JP2016002704A - Composition liquid for 3d shaping, ink set for 3d shaping, and method for manufacturing 3d shaped object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition liquid for 3D shaping that can be cured by ultraviolet irradiation and can obtain high toughness, and a 3D shaped object manufacturing method using the composition liquid.SOLUTION: A composition liquid for 3D shaping contains at least two monofunctional monomers having an ethylenically polymerizable group and a photoinitiator. The monofunctional monomers comprise a monofunctional monomer having an ionic group and a monofunctional monomer not having an ionic group. The composition liquid further contains the counter ion of the ionic groups.

Description

  The present invention relates to a 3D modeling optical composition liquid, a 3D modeling ink set, and a method for manufacturing a 3D modeling object.

  In recent years, as a method for producing a 3D model, a liquid photocuring composition is irradiated with laser light or ultraviolet rays to cure and laminate the irradiated part, or the photocuring composition is landed on a substrate by inkjet. A method of irradiating and curing the landed photocuring composition with ultraviolet rays is widely known.

  Recently, there is a demand to confirm not only the shape of the prototype but also the function at the prototype stage of the 3D model. In particular, there is a demand for confirming the properties of a prototype using ABS-like material with a molded object having the same toughness as ABS.

  Toughness is a property that combines high rigidity and resistance to breakage due to elongation after yielding. As a high-toughness polymer, for example, it is achieved by blending butadiene rubber with hard polystyrene acrylonitrile resin such as ABS resin. Such as rubber-added resins and polyethylene terephthalate and polycarbonate resins, which are rigid and have high intermolecular interactions. However, in the 3D modeling method by photocuring, since a model is manufactured by polymerizing monomers, a manufacturing method in which another rubber is blended in the same manner as the above resin cannot be adopted. For example, even if a monomer blended with rubber was used to create a 3D model by photopolymerization, only a low toughness was produced.

  As a method for obtaining a 3D shaped article having high toughness, there is a method in which a cationic polymerization system and a radical polymerization system are used in combination, and phase separation is caused in the cured product using a difference in curing speed (Patent Document 1, Patent). Reference 2).

  On the other hand, as a method for obtaining a high-strength stereolithography using UV inkjet, Patent Document 3 discloses that a polyfunctional acrylate and a thiol of a chain transfer material are used in order to prevent unnecessary curing while increasing photocuring sensitivity. Methods using compounds are described.

JP 2013-151703 A JP 2013-166893 A Special table 2007-530724 JP 2012-255045 A JP 2012-219255 A

  As described in Patent Document 1 and Patent Document 2, when a 3D shaped article is manufactured using a composition in which a cationic polymerization system and a radical polymerization system are used in combination, photocuring is performed as compared with a case where a radical polymerization system is used alone. Since the sensitivity is lowered, the composition is not cured by ultraviolet rays, and an expensive laser beam must be used. For this reason, there is a drawback that the manufacturing cost is increased.

  Further, in the method described in Patent Document 3, since a large amount of polyfunctional acrylate is used, high rigidity is obtained, but there is almost no elongation and the molded article has low toughness.

  In view of the above problems, the problem to be solved by the present invention is a composition liquid for 3D modeling that can be cured by ultraviolet irradiation and that can provide a 3D modeled article with high toughness, and for 3D modeling including the same An ink set and a method for producing a 3D structure using the ink set are provided.

In view of the above problems, the first of the present invention relates to a 3D modeling composition liquid.
[1] A composition liquid for 3D modeling containing at least two types of monofunctional monomers having an ethylene polymerizable group and a photoinitiator, wherein the monofunctional monomer includes a monofunctional monomer having an ionic group and an ionic group A composition liquid comprising a monofunctional monomer having no group, wherein the composition liquid further contains a counter ion of the ionic group.
[2] The composition liquid according to [1], wherein the monofunctional monomer having no ionic group contains at least one of a monomer having an aromatic group and a monomer having an alicyclic group. .
[3] The composition liquid according to [1] or [2], further containing a polyfunctional monomer having an ethylene polymerizable group.
[4] The composition according to any one of [1] to [3], wherein the ionic group is at least one of a carboxylic acid group and a phosphoric acid group, and the counter ion is a 1 to 3 valent cation. liquid.
[5] The ionic group is at least one of a tertiary amino group and a quaternary ammonium group, and the counter ion is a 1-3 valent anion, according to any one of [1] to [3]. Composition liquid.
[6] The composition liquid according to any one of [1] to [5], wherein the composition liquid does not substantially contain a cationically polymerizable compound.
[7] The composition liquid according to any one of [1] to [6], further containing a release agent.

The second aspect of the present invention relates to an ink set for 3D modeling.
[8] A 3D modeling ink set comprising the composition liquid according to any one of [1] to [7] and a support material composition liquid.

Moreover, the 3rd of this invention is related with the manufacturing method of 3D modeling thing.
[9] A method for producing a 3D structure, comprising a step of irradiating the composition liquid according to any one of [1] to [7] with actinic rays.

  By modeling the 3D model using the composition liquid for 3D modeling of the present invention, a 3D model that can be cured by irradiation with ultraviolet rays and that has high toughness and is difficult to break is obtained. Moreover, according to this invention, it can provide the manufacturing method of the 3D modeling thing which has high toughness and can obtain the 3D modeling thing which is hard to break.

