JP2019059035A - Support material for three-dimensional modeling, material set for three-dimensional modeling and three-dimensional modeling apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a support material for three-dimensional modeling which is excellent in inkjet ejection property and water removal property in a support material after curing. A support material for three-dimensional modeling containing a water-soluble monomer, a photopolymerization initiator, an alkyl ester compound of an unsaturated fatty acid having one hydroxy group, and a water-soluble compatibilizer. A three-dimensional modeling material set including the three-dimensional modeling support material and the three-dimensional modeling material. A first discharge unit that discharges a three-dimensional modeling material containing a polymerizable compound, a second discharge unit that houses the support material for three-dimensional modeling and discharges the support material, the three-dimensional modeling material that has been discharged, and the above. A three-dimensional modeling device including a light irradiation unit that irradiates light that cures the support material. [Selection diagram] Fig. 1

Description

  The present invention relates to a three-dimensional modeling support material, a three-dimensional modeling material set, and a three-dimensional modeling apparatus.

Conventionally, layers of the powder for layered modeling are bonded with a binder in accordance with cross-sectional shapes obtained by cutting a three-dimensional object to be formed by a plurality of parallel surfaces, and the cross-sectional shapes formed of the bonded layers are sequentially stacked There is known a technique for producing a three-dimensional structure which is to be a three-dimensional model of an object to be formed.
The above-mentioned technology is also referred to as three-dimensional shaping by a powder adhering and laminating method.

  Further, Patent Document 1 discloses a model material for forming an optically shaped article in an inkjet light shaping method, which contains a curable resin component having a weighted average value of 9.0 to 10.3 of SP value.

  In Patent Document 2, an acid number is 20 or less, and a model material printing step of printing using a model material which is an active energy ray curable ink, and an acid number of 80 or more, an active energy ray curable ink There is disclosed a method of manufacturing a three-dimensional structure including a support material printing process for printing a support material and a support material removing process for removing the support material printed by the support material printing process. .

  In Patent Document 3, a printer head for a model material that discharges a model material on a modeling table, a printer head for a support material that discharges a support material on a modeling table, the model material that is discharged on a modeling table, and a support A three-dimensional modeling method for forming a three-dimensional model using an inkjet optical modeling apparatus having a light source for curing a material, wherein a model printer head for a model material is used to form each layer on the modeling table. And discharging the support material from the printer head for the support material; and curing the model material and the support material discharged onto the modeling table with light from the light source to form a layer Forming the three-dimensional structure of the model material and the support material by repeating the step of forming the layer; The model material discharged from the printer head for model material contains a curable resin component having a weighted average value of 9.0 to 10.3 of SP value, and the curable resin component of the model material is a monofunctional ethylenic non-curable resin component. A saturated monomer (A), a polyfunctional ethylenically unsaturated monomer (B) not containing a urethane group, a urethane-containing ethylenically unsaturated monomer (C), and a photopolymerization initiator (D) And the content of (A) is 50% to 90%, the content of (B) is 3% to 25%, and the content of (C) is 5% to 35 based on the weight of the model material. %, And the support material discharged from the printer head for support material is a water-soluble monofunctional ethylenically unsaturated monomer (F) and the water-soluble monofunctional ethylenically unsaturated monomer (F) Alkylene oxide which is a water soluble compound which is compatible and incompatible with the photo-cured product of (F) Additive and / or water (G) and a photopolymerization initiator (D), and based on the weight of the support material, the content of (F) is 3 to 45%, the content of (G) Is 50 to 95%, and the three-dimensional structure consisting of the model material and the support material is separated from the light-cured product of the model material by immersing in water, so that the light-cured product of the support material is separated. A three-dimensional shaping method is disclosed, which is characterized in that it is possible to extract a photocured product of a model material.

  Patent Document 4 relates to a resin composition for model material used to model a model material by an inkjet light shaping method, and is 19 to 49 parts by weight of non-water-soluble with respect to 100 parts by weight of the entire resin composition. Monofunctional Ethylenically Unsaturated Monomer (A), 15 to 50 parts by Weight of a Bifunctional or Higher Multifunctional Ethylenically Unsaturated Monomer (B), and 10 to 45 Parts by Weight of Oligomer (C) A resin composition for model material is disclosed that contains 3 to 15 parts by weight of a photopolymerization initiator (D) and 0.005 to 3.0 parts by weight of a surface conditioner (E).

  Patent Document 5 shows a photocurable resin composition for use in forming a support portion when producing an optical three-dimensional object by an inkjet method using a photocurable resin composition, wherein the support portion is formed. Based on the total mass of the photocurable resin composition for (A) the following general formula (I);

(Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear or branched alkylene group having 2 to 4 carbon atoms.)

And 2 to 20% by mass of N-hydroxyalkyl (meth) acrylamide (I) represented by the formula: (B) the following general formula (II);

(Wherein, R ³ represents a hydrogen atom or a methyl group)

2 to 20% by mass of (meth) acryloyl morpholine (II) represented by; (C) 3 to 30% by mass of a (meth) acrylate compound having one or more (meth) acryloyloxy groups; (D) 2 40 to 90% by mass of the polyhydroxy compound having the above hydroxyl group; and (E) 0.1 to 5% by mass of the radical photopolymerization initiator (E); for forming a support portion A photocurable resin composition is disclosed.

JP, 2012-111226, A JP, 2015-123684, A JP, 2015-227057, A JP 2017-31249 A JP, 2015-183103, A

  The problems to be solved by the present invention are inkjet dischargeability, and a support material containing a water-soluble monomer, a photopolymerization initiator, an alkyl ester compound of unsaturated fatty acid having no hydroxy group, and a water-soluble compatibilizer, and It is providing the support material for three-dimensional modeling which is excellent in the water removability in the support material after hardening.

The following aspects are included in the specific means for solving the said subject.
The invention according to claim 1 is
A three-dimensional shaping support material comprising a water-soluble monomer, a photopolymerization initiator, an alkyl ester compound of unsaturated fatty acid having one hydroxy group, and a water-soluble compatibilizer.

