JP2017222049A - Liquid for supporting shape, method for producing three-dimensional modeled product, and apparatus for producing three-dimensional modeled product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid for supporting a shape, which has favorable handleability at ordinary temperature, has a viscosity at which the liquid can be discharged by an ink-jet method, is excellent in molding accuracy and ability for supporting a shape, and is capable of obtaining a support portion for supporting a shape, which can be easily removed by water.SOLUTION: The liquid for supporting a shape includes a monomer (A) having a hydrogen binding capacity, a solvent (B) having a hydrogen binding capacity, and a polymerization initiator (C). For example, an aspect is preferred in which the solvent (B) having a hydrogen binding capacity is at least one selected from a diol having 3 or more but 6 or less carbon atoms, a carboxylic compound, an amine compound, an ester compound, a ketone compound, and a urea compound.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a shape support liquid, a method for manufacturing a three-dimensional model, and a manufacturing apparatus for a three-dimensional model.

  As a technique for modeling a three-dimensional solid object, a technique called additive manufacturing (AM) is known.

  This technique is a technique for modeling a three-dimensional object by calculating a cross-sectional shape sliced thinly in the stacking direction, and forming and stacking each layer according to the shape. In addition, as a technique for modeling a three-dimensional object, a hot melt lamination method (FDM), an ink jetting method, a binder jetting method, a stereolithography method (SLA), a powder sintering layered molding method (SLA) SLS (Selective Laser Sintering) and the like are known. Among these, in recent years, a method of forming a three-dimensional solid object by forming an image of a liquid photocurable resin at a necessary portion of a modeled object by a material jetting method and multilayering the same is known.

  In addition, as a material jetting method, that is, an optical modeling technique using an inkjet method, it is known that a shape that is difficult to model in principle (for example, a shape having an overhang portion) can be produced when a model portion is modeled. Yes. In the said technique, the method of forming a support part simultaneously for shape support and supporting a model part is generally employ | adopted. A method has been proposed in which the support part is formed with the same material as that of the model part and removed by post-processing such as cutting or polishing (for example, see Patent Document 1).

  Furthermore, in the optical modeling technique using the ink jet method, it is possible to perform optical modeling by discharging each of a plurality of photocurable resin compositions of different types and physical properties from a nozzle into fine droplets. Is formed using a photocurable resin composition that forms a water-insoluble cured product, and the support material is formed using a photocurable resin composition that forms a water-soluble cured product. There has been proposed a technique for removing the support part by dissolving in (see, for example, Patent Document 2).

  The present invention has a shape capable of obtaining a support portion for shape support that has good handleability at room temperature, has a viscosity that can be discharged by an ink jet method, is excellent in modeling accuracy and shape support capability, and can be easily removed by water. An object is to provide a supporting liquid.

  The shape supporting liquid of the present invention as a means for solving the above problems comprises a monomer (A) having a hydrogen bonding ability, a solvent (B) having a hydrogen bonding ability, and a polymerization initiator (C). Including.

  According to the present invention, it is possible to obtain a support portion for shape support that has good handleability at room temperature, has a viscosity that can be discharged by an ink jet method, is excellent in modeling accuracy and shape support capability, and can be easily removed by water. A shape-supporting liquid can be provided.

FIG. 1 is a schematic diagram illustrating an example of forming a liquid film using the three-dimensional modeling apparatus for a three-dimensional modeled object of the present invention. FIG. 2 is a schematic diagram illustrating an example of a three-dimensional structure formed by laminating the liquid films illustrated in FIG. 1.

(Shape support liquid)
The shape supporting liquid of the present invention contains a monomer (A) having hydrogen bonding ability, a solvent (B) having hydrogen bonding ability, and a polymerization initiator (C), and further contains other components as necessary. including.
In the case of the conventional technology, the shape supporting liquid according to the present invention is easily removed when the solubility of the support portion is increased, but the support performance is insufficient, and the modeling apparatus is enlarged to increase the modeling volume. This is based on the knowledge that there is a problem that the shape support ability is insufficient.

