be obtained when it is cured by light as compared with the case where the content of the perfume is 0.7% by mass. An ink composition for three-dimensional shaping is provided.

  According to the invention as set forth in claim 8, compared to the case where only the perfume having no ring structure is contained as the perfume, three-dimensional shaping is possible in which a cured product of the ink in which the odor is suppressed is obtained when cured by light. Ink cartridge is provided.

  According to the invention as set forth in claim 9, compared with the case where only the perfume having no ring structure is contained as the perfume, three-dimensional shaping that a cured product of the ink in which the odor is suppressed is obtained when it is cured by light. An apparatus is provided.

It is a schematic block diagram which shows an example of the three-dimensional shaping apparatus which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional structure which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional structure which concerns on this embodiment. It is process drawing which shows an example of the manufacturing method of the three-dimensional structure which concerns on this embodiment.

Hereinafter, an embodiment which is an example of the present invention will be described.
In addition, the description of "mass part" and "mass%" is respectively synonymous with "weight part" and "weight%."
In the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Means

(Ink composition for three-dimensional modeling)
The three-dimensional structure forming ink composition according to the present embodiment includes a polymerizable compound having a ring structure, and a fragrance having a ring structure.

At the time of production of a three-dimensional object, each layer formed of the ink composition for three-dimensional formation is cured by irradiation of light (for example, UV) and laminated, and after completion of lamination, complete curing is performed by heat etc. Has been done.
Moreover, in the ink composition for three-dimensional modeling, in order to reduce the cure shrinkage in the hardened | cured material obtained, the polymeric compound which has ring structure may be used.
Here, many polymerizable compounds having a ring structure have an odor.
For example, isobornyl acrylate, which is one of the polymerizable compounds contained in the three-dimensional modeling ink composition, is a compound having a small cure shrinkage, but has an irritating odor resembling camphor.
Moreover, in a three-dimensional structure, the layer formed of the ink has a thickness rather than a plane image, and in order to improve the formation speed of the structure, it is required to increase the thickness of each layer. ing. It is believed that the thicker the layer, the greater the amount of polymerizable compound remaining without polymerization in the cured product by light irradiation.
Therefore, when a thick layer in the production of a three-dimensional structure is formed using a three-dimensional modeling ink containing a polymerizable compound having a ring structure, an odor derived from the polymerizable compound having a ring structure in a cured product Could occur.
However, according to the present embodiment, since the polymerizable compound and the fragrance both have a structural common point having a ring structure, the fragrance and the polymerizable compound are on human olfactory cells. It is inferred that the odor derived from the polymerizable compound having a ring structure in the cured product is reduced when it is cured by light by adsorbing to the same or similar receptor of
Further, it is considered that the odor in the ink before curing, which includes the polymerizable compound having a ring structure, is also easily suppressed by the same mechanism.
Hereinafter, the details of the ink composition for three-dimensional modeling according to the present embodiment will be described.

<Polymerizable Compound Having a Ring Structure>
The three-dimensional structure forming ink composition according to the present embodiment includes a polymerizable compound having a ring structure (hereinafter, also referred to as a "specific polymerizable compound").
The specific polymerizable compound is not particularly limited as long as it has a ring structure, but a radically polymerizable compound is preferable, an ethylenically unsaturated compound is more preferable, and a compound having a (meth) acryloyl group is further preferable. It is particularly preferable that it is a (meth) acrylic acid ester compound.
In the present specification, the (meth) acryloyl group represents an acryloyl group or a methacryloyl group, and the (meth) acrylic acid represents an acrylic acid or a methacrylic acid.
The specific polymerizable compound may be a compound having one or more polymerizable groups, but is preferably a compound having one or more and six or less polymerizable groups, and a compound having one or more and three or less. Is more preferable, a compound having one or two is more preferable, and a compound having only one is particularly preferable.
That is, the specific polymerizable compound is most preferably a monofunctional (meth) acrylic acid ester compound.

Ring structure
The ring structure contained in the specific polymerizable compound is not particularly limited, and may be either an aromatic ring structure or an alicyclic structure, but from the viewpoint of suppressing the cure shrinkage of the three-dimensional forming ink composition From the above, an alicyclic structure is preferable.
The alicyclic structure is preferably a cycloalkyl structure, more preferably a cycloalkyl structure having 6 to 20 carbon atoms.
Examples of the alicyclic structure include an isobornyl ring structure, a cyclohexyl structure, a dicyclopentanyl structure, a dicyclopentenyl structure and the like, and from the viewpoint of suppressing curing shrinkage in a cured product, an isobornyl ring structure is more preferable. As a formula structure, a benzene ring structure, a naphthalene ring structure, an anthracene ring structure etc. are mentioned.
The ring structure may contain hetero atoms such as oxygen atom, sulfur atom and nitrogen atom, but it is more preferable not to contain hetero atoms.