The invention according to claim 2 is
The three-dimensional modeling support material according to claim 1, wherein the alkyl ester compound of unsaturated fatty acid having one hydroxy group is an alkyl ester compound of 1 to 8 carbon atoms of unsaturated fatty acid having one hydroxy group. is there.

The invention according to claim 3 is
The support material for three-dimensional structure according to claim 2, wherein the alkyl ester compound of unsaturated fatty acid having one hydroxy group is a methyl or ethyl ester compound of unsaturated fatty acid having one hydroxy group.

The invention according to claim 4 is
The alkyl ester compound of unsaturated fatty acid having one hydroxy group is exemplified by ricinoleic acid, 10-hydroxy-cis-12-octadecenoic acid, oxooctadecanoic acid, 10-oxo-11-octadecenoic acid, ricineridiic acid, and 10- The support material for three-dimensional structure formation according to any one of claims 1 to 3, which is an alkyl ester compound of at least one unsaturated fatty acid selected from the group consisting of hydroxyoctadecanoic acid.

The invention according to claim 5 is
The support material for three-dimensional structure according to claim 4, wherein the alkyl ester compound of unsaturated fatty acid having one hydroxy group is an alkyl ester compound of ricinoleic acid.

The invention according to claim 6 is
The support material for three-dimensional modeling according to any one of claims 1 to 5, wherein the water-soluble monomer comprises a monomer having a hydroxy group.

The invention according to claim 7 is
It is a support material for three-dimensional modeling of Claim 6 in which the said water-soluble monomer contains a hydroxyalkyl acrylamide compound.

The invention according to claim 8 is
The support material for three-dimensional formation according to any one of claims 1 to 7, wherein the water-soluble compatibilizer is a polyalkylene glycol monoalkyl ether compound.

The invention according to claim 9 is
The support material for three-dimensional modeling according to any one of claims 1 to 8, wherein the water-soluble compatibilizer is a di- or tri-alkylene glycol monoalkyl ether compound.

The invention according to claim 10 is
It is the support material for three-dimensional shaping | molding of any one of the Claims 1-9 which further contain surfactant.

The invention according to claim 11 is
The support material for three-dimensional modeling according to any one of claims 1 to 10, further comprising a polymerization inhibitor.

The invention according to claim 12 is
A three-dimensional modeling material set including the three-dimensional modeling support material according to any one of claims 1 to 11 and a three-dimensional modeling material.

The invention according to claim 13 is
The 1st discharge part which discharges the three-dimensional modeling material containing a polymerizable compound, The support material for three-dimensional structures of any one of Claim 1 thru | or 11 is accommodated, The said discharge apparatus which discharges the said support material It is a three-dimensional modeling apparatus provided with 2 discharge parts and the light irradiation part which irradiates the light which harden | cures the three-dimensional modeling material and the support material which were discharged.

According to the invention as set forth in claim 1, 4 or 5, ink jet discharge is carried out as compared with a support material containing a water soluble monomer, a photo polymerization initiator, an alkyl ester compound of unsaturated fatty acid having no hydroxy group, and a water soluble compatibilizer. The support material for three-dimensional shaping | molding which is excellent in the property and the water removability in the support material after hardening is provided.
According to the invention of claim 2, the alkyl ester compound of unsaturated fatty acid having one hydroxy group is an alkyl ester compound having 9 or more carbon atoms of unsaturated fatty acid having one hydroxy group, Provided is a support material for three-dimensional shaping which is more excellent in the water removability of the support material after curing.
According to the third aspect of the present invention, the alkyl ester compound of unsaturated fatty acid having one hydroxy group is an alkyl ester compound having 3 to 8 carbon atoms of unsaturated fatty acid having one hydroxy group. The support material for three-dimensional shaping | molding which is excellent by the water removability in the support material after hardening is provided.
According to the invention which concerns on Claim 6, compared with the case where the said water-soluble monomer is a monomer which has a carboxy group, the support material for three-dimensional shaping | molding which is excellent by inkjet discharge stability is provided.
The invention according to claim 7 provides a support material for three-dimensional shaping that is more excellent in water removability in the support material after curing compared to the case where the water-soluble monomer is a (meth) acrylate compound having a hydroxy group. Be done.
According to the invention which concerns on Claim 8, the support material for three-dimensional shaping | molding which is excellent by the water removability in the support material after hardening is provided compared with the case where the said water-soluble compatibilizer is a water-soluble cellulose compound.
According to the invention as set forth in claim 9, the support for three-dimensional shaping which is more excellent in the water removability in the support material after curing as compared with the case where the water soluble compatibilizer is a tetra- or higher polyalkylene glycol monoalkyl ether compound. The material is provided.
According to the invention as set forth in claim 10, the ink jet discharge is carried out as compared with the case of containing only a water soluble monomer, a photo polymerization initiator, an alkyl ester compound of unsaturated fatty acid having one hydroxy group, and a water soluble compatibilizer. The support material for three-dimensional shaping | molding which is excellent by the property and the water removability in the support material after hardening is provided.
According to the invention as set forth in claim 11, the ink jet discharge as compared with the case of containing only a water soluble monomer, a photo polymerization initiator, an alkyl ester compound of unsaturated fatty acid having one hydroxy group, and a water soluble compatibilizer The support material for three-dimensional shaping | molding which is excellent by the property and the water removability in the support material after hardening is provided.
According to the invention of claim 12, compared to the case of using a support material containing a water-soluble monomer, a photopolymerization initiator, an alkyl ester compound of unsaturated fatty acid having no hydroxyl group, and a water-soluble compatibilizer, A material set for three-dimensional modeling that is excellent in inkjet dischargeability and water removability in a cured support material is provided.
According to the invention of claim 13, compared to the case of using a support material containing a water-soluble monomer, a photopolymerization initiator, an alkyl ester compound of unsaturated fatty acid having no hydroxy group, and a water-soluble compatibilizer, There is provided a three-dimensional modeling apparatus which is excellent in ink jet dischargeability and water removability in a cured support material.

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 same code | symbol may be provided to the member which has a substantially the same function through all the drawings, and the overlapping description may be abbreviate | omitted suitably.
Also, in the present specification, “(meth) acrylic” is a term used in a concept including both acrylic and methacrylic, and “(meth) acrylate” is used as a concept including both acrylate and methacrylate. Is a word that

(Support material for 3D modeling)
The three-dimensional shaping support material according to the present embodiment includes a water-soluble monomer, a photopolymerization initiator, an alkyl ester compound of unsaturated fatty acid having one hydroxy group, and a water-soluble compatibilizer.