FIG. 1 is a schematic diagram showing one embodiment of a 3D modeling system based on the UV-IJ method. FIG. 2 is a flowchart of a method for producing a 3D structure by the UV-IJ method. FIG. 3 is a side view of the process (part 1) of the method for producing a 3D structure by the UV-IJ method. FIG. 4A is a side view of the process (part 2) of the method for producing a 3D structure by the UV-IJ method, and FIG. 4B is a top view thereof. FIG. 5A is a side view of the process (part 3) of the method for manufacturing a 3D structure by the UV-IJ method, and FIG. 5B is a top view thereof. FIG. 6A is a side view of the process (part 4) of the method for producing a 3D structure by the UV-IJ method, and FIG. 6B is a top view thereof. FIG. 7A is a side view of the process (part 5) of the method for manufacturing a 3D structure by the UV-IJ method, and FIG. 7B is a top view thereof. FIG. 8 is a perspective view of a model material obtained by the method for manufacturing a 3D structure of the present invention.

  The present invention will be described below with reference to embodiments, but the present invention is not limited to the following embodiments.

1.3D modeling composition liquid The 3D modeling composition liquid of the present invention is a 3D modeling composition liquid containing at least two types of monofunctional monomers having an ethylene polymerizable group and a photoinitiator, and the monofunctional composition liquid. The monomer includes a monofunctional monomer having an ionic group and a monofunctional monomer having no ionic group, and the composition liquid further contains a counter ion of the ionic group.

1-1. Monofunctional monomer having an ethylene polymerizable group The monofunctional monomer having an ethylene polymerizable group is a monomer having one ethylene polymerizable group in the molecule. The composition liquid for 3D modeling of the present invention includes at least two types of monofunctional monomers having an ethylene polymerizable group, and as the monofunctional monomer, a monofunctional monomer having an ionic group and a monofunctional monomer having no ionic group Containing.

1-1-1. Monofunctional monomer having ionic group The monofunctional monomer having an ionic group of the present invention is a monomer having one ethylene polymerizable group in the molecule and further having an ionic group in the molecule.

  An ionic group means a functional group having a positive or negative charge. Since the ionic group has high polarity, the ionic group gathers in a polymer composed of hydrocarbon chains obtained by polymerizing the composition liquid for 3D modeling of the present invention to form a domain. This domain aggregates with a relatively weak force and has the property of being easily destroyed when subjected to stress, but also readily reformed. In the 3D modeling object manufactured by irradiating the composition liquid for 3D modeling of the present invention with actinic rays, this domain is scattered in the 3D modeling object. Is dispersed, and the strength and elongation are considered to be improved.

  Moreover, when manufacturing 3D modeling thing, an ionic group is easy to be excluded on the surface of each layer during photocuring. When forming the next layer, the ionic group excreted on the surface forms a domain with the ionic group of the next layer, so that in the present invention, the strength and elongation between stacks of the 3D structure are also improved. Conceivable.

  Ethylene polymerizable groups include ethylene, propenyl, butenyl, vinylphenyl, (meth) acryl, allyl ether, vinyl ether, maleyl, maleimide, (meth) acrylamide, acetylvinyl and vinylamide Group etc. are included. In the present invention, “(meth) acryl” means “acryl” and / or “methacryl”, and “(meth) acrylate” means both “acrylate” and “methacrylate”. To do.

  Of these, (meth) acrylate groups, vinyl ether groups and (meth) acrylamide groups are preferred, and (meth) acrylate groups are more preferred.

  As the ionic group, either an acidic group or a basic group can be used. Examples of the acidic group that the monofunctional monomer having an ionic group can have include a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group. Examples of the basic group include a primary to tertiary amino group, a quaternary ammonium group, and the like. Among these, the acidic group is preferably at least one of a carboxylic acid group and a phosphoric acid group, and the basic group is preferably at least one of a tertiary amino group and a quaternary ammonium group. .

  By setting the number-average molecular weight of the monofunctional monomer having an ionic group to 150 to 1000, it is possible to improve the ink jetting property at the time of manufacturing a 3D shaped article by the UV-IJ (ultraviolet-inkjet) method. It is possible to prevent convection of liquid during manufacturing of a 3D structure by stereolithography method, increase curability, and increase breaking stress. Moreover, inkjet output property and sclerosis | hardenability can further be improved by making the number average molecular weight of the monofunctional monomer which has an ionic group into 150-600.

  Although the ratio of the monofunctional monomer which has an ionic group contained in the composition liquid for 3D modeling is not specifically limited, It is preferable that it is 5 mass%-40 mass% with respect to the total mass of a composition liquid, and 10 mass%. More preferably, it is -30 mass%. By making the amount of the monofunctional monomer having an ionic group 5% by mass or more, the rigidity is improved, and by making the amount of the monofunctional monomer having an ionic group 40% by mass or less, the elongation after yielding is increased. Can be held.

  Examples of the monofunctional monomer having a carboxylic acid group that can be contained in the 3D modeling composition liquid of the present invention include 2- (meth) acryloyloxyethyl hexahydrophthalic acid and 2- (meth) acryloyl. Roxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, N- (meth) acryloylaspartic acid, 2-acetoacetoxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (Meth) acryloyloxyethyl hydrogen maleate, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, 11- (meth) acryloyloxyundecane-1 , 1-Dicarboxylic acid, 10- (meth) acryloyloxydecane 1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2- (meth) acryloyloxyethyl-3 ′ -Methacryloyloxy-2 '-(3,4-dicarboxybenzoyloxy) propyl succinate, 1,4-bis (2- (meth) acryloyloxyethyl) pyromellitate, 4- (2- (meth) acryloyloxyethyl) Trimellitate anhydride, 4- (2- (meth) acryloyloxyethyl) trimellitate, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyl Oxyhexyl trimellitate, 4- (meth) acrylo Luoxydecyl trimellitate, 4-acryloyloxybutyl trimellitate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid anhydride, 6- (meth) acryloyloxyethylnaphthalene-2,3 , 6-tricarboxylic acid anhydride, 4- (meth) acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic acid anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic acid anhydride, etc. A polymerizable monomer having a plurality of carboxyl groups or acid anhydride groups thereof is included in the molecule.