[Example of monofunctional (meth) acrylic acid ester compound]
Examples of monofunctional (meth) acrylic acid ester compounds include isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclo (meth) acrylate. Pentenyl, tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclohexyl-1,3- Examples thereof include dioxolane and adamantyl (meth) acrylate, and from the viewpoint of suppressing the cure shrinkage of a cured product and obtaining a cured product excellent in hardness, isobornyl (meth) acrylate is preferable.

[Characteristics of Specified Polymerizable Compound]
The molecular weight of the specific polymerizable compound is preferably several hundred or more and several hundred thousand or less, and more preferably several hundred or more and several thousand or less.
In particular, a compound having a molecular weight of several hundred or less is considered to easily generate an odor, but in the present embodiment, a compound having such a molecular weight of several hundred or less is used by using it in combination with a specific perfume. Even in such cases, the odor is likely to be suppressed.
The molecular weight of the specific polymerizable compound is measured by electrospray ionization mass spectrometry.

〔Content〕
The ink composition for three-dimensional modeling which concerns on this embodiment may contain a specific polymeric compound individually by 1 type, and may use 2 or more types together.
The content of the specific polymerizable compound is preferably 10% by mass to 70% by mass, and more preferably 20% by mass to 50% by mass, based on the total mass of the three-dimensional modeling ink composition. .

<Perfuming>
The three-dimensional structure forming ink composition according to the present embodiment includes a fragrance having a ring structure (hereinafter, also referred to as a “specified fragrance”).
The specific perfume is not particularly limited as long as it has a ring structure, and known natural or synthetic perfumes may be used.

Ring structure
The ring structure contained in the specific fragrance is not particularly limited, and may be an aromatic ring structure or an alicyclic structure, but from the viewpoint of suppressing the cure shrinkage of the three-dimensional modeling ink composition, It is preferable that it is an alicyclic structure.
The alicyclic structure is preferably a cycloalkyl structure, more preferably a cycloalkyl structure having 6 to 20 carbon atoms.
Examples of the alicyclic structure include an isobornyl ring structure, a cyclohexyl structure, a dicyclopentanyl structure, a dicyclopentenyl structure and the like, and from the viewpoint of suppressing curing shrinkage in a cured product, an isobornyl ring structure is more preferable. As a formula structure, a benzene ring structure, a naphthalene ring structure, an anthracene ring structure etc. are mentioned.
The ring structure may contain a heteroatom such as oxygen atom, sulfur atom or nitrogen atom, but preferably contains no heteroatom.

It is preferable that the ring structure contained in the specific polymerizable compound and the ring structure contained in the specific fragrance be the same ring structure or a ring structure having a stereoisomer relationship.
If the ring structure has the same ring structure or in a stereoisomer relationship, from the structural common point, the specified fragrance and the specified polymerizable compound are the same or similar on human olfactory cells It is likely to be adsorbed to the receptor and the odor is likely to be suppressed.
As an example of the combination in which the ring structure contained in the specific polymerizable compound and the ring structure contained in the specific fragrance are the same ring structure, for example, the specific polymerizable compound is isobornyl acrylate, and the specific fragrance Preferred is a combination in which is isobornyl acetate.
In addition, as an example of the combination in which the ring structure contained in the specific polymerizable compound and the ring structure contained in the specific fragrance are in a stereoisomer relationship, for example, the specific polymerizable compound is isobornyl acrylate And combinations in which the specific perfume is bornyl acetate are preferably mentioned.
From the viewpoint of suppressing the generation of odor, the ring structure contained in the specific polymerizable compound and the ring structure contained in the specific fragrance are the same ring structure or a ring structure having a stereoisomer relationship In some cases, both of the ring structure contained in the specific polymerizable compound and the ring structure contained in the specific fragrance are preferably alicyclic structures, and at least one of the alicyclic structures is an isobornyl ring More preferred is a structure.

  Moreover, as a specific fragrance, it is preferable that it is an ester compound of a carboxylic acid compound and an alcohol compound having a ring structure from the viewpoint of suppressing odor, and the specific polymerizable compound has a ring structure with (meth) acrylic acid It is more preferable that it is an ester compound with an alcohol compound, and a specific fragrance is an ester compound with a carboxylic acid compound and an alcohol compound having a ring structure.

[Example of specified perfume]
Specific flavors include isobornyl acetate, bornyl acetate, 2-phenylethyl acetate, methyl dihydrojasmonic acid, benzyl benzoate, methyl salicylate, methyl N, N-dimethylanthranilate, 4-methoxybenzyl acetate, etc. Isobornyl or bornyl acetate is preferred, and isobornyl acetate is more preferred.

〔Content〕
In the ink composition for three-dimensional modeling according to the present embodiment, the content of the specific fragrance is preferably 0.7% by mass or more and 2.5% by mass or less with respect to the total mass of the ink composition, It is more preferable that it is 0 mass% or more and 2.0 mass% or less.
When the content is 1.0% by mass or more, the odor of the obtained cured product is easily suppressed, and when the content is 2.0% by mass or less, an ink excellent in curability is easily obtained.

<Other polymerizable compounds>
The three-dimensional structure forming ink composition according to the present embodiment preferably further contains another polymerizable compound.
The other polymerizable compound is a polymerizable compound other than the specific polymerizable compound described above.
The other polymerizable compound may be a radically polymerizable compound or a cationically polymerizable compound, and these may be used in combination.