The shape supporting liquid of the present invention preferably has water disintegration properties.
In addition, the said water disintegration means that hardened | cured material is decomposed | disassembled finely when immersed in water, and it becomes impossible to maintain the shape and property which it had initially.
In addition, in this invention, normal temperature is 20 degreeC or more and 40 degrees C or less etc., for example.

The shape supporting liquid of the present invention preferably satisfies the following conditions.
<Conditions>
When a cured product having a length of 20 mm, a width of 20 mm and a height of 5 mm obtained by irradiating with ultraviolet rays of 500 mJ / cm ² by an ultraviolet irradiation device is placed in 20 mL of water and allowed to stand at 25 ° C. for 1 hour, at least one direction is It is a solid having a size of 1 mm or less or completely dissolved.

The cured product having a length of 20 mm, a width of 20 mm, and a height of 5 mm can be produced as follows.
A shape supporting liquid is poured into a silicone rubber mold having a length of 20 mm, a width of 20 mm, and a height of 5 mm, and an ultraviolet ray irradiation amount (apparatus name: SubZero-LED, manufactured by Integration Technology Co., Ltd.) is used to emit an ultraviolet ray of 500 mJ / cm ² ( Irradiation is performed at an illuminance of 100 mW / cm ² and an irradiation time of 5 seconds. A support portion that is a cured product of 20 mm long × 20 mm wide × 5 mm high can be obtained.

In addition, the shape supporting liquid of the present invention preferably satisfies the following conditions.
<Conditions>
The cured product obtained by irradiating 500 mJ / cm ² of ultraviolet rays with an ultraviolet irradiation device is a solid having a compression stress of 2.0 kPa or more at 1% compression in an environment of 25 ° C., and 2 g of the solid is added to 20 mL of water. And the volume of the residual solid when left to stand at 25 ° C. for 1 hour is 50% by volume or less.
The volume of the remaining solid can be measured by Archimedes method.

When the cured product obtained by irradiating the ultraviolet ray with 500 mJ / cm ² by the ultraviolet irradiation device satisfies the above-mentioned conditions, the function of the shape supporting support portion can be improved.

Moreover, it is preferable that it is 0.5 kPa or more as a compressive stress at the time of 1-% compression of the hardened | cured material obtained by irradiating an ultraviolet-ray with 500 mJ / cm < ² > with an ultraviolet irradiation device. When the compressive stress at the time of 1% compression is 0.5 kPa or more, the function of the shape supporting support portion can be improved.
The compressive stress at the time of 1% compression is also affected by the size of the model portion that supports the shape, and when the size of the model portion is large, it is 2.0 kPa or more from the point of shape support. More preferred.
The compressive stress at the time of 1% compression can be measured using a universal testing machine (device name: AG-I, manufactured by Shimadzu Corporation, load cell 1 kN, compression jig for 1 kN).
There is no restriction | limiting in particular as said ultraviolet irradiation apparatus, According to the objective, it can select suitably, For example, it can measure using apparatus name: AG-I (made by Shimadzu Corporation).
At the irradiation dose of 500 mJ / cm ² , the illuminance is preferably 100 mW / cm ² and the irradiation time is preferably 5 seconds.

<Monomer (A) having hydrogen bonding ability>
The monomer (A) having hydrogen bonding ability is not particularly limited as long as it has hydrogen bonding ability, and can be appropriately selected according to the purpose. For example, polymerization that undergoes radical polymerization by irradiation with active energy rays such as ultraviolet rays. And monofunctional monomers and polyfunctional monomers having properties. These may be used individually by 1 type and may use 2 or more types together. Among these, a monofunctional monomer is preferable from the viewpoint of improving water disintegration.

  Examples of the monomer (A) having hydrogen bonding ability include monomers having an amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, epoxy group, sulfo group, and the like.

  Examples of the polymerization reaction of the monomer (A) having hydrogen bonding ability include radical polymerization, ionic polymerization, coordination polymerization, and ring-opening polymerization. Among these, radical polymerization is preferable from the viewpoint of controlling the polymerization reaction. Therefore, the monomer (A) having hydrogen bonding ability is preferably an ethylenically unsaturated monomer, more preferably a water-soluble monofunctional ethylenically unsaturated monomer or a water-soluble polyfunctional ethylenically unsaturated monomer, and has a hydrogen bonding ability. From the viewpoint of high points, water-soluble monofunctional ethylenically unsaturated monomers are particularly preferable.