  Examples of the monofunctional monomer having a phosphate group that can be contained in the 3D modeling composition liquid of the present invention include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxy). Ethyl) hydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, and 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogenphosphate and other polymerizable monomers having a phosphinicooxy group or phosphonooxy group in the molecule, and vinyl phosphate, p-vinylbenzene phosphate, etc. Phosphono group in the molecule It includes polymerizable monomer is.

  Examples of the monofunctional monomer having a sulfonic acid group that can be contained in the 3D modeling composition liquid of the present invention include 2- (meth) acrylamido-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, And polymerizable monomers such as vinyl sulfonic acid.

  Examples of the monofunctional monomer having a tertiary amino group or a quaternary ammonium group that can be contained in the 3D modeling composition liquid of the present invention include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Examples thereof include trimethylammonium ethyl (meth) acrylate, dimethylaminopropylacrylamide, and p-vinyl-N-dimethylaniline and quaternized products thereof.

1-1-2. Monofunctional monomer having no ionic group The monofunctional monomer having no ionic group of the present invention is a monomer having one ethylene polymerizable group in the molecule and further having no ionic group in the molecule. .

  The monofunctional monomer having no ionic group can increase the elongation of the produced 3D shaped article by forming a linear structure when polymerized.

  The ethylene polymerizable group includes an ethylene group, a propenyl group, a butenyl group, a vinylphenyl group, a (meth) acryl group, an allyl ether group, a vinyl ether group, a maleyl group, and a maleimide as in the case of the monofunctional monomer having the ionic group. Groups, (meth) acrylamide groups, acetylvinyl groups, vinylamide groups and the like.

  Of these, a (meth) acryl group, an allyl ether group, a vinyl ether group, and a maleimide group are preferable, and a (meth) acryl group is more preferable.

  When the number average molecular weight of the monofunctional monomer having no ionic group is 150 to 1000, the inkjet emission property can be improved at the time of producing the 3D model by the UV-IJ method, and the 3D model by the SLA method. It is possible to prevent convection of the liquid at the time of manufacturing, increase the curability, and increase the breaking stress.

  Although the ratio of the monofunctional monomer which does not have an ionic group contained in the composition liquid for 3D modeling is not specifically limited, It is preferable that it is 50 mass%-95 mass% with respect to the total mass of a composition liquid, and 65 mass It is more preferable that it is% -90 mass%. By setting the amount of the monofunctional monomer having an ionic group to 5 mass% or more and 40 mass%, rigidity and elongation, that is, toughness can be improved.

  Examples of the monofunctional monomer having a (meth) acryl group and not having an ionic group that can be contained in the 3D modeling composition liquid of the present invention include butyl acrylate, 2-ethylhexyl acrylate, pentyl acrylate, and isoamyl. Acrylate, octyl acrylate, isooctyl (meth) acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl acrylate, isostearyl acrylate, n-stearyl acrylate, cyclohexyl acrylate, Benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, methoxyethoxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl-diglycol acrylate, 4-hydroxybutyl acrylate, methoxytriethylene glycol acrylate, ethoxy Examples include diethylene glycol acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, and 2-ethylhexyl carbitol acrylate.

  Examples of the monofunctional monomer having an allyl ether group and not having an ionic group that can be contained in the 3D modeling composition liquid of the present invention include phenyl allyl ether, o-, m-, p-cresol mono. Examples include allyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, and cyclohexane methanol monoallyl ether.

  Examples of the monofunctional monomer having a vinyl ether group and not having an ionic group that can be contained in the 3D modeling composition liquid of the present invention include butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, Examples include ethyl hexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, cyclohexyl vinyl ether, and adamantyl vinyl ether.

  Examples of the monofunctional monomer having a maleimide group and not having an ionic group that can be contained in the 3D modeling composition liquid of the present invention include phenylmaleimide, cyclohexylmaleimide, and n-hexylmaleimide. .

  The monofunctional monomer having no ionic group preferably contains at least one of a monomer having an aromatic group and a monomer having an alicyclic group. In the present invention, the aromatic group includes both a carbocyclic aromatic group and a heterocyclic aromatic group. The aromatic group may contain two or more cyclic structures and may be optionally substituted. In the present invention, the alicyclic group means a functional group containing a saturated or unsaturated carbocycle other than aromatic. A carbocycle may contain atoms other than carbon and may be optionally substituted. The alicyclic group may contain two or more carbocycles.

  When the monofunctional monomer having no ionic group contains at least one of a monomer having an aromatic group and a monomer having an alicyclic group, the aromatic group or alicyclic group becomes a π-π bond or steric hindrance. Since the movement of the polymer chain is hindered by, for example, the toughness of the manufactured 3D structure can be further increased.

  Examples of such monomers include benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, bisphenol A diacrylate, bisphenol EO adduct bis (meth) acrylate of A, PO adduct bis (meth) acrylate of bisphenol A, EO adduct bis (meth) acrylate of hydrogenated bisphenol A, and the like are included.

1-2. Counter ion The composition liquid for 3D modeling of the present invention contains a counter ion of an ionic group possessed by the monomer having the ionic group. The counter ion refers to an ion capable of forming an ion pair with the ionic group. When the ionic group is an acidic group, a basic ion is used. When the ionic group is a basic group, an acidic ion is used. Can be used respectively.

  For example, when a monomer having an acidic group is used as the monomer having an ionic group, a hydrogen atom or a 1 to 3 valent cation can be used as the counter ion. Cations that can be used are metal ions such as lithium ion, sodium ion, zinc ion, titanium ion, calcium ion, iron ion, copper ion, hydrogen ion, trimethylammonium, tetramethylammonium, triethylammonium, tetraethylammonium, etc. An organic ammonium ion is mentioned.