  As a result of detailed investigations by the present inventors, when a conventional photo-curing type support material used for three-dimensional modeling is used, the non-reactive component and the polymer produced by the polymerization of the monomer become compatible. It does not form a clear sea-island structure, the viscosity of the mixture of the polymer and the non-reactive component is high, and the diffusion rate to water is slow, so it is difficult to dissolve and water removability may not be sufficient. I found it.

On the other hand, the support material for three-dimensional modeling which concerns on this embodiment is excellent in the inkjet discharge property and the water removability in the support material after hardening by the said structure. The reason is not clear, but is presumed as follows.
By including the alkyl ester compound of unsaturated fatty acid having one hydroxy group, the phase separation between the polymer formed by the polymerization of the monomer and the non-reactive component can be further advanced to form a sea-island structure, which is easy to remove. In addition, in order to promote the dispersion of the oily component in water at the time of removal, it is considered that a three-dimensional shaping support material excellent in water removability in the support material after curing is obtained.
In addition, by using the support material for three-dimensional modeling according to the present embodiment, the alkyl ester compound of unsaturated fatty acid having one hydroxy group and the water-soluble compatibilizer act in concert to achieve inkjet discharge stability. Is considered to be excellent.
Hereinafter, the detail of the support material for three-dimensional modeling which concerns on this embodiment is demonstrated.

<Alkyl ester compound of unsaturated fatty acid having one hydroxy group>
The support material for three-dimensional shaping according to the present embodiment includes an alkyl ester compound of unsaturated fatty acid having one hydroxy group.
The alkyl ester compound of unsaturated fatty acid having one hydroxy group has 1 to 5 carbon atoms of unsaturated fatty acid having one hydroxy group from the viewpoint of water removability in the support material after curing and ink jet ejection stability. It is preferably an alkyl ester compound of 20, more preferably an alkyl ester compound of 1 to 8 carbon atoms of unsaturated fatty acid having one hydroxy group, and methyl or ethyl of unsaturated fatty acid having one hydroxy group More preferably, it is an ester compound.

  The alkyl ester compound of unsaturated fatty acid having one hydroxy group is preferably ricinoleic acid or 10-hydroxy-cis-12-octadecene from the viewpoint of water removability in the support material after curing and ink jet ejection stability. It is preferable that it is an alkyl ester compound of at least one unsaturated fatty acid selected from the group consisting of an acid, oxooctadecanoic acid, 10-oxo-11-octadecenoic acid, ricyneradinic acid, and 10-hydroxyoctadecanoic acid, and ricinol An alkyl ester compound of an acid is more preferable, an alkyl ester compound having 1 to 8 carbon atoms of ricinoleic acid is further preferable, and a methyl or ethyl ester compound of ricinoleic acid is particularly preferable.

  Specific examples of the alkyl ester compound of unsaturated fatty acid having one hydroxy group include methyl ricinoleate, ethyl ricinoleate, n-propyl ricinoleate, isopropyl ricinoleate, n-butyl ricinoleate, and ricinoleic acid Hexyl, n-octyl ricinoleate, methyl 10-hydroxy-cis-12-octadecenoate, ethyl 10-hydroxy-cis-12-octadecenoate, methyl oxooctadecanoate, ethyl oxooctadecanoate, 10-oxo-11-octadecenoate Examples thereof include methyl, ethyl 10-oxo-11-octadecenoate, methyl ricineraidinate, ethyl ricineraidinate, methyl 10-hydroxyoctadecanoate, ethyl 10-hydroxyoctadecanoate and the like.

The support material for three-dimensional modeling according to the present embodiment may contain one kind of alkyl ester compound of unsaturated fatty acid having one hydroxy group, or may contain two or more kinds.
The content of the alkyl ester compound of unsaturated fatty acid having one hydroxy group in the support material for three-dimensional modeling according to the present embodiment is from the viewpoint of water removability in the support material after curing and inkjet discharge stability. It is preferably 10 mass% or more and 60 mass% or less, more preferably 15 mass% or more and 55 mass% or less, and more preferably 20 mass% or more and 45 mass% or less with respect to the total mass of the support material for three-dimensional formation. Being particularly preferred.

<Water-soluble compatibilizer>
The support material for three-dimensional modeling which concerns on this embodiment contains a water-soluble compatibilizer.
The water-soluble compatibilizer is preferably a compound that is water-soluble and does not have an ethylenically unsaturated group, and a low molecular weight compound having a molecular weight of less than 1,000 also has a molecular weight (weight-average molecular weight) May be 1,000 or more polymers. Among them, low molecular compounds having a molecular weight of 100 or more and less than 250 are more preferable. Also, in view of the heating temperature of the head, a low molecular weight compound having a flash point of 100 ° C. or higher is preferable.
The water solubility in the present embodiment means that the amount of the target substance dissolved in 100 parts by mass of water at 25 ° C. is 1 part by mass or more.

The water-soluble compatibilizer is preferably a compound having a polyalkylene glycol structure from the viewpoint of water removability in a support material after curing and inkjet discharge stability, and a polyethylene glycol structure and a polypropylene glycol More preferably, it is a compound having at least one structure selected from the group consisting of structures.
The water-soluble compatibilizer is preferably a compound having a hydrophilic group such as a hydroxy group, an amino group or a carboxy group, from the viewpoint of water removability in the support material after curing, and has a hydroxy group. It is more preferable that it is a compound.
Further, the water-soluble compatibilizer is more preferably a compound having one or two hydroxy groups from the viewpoint of water removability in the support material after curing, and is a compound having one hydroxy group. Particularly preferred.

  The molecular weight of the water-soluble compatibilizer is preferably less than 1,000, more preferably 700 or less, from the viewpoint of water removability in the support material after curing and inkjet discharge stability. The following is more preferable, and 120 or more and 400 or less is particularly preferable.