<< Water-soluble monofunctional ethylenically unsaturated monomer having hydrogen bonding ability >>
Examples of the water-soluble monofunctional ethylenically unsaturated monomer having hydrogen bonding ability include monofunctional vinylamide group-containing monomers [N-vinyl-ε-caprolactam, N-vinylformamide, N-vinylpyrrolidone, etc.]; monofunctional hydroxyl group Containing (meth) acrylate [hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.]; hydroxyl group-containing (meth) acrylate [polyethylene glycol mono (meth) acrylate, monoalkoxy (C1 -4) Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, monoalkoxy (C1-4) polypropylene glycol mono (meth) acrylate, PEG-PPG block polymer (Meth) acrylamide derivatives [(meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide] N, N′-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, etc.], (meth) acryloylmorpholine, and the like. . These may be used individually by 1 type and may use 2 or more types together. Among these, (meth) acrylate and (meth) acrylamide derivatives are preferable from the viewpoint of photoreactivity, and hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylamide, acryloylmorpholine, N-methylacrylamide, N- Ethyl acrylamide, N-propyl acrylamide, N-butyl acrylamide, N, N′-dimethyl acrylamide, N-hydroxyethyl acrylamide, N-hydroxypropyl acrylamide, N-hydroxybutyl acrylamide, and diethyl acrylamide are more preferable, and the skin to human body is low. From the viewpoint of irritation, acryloylmorpholine (molecular weight: 141.17) and N-hydroxyethylacrylamide (molecular weight: 115.15) are particularly preferred. Yes.

<< Water-soluble polyfunctional ethylenically unsaturated monomer having hydrogen bonding ability >>
Examples of the water-soluble polyfunctional ethylenically unsaturated monomer having hydrogen bonding ability include tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate ester di (meth) acrylate (MANDA), hydroxypivalate neopentyl glycol ester di (meth) acrylate (HPNDA), 1,3-butanediol di (Meth) acrylate (BGDA), 1,4-butanediol di (meth) acrylate (BUDA), 1,6-hexanediol di (meth) acrylate (HDDA), 1,9-nonanediol (Meth) acrylate, diethylene glycol di (meth) acrylate (DEGDA), neopentyl glycol di (meth) acrylate (NPGDA), tripropylene glycol di (meth) acrylate (TPGDA), caprolactone-modified hydroxypivalic acid neopentyl glycol ester di ( (Meth) acrylate, propoxylated opentyl glycol di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate; trifunctional or higher functional monomers such as triallyl isocyanate, tris (2-hydroxyethyl) ) Isocyanurate tri (meth) acrylate and the like. These may be used individually by 1 type and may use 2 or more types together.

  The molecular weight of the monomer (A) having hydrogen bonding ability is preferably 70 or more and 2,000 or less, and more preferably 100 or more and 500 or less. When the molecular weight is 70 or more and 2,000 or less, the viscosity can be adjusted to be optimal for the ink jet system.

  The content of the monomer (A) having hydrogen bonding ability is preferably 30% by mass or more and 60% by mass or less based on the total amount of the shape supporting liquid. When the content is 30% by mass or more and 60% by mass or less, it is possible to achieve both compressive stress and water disintegration sufficient for the shape supporting support part.

<Solvent (B) having hydrogen bonding ability>
The solvent (B) having hydrogen bonding ability has a hydrogen bonding ability with the monomer (A) having hydrogen bonding ability, and forms a hydrogen bond with the monomer (A) having hydrogen bonding ability, thereby supporting the shape. The function of the support part can be demonstrated.
The solvent (B) having hydrogen bonding ability is preferably liquid at 25 ° C.

  The solvent (B) having hydrogen bonding ability is preferably at least one selected from diols having 3 to 6 carbon atoms, carboxylic acid compounds, amine compounds, ester compounds, ketone compounds, and urea compounds. A diol having 3 to 6 carbon atoms is more preferable.