  When a monomer having a base group is used as the monomer having an ionic group, a hydrogen atom or a 1 to 3 valent anion can be used as the counter ion. Examples of counter ions that can be used include chlorine ions, bromine ions, acetate ions, phthalate ions, sulfate ions, and succinate ions.

1-3. Polyfunctional monomer having an ethylene polymerizable group The 3D modeling composition liquid of the present invention may further contain a polyfunctional monomer having an ethylene polymerizable group.

  In order to ensure the elongation and strength of the 3D modeling object, the composition liquid for 3D modeling of the present invention contains 0 to 20% by mass of a polyfunctional monomer having an ethylene polymerizable group, preferably 5 to 15% by mass. Hereinafter, it may be included.

  The ethylene polymerizable group includes an ethylene group, a propenyl group, a butenyl group, a vinylphenyl group, a (meth) acryl group, an allyl ether group, a vinyl ether group, a maleyl group, and a maleimide as in the case of the monofunctional monomer having the ionic group. Groups, (meth) acrylamide groups, acetylvinyl groups, vinylamide groups and the like.

  Among these, a (meth) acryl group, an allyl ether group, and a vinyl ether group are preferable, and a (meth) acryl group is more preferable.

  The polyfunctional monomer having a (meth) acryl group that can be contained in the composition liquid for 3D modeling of the present invention may be a bifunctional or trifunctional or higher (meth) acrylate compound.

  Examples of the bifunctional (meth) acrylate compound that can be contained in the 3D modeling composition liquid of the present invention include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meta). ) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, bisphenol A PO adduct di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate Such rates and polytetramethylene glycol di (meth) acrylates include.

  Examples of tri- or higher functional (meth) acrylate compounds that can be contained in the 3D modeling composition liquid of the present invention include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth). ) Acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, and the like.

  Urethane acrylate may be sufficient as the polyfunctional monomer which has the said (meth) acryl group which the composition liquid for 3D modeling of this invention can contain.

  A modified product may be sufficient as the polyfunctional monomer which has the said (meth) acryl group which the composition liquid for 3D modeling of this invention can contain. Examples of modified products include ethylene oxide-modified (meth) acrylate compounds such as ethylene oxide-modified trimethylolpropane tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetraacrylate; caprolactone such as caprolactone-modified trimethylolpropane tri (meth) acrylate Modified (meth) acrylate compounds; and caprolactam-modified (meth) acrylate compounds such as caprolactam-modified dipentaerythritol hexa (meth) acrylate.

  The polyfunctional monomer having an allyl ether group that can be contained in the 3D modeling composition liquid of the present invention may be a bifunctional or trifunctional or higher functional allyl ether compound.

  Examples of the bifunctional allyl ether compound that the 3D modeling composition liquid of the present invention can contain include 1,4-cyclohexanedimethanol diallyl ether, alkylene (2 to 5 carbon atoms) glycol diallyl ether, and polyethylene glycol (Weight average molecular weight: 100 to 4000) diallyl ether and the like. Further, glyceryl diallyl ether, trimethylolpropane diallyl ether, pentaerythritol diallyl ether, polyglycerol (degree of polymerization 2 to 5) diallyl ether and the like are included.

  Examples of trifunctional or higher functional allyl ether compounds that can be contained in the 3D modeling composition liquid of the present invention include trimethylolpropane triallyl ether, glyceryl triallyl ether, pentaerythritol tetraallyl ether, and tetraallyloxyethane, And pentaerythritol triallyl ether, diglyceryl triallyl ether, sorbitol triallyl ether, polyglycerin (polymerization degree 3 to 13) polyallyl ether, and the like.

  The polyfunctional monomer having a vinyl ether group that can be contained in the composition liquid for 3D modeling of the present invention may be a bifunctional, trifunctional, or tetrafunctional or higher vinyl ether compound.

  Examples of the bifunctional vinyl ether compound that can be contained in the composition liquid for 3D modeling of the present invention include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol vinyl ether, buty Examples thereof include range vinyl ether, dibutylene glycol divinyl ether, neopentyl glycol divinyl ether, cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, norbornyl dimethanol divinyl ether, isovinyl divinyl ether, divinyl resorcin, and divinyl hydroquinone.

  Examples of the tri- or higher functional vinyl ether compound that can be contained in the composition liquid for 3D modeling of the present invention include glycerin trivinyl ether, glycerin ethylene oxide adduct trivinyl ether (addition mole number of ethylene oxide 6), trimethylolpropane trivinyl ether. And trifunctional ether ether compounds such as trivinyl ether (addition mole number of ethylene oxide 3), and trifunctional vinyl ether compounds such as pentaerythritol trivinyl ether, ditrimethylolpropane hexavinyl ether and their oxyethylene adduct, etc. Is included.

1-4. Photoinitiator The 3D modeling composition liquid of the present invention contains a photoinitiator. As the photoinitiator, a photoradical initiator can be used.

  The photo radical initiator includes a cleavage type and a hydrogen abstraction type. The 3D modeling composition liquid of the present invention preferably contains at least a cleavage type photoinitiator. That is, the 3D modeling composition liquid of the present invention may contain (a) both a cleavage type and a hydrogen abstraction type photoinitiator, and (b) contain only a cleavage type photoinitiator. Also good. What is necessary is just to use properly the kind of photoinitiator to be used according to a desired effect.

  When the composition liquid for 3D modeling contains (a) both a cleavage type and a hydrogen abstraction type photoinitiator, it is preferable to contain a large amount of the cleavage type initiator as a mass ratio. The ratio of the hydrogen abstraction type initiator in the photoinitiator is preferably 30% by mass or less, and more preferably 20% by mass or more and 30% by mass or less.