Among them, the water-soluble compatibilizer is preferably a polyalkylene glycol monoalkyl ether compound from the viewpoint of water removability in a support material after curing and inkjet discharge stability, and di- or tri-alkylene glycol monoalkyl It is more preferable that it is an ether compound.
The monoalkyl ether in the polyalkylene glycol monoalkyl ether compound is preferably a monoalkyl ether having 1 to 8 carbon atoms from the viewpoint of water removability in the support material after curing and ink jet ejection stability. And C 1-4 monoalkyl ethers are more preferable.
The polyalkylene glycol in the polyalkylene glycol monoalkyl ether compound is preferably polyethylene glycol or polypropylene glycol from the viewpoint of water removability in a support material after curing and inkjet discharge stability, and is polyethylene glycol Is more preferred.
In addition, the repeating number of the alkyleneoxy structure of the polyalkylene glycol in the polyalkylene glycol monoalkyl ether compound is 2 or more and 10 or less from the viewpoint of water removability in the support material after curing and ink jet ejection stability. Is more preferably 2 or more and 6 or less, still more preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

  Specific examples of the water-soluble compatibilizer include triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol, diethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisopropylene ether, and triethylene. Glycol monobutyl ether, diethylene glycol monobenzoyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether and the like can be mentioned.

The support material for three-dimensional modeling according to the present embodiment may contain the water-soluble compatibilizer singly or in combination of two or more.
The content of the water-soluble compatibilizing agent in the support material for three-dimensional formation according to the present embodiment is the entire content of the support material for three-dimensional formation from the viewpoint of water removability in the support material after curing and ink jet ejection stability. The content is preferably 10% by mass to 45% by mass, more preferably 15% by mass to 40% by mass, and particularly preferably 20% by mass to 35% by mass.

<Water-soluble monomer>
The support material for three-dimensional modeling which concerns on this embodiment contains a water-soluble monomer.
As the water soluble monomer, a water soluble ethylenically unsaturated compound is preferably mentioned.
The water-soluble monomer may be a monofunctional monomer or a polyfunctional monomer, but is preferably a monofunctional monomer from the viewpoint of water removability in a support material after curing.
Preferred examples of the water-soluble monomer include unsaturated carboxylic acid compounds, (meth) acrylate compounds having a hydroxy group, and (meth) acrylamide compounds.

Examples of unsaturated carboxylic acid compounds include (meth) acrylic acid.
As a (meth) acrylate compound having a hydroxy group, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) Acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, mono (meth) acrylate of block polymer of polyethylene glycol-polypropylene glycol, and the like can be mentioned.
Examples of (meth) acrylamide compounds include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N Examples include '-dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide and N-hydroxybutyl (meth) acrylamide.

The water-soluble monomer is preferably a monomer having a hydroxy group from the viewpoint of water removability in a support material after curing and inkjet discharge stability, and a (meth) acrylate compound having a hydroxy group and a hydroxy group It is more preferable to include at least one compound selected from the group consisting of (meth) acrylamide compounds having a carbamide, more preferably including a (meth) acrylamide compound having a hydroxy group, and including a hydroxyalkyl acrylamide compound Particularly preferred.
The hydroxyalkyl acrylamide compound is preferably N-hydroxyethyl acrylamide, N-hydroxypropyl acrylamide or N-hydroxybutyl acrylamide from the viewpoint of water removability in the support material after curing and inkjet discharge stability, N More preferably, it is hydroxyethyl acrylamide.

  In addition, the support material for three-dimensional modeling according to the present embodiment preferably contains, as the water-soluble monomer, 50% by mass or more, and 80% by mass or more, of the monomer having a hydroxy group based on the total mass of the water-soluble monomer. Is more preferable, and 90% by mass or more is particularly preferable.

The support material for three-dimensional modeling according to the present embodiment may contain the water-soluble monomer singly or in combination of two or more.
The content of the water-soluble monomer in the support material for three-dimensional formation according to the present embodiment is the total mass of the support material for three-dimensional formation from the viewpoint of water removability in the support material after curing and ink jet ejection stability. In contrast, the content is preferably 20% by mass to 55% by mass, more preferably 25% by mass to 45% by mass, and particularly preferably 30% by mass to 40% by mass.

<Photoinitiator>
The support material for three-dimensional modeling which concerns on this embodiment contains a photoinitiator.
As a photoinitiator, a radical photopolymerization initiator is preferable.
As a radical photopolymerization initiator, for example, aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds And keto oxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, alkylamine compounds and the like.

Specific examples of the photoradical polymerization initiator include, for example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4- (4-) Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, di- Tylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4-diethyl thioxanthone, and bis (2,6-dimethoxy benzoyl) -2,4,4-trimethylpentyl phosphine oxide Well-known photoinitiators are mentioned.
Among them, from the viewpoint of curability, it is preferable to contain an aromatic ketone, and it is more preferable to contain an aromatic ketone and a thioxanthone compound.

The support material for three-dimensional modeling according to the present embodiment may contain a single type of photopolymerization initiator or may contain two or more types of photopolymerization initiators.
From the viewpoint of curability, the content of the photopolymerization initiator in the support material for three-dimensional formation according to the present embodiment is 1 mass% or more and 10 mass% or less with respect to the total mass of the support material for three-dimensional formation Is preferable, and 2 to 5% by mass is more preferable.

<Surfactant>
It is preferable that the support material for three-dimensional modeling which concerns on this embodiment further contains surfactant from a viewpoint of water removability in the support material after hardening, and inkjet discharge stability.
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 support material for three-dimensional modeling according to the present embodiment may contain one surfactant alone or two or more surfactants.
The content of the surfactant in the support material for three-dimensional formation according to the present embodiment is the total mass of the support material for three-dimensional formation from the viewpoint of water removability in the support material after curing and inkjet discharge stability. In contrast, the content is preferably 0.05% by mass or more and 2% by mass or less, and more preferably 0.1% by mass or more and 1% by mass or less.

<Polymerization inhibitor>
It is preferable that the support material for three-dimensional modeling which concerns on this embodiment further contains a polymerization inhibitor from the viewpoint of the water removability in the support material after hardening, and inkjet discharge stability.
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.