[Radical polymerizable compound]
The radically polymerizable compound is not particularly limited, but an ethylenically unsaturated compound is preferable, and a (meth) acrylic acid ester compound or a (meth) acrylamide compound is preferable.
The radically polymerizable compound may be any of a monomer, an oligomer and a prepolymer.
Specifically, as a compound which has a radically polymerizable group, urethane (meth) acrylate, an epoxy (meth) acrylate, polyester (meth) acrylate etc. are mentioned suitably, for example. Among these, as a compound which has a radically polymerizable group, urethane (meth) acrylate is preferable.

-Urethane (meth) acrylate-
Urethane (meth) acrylate (hereinafter, also simply referred to as "urethane (meth) acrylate") is a compound having a urethane structure and two or more (meth) acryloyl groups in one molecule. The urethane (meth) acrylate may be a monomer or an oligomer, but is preferably an oligomer.

  The functional number (number of (meth) acryloyl groups) of urethane (meth) acrylate is preferably 2 or more and 20 or less (preferably 2 or more and 15 or less).

  As urethane (meth) acrylate, the reaction product using a polyisocyanate compound, a polyol compound, and a hydroxyl-containing (meth) acrylate is mentioned, for example. Specifically, the urethane (meth) acrylate is, for example, a prepolymer obtained by reacting a polyisocyanate compound and a polyol compound, and a reaction of a prepolymer having an isocyanate group at an end and a hydroxyl group-containing (meth) acrylate. The product is mentioned. Moreover, as urethane (meth) acrylate, the reaction product of a polyisocyanate compound and hydroxyl-containing (meth) acrylate is mentioned.

Polyisocyanate Compound Examples of the polyisocyanate compound include linear saturated hydrocarbon isocyanates and the like. Among these, the polyisocyanate compound is preferably a chain-like saturated hydrocarbon isocyanate having no light absorption band in the near ultraviolet region, or a cyclic saturated hydrocarbon isocyanate having no light absorption band in the near ultraviolet region.
Examples of linear saturated hydrocarbon isocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.
Examples of cyclic saturated hydrocarbon isocyanates include isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate and the like.
Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1, 3-phenyl diisocyanate, 1, 5- naphthalene diisocyanate etc. are mentioned.

-Polyol compound As a polyol compound, diol, polyhydric alcohol, etc. are mentioned, for example.
As the diol, for example, alkylene glycol (eg, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol) Butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanedio Le, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, etc.) and the like.
As polyhydric alcohols, for example, alkylene polyhydric alcohols containing three or more hydroxyl groups (for example, glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol Erythritol, sorbitol, pentaerythritol, dipentaerythritol, mannitol and the like).

  As a polyol compound, a polyether polyol, polyester polyol, a polycarbonate polyol etc. are also mentioned, for example.

Examples of polyether polyols include multimers of polyhydric alcohols, adducts of polyhydric alcohols and alkylene oxides, and ring-opening polymers of alkylene oxides.
Here, as polyhydric alcohols, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, 1, 2-hexanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and the like.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like.

Examples of polyester polyols include reaction products of polyhydric alcohols and dibasic acids, ring-opening polymers of cyclic ester compounds, and the like.
Here, as the polyhydric alcohol, for example, the polyhydric alcohol exemplified in the description of the polyether polyol can be mentioned.
Examples of dibasic acids include carboxylic acids (eg, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.), anhydrides of carboxylic acids, and the like.
Examples of cyclic ester compounds include ε-caprolactone and β-methyl-δ-valerolactone.

Examples of polycarbonate polyols include reaction products of glycols and alkylene carbonates, reaction products of glycols and diaryl carbonates, and reaction products of glycols and dialkyl carbonates.
Here, as an alkylene carbonate, ethylene carbonate, a 1, 2- propylene carbonate, a 1, 2- butylene carbonate etc. are mentioned, for example. Examples of diaryl carbonates include diphenyl carbonate, 4-methyl diphenyl carbonate, 4-ethyl diphenyl carbonate, 4-propyl diphenyl carbonate, 4,4'-dimethyl diphenyl carbonate, 2-tolyl-4-tolyl carbonate, 4,4 '. Diethyldiethyl carbonate, 4,4'-dipropyl diphenyl carbonate, phenyl toluyl carbonate, bischlorophenyl carbonate, phenylchlorophenyl carbonate, phenyl naphthyl carbonate, dinaphthyl carbonate and the like.
As a dialkyl carbonate, for example, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, diisoamyl carbonate Etc.

Hydrogen group-containing (meth) acrylate As hydrogen group-containing (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy -3- phenoxy propyl (meth) acrylate, glycerin di (meth) acrylate, trimethylol propane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are mentioned. As a hydrogen group containing (meth) acrylate, the adduct of a glycidyl group containing compound (For example, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate etc.) and (meth) acrylic acid is also mentioned, for example.