  When the 3D modeling composition liquid contains both types of polymerization initiators as a photoinitiator, a cleavage type and a hydrogen abstraction type, the curing speed of the 3D modeling composition liquid increases. Although the reason for this is not clear, it is considered that when the photoinitiator of the cleavage type and the hydrogen abstraction type coexist, the polymerization rate of the hydrogen abstraction type initiator functions as a sensitizer so that the polymerization rate is improved. . This is important in the production of 3D objects that require much longer time than ordinary printing.

  When the composition liquid for 3D modeling contains only (b) a cleavage type photoinitiator (no hydrogen abstraction type initiator), (a) both the cleavage type and the hydrogen abstraction type The elongation or elasticity of the cured product of the 3D modeling composition liquid may be improved as compared with the case where the photoinitiator is contained. The reason for this is not clear, but can be considered as follows. If a graft reaction occurs between linear polymers obtained by polymerization of monofunctional monomers with a hydrogen abstraction type polymerization initiator, irregular crosslinking may occur. If the cross-linking is regular, a uniform force is applied when the cured product is stretched, so that high stretchability can be maintained. However, if there are irregular crosslinks in the cured product, stress is concentrated at specific sites in the composition when the cured product is stretched. For this reason, it is considered that elongation or elasticity is lowered in order to cause breakage of the cross-linked site or the linear polymer chain.

  Therefore, when it is required to increase the production speed of the 3D modeling object, it is preferable that the 3D modeling composition liquid contains (a) both types of polymerization initiators of a cleavage type and a hydrogen abstraction type. On the other hand, when importance is attached to the durability of the cured product, it is preferable to contain only (b) a cleavage type photoinitiator (substantially contain no hydrogen abstraction type photoinitiator).

  Examples of cleavage type photoinitiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) ) Acetophenones such as propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6 -Acylphosphine oxide systems such as trimethylbenzoindiphenylphosphine oxide; benzyl and methylpheny Luglyoxyester and the like are included.

  Examples of hydrogen abstraction type photoinitiators include benzophenones (benzophenone, N, N-diethylbenzophenone, etc.), thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, etc.), Anthraquinones (ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone, etc.), acridines (9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.) and the like are included.

  The content of the photoinitiator in the 3D modeling composition liquid is preferably 0.01% by mass to 10% by mass, although it depends on the actinic rays and the types of various monomers used in the present invention.

1-5. Release agent The 3D modeling composition liquid may further contain a release agent in order to facilitate the release of the cured product and the cured product of the support material composition liquid described below. The release agent is preferably contained in an amount of 0.01% by mass to 3.0% by mass with respect to the total mass of the ink. If it is less than 0.01% by mass, the releasability from the substrate is lowered, and if it exceeds 3.0% by mass, the droplets of the 3D modeling composition liquid before curing are likely to coalesce and cause ink bleeding. Sometimes.

  Examples of the release agent include silicon surfactants, fluorine surfactants, and higher fatty acid esters such as stearyl sebacate, and silicon surfactants are preferable. Further, the release agent may be contained in either the 3D modeling composition liquid or the support material composition liquid described below, but it is more preferable to contain both in both.

1-6. Other ink components The composition liquid for 3D modeling of the present invention may further contain a photoinitiator auxiliary agent or a polymerization inhibitor, if necessary. The photoinitiation assistant may be, for example, a tertiary amine compound, and is preferably an aromatic tertiary amine compound. Examples of aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included. Of these, N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. Only 1 type of these compounds may be contained in the composition liquid for 3D modeling, and 2 or more types may be contained.

  Examples of polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone , Nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino- 1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime and the like.

  In addition, the 3D modeling composition liquid may contain a polymerizable compound other than the monofunctional monomer having an ionic group, a monomer having no ionic group, or a polyfunctional monomer. Examples of the polymerizable compound that may be contained include monomers other than those described above, oligomers having a polymerization degree of 2 to 20 and polymerizability, and polymers having polymerizability.

  The composition liquid for 3D modeling of the present invention may contain a cationically polymerizable compound such as a compound having an epoxy group. The vinyl ether group is not included in the cationically polymerizable compound here because it can be either radical polymerization or cationic polymerization. The content of the cationically polymerizable compound can be 0% by mass or more and 10% by mass or less with respect to the total mass of the composition, but the 3D modeling composition liquid of the present invention substantially contains the cationically polymerizable compound. It is preferably not included. By reducing the cation polymerizable compound to 0% by mass or more and 10% by mass or less, it is possible to prevent a decrease in photocuring sensitivity and to cure the composition liquid even with ultraviolet rays. The phrase “substantially free of cationically polymerizable compound” means that the content ratio of the cationically polymerizable compound is 1% by mass or less with respect to the total mass of the composition liquid.

  When the 3D modeling composition liquid of the present invention is emitted from the inkjet head, the viscosity of the 3D modeling composition liquid is 100 mPa.s. It is preferable that it is s or less.

2.3 Ink set for 3D modeling When the 3D modeling composition liquid of the present invention is used as a model material composition liquid in a method for producing a 3D molded article by the UV-IJ method described later, the 3D modeling of the present invention as a model material composition liquid The composition liquid may be combined with the support material composition liquid to form a 3D modeling ink set. The support material composition liquid is used to form the space portion of the 3D structure and support the 3D structure composition liquid of the present invention as a model material composition liquid during manufacture in one aspect of the method for manufacturing a 3D structure to be described later. be able to. The support material composition liquid contained in the 3D modeling ink set is not particularly limited, but is preferably one that melts by heat, or is photocurable and the cured product is water-soluble or water-swellable. Moreover, it is preferable that the hardened | cured material of a support material composition liquid and the hardened | cured material of a model material composition liquid peel easily.