The support material for three-dimensional modeling according to the present embodiment may contain the polymerization inhibitor singly or in combination of two or more.
The content of the polymerization inhibitor in the support material for three-dimensional formation according to the present embodiment is the total mass of the support material for three-dimensional formation from the viewpoint of water removability in the support material after curing and ink jet ejection stability. In contrast, the content is preferably 0.1% by mass or more and 1% by mass or less, and more preferably 0.2% by mass or more and 0.8% by mass or less.

<Other additives>
The support material for three-dimensional modeling according to the present embodiment may further include other additives. As other additives, known additives can be used. For example, colorants, solvents, sensitizers, fixing agents, fungicides, preservatives, antioxidants, ultraviolet absorbers, chelating agents, Well-known additives such as thickeners, dispersants, polymerization accelerators, penetration enhancers, wetting agents (humectants) and the like can be mentioned.

<Characteristics of support material for 3D modeling>
The surface tension of the support material for three-dimensional modeling according to the present embodiment is preferably in the range of 20 mN / m to 40 mN / m. In addition, in view of suppressing the movement of the liquid due to the surface tension difference when the three-dimensional modeling material and the support material are adjacent to each other before curing, the surface tension of the three-dimensional modeling material used and the third order according to the present embodiment 2 mN / m or less is preferable and, as for the difference of the absolute value with the surface tension of the support material for original modeling, 1 mN / m or less is more preferable.
In addition, the surface tension of the support material for three-dimensional modeling and the three-dimensional modeling material to be described later 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.). is there.

The viscosity of the support material for three-dimensional modeling according to the present embodiment is preferably in the range of 30 mPa · s to 50 mPa · s.
Here, the viscosity of the support material for three-dimensional formation and the three-dimensional formation material to be described later is measured using a rheomat 115 (manufactured by Contraves) as a measuring device, the measurement temperature is 23 ° C., and the shear rate is 1,400 s ⁻¹ . It is the value measured by.

(Material set for 3D modeling)
The material set for three-dimensional formation according to the present embodiment includes the support material for three-dimensional formation according to the present embodiment, and a formation ink.

<Three-dimensional modeling material (model material)>
Although the three-dimensional modeling material used in the present embodiment is not particularly limited, it may be a one-component curing three-dimensional modeling material or a two-component curing three-dimensional modeling material, but radical polymerization It is preferable that it is a three-dimensional modeling material, more preferably containing a polymerizable compound, and particularly preferably containing a polymerizable compound and a photopolymerization initiator.
In addition, the three-dimensional modeling material used in the present embodiment may contain other additives such as a polymerization inhibitor and a surfactant.

-Polymerizable compound-
The polymerizable compound used for the three-dimensional modeling material is not particularly limited, but is preferably an ethylenically unsaturated compound.
The ethylenically unsaturated compound is not particularly limited as long as it is a compound having an ethylenically unsaturated bond, and may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound.
Among them, the three-dimensional modeling material used in the present embodiment preferably contains urethane (meth) acrylate as the ethylenically unsaturated compound.

-Urethane (meth) acrylate-
The 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 may be an oligomer.
In the present specification, (meth) acrylate means both acrylate and methacrylate. Also, (meth) acryloyl means both an acryloyl group and a methacryloyl group.

  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 group 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 having a prepolymer having an isocyanate group at an end, and a hydroxy group-containing (meth) acrylate. Reaction products are mentioned. Moreover, as urethane (meth) acrylate, the reaction product of a polyisocyanate compound and a hydroxyl group containing (meth) acrylate is mentioned.

Polyisocyanate Compound Examples of the polyisocyanate compound include linear saturated hydrocarbon isocyanate, cyclic saturated hydrocarbon isocyanate, and aromatic polyisocyanate. 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.

· Hydroxy group-containing (meth) acrylate As the hydroxy 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. Examples of the hydroxy group-containing (meth) acrylate also include adducts of glycidyl group-containing compounds (eg, alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, etc.) with (meth) acrylic acid.

-Urethane (meth) acrylate weight average molecular weight-
As a weight average molecular weight of urethane (meth) acrylate, 500 or more and 5,000 or less are preferable, and 1,000 or more and 3,000 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 ethylenically unsaturated compounds-
Other ethylenically unsaturated compounds include ethylenically unsaturated compounds having at least one group selected from the group consisting of N-vinyl group, vinyl ether group and (meth) acryloyl group.

  Specifically, examples of other ethylenically unsaturated compounds include (meth) acrylates (monofunctional (meth) acrylates, polyfunctional (meth) acrylates) and the like.

As a monofunctional (meth) acrylate, for example, linear, branched or cyclic alkyl (meth) acrylate, (meth) acrylate having a hydroxyl group, (meth) acrylate having a heterocyclic ring, (meth) acrylamide compound Etc.
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) acrylate, cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate 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.
As the (meth) acrylate having a heterocyclic ring, for example, tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxy Methyl-2-cyclohexyl-1,3-dioxolane, adamantyl (meth) acrylate and the like can be mentioned.
Examples of (meth) acrylamide compounds include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N Examples include '-dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide and N-hydroxybutyl (meth) acrylamide.

  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, tetramethylol methane triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO (ethylene oxide) modified diglycerin tetraacrylate, ditrimethylol propane tetraacrylate modified acrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate Pentaerythritol hexaacrylate etc. are mentioned.

90 mass% or more and 99 mass% or less are preferable with respect to the whole three-dimensional modeling material, and, as for content of a polymeric compound, 93 mass% or more and 97 mass% or less are more preferable.
In particular, as the polymerizable compound, it is preferable to use urethane (meth) acrylate in combination with the other ethylenically unsaturated compound. In this case, the content of the urethane (meth) acrylate is preferably 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less with respect to the entire three-dimensional modeling material. On the other hand, 40 mass% or more and 75 mass% or less are preferable with respect to the whole three-dimensional modeling material, and, as for content of the said other ethylenically unsaturated compound, 50 mass% or more and 65 mass% or less are more preferable.
In addition, a polymeric compound may be used individually by 1 type, and may be used together 2 or more types.