-Urethane (meth) acrylate weight average molecular weight-
As a weight average molecular weight of urethane (meth) acrylate, 500 or more and 5000 or less are preferable, and 1000 or more and 3000 or less are more preferable.
The weight average molecular weight of the urethane (meth) acrylate is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

-Other radically polymerizable compounds-
As a compound which has a radically polymerizable group, the compound which has another radically polymerizable group besides the above-mentioned is also mentioned.
As a compound which has another radically polymerizable group, the (meth) acrylate (monofunctional (meth) acrylate, polyfunctional (meth) acrylate) etc. which are illustrated below are mentioned, for example.

Examples of monofunctional (meth) acrylates include linear or branched alkyl (meth) acrylates, (meth) acrylates having a hydroxyl group, and (meth) acrylamide compounds.
As the alkyl (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl Examples include (meth) acrylates and the like.
As a (meth) acrylate having a hydroxyl group, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, Examples thereof include polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, and mono (meth) acrylate of a block polymer of polyethylene glycol-polypropylene glycol.

  Among the polyfunctional (meth) acrylates, examples of difunctional (meth) acrylates include 1,10-decanediol diacrylate, 2-methyl-1,8-octanediol diacrylate, and 2-butyl-2- Ethyl 1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, polytetramethylene glycol diacrylate, 3-methyl-1 5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, tripropylene glycol diacrylate, 1,4-butanediol diacrylate Propylene glycol diacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, EO (ethylene oxide) modified bisphenol A diacrylate, PO (propylene oxide) modified bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, EO ( Ethylene oxide) modified bisphenol F diacrylate etc. are mentioned.

  Among the polyfunctional (meth) acrylates, examples of trifunctional or more functional (meth) acrylates include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, Ethoxylated glycerin triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO (ethylene oxide) modified diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate modified acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. It can be mentioned.

-Compound having radically polymerizable group and cationically polymerizable group-
The three-dimensional modeling ink composition according to the present embodiment may contain a compound having a radically polymerizable group and a cationically polymerizable group.
As a radically polymerizable group in the compound which has a radically polymerizable group and a cationally polymerizable group, a (meth) acryloyl group is preferable, and a vinyl ether group is preferable as a cationically polymerizable group.

  Examples of the compound having a radically polymerizable group and a cationically polymerizable group include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, ethyl oxetane methyl vinyl ether, cyclohexane dimethanol vinyl glycidyl ether and the like. .

  Commercially available compounds may be used as the compound having a radically polymerizable group and a cationically polymerizable group, for example, VEEA and VEEM (both manufactured by Nippon Shokubai Co., Ltd.), EOXTVE and CHDMVG (both Maruzen Petrochemicals) Co., Ltd.).

The radically polymerizable compounds may be used alone or in combination of two or more.
In the embodiment, the content of the radically polymerizable compound in the ink composition for three-dimensional modeling is preferably 10% by mass to 95% by mass, and is 30% by mass to 70% by mass, with respect to the total mass of the ink composition. Is more preferred.

<Polymerization initiator>
The three-dimensional modeling ink composition according to this embodiment preferably contains a polymerization initiator.
As a polymerization initiator, a radical polymerization initiator is preferable, and a photo radical polymerization initiator is more preferable

As a radical polymerization initiator, a photo radical polymerization initiator is preferable.
There is no restriction | limiting in particular as an optical radical polymerization initiator, For example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyl Examples include dione compounds, disulfide compounds, fluoroamine compounds and aromatic sulfoniums.
Among the above compounds, phosphine oxides are preferable from the viewpoint of curability.
As acetophenones, for example, 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2- Examples thereof include benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like.
Examples of benzoins include benzoin benzenesulfonic acid ester, benzoin toluenesulfonic acid ester, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.
Examples of benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone and the like.
As phosphine oxides, for example, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (manufactured by BASF, IRGACURE TPO, manufactured by IGM Resins, Omnirad TPO), bis (2,4,6-trimethyl benzoyl) -phenyl phos Fin oxide (manufactured by BASF, IRGACURE 819, manufactured by IGM Resins, Omnirad 819) and the like can be mentioned.

  In addition, as the radical polymerization initiator, various compounds described in “Application of UV / EB curing technology and market (CMC Publishing, supervised by Riceho Tabata / edited by RadTech Research Group)” are also used.

  The content of the photo radical polymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less, and is 1 part by mass or more and 10 parts by mass or less based on the total mass of the three-dimensional modeling ink composition from the viewpoint of curability. Is more preferred.

  In addition to the photo radical polymerization initiator, a photosensitizer may be used. Specific examples of photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, thioxanthone, and the like.

<Polymerization inhibitor>
The three-dimensional structure forming ink composition according to the present embodiment preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include phenolic polymerization inhibitors (for example, p-methoxyphenol, cresol, t-butyl catechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2′-methylene bis ( 4-Methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), etc.), hindered amines, hydroquinones Well-known polymerization inhibitors such as monomethyl ether (MEHQ), hydroquinone and the like can be mentioned.