  Examples of the material that melts hot include waxes such as paraffin wax, microcrystalline wax, carnauba wax, ester wax, amide wax, and PEG 20000. What is photocurable and the cured product is water-soluble or water-swellable is, for example, a water-soluble compound (water-soluble monomer) having a photopolymerizable functional group (carbon-carbon unsaturated group, etc.) The photocurable resin composition may contain a photocleavable initiator and water, but is not particularly limited. The support material composition liquid may further contain a water-soluble polymer.

  Examples of water-soluble monomers contained in the support material composition liquid include water-soluble (meth) acrylate, polyoxyethylene diacrylate, polyoxypropylene diacrylate, achloroyl morpholine, hydroxyalkyl acrylate; water-soluble acrylamide, acrylamide, N, N-dimethylacrylamide, N-hydroxyethylacrylamide and the like are included. Examples of the water-soluble polymer contained in the support material composition liquid include polyethylene glycol, polypropylene glycol, polyvinyl alcohol and the like. Examples of the photocleavable initiator contained in the support material composition liquid include 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propan-1-one, but are particularly limited. Not.

  When the support material composition liquid is emitted from the inkjet head, the viscosity of the support material composition liquid is 100 mPa.s. It is preferable that it is s or less.

3. Manufacturing method of 3D modeling object The manufacturing method of the 3D modeling object of this invention includes the process of irradiating an active light to the above-mentioned 3D modeling composition liquid. The actinic light is not particularly limited, and ultraviolet rays, electron beams, laser light, and the like can be used.

  In the UV-IJ method, a 3D modeling composition liquid is applied to a base material using an ink jet, and the 3D modeling composition liquid landed on the base material is irradiated with actinic rays to be cured. Then, 3D modeling thing is manufactured by repeating application and hardening. In the SLA method, the 3D modeling composition liquid placed in the container is irradiated with actinic rays to cure the irradiated 3D modeling composition liquid. Thereafter, the cured 3D modeling composition liquid is lowered by a thickness of one layer, and then the active layer is irradiated again to cure the layer thereon.

When the actinic ray is an ultraviolet ray, examples of the actinic ray irradiation unit (ultraviolet irradiation means) include a fluorescent tube (low pressure mercury lamp, germicidal lamp), a cold cathode tube, an ultraviolet laser, and an operating pressure of several hundreds Pa to 1 MPa. Low pressure, medium pressure, high pressure mercury lamp, metal halide lamp, LED (light emitting diode) and the like are included. From the viewpoint of curability, ultraviolet irradiation means for irradiating ultraviolet rays having an illuminance of 100 mW / cm ² or more; specifically, high-pressure mercury lamps, metal halide lamps and LEDs are preferable, and LEDs are more preferable from the viewpoint of low power consumption. Specifically, a 395 nm, water-cooled LED manufactured by Phoseon Technology can be used.

  When the active light beam is an electron beam, examples of the active light beam irradiation unit (electron beam irradiation unit) include electron beam irradiation units such as a scanning method, a curtain beam method, and a broad beam method. From the viewpoint of processing capability, a curtain beam type electron beam irradiation means is preferable. Examples of the electron beam irradiation means include “Curetron EBC-200-20-30” manufactured by Nissin High Voltage Co., Ltd., “Min-EB” manufactured by AIT Co., Ltd., and the like.

  When the actinic ray is an electron beam, the acceleration voltage for electron beam irradiation is preferably 30 to 250 kV and more preferably 30 to 100 kV in order to perform sufficient curing. When the acceleration voltage is 100 to 250 kV, the electron beam irradiation amount is preferably 30 to 100 kGy, and more preferably 30 to 60 kGy.

  When the actinic ray is a laser beam, an ultraviolet laser such as a semiconductor excitation solid laser, an Ar laser, or a He—Cd laser can be used.

  Since the composition liquid for 3D modeling of the present invention does not substantially contain the content of the cationic polymerizable compound, it can be sufficiently cured even with ultraviolet rays having the least energy load and apparatus load. Therefore, although an electron beam and laser light having higher energy than ultraviolet rays may be used, 3D shaped objects can be manufactured at a lower cost by using ultraviolet rays.

3-1. Method for Producing 3D Modeled Object by UV-IJ Method In the method for producing 3D modeled object by UV-IJ method, it is preferable to use a model material composition liquid containing the above-mentioned 3D modeling composition liquid and a support material composition liquid. . In the 3D modeling process, the physical and chemical properties of the 3D modeling composition before and after curing change. Therefore, it is more preferable to manufacture while maintaining the shape of the model material composition liquid by using the model material composition liquid containing the above-described 3D modeling composition liquid and a support material composition liquid described later. The cured product of the 3D modeling composition liquid and the cured product of the support material composition liquid are relatively easy to peel.

  At this time, the support material composition liquid is ejected with an ink jet to form a space portion of the 3D modeled object, and the model material composition liquid is ejected with an ink jet to form a 3D modeled object. The support material composition liquid and the model material composition liquid may be discharged simultaneously, or the support material composition liquid may be discharged first and then the model material composition liquid may be discharged. When the nth film containing at least one of the support material composition liquid and the model material composition liquid discharged by inkjet is cured to form the nth cured layer, and the n + 1th film discharged in the same manner is cured thereon. The (n + 1) th film is cured while adhering to the nth cured layer, and thus is cured while adhering in the stacking direction. After all the cured layers are formed in this way, the target 3D modeled product can be obtained by removing the cured product of the support material composition liquid.

  An example of a specific manufacturing method by the UV-IJ method is based on first plane data included in a plurality of plane data representing the discharge positions of the model material composition liquid and the support material composition liquid in each layer of the 3D modeled object. At least one of the model material composition liquid and the support material composition liquid is ejected from the nozzle of the ink jet head onto the base material to form a first film, and the first film is photocured to form a first cured layer. And a nozzle of an ink jet head based on at least one of the model material composition liquid and the support material composition liquid based on the nth (n is an integer of 2 or more) plane data included in the plurality of plane data. Forming an nth film by discharging onto the (n-1) th hardened layer to form an nth hardened layer by photocuring the nth film. N-th cured layer is formed That step was carried out at least once, further comprising the step of removing the subsequent support material composition liquid.