<< Diol having 3 to 6 carbon atoms >>
The diol having 3 to 6 carbon atoms is a material that is not reactive with a water-soluble acrylic monomer, does not inhibit a radical polymerization reaction during curing, has fluidity at room temperature, and is soluble in water. It is preferable.
As the diol having 3 to 6 carbon atoms, either monofunctional or polyfunctional can be used.

Examples of the diol having 3 to 6 carbon atoms include propanediol, butanediol, pentanediol, and hexanediol. These may be used individually by 1 type and may use 2 or more types together. Among these, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are preferable.
The carbon number is 3 or more and 6 or less, and preferably 3 or more and 5 or less. When the carbon number is 3 or more, the compressive stress at 1% compression can be improved, and when it is 6 or less, the viscosity of the shape supporting liquid can be lowered.
The carbon chain of the diol having 3 to 6 carbon atoms may be linear or branched.

<< carboxylic acid compound >>
Examples of the carboxylic acid compounds include linear aliphatic acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, and hexyl acid; isobutyric acid, t-butyric acid, isopentylic acid, isooctylic acid, and 2-ethylhexylic acid. And various branched aliphatic carboxylic acids such as: aromatic carboxylic acids such as benzoic acid and benzenesulfonic acid; and hydroxycarboxylic acids such as glycolic acid and lactic acid. These may be used individually by 1 type and may use 2 or more types together. Among these, from the viewpoint of solubility in water, acetic acid, propionic acid, butanoic acid, and lactic acid are preferable, and butanoic acid and lactic acid are more preferable.

<< Amine compound >>
Examples of the amine compound include primary to tertiary amines such as monoalkylamines, dialkylamines, and trialkylamines; divalent amines such as ethylenediamine; trivalent amines such as triethylenediamine; and aliphatic amines such as pyridine and aniline. Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, a divalent or trivalent primary amine is preferable, and ethylenediamine is more preferable from the viewpoint of crosslinking strength due to hydrogen bonding and solubility in water.

<< Ester compound >>
Examples of the ester compound include monofunctional esters such as ethyl acetate, butyl acetate, and ethyl propionate; polyfunctional aliphatic esters such as dimethyl succinate and dimethyl adipate; and polyfunctional aromatic esters such as dimethyl terephthalate. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, dimethyl adipate is preferable from the viewpoints of solubility in water, evaporation and odor during modeling, and safety.

<< ketone compound >>
Examples of the ketone compound include monofunctional ketones such as acetone and methyl ethyl ketone, and polyfunctional ketones such as acetylacetone and 2,4,6-heptatrione. These may be used individually by 1 type and may use 2 or more types together. Among these, acetylacetone is preferable from the viewpoints of volatility and solubility in water.

  As content of the said solvent (B) which has the hydrogen bonding ability, 10 mass% or more and 50 mass% or less are preferable with respect to the total liquid for shape support. When the content is 10% by mass or more and 50% by mass or less, it is possible to achieve both compressive stress and water disintegrability sufficient for the shape supporting support part.

[Mass ratio (A / B)]
The mass ratio (A / B) between the content (% by mass) of (A) and the content (% by mass) of (B) is preferably 0.3 or more and 2.5 or less, and 0.5 or more. 2.5 or less is more preferable. When the mass ratio (A / B) is 0.3 or more and 2.5 or less, the compressive stress during 1% compression can be improved.

<Polymerization initiator (C)>
As the polymerization initiator (C), any substance that generates radicals upon irradiation with light (particularly, ultraviolet rays having a wavelength of 220 nm to 400 nm) can be used.

  Examples of the polymerization initiator (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p′-dichlorobenzophenone, p, p-bisdiethylaminobenzophenone. , Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl methyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy 2-methyl-1-phenyl-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylben Yl formate, 1-hydroxycyclohexyl phenyl ketone, azobisisobutyronitrile, benzoyl peroxide, and di -tert- butyl peroxide. These may be used individually by 1 type and may use 2 or more types together. Moreover, it is preferable to select a polymerization initiator that matches the ultraviolet wavelength of the ultraviolet irradiation device.