0.01 mass% or more and 3 mass% or less are preferable with respect to the total mass of the compound which has a radically polymerizable group, as for content of a polymerization inhibitor, 0.05 mass% or more and 1 mass% or less are more preferable.
In addition, a polymerization inhibitor may be used individually by 1 type, and may be used together 2 or more types.

<Surfactant>
It is preferable that the ink composition for three-dimensional modeling which concerns on this embodiment contains surfactant.
As the surfactant, for example, silicone surfactants, acrylic surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, fluorine surfactants, etc. Well-known surfactant is mentioned.

The content of the surfactant is preferably 0.05% by mass or more and 15% by mass or less, and more preferably 0.1% by mass or more and 10.0% by mass or less based on the total mass of the ink composition for three-dimensional modeling .
In addition, surfactant may be used individually by 1 type, and may be used together 2 or more types.

<Colorant>
It is preferable that the ink composition for three-dimensional modeling which concerns on this embodiment contains a coloring agent.
As the colorant, various conventionally known colorants such as pigments and dyes can be used, and pigments are particularly preferable from the viewpoint of improving the weather resistance of the three-dimensional structure.

  The pigment is not particularly limited, and generally all commercially available organic pigments and inorganic pigments, or pigments dispersed in a resin as a dispersion medium, or those grafted with a resin on the pigment surface Etc. are used. Also, resin particles dyed with a dye may be used.

  As specific examples of the organic pigment and the inorganic pigment used in the present embodiment, the compounds described in paragraphs 0036 to 0039 of Japanese Patent No. 5372295 can be mentioned, and these are also applied to the present embodiment.

  The content of the colorant is preferably 0.01% by mass to 50% by mass, and more preferably 0.1% by mass to 20% by mass, with respect to the total mass of the three-dimensional modeling ink composition. When an oil-soluble dye is used as the colorant, 0.01% by mass or more and 10% by mass or less is particularly preferable with respect to the total mass (including the solvent) of the three-dimensional modeling ink composition.

<Other additives>
As other additives other than the above, for example, solvents, sensitizers, fixing agents, fungicides, preservatives, antioxidants, ultraviolet absorbers, chelating agents, thickeners, dispersants, polymerization accelerators Well known additives such as penetration enhancers, wetting agents (humectants) and the like.

<Characteristics of ink composition for three-dimensional shaping>
The surface tension of the ink composition for three-dimensional modeling is, for example, in the range of 28 mN / m to 40 mN / m.
Here, the surface tension is a value measured in an environment of 23 ° C. and 55% RH using a Wilhelmy type surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.).

The viscosity of the ink composition for three-dimensional shaping is, for example, in the range of 3 mPa · s to 100 mPa · s.
Here, using a TVE-25L manufactured by Toki Sangyo Co., Ltd. as a measuring device, the viscosity is measured at a measurement temperature of 25 ° C. and a shear rate of 200 (1 / s).

(Ink cartridge for three-dimensional modeling, three-dimensional modeling apparatus, and method of manufacturing three-dimensional model)
The three-dimensional modeling apparatus according to the present embodiment accommodates an ink composition for three-dimensional modeling, and discharges the three-dimensional modeling ink composition, and cures the three-dimensional modeling ink composition discharged. And a light emitting unit for emitting light. And the ink composition for three-dimensional modeling which concerns on the said this embodiment is applied to the ink composition for three-dimensional modeling.
The three-dimensional modeling apparatus may include a three-dimensional modeling ink composition cartridge that accommodates the three-dimensional modeling ink composition and that is cartridge-detachable to be attached to and detached from the three-dimensional modeling apparatus.
In the above three-dimensional modeling apparatus, for example, a three-dimensional model is obtained through a discharge process of discharging a three-dimensional modeling ink composition and a light irradiation process of curing the discharged three-dimensional modeling ink composition by light irradiation. It manufactures (that is, the manufacturing method of the three-dimensional structure which concerns on this embodiment is implemented).

Note that the three-dimensional modeling apparatus includes a first discharge unit that accommodates the three-dimensional modeling ink composition and discharges the three-dimensional modeling ink composition, and a support material that accommodates the support material (the three-dimensional modeling support material). You may provide the 2nd discharge part to discharge, and the light irradiation part which irradiates the light which hardens the ink composition for 3D modeling and the support material which were discharged.
In addition to the ink composition cartridge for three-dimensional modeling, in the three-dimensional modeling apparatus provided with the first ejection unit, the second ejection unit, and the light irradiation unit, the cartridge is formed so as to contain the support material and be attached and detached to the three-dimensional modeling apparatus A support material cartridge (support material cartridge for three-dimensional modeling) may be provided.
In addition, in the three-dimensional modeling apparatus including the first ejection unit, the second ejection unit, and the light irradiation unit, for example, the three-dimensional modeling ink composition is ejected and cured by light irradiation to form a three-dimensional object. The material is discharged and cured by light irradiation to form a support portion (support portion) that supports at least a part of the shaped object. And after formation of a molded article, a support part is removed and a three-dimensional molded article is manufactured.