-Photopolymerization initiator-
As a photoinitiator, a radical photopolymerization initiator is preferable.
As the photopolymerization initiator, those mentioned above are preferably mentioned.
1 mass% or more and 10 mass% or less are preferable with respect to a three-dimensional modeling material, for example, as for content of a photoinitiator, 3 mass% or more and 5 mass% or less are more preferable.
In addition, a photoinitiator may be used individually by 1 type, and may be used together 2 or more types.

-Polymerization inhibitor-
As the polymerization inhibitor, those described above are preferably mentioned.
For example, 0.1 mass% or more and 1 mass% or less are preferable with respect to a three-dimensional modeling material, and, as for content of a polymerization inhibitor, 0.3 mass% or more and 0.5 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-
As the surfactant, those mentioned above are preferably mentioned.
The content of the surfactant is, for example, preferably 0.05% by mass or more and 0.5% by mass or less, and more preferably 0.1% by mass or more and 0.3% by mass or less with respect to the three-dimensional modeling material.
In addition, surfactant may be used individually by 1 type, and may be used together 2 or more types.

-Other additives-
Besides the above, as other additives, for example, colorants, solvents, sensitizers, fixing agents, fungicides, preservatives, antioxidants, ultraviolet absorbers, chelating agents, thickeners, dispersants, Well-known additives, such as a polymerization accelerator, a penetration promoter, a moistening agent (humectant), etc. are mentioned.

-Characteristics of 3D modeling material-
The surface tension of the three-dimensional modeling material is preferably in the range of 20 mN / m to 40 mN / m. In addition, in view of suppressing the movement of the liquid due to the surface tension difference when the three-dimensional modeling material and the support material are adjacent to each other before curing, the surface tension of the three-dimensional modeling material and for three-dimensional modeling according to the present embodiment 2 mN / m or less is preferable and, as for the difference of absolute value with the surface tension of a support material, 1 mN / m or less is more preferable.
The viscosity of the three-dimensional modeling material is preferably in the range of 30 mPa · s to 50 mPa · s.

(3D modeling device)
The three-dimensional modeling apparatus according to the present embodiment is not particularly limited as long as it is a three-dimensional modeling apparatus provided with the support material for three-dimensional modeling according to the present embodiment, but discharges a three-dimensional modeling material containing a polymerizable compound. A first discharge unit, and a second discharge unit that accommodates the support material for three-dimensional modeling according to the present embodiment and discharges the support material, and emits light that cures the discharged three-dimensional modeling material and the support material It is preferable to provide the light irradiation part which
Further, the three-dimensional modeling apparatus according to the present embodiment may be any three-dimensional modeling apparatus such as an optical modeling method, a powder method, a hot melt lamination method, or an inkjet method, but the three-dimensional modeling apparatus using an optical modeling method A modeling apparatus is preferably mentioned.

The first discharge portion and the second discharge portion in the three-dimensional modeling apparatus according to the present embodiment are not particularly limited as long as they are discharge devices that discharge by an inkjet method, but an ink jet head is preferable.
The inkjet head is not particularly limited, and a known inkjet head is used. For example, a piezo-type inkjet head can be mentioned.
Further, the number of ink jet heads and the number of nozzles in the ink jet heads are not particularly limited, and may be set as appropriate.
The discharge temperatures of the three-dimensional structure support material and the three-dimensional structure material are not particularly limited, and can be respectively adjusted according to the three-dimensional structure support material and the three-dimensional structure used.
There is no restriction | limiting in particular also about the discharge amount in the said support material for three-dimensional modeling and the said three-dimensional modeling material, What is necessary is just to discharge the quantity used as the target thickness. In addition, the discharge may be performed a plurality of times as necessary.

The light irradiation unit in the three-dimensional modeling apparatus according to the present embodiment may be any apparatus that emits light for curing the three-dimensional modeling support material and the three-dimensional modeling material, but an ultraviolet irradiation apparatus and electron beam irradiation An apparatus is preferably mentioned.
In addition, unless there is particular notice, "light" in this embodiment shall contain not only visible light but ultraviolet rays, infrared rays, etc.
It is preferable that the said light irradiation part irradiates an ultraviolet-ray.
In the curing at the time of the light irradiation, the three-dimensional modeling support material and the three-dimensional modeling material may be cured at one time or may be separately cured.

There is no restriction | limiting in particular as a light irradiation apparatus used for the said hardening, A well-known thing is used. Especially, an ultraviolet irradiation device and an electron beam irradiation device are mentioned preferably, and an ultraviolet irradiation device is mentioned more preferably.
The ultraviolet (UV) irradiation device is not particularly limited, but light emitting diodes (UV-LEDs), high pressure mercury lamps, ultra high pressure mercury lamps, deep ultraviolet lamps, lamps using microwaves to excite mercury lamps from the outside without electrodes, and ultraviolet light A laser, a xenon lamp, a metal halide lamp etc. are mentioned.
The light irradiation unit may have only one, or two or more.
In addition, the light irradiation part which hardens the said support material for three-dimensional modeling, and the light irradiation part which hardens the said three-dimensional modeling material may be the same, and may differ.

In addition, the three-dimensional modeling apparatus according to the present embodiment may be provided with a support material removing unit that removes the support material for three-dimensional modeling, and an apparatus different from the three-dimensional modeling apparatus according to the present embodiment The support material removing unit may be provided.
Furthermore, the three-dimensional modeling apparatus according to the present embodiment may further include known apparatuses and members.

Hereinafter, the three-dimensional modeling apparatus according to the present embodiment will be described with reference to the drawings.
FIG. 1: is a schematic block diagram which shows an example of the three-dimensional shaping apparatus which concerns on this 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 model material cartridge 30 that accommodates a radically polymerizable three-dimensional modeling material (model material) and a support material cartridge 32 that accommodates a support material so as to be removable from the apparatus. There is. In addition, in FIG. 1, MD shows a three-dimensional structure, SP shows a support part.

  The modeling unit 10 includes, for example, a model material discharge head 12 (an example of a first discharge unit) that discharges droplets of a model material, and a support material discharge head 14 that discharges droplets of a support material (an example of a second discharge unit And a light irradiation device 16 (light irradiation device) for irradiating light. In addition, although not shown in figure, modeling unit 10 may be provided with a rotation roller which removes an excess model material and a support material among model materials and a support material discharged on modeling stand 20, for example. .