  The specific manufacturing method based on the UV-IJ method includes a step of converting CAD (Computer Aided Design) data into STL (Stereo Lithography) data which is 3D modeling data, and the plurality of planes based on the STL data. You may further have the process of producing data. Further, STL data obtained by a method such as purchase or a plurality of plane data may be used.

3-2. FIG. 1 shows an outline of an example of a 3D modeling system based on the UV-IJ method. The 3D modeling system based on the UV-IJ method shown in FIG. 1 is movable in the left and right (drawing XY directions) with a stage 11 provided with driving means (not shown) for driving the inkjet unit 1 up and down (drawing Z direction). And an inkjet device 12 for discharging a model material composition liquid or a support material composition liquid, which is disposed on a rail (not shown).

  The ink jet device 12 includes a model material composition ink jet head 13, a support material composition ink jet head 14, a film thickness adjusting roller 15, and a light source 16. The ink jet head 13 for model material composition liquid and the ink jet head 14 for support material composition liquid each have a nozzle for ejection. The ink jet head 13 for a model material composition liquid communicates with a pump 13b and a photocurable composition tank 13c through a pipe 13a. The photocurable composition tank 13c can contain a model material composition liquid containing the 3D modeling composition liquid of the present invention. The support material composition liquid-jet head 14 communicates with a pump 14b and a photocurable composition tank 14c via a pipe 14a. A support material composition liquid can be placed in the photocurable composition tank 14c.

  As shown in FIG. 1, the 3D modeling system based on the UV-IJ method further includes an arithmetic control unit 2, an input device 4 for inputting 3D modeling data such as CAD data, and STL data converted from CAD data. Output device 5 that outputs slice data obtained from STL data, display device 6 that displays STL data, virtual 3D objects, etc., and various information necessary for manufacturing 3D objects, such as lots And a storage device 3 for associating and recording the number, the CAD data number, the STL data number, the number of the photocurable composition set including the model material composition liquid and the support material composition liquid, and the like.

  The calculation control unit 2 includes an STL calculation unit 21 that calculates STL data based on CAD data, an ink set control unit 22 that sends information to select a photocurable composition set suitable for a desired 3D model, and Stage control means 23 for sending information for driving the stage, inkjet control means 24 for sending information for discharging the model material composition liquid or the support material composition liquid, and roller control for sending information for polishing the layer to a desired thickness Means 25 and UV light source control means 26 for sending information to irradiate light to cure the discharged photocurable composition.

  The arithmetic control unit 2 may be configured by an arithmetic device used in a normal computer system such as a CPU. Examples of the input device 4 include pointing devices such as a keyboard and a mouse. Examples of the output device 5 include a printer. Examples of the display device 6 include an image display device such as a liquid crystal display and a monitor. As the storage device 3, a storage device such as a ROM, a RAM, or a magnetic disk can be used.

3-3. Manufacturing flow of 3D modeling object using 3D modeling system by UV-IJ method About the manufacturing method of 3D modeling object by UV-IJ method using the 3D modeling system by UV-IJ method shown in FIG. 1, the flowchart of FIG. Details will be described with reference to FIG.

  (A) In step S101, for example, CAD data is input. In step S102, the CAD data is converted into STL data as 3D modeling data. It should be noted that a virtual 3D structure formed from the STL data is displayed on the output device 5 to check whether a desired shape is formed. If the desired shape is not formed, the STL data is corrected. May be.

  (B) In step S103, as shown in FIG. 3, the virtual 3D structure is finely divided into a plurality of lamellar layers in the Z direction of FIG. 3, and discharge position data of the model material composition liquid in each layer is obtained. Further, in each plane data, discharge position data of the support material composition liquid for supporting or fixing the model material composition liquid is also created. By discharging the support material composition liquid around the X and Y directions of the model material composition liquid, a so-called overhang portion, for example, the second image portion of the letter “K” is supported from below by the support material composition liquid. be able to. By combining the discharge position data of the model material composition liquid and the discharge position data of the support material composition liquid for each layer, the “first plane data D1, second plane data D2,. Get.

  (C) In step S105, an optimal photocurable composition set is prepared based on the data of the virtual 3D structure and the plurality of plane data.

  (D) In step S108, based on the first plane data D1, the driving means is operated to align the relative positions of the stage and the ink jet apparatus.

  (E) In step S110, as shown in FIG. 4, the position of the ink jet is controlled based on the first plane data D1, and the model material composition liquid (Ma) and the support material composition liquid are placed at appropriate positions on the stage. At least one of (S) is discharged from the nozzles of the inkjet head to form the first film. The amount of droplets ejected from each nozzle is preferably 1 pl to 70 pl, more preferably 2 to 50 pl, although it depends on the resolution of the image. Thereafter, in step S112, the first film is photocured by irradiating actinic rays to obtain a first cured layer. In addition, it is preferable to confirm whether or not the thickness of the first hardened layer is uniform, and if not uniform, the thick portion is polished to make the thickness of the first hardened layer uniform. In addition, it is preferable that the thickness of each hardened layer after hardening is about 1-25 micrometers.

  Irradiation with actinic rays is performed within 10 seconds, preferably within 0.001 second to 5 seconds, and more preferably within 0.01 second to 2 seconds after the 3D modeling composition droplet is deposited on the recording medium. This is to prevent the adjacent 3D modeling composition droplets from being united. Irradiation with actinic rays is preferably performed after discharging the composition liquid for 3D modeling for one layer.