Hereinafter, as an example of the three-dimensional modeling apparatus according to the present embodiment, a three-dimensional modeling apparatus including a first discharge unit, a second discharge unit, and a light irradiation unit will be described with reference to the drawings.
FIG. 1 is a schematic configuration view showing an example of a three-dimensional modeling apparatus provided with a first discharge unit, a second discharge unit, and a light irradiation unit in the three-dimensional modeling apparatus according to the present embodiment.

  The three-dimensional modeling apparatus 101 according to the present embodiment is an inkjet three-dimensional modeling apparatus. As shown in FIG. 1, the three-dimensional modeling apparatus 101 includes, for example, a modeling unit 10 and a modeling table 20. In addition, the three-dimensional modeling apparatus 101 includes a three-dimensional modeling ink composition cartridge 30 containing a three-dimensional modeling ink composition and a support material cartridge 32 housing a support material so as to be desorbed into the apparatus. Have. In addition, in FIG. 1, MD shows a modeling thing and SP shows a support part.

  For example, the shaping unit 10 includes a three-dimensional shaping ink composition ejection head 12 (one example of a first ejection unit) that ejects droplets of the three-dimensional shaping ink composition, and a support material that ejects droplets of the support material. An ejection head 14 (an example of a second ejection unit) and a light irradiation device 16 for irradiating light are provided. In addition, although not shown, for example, the modeling unit 10 removes excess three-dimensional modeling ink composition and support material out of the three-dimensional modeling ink composition and the support material discharged onto the modeling table 20, and is flat. May be provided with a rotating roller.

  The modeling unit 10 moves, for example, by a driving device (not shown) on a modeling area of the modeling table 20 in the sub-scanning direction crossing (for example, orthogonal to) the main scanning direction and this (so-called carriage system) It has become.

  The three-dimensional modeling ink composition discharge head 12 and the support material discharge head 14 each employ a piezoelectric (piezoelectric) discharge head which discharges droplets of each material by pressure. Each discharge head is not limited to this, and may be a discharge head of a type that discharges each material by pressure from a pump.

The three-dimensional shaping ink composition ejection head 12 is connected to, for example, a three-dimensional shaping ink composition cartridge 30 through a supply pipe (not shown). Then, the three-dimensional shaping ink composition cartridge 30 supplies the three-dimensional shaping ink composition to the three-dimensional shaping ink composition discharge head 12.
The support material discharge head 14 is connected to, for example, a support material cartridge 32 through a supply pipe (not shown). Then, the support material cartridge 32 supplies the ink composition for three-dimensional modeling to the support material ejection head 14.

The three-dimensional shaping ink composition ejection head 12 and the support material ejection head 14 each have an effective ejection area (arrangement area of a nozzle for ejecting the three-dimensional shaping ink composition and the support material). It is a short discharge head smaller than the area.
The three-dimensional shaping ink composition ejection head 12 and the support material ejection head 14 each have, for example, an effective ejection area (arrangement area of nozzles for ejecting the three-dimensional shaping ink composition and the support material). It may be a long head having a width of the shaping area on the table 20 (a length in a direction intersecting (for example, at right angles) with the moving direction (main scanning direction) of the shaping unit 10). In this case, the modeling unit 10 is moved only in the main scanning direction.

  The light irradiation device 16 is an ultraviolet light irradiation device that irradiates ultraviolet light of at least 350 nm or more and 400 nm or less. As an ultraviolet irradiation device, for example, a metal halide lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a deep ultraviolet lamp, a lamp for exciting a mercury lamp with no electrode from the outside using microwaves, an ultraviolet laser, a xenon lamp, UV-LED (ultraviolet light emitting diode Etc.) is applied. Among these, an ultraviolet laser and a UV-LED (ultraviolet light emitting diode) are preferable from the viewpoint of suppressing the temperature rise during the production of the three-dimensional structure.

  The forming table 20 has a surface having a forming area in which a three-dimensional forming ink composition and a support material are discharged to form a formed object. And the modeling stand 20 is raised / lowered by the drive device not shown.

  Next, an operation (a method of manufacturing a three-dimensional structure) of the three-dimensional structure forming apparatus 101 according to the present embodiment will be described.

  First, for example, from a three-dimensional CAD (Computer Aided Design) data of a three-dimensional structure to be formed by a three-dimensional structure forming ink composition by a computer (not shown), for example, Generate two-dimensional shape data (slice data) for forming. At this time, two-dimensional shape data (slice data) for forming a support portion by the support material is also generated. In the two-dimensional shape data for forming the support portion, if the width of the shaped object at the upper position is larger than the width of the shaped object at the lower position, and there is a so-called overhang portion, this overhang portion is A support portion is formed to support.

  Next, based on the two-dimensional shape data for forming a three-dimensional object, the three-dimensional formation ink composition is discharged from the three-dimensional formation ink composition discharge head 12 while moving the formation unit 10, and formation is performed. A layer of the three-dimensional modeling ink composition is formed on the table 20. Then, the layer of the ink composition for three-dimensional modeling is irradiated with light by the light irradiation device 16 to cure the ink composition for three-dimensional modeling, and a layer to be a part of a modeled object is formed.