  For example, the modeling unit 10 can move in the sub scanning direction crossing (for example, at right angles) the main scanning direction with the main scanning direction on the modeling region of the modeling table 20 by a driving device (not shown) (so-called carriage system) It has become.

  The model material discharge head 12 and the support material discharge head 14 each use 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 model material discharge head 12 is connected to, for example, a model material cartridge 30 through a supply pipe (not shown). Then, the model material cartridge 30 supplies the model material to the model material 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 support material to the support material discharge head 14.

Each of the model material discharge head 12 and the support material discharge head 14 has a short discharge head whose effective discharge area (arrangement area of nozzles for discharging the model material and the support material) is smaller than the modeling area of the modeling table 20 It has become.
Each of the model material discharge head 12 and the support material discharge head 14 has, for example, an effective discharge area (arrangement area of nozzles for discharging the model material and the support material) in the modeling area width (modeling unit) on the modeling table 20 The head may be a long head having a length of 10 or more in a direction crossing (for example, at right angles) with the moving direction (main scanning direction). In this case, the modeling unit 10 is moved only in the main scanning direction.

  The light irradiation device 16 is selected according to the type of model material and support material. As the light irradiation apparatus 16, an ultraviolet irradiation apparatus etc. are mentioned, for example. As an ultraviolet irradiation device, those mentioned above are mentioned.

  The modeling table 20 can be moved up and down by a 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, using a computer (not shown) or the like, for example, from three-dimensional CAD (Computer Aided Design) data of a three-dimensional structure formed by a model material, for example, two for forming a structure as data for three-dimensional formation. Generate dimensional shape data (slice data). 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, the model material is discharged from the model material discharge head 12 while moving the modeling unit 10 based on two-dimensional shape data for forming a modeled object, and a layer of the model material is formed on the modeling table 20. Form. Then, the layer of the model material is irradiated with light by the light irradiation device 16 to cure the model material, thereby forming a layer to be a part of the shaped object.

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 a layer of the model material is formed on the modeling table 20. Adjacent to, form a layer of support material. 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 shaped object and, if necessary, the layer to be a part of the support portion (see FIG. 2A). Here, in FIG. 2A, 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 portion 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. 2B). Here, in FIG. 2B, 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. 2C). Here, in FIG. 2C, MDn indicates a layer to be a part of a shaped object in the n-th layer LAYn. MD indicates a shaped object. SP indicates a support unit.

Thereafter, when the support portion is removed from the shaped object, the intended shaped object is obtained. 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.
In addition, you may perform post-processes, such as a grinding | polishing process, to the obtained molded article.

  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.

<Preparation of Support Material 1>
Water-soluble monomer: 28.5 parts by mass of HEAA (hydroxyethyl acrylamide, manufactured by KJ Chemicals, Inc.),
· Alkyl ester compound of unsaturated fatty acid having one hydroxy group: 52.5 parts by mass of URIC H31 (Methyl ricinoleate manufactured by Ito Oil Co., Ltd.),
Compatibilizer: 17.5 parts by mass of MTG (triethylene glycol monomethyl ether, manufactured by Nippon Nyukazai Co., Ltd.),
Polymerization initiator: 1 part by mass of Irgacure 819 (2,4,6-trimethyl benzoyl diphenyl phosphine oxide, manufactured by BASF),
Polymerization inhibitor: 0.2 parts by mass of MEHQ (hydroquinone monomethyl ether),
Surfactant: 0.3 parts by mass of TEGO Wet 270 (polyether modified siloxane copolymer, manufactured by Evonik Co., Ltd.) The above components were mixed to prepare a support material 1.

<Preparation of Support Material 2>
Only by changing the MTG of the support material 1 to BDG (diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd.), the above components were similarly mixed similarly, and a support material 2 was prepared.

<Preparation of Support Material 3>
Only by changing the MTG of the support material 1 to iBDG (diethylene glycol monoisobutyl ether, manufactured by Nippon Emulsifier Co., Ltd.), the above components were similarly mixed similarly to prepare a support material 3.

<Preparation of Support Material 4>
The above components were similarly mixed only by changing the MTG of the support material 1 to MFTG (tripropylene glycol monomethyl ether, manufactured by Nippon Emulsifier Co., Ltd.), and a support material 4 was prepared.

<Preparation of Support Material 5>
The above components were similarly mixed only by changing URIC H31 of the support material 1 to methyl ricinera diinate (manufactured by Kanto Chemical Co., Ltd.), and a support material 5 was prepared.

Preparation of Support Material C1 of Comparative Example 1
Water soluble monomer: 28.5 parts by mass of HEAA (KJ Chemicals Co., Ltd.),
An alkyl ester compound of unsaturated fatty acid having one hydroxy group: 70 parts by mass of methyl ricinoleate URIC H31 (manufactured by Ito Oil Co., Ltd.)
Polymerization initiator: 1 part by mass of Irgacure 819 (manufactured by BASF),
Polymerization inhibitor: 0.2 parts by mass of MEHQ,
Surfactant: 0.3 parts by mass of TEGO Wet 270 (manufactured by Evonik Co., Ltd.) The above components were mixed to prepare a support material C1 as Comparative Example 1.

Preparation of Support Material C2 of Comparative Example 2
Water soluble monomer: 28.5 parts by mass of HEAA (KJ Chemicals Co., Ltd.),
Compatibilizer: 70 parts by mass of MTG (manufactured by Nippon Emulsifier Co., Ltd.),
Polymerization initiator: 1 part by mass of Irgacure 819 (manufactured by BASF),
Polymerization inhibitor: 0.2 parts by mass of MEHQ,
Surfactant: 0.3 parts by mass of TEGO Wet 270 (manufactured by Evonik Co., Ltd.) The above components were mixed to prepare a support material C2 as Comparative Example 2.