  As content of the said polymerization initiator (C), 0.5 mass% or more and 10 mass% or less are preferable with respect to the liquid for shape support.

The surface tension of the shape supporting liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 20 mN / m or more and 45 mN / m or less, more preferably 25 mN / m or more and 34 mN / m or less. preferable. When the surface tension is 20 mN / m or more, discharge can be prevented from becoming unstable (the discharge direction is bent or not discharged) during modeling, and when it is 45 mN / m or less, the discharge nozzle for modeling For example, the liquid can be easily filled.
The surface tension can be measured using, for example, a surface tension meter (automatic contact angle meter DM-701, manufactured by Kyowa Interface Science Co., Ltd.).

-Viscosity-
The viscosity of the shape supporting liquid is preferably 100 mPa · s or less at 25 ° C., more preferably 3 mPa · s or more and 20 mPa · s or less, and particularly preferably 6 mPa · s or more and 12 mPa · s or less at 25 ° C.
When the viscosity is 100 mPa · s or less, ejection stability can be improved.
In addition, the said viscosity can be measured in 25 degreeC environment using a rotational viscometer (VISCOMATE VM-150III, the Toki Sangyo Co., Ltd. make), for example.

-Viscosity change rate-
The shape supporting liquid preferably has a viscosity change rate of ± 20% or less before and after being left at 50 ° C. for 2 weeks, more preferably ± 10% or less.
When the viscosity change rate is ± 20% or less, the storage stability is appropriate and the ejection stability is good.

The viscosity change rate before and after leaving at 50 ° C. for 2 weeks can be measured as follows.
The shape support liquid is put into a polypropylene wide-mouth bottle (50 mL), left in a thermostatic bath at 50 ° C. for 2 weeks, then taken out from the thermostatic bath and left to reach room temperature (25 ° C.) to measure the viscosity. Do. The viscosity of the shape supporting liquid before entering the thermostatic bath is the viscosity before storage, and the viscosity of the shape supporting liquid after taking out from the thermostatic bath is the viscosity after storage, and the viscosity change rate can be calculated by the following formula. The pre-storage viscosity and the post-storage viscosity can be measured at 25 ° C. using, for example, an R-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
Viscosity change rate (%) = [(viscosity after storage) − (viscosity before storage)] / (viscosity before storage) × 100

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, it superposes | polymerizes separately from a solvent, a polymerization inhibitor, the mineral dispersible in the shape support liquid, and said (A) component. Monomer, thermal polymerization initiator, colorant, antioxidant, chain transfer agent, anti-aging agent, crosslinking accelerator, ultraviolet absorber, plasticizer, preservative, dispersant and the like.

-Solvent-
Examples of the solvent include alcohols, ether compounds, triols, triethylene glycol, and polypropylene glycol. These may be used individually by 1 type and may use 2 or more types together.

The SP value of the solvent, from the viewpoint of the water disintegratability, preferably 18 MPa ^1/2 or more, 23 MPa ^1/2 or more is more preferable.

  The content of the solvent is preferably 50% by mass or less, and more preferably 30% by mass or less.

--- Polymerization inhibitor ---
Examples of the polymerization inhibitor include phenol compounds [hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol). ), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, etc.], sulfur compounds [dilauryl thiodipropionate, etc.], phosphorus compounds [triphenyl phosphite, etc. ], Amine compounds [phenothiazine and the like] and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the polymerization inhibitor is usually preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of compressive stress with respect to the total amount of the shape support liquid.

--- Minerals dispersible in shape support liquid-
There is no restriction | limiting in particular as a mineral dispersible in the said shape support liquid, According to the objective, it can select suitably, For example, a layered clay mineral etc. are mentioned.

Examples of the layered clay mineral include smectite such as montmorillonite, beidellite, hectorite, saponite, nontronite, stevensite, etc .; vermiculite; bentonite; These may be used individually by 1 type and may use 2 or more types together.
The layered clay mineral may be produced as a natural mineral or may be produced by a chemical synthesis method.