If necessary, the support material is discharged from the support material discharge head 14 while moving the modeling unit 10 based on two-dimensional data for forming the support portion, and on the modeling table 20, for three-dimensional modeling Adjacent to the layer of ink composition, a layer of support material is formed. Then, light is irradiated to the layer of the support material by the light irradiation device 16 to cure the support material, and a layer to be a part of the support portion is formed.
In this manner, a first layer LAY1 is formed, which includes the layer to be a part of the object and, if necessary, the layer to be a part of the support (see FIG. 2). Here, in FIG. 2, MD1 indicates a layer to be a part of a shaped object in the first layer LAY1, and SP1 indicates a layer to be a part of a support in the first layer LAY1.

  Next, the molding table 20 is lowered. The descent of the forming table 20 corresponds to the thickness of a second layer to be formed next (a second layer including a layer to be a part of a shaped object and, if necessary, a layer to be a part of a support portion) Do.

  Next, similarly to the first layer LAY1, a second layer LAY2 is formed, which is a layer to be a part of a shaped object and, if necessary, a layer to be a part of a support (see FIG. 3). Here, in FIG. 3, MD2 indicates a layer to be a part of a shaped object in the second layer LAY2, and SP2 indicates a layer to be a part of a support in the second layer LAY2.

  Then, the operation of forming the first layer LAY1 and the second layer LAY2 is repeated to form the n-th layer LAYn. Thereby, a three-dimensional object supported at least in part by the support portion is formed (see FIG. 4). Here, in FIG. 4, MDn indicates a layer to be a part of a shaped object in the nth layer LAYn. MD indicates a shaped object. SP indicates a support unit.

Thereafter, the support portion is removed from the object to obtain a desired three-dimensional object. Here, for the removal of the support portion, for example, a method of removing by hand (break-away method), a method of injecting and removing gas or liquid, or the like is adopted.
The obtained three-dimensional structure may be subjected to a post-treatment such as polishing.

  Hereinafter, the present embodiment will be described in detail by way of examples, but the present embodiment is not limited to these examples. In the following description, "parts" and "%" are all based on mass unless otherwise noted.

Example 1
<Preparation of Ink Composition for Three-Dimensional Sizing>
In each example, each component described in the following Table 1 or Table 2 was mixed to obtain an ink composition for three-dimensional shaping.
Specifically, under ultraviolet light-cut illumination, measure the amount of oligomers listed in Table 1 or Table 2 into brown glass sample bottles, and then add the amount of monomers listed in Table 1 or Table 2. The solution was stirred and dissolved using a magnetic stirrer.
The numerical values described in Table 1 or Table 2 represent the content (parts by mass) of each component.
After visually confirming that the solution became uniform, the polymerization inhibitor, the photopolymerization initiator, the additive, and the surfactant described in Table 1 or Table 2 were added, and the solution was again stirred and dissolved using a magnetic stirrer.
After visually confirming that the solid matter was dissolved and the solution became homogeneous, a flavoring agent was added and dissolved by stirring with a magnetic stirrer.
In Table 1 or Table 2, the description of "-" indicates that the corresponding compound is not contained.

The details of the compounds described in Table 1 and Table 2 are as follows.
U-15 HA: Urethane acrylate oligomer (weight average molecular weight: 2300), Shin-Nakamura Chemical Co., Ltd. product U-200 PA: urethane acrylate oligomer (polyester urethane acrylate, weight average molecular weight: 2700) Shin-Nakamura Chemical Co., Ltd. Inc. VA-4200: Urethane acrylate oligomer (polyether urethane acrylate, weight average molecular weight: 1000), Shin-Nakamura Chemical Co., Ltd. VEEA-AI: 2- (2-vinyloxyethoxy) ethyl acrylate, Ltd. Nippon Shokuhin Co., Ltd. · IBOA: Isobornyl acrylate, Nippon Shokuhin Co., Ltd. · Omnirad 819: bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, photopolymerization initiator, IGM Resins, Inc. MEHQ: Hydroquinone Nomethylether (4-methoxyphenol), polymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd. Omnirad EDB: ethyl 4- (dimethylamino) benzoate, additive (polymerization accelerator), IGM Resins, Inc. TEGO Rad 2011 : Silicone-based surfactant, Evonik Co., Linalool: 3, 7-dimethyl-1, 6-octadien-3-ol, perfume, Kanto Chemical Co., Ltd. Linalyl acetate: acetic acid 3, 7-dimethyl-1, 6-octadien-3-yl, fragrance, Kanto Chemical Co., Ltd. product, 2-phenylethyl acetate :, fragrance, Kanto Chemical Co., Ltd. product, methyl dihydrojasmonate :, fragrance, Kanto Chemical Co., Ltd. product, bornyl acetate :, Perfume, made by Kanto Chemical Co., Ltd., isobornyl acetate :, perfume, made by Kanto Chemical Co., Ltd.

<Evaluation>
[Panel evaluation]
Prior to the experiment, five panelists having an appropriate sense of smell were selected by the 5-2 method using a five standard odor set made by Daiichiyaku Sangyo Co., Ltd.
The details of Method 5-2 are as follows.