<Preparation of Model Material 1>
-Urethane acrylate oligomer: 12.70 parts by mass ("U-200PA" Shin-Nakamura Chemical Co., Ltd. product)
-Urethane acrylate oligomer: 16.40 parts by mass ("UA-4200" Shin-Nakamura Chemical Co., Ltd. product)
Acrylate monomer: 50.40 parts by mass ("VEEA" manufactured by Nippon Shokubai Co., Ltd., 2- (2-vinyloxyethoxy) ethyl acrylate)
Acrylate monomer: 14.60 parts by mass ("IBXA" manufactured by Osaka Organic Chemical Industry Co., Ltd., isobornyl acrylate)
Polymerization inhibitor: 0.50 parts by mass (MEHQ (hydroquinone monomethyl ether))
Polymerization initiator: 3.00 parts by mass (Irgacure 819: manufactured by BASF, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide)
Polymerization initiator: 1.00 parts by mass (Irgacure 379: manufactured by BASF, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 -On)
. Sensitizer: 1.00 parts by mass (ITX (2-isopropylthioxanthone))
-Cyan pigment: 1.00 parts by mass (KY410-4B: manufactured by Taisei Chemical Industry Co., Ltd.)
Surfactant: 0.20 parts by mass (TEGO Wet 270: manufactured by Evonik, polyether-modified siloxane copolymer)
The above components were mixed to prepare a model material 1.

(Examples 1 to 5 and Comparative Examples 1 and 2)
<Production of 3D object>
The three-dimensional shaping apparatus selects a Polaris head (model number: PQ 512/85) manufactured by Fujifilm Dimatics Co., Ltd. as an ink jet head, and Subzero-055 (intensity of 100 w / cm) manufactured by INTEGRATION TECHNOLOGY LTD. These were installed in the modeling apparatus which consists of a drive part and a control part, and this was made into the modeling apparatus for a test. The modeling apparatus is a system in which the ink jet head and the light source reciprocate together, and a model material layer with a thickness of 20 μm and a support material layer as needed for each scan (scan), and curing by ultraviolet irradiation It was set as the apparatus which processes and forms the support part (support part) by a three-dimensional molded article and a support material as needed. Also, in the modeling apparatus, the model material and the support material are supplied from a storage tank by a liquid transfer pump via a Tygon 2375 drug resistant tube manufactured by Saint-Gobain under light-shielded conditions, and by Nippon Paul Co., Ltd. profile star A050 filter (filtration accuracy 5 μm ), And after removing the foreign matter, the liquid is sent to the ink jet head.
A doughnut-shaped three-dimensional plate having a thickness of 2 mm, a central hole diameter of 1 cm, and an outer diameter of 3 cm, using the support materials 1 to 5, C1 or C2 of each example prepared above and the model material 1 The support material 1 was filled in a hole of 1 cm in diameter of a shaped object, and a hardened support material remained attached.

<Water removability evaluation>
A test three-dimensional structure is placed in a beaker containing 100 mL of water, set in a shaker MK161 manufactured by Yamato Scientific Co., Ltd., elliptically shaken at 60 rpm at a temperature of 30 ° C., support material after 1 hour It was judged by the remaining of. In the case where A (残 っ) does not remain, in the case where B (△) has a hole but half remains, C (×) does not have a hole either. The support materials of Examples 1 to 5 and Comparative Example 1 cause phase separation by ultraviolet irradiation and become a white chocolate-like cured product, but the support materials of Comparative Example 2 are in a phase separated state by ultraviolet irradiation. Moreover, it did not function as a support material only by producing a highly viscous liquid (improper).

<Inkjet discharge evaluation>
Continuous discharge of 25.60000 was performed with a head temperature of 50 ° C., an applied voltage of 60 V, and a frequency of 5 kHz, and the ratio of non-discharge nozzles was measured by the discharge mass. When A (o) is less than 10%, B (Δ) is 10% or more and less than 30%, and C (x) is 30% or more.

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

Claims (13)

Water soluble monomer,
Photo initiator,
An alkyl ester compound of unsaturated fatty acid having one hydroxy group, and
Support material for three-dimensional modeling that contains a water-soluble compatibilizer.   The three-dimensional modeling support material according to claim 1, wherein the alkyl ester compound of unsaturated fatty acid having one hydroxy group is an alkyl ester compound of 1 to 8 carbon atoms of unsaturated fatty acid having one hydroxy group.   The support material for three-dimensional shaping according to claim 2, wherein the alkyl ester compound of unsaturated fatty acid having one hydroxy group is a methyl or ethyl ester compound of unsaturated fatty acid having one hydroxy group.   The alkyl ester compound of unsaturated fatty acid having one hydroxy group is exemplified by ricinoleic acid, 10-hydroxy-cis-12-octadecenoic acid, oxooctadecanoic acid, 10-oxo-11-octadecenoic acid, ricineridiic acid, and 10- The support material for three-dimensional structure formation according to any one of claims 1 to 3, which is an alkyl ester compound of at least one unsaturated fatty acid selected from the group consisting of hydroxyoctadecanoic acid.   The support material for three-dimensional modeling according to claim 4, wherein the alkyl ester compound of unsaturated fatty acid having one hydroxy group is an alkyl ester compound of ricinoleic acid.   The support material for three-dimensional modeling according to any one of claims 1 to 5, wherein the water-soluble monomer comprises a monomer having a hydroxy group.   The support material for three-dimensional modeling according to claim 6, wherein the water-soluble monomer comprises a hydroxyalkyl acrylamide compound.   The support material for three-dimensional modeling according to any one of claims 1 to 7, wherein the water-soluble compatibilizer is a polyalkylene glycol monoalkyl ether compound.   The support material for three-dimensional structure formation according to any one of claims 1 to 8, wherein the water-soluble compatibilizer is a di- or tri-alkylene glycol monoalkyl ether compound.   The support material for three-dimensional modeling according to any one of claims 1 to 9, further comprising a surfactant.   The support material for three-dimensional modeling according to any one of claims 1 to 10, further comprising a polymerization inhibitor. The support material for three-dimensional modeling according to any one of claims 1 to 11.
And three-dimensional modeling materials,
Material set for 3D modeling. A first discharge unit that discharges a three-dimensional modeling material containing a polymerizable compound;
The 2nd discharge part which accommodates the support material for three-dimensional modeling of any one of Claim 1 thru | or 11, and discharges the said support material,
A three-dimensional structure forming apparatus comprising: a light emitting unit configured to emit light for curing the discharged three-dimensional modeling material and the support material.