The layered clay mineral may be subjected to organic treatment on the surface.
The layered inorganic material such as the layered clay mineral can be treated with an organic cationic compound so that the cation between the layers can be ion-exchanged with a cationic group such as a quaternary salt.
Examples of the cation of the layered clay mineral include metal cations such as sodium ion and calcium ion.

The layered clay mineral treated with the organic cationic compound is easily swollen and dispersed in the polymer and the polymerizable monomer.
Examples of the layered clay mineral treated with the organic cationic compound include Lucentite series (manufactured by Coop Chemical Co., Ltd.). Examples of the Lucentite series (Coop Chemical Co., Ltd.) include Lucentite SPN, Lucentite SAN, Lucentite SEN, and Lucentite STN. These may be used individually by 1 type and may use 2 or more types together.

--Polymerizable monomer--
There is no restriction | limiting in particular as said polymerizable monomer, According to the objective, it can select suitably, For example, (meth) acrylate etc. are mentioned.

  Examples of the (meth) acrylate include 2-ethylhexyl (meth) acrylate (EHA), isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, lauryl (meth) acrylate, and 2-phenoxyethyl (meth) acrylate. , Isodecyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

--- Thermal polymerization initiator-
The thermal polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an azo initiator, a peroxide initiator, a persulfate initiator, or a redox (oxidation reduction) initiator. Etc. However, from the viewpoint of storage stability, a photopolymerization initiator is preferable to a thermothermal polymerization initiator.

  Examples of the azo initiator include VA-044, VA-46B, V-50, VA-057, VA-061, VA-067, VA-086, 2,2′-azobis (4-methoxy-2). , 4-dimethylvaleronitrile) (VAZO 33), 2,2′-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2′-azobis (2,4-dimethylvaleronitrile) (VAZO 52) ), 2,2′-azobis (isobutyronitrile) (VAZO64), 2,2′-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO) 88) (both available from DuPont Chemical), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2 - azobis (methyl isobutyrate - DOO) (V-601) (manufactured by Wako Pure Chemical Industries, available from KK).

  Examples of the peroxide initiator include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S). ) (Available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butylperoxy-2-ethyl Hexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

  Examples of the persulfate initiator include potassium persulfate, sodium persulfate, and ammonium persulfate.

  Examples of the redox initiator include a combination of the persulfate initiator and a reducing agent such as sodium metabisulfite and sodium bisulfite, a system based on the organic peroxide and a tertiary amine. (For example, a system based on benzoyl peroxide and dimethylaniline), a system based on an organic hydroperoxide and a transition metal (for example, a system based on cumene hydroperoxide and cobalt naphthate), and the like.

--Colorant--
Examples of the colorant include pigments and dyes.
Examples of the pigment include organic pigments and inorganic pigments.

  Examples of the organic pigment include azo pigments, polycyclic pigments, azine pigments, daylight fluorescent pigments, nitroso pigments, nitro pigments, and natural pigments.

  Examples of the inorganic pigment include metal oxides (iron oxide, chromium oxide, titanium oxide, etc.), carbon black, and the like.

--Antioxidant--
Examples of the antioxidant include a phenol compound [monocyclic phenol (2,6-di-t-butyl-p-cresol, etc.), bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol). ], Etc.], polycyclic phenol [1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc.], etc.], sulfur compounds (dilauryl 3) , 3'-thiodipropionate etc.), phosphorus compounds (triphenyl phosphite etc.), amine compounds (octylated diphenylamine etc.) and the like.