Method-5-2
One standard odorant solution was soaked about 1 cm from the tip in any two of the odor paper with a number of 1 to 5 written so that the subject could not see it. The remaining three were similarly immersed in the control solution.
The subject sniffed the smell by bringing one of the five pieces of hand-made odor paper close enough to touch the tip of the nose.
After sniffing the five odors in this way, I answered the numbers of the two odorant papers that appeared to have been applied (with odor) to the standard odorant. This was repeated with five types of odor included in the five reference odor set, and a subject who answered correctly in all the tests was regarded as a panelist having an appropriate sense of smell.

-Odor evaluation of the ink composition for three-dimensional shaping before UV curing (before UV curing)-
The odor evaluation of the ink composition for three-dimensional shaping before UV curing is carried out by immersing the liquid before curing in the tip 1 cm of the odor paper included in the 5 standard odor set made by Daiichiyaku Sangyo Co., Ltd. A five-point rating of 5 (Fu) was made, and the average value of 5 panelists was rounded and quantified.
As the evaluation result is closer to 5, it can be said that the generation of the odor is suppressed, and 3 or more is not a problem. In addition, the evaluation result is preferably 4 or 5, and more preferably 5.

-Odor evaluation of the ink composition for three-dimensional modeling after UV curing (after UV curing)-
The odor evaluation of the three-dimensional modeling ink composition after UV curing was performed by dropping one drop of the liquid before curing onto a slide glass and curing with UV light of 365 nm using a UV-LED light source Omnicure LX400 manufactured by EXFO. After the evaluation, the same five-step evaluation was performed.
As the evaluation result is closer to 5, it can be said that the generation of the odor is suppressed, and 3 or more is not a problem. In addition, the evaluation result is preferably 4 or 5, and more preferably 5.

[Curable evaluation]
One drop of the liquid before curing was dropped onto a slide glass, and curing treatment was performed with UV light of 365 nm using a UV-LED light source Omnicure LX400 manufactured by EXFO, and the surface state after curing was observed.
Bleed out refers to a state in which a liquid thing oozes out on the surface of the cured product.
The surface of the cured product was dry, and no stickiness or bleeding was observed.

〔sensory evaluation〕
-Odor sensory evaluation of the ink composition for three-dimensional shaping before UV curing (before UV curing)-
One panelist immerses the liquid before curing in the tip 1 cm of the odor paper included in the 5 standard odor set made by Daiichiyaku Sangyo Co., Ltd., and the result of sensory evaluation is shown.
Evaluation was performed about the presence or absence of a pungent smell, and the kind of smell, and the evaluation result was described in Table 1 or Table 2.

-Odor sensory evaluation of the ink composition for three-dimensional shaping after UV curing (after UV curing)-
The odor evaluation of the three-dimensional modeling ink composition after UV curing was performed by dropping one drop of the liquid before curing onto a slide glass and curing with UV light of 365 nm using a UV-LED light source Omnicure LX400 manufactured by EXFO. After performing, sensory evaluation was similarly performed.

DESCRIPTION OF SYMBOLS 10 modeling unit 12 three-dimensional modeling material discharge head 14 support material discharge head 16 light irradiation apparatus 20 modeling stand 30 three-dimensional modeling material cartridge 32 support material cartridge 101 three-dimensional modeling apparatus

Claims (9)

A polymerizable compound having a ring structure,
And a perfume having a ring structure.   The ring structure according to claim 1, wherein the ring structure contained in the polymerizable compound and the ring structure contained in the perfume are the same ring structure or a ring structure having a stereoisomer relationship with each other. The ink composition for three-dimensional modeling as described.   The three-dimensional structure forming ink composition according to claim 2, wherein both of the ring structure contained in the polymerizable compound and the ring structure contained in the fragrance are alicyclic structures.   The three-dimensional structure forming ink composition according to claim 3, wherein at least one of the ring structure contained in the polymerizable compound and the ring structure contained in the perfume is an isobornyl ring structure.   The polymerizing compound is an ester compound of (meth) acrylic acid and an alcohol compound having a ring structure, and the perfume is an ester compound of a carboxylic acid compound and an alcohol compound having a ring structure. The ink composition for three-dimensional shaping | molding of any one of Claims 1-4.   The three-dimensional structure forming ink composition according to claim 5, wherein the polymerizable compound is isobornyl (meth) acrylate, and the fragrance is isobornyl acetate.   The three-dimensional structure according to any one of claims 1 to 6, wherein the content of the fragrance is 0.7% by mass or more and 2.5% by mass or less with respect to the total mass of the ink composition. Ink composition.   An ink cartridge for three-dimensional shaping, containing the ink composition for three-dimensional shaping according to any one of claims 1 to 7. A discharge unit for containing the three-dimensional structure forming ink composition according to any one of claims 1 to 7 and discharging the three-dimensional structure forming ink composition,
A light irradiator that emits light for curing the discharged three-dimensional modeling ink composition;
3D modeling device equipped with