  (F) In step S114, it is determined whether there are more layers to be formed. If there are more layers to be formed, the process returns to step S108, and the position of the stage 11 is moved downward (Z direction) by the thickness of one hardened layer, as shown in FIG. Then, an nth hardened layer is formed on the n-1st hardened layer by steps S110 and S112. Then, as shown in FIGS. 6 and 7, the steps S108, S110, S112, and S114 are repeated until a final layer (Xth cured layer) is stacked, and a plurality of layers are stacked. If there are no more layers to be formed in step S114, the process proceeds to step S116.

  (G) In step S116, the cured product of the support material composition liquid is removed. For example, the cured product of the support material composition liquid is removed by swelling with water. In addition to this removal step, the cured product of the support material composition liquid may be removed from the cured product of the model material by spraying high-pressure water on the cured product of the support material composition solution, for example.

  As described above, a 3D structure M as shown in FIG. 8 can be produced.

[Modification of Embodiment]
In the embodiment described above, one example of the inkjet head for the model material composition liquid is shown, but the number of inkjet heads for the model material composition liquid is not limited to one. For example, two ink jet heads may be provided for the model material composition liquid, model material composition liquids having different physical properties may be simultaneously discharged from the nozzles of the respective ink jet heads, and the model material composition liquid may be mixed to form a composite material.

(Example 1)
(Preparation of model material composition)
2-acryloyloxyhexahydrophthalic acid (counter ion: hydrogen) 5 parts by mass Phenoxyethyl acrylate 58.6 parts by mass Isobornyl acrylate 15 parts by mass Isostearyl acrylate 10 parts by mass Tricyclodecane dimethanol dimethacrylate 15 parts by mass 2 , 4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (TPO) 1 part by mass 2,4-diethylthioxanthen-9-one (DETX) 0.3 part by mass KF-969 (silicon oil) 0.1 part by mass Were mixed and heated to obtain a model material composition liquid.

(Preparation of support material composition)
A support material prepared by mixing 40 g of polyoxyethylene (n≈9) diacrylate, 60 g of water, 5 g of photoinitiator irgacure 2959 (manufactured by BASF), and 0.1 g of silicon surfactant (TSF-4442). It was set as the composition liquid.

(Manufacture of 3D objects)
A support layer was formed on the polyethylene terephthalate film using the support material composition liquid using an inkjet head KM512MH manufactured by Konica Minolta IJ. Specifically, the amount of droplets per dot was 14 pl, and the droplets were emitted at 720 dpi × 720 dpi. The landing droplets were irradiated with ultraviolet rays having a light amount of 400 ml / cm ² by a high-pressure mercury lamp and cured, and a support layer having a thickness of 10 cm × 2 cm and a thickness of 1 mm was formed.

  On the formed support layer, a model layer having a size of 10 cm × 2 cm and a thickness of 5 mm was formed by using the model material composition liquid in the same manner as the support layer. Next, the model layer was separated from the polyethylene terephthalate film and the support layer by immersing the laminate of the support layer and the model layer in water to obtain a 3D structure (cured film).

  The composition of the model material composition liquid was changed as shown in Tables 1 to 3, and 3D objects were obtained by the same procedure for each.

[Measurement of yield stress, elongation at break and stress]
The yield stress, the breaking elongation at break and the breaking stress were measured by applying a constant load at room temperature at a tensile rate of 20 mm / min in the scanning direction and the laminating direction.

[Comprehensive evaluation]
Comprehensive evaluation was performed according to the following criteria.
○: Yield stress 25 MPa or more and 0.85 <= breaking stress / yield stress <= 1.2 and elongation at break 5% or more Δ: Yield stress 15 MPa or more and 0.6 <breaking stress / yield stress <= 1.7 and elongation at break of 3% or more, other than x: When broken by yield point or worse than the above conditions

  The 3D model produced using the 3D modeling composition liquid of the present invention had a good balance of yield stress, breaking stress and breaking elongation, and had high toughness. Further, all of the inks examined in this example had good emission characteristics.

  The composition liquid for 3D modeling of the present invention can be cured by ultraviolet rays, and the cured product has high toughness. Therefore, a prototype having desirable characteristics can be manufactured inexpensively by 3D modeling.

DESCRIPTION OF SYMBOLS 1 Inkjet part 2 Arithmetic control part 3 Memory | storage device 4 Input device 5 Output device 6 Display apparatus 11 Stage 12 Inkjet apparatus 13 Inkjet head for model materials 14 Inkjet head for support materials 16 Light source

Claims (9)

A composition liquid for 3D modeling containing at least two types of monofunctional monomers having an ethylene polymerizable group and a photoinitiator,
The monofunctional monomer includes a monofunctional monomer having an ionic group and a monofunctional monomer having no ionic group,
The composition liquid further contains a counter ion of the ionic group.   The composition liquid according to claim 1, wherein the monofunctional monomer having no ionic group contains at least one of a monomer having an aromatic group and a monomer having an alicyclic group.   The composition liquid according to claim 1 or 2, further comprising a polyfunctional monomer having an ethylene polymerizable group.   The composition liquid according to any one of claims 1 to 3, wherein the ionic group is at least one of a carboxylic acid group and a phosphoric acid group, and the counter ion is a 1 to 3 valent cation.   The composition liquid according to claim 1, wherein the ionic group is at least one of a tertiary amino group and a quaternary ammonium group, and the counter ion is a 1-3 valent anion. .   The composition liquid according to claim 1, wherein the composition liquid does not substantially contain a cationically polymerizable compound.   The composition liquid according to any one of claims 1 to 6, further comprising a release agent.   An ink set for 3D modeling comprising the composition liquid according to claim 1 and a support material composition liquid.   The manufacturing method of 3D modeling thing which has the process of irradiating actinic light to the composition liquid of any one of Claims 1-7.

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