-Chain transfer agent-
Examples of the chain transfer agent include hydrocarbons [compounds having 6 to 24 carbon atoms, such as aromatic hydrocarbons (toluene, xylene, etc.), unsaturated aliphatic hydrocarbons (1-butene, 1-nonene, etc.). Halogenated hydrocarbons (compounds having 1 to 24 carbon atoms, such as dichloromethane, carbon tetrachloride, etc.); alcohols (compounds having 1 to 24 carbon atoms, such as methanol, 1-butanol, etc.); thiols (carbon Compounds having a number of 1 to 24, such as ethyl thiol, 1-octyl thiol, etc .; ketones (compounds having a carbon number of 3 to 24, such as acetone, methyl ethyl ketone); aldehydes (compounds having a carbon number of 2 to 18; For example, 2-methyl-2-propylaldehyde, 1-pentylaldehyde); phenol (a compound having 6 to 36 carbon atoms) For example, phenol, m-cresol, p-cresol, o-cresol, etc.); quinone (compound having 6 to 24 carbon atoms, such as hydroquinone); amine (compound having 3 to 24 carbon atoms, such as diethylmethyl) Amines, diphenylamines); disulfides (compounds having 2 to 24 carbon atoms, such as diethyl disulfide and di-1-octyl disulfide).

[Supporting power of cured product of shape support liquid]
The supporting force of the cured product of the shape supporting liquid in the present invention (hereinafter also referred to as “support part”) is the performance of the support part to support the model part, and is expressed by compressive stress at 1% compression. Can do.

The support force of the support part is preferably 0.5 kPa or more, more preferably 2.0 kPa or more, at a compression rate of 1% in a 25 ° C. environment from the viewpoint of modeling accuracy of the shaped product and solubility of the support part. preferable.
The supporting force of the support part can be adjusted to the above range by selecting the type and content of the components (A) and (B) constituting the support part. In addition, the compressive stress at the time of 1% compression can be measured using a universal testing machine (manufactured by Shimadzu Corporation, AG-I).

  As the supporting force of the support part in the present invention, it is considered that a high supporting force is secured by hydrogen bonding of the component (B) to the polymer obtained by polymerizing the component (A).

[Removability of support part]
As described above, the support force of the support portion in the present invention is derived from hydrogen bonding. The support force of the support portion is weakened by being immersed in water, and can be removed by collapse. Further, when the (B) has a low molecular weight, diffusion is fast and it is possible to remove it in a short time.

--Dissolved solution--
Examples of the solution include those having hydrogen bonding ability.
Examples of the solution include water, alcohol butanol and hexanol, amine hexylamine and pentylamine, and aromatic compounds benzene and toluene. These may be used individually by 1 type and may use 2 or more types together. Among these, water and alcohol are preferable from the viewpoint of safety.

Moreover, you may add an additive to the said solution.
Examples of the additive include a surfactant. The affinity for the linear alkyl chain can be increased by adjusting the type and amount of the surfactant.
Although 40 degreeC or more is preferable from the point which softens a support part and the said solution is easy to osmose | permeate inside, the temperature lower than 40 degreeC can also be selected from the point which prevents the curvature of a three-dimensional molded item.

(Manufacturing method of three-dimensional structure and manufacturing apparatus of three-dimensional structure)
The manufacturing method of the three-dimensional molded item of this invention manufactures a three-dimensional molded item using the shape support liquid of this invention.
As a manufacturing method of the said three-dimensional molded item, the liquid film formation process which forms a liquid film using a model material and the shape support liquid (support material) of this invention, and the hardening process which hardens the said liquid film are repeated. Thus, it is preferable to remove the support part after producing a three-dimensional modeled object composed of a model part that is a cured product of the model material and a support part that is a cured product of the shape supporting liquid (support material).
The removal of the support part is preferably performed with water or steam.
The manufacturing apparatus for a three-dimensional structure according to the present invention includes: a storage unit that stores a shape supporting liquid; a liquid film forming unit that forms a liquid film using the shape supporting liquid; and a curing unit that cures the liquid film. Have.
The manufacturing method of the said three-dimensional molded item can be suitably implemented with the manufacturing apparatus of the said three-dimensional molded item.

<Liquid film forming step and liquid film forming means>
The liquid film forming step is a step of forming a liquid film while controlling the application position and the application amount of the shape supporting liquid of the present invention.
The liquid film forming means is means for forming a liquid film while controlling the application position and the application amount of the shape supporting liquid of the present invention.
The liquid film forming step can be preferably performed by the liquid film forming means.

  As the shape supporting liquid, the same liquid as the shape supporting liquid of the present invention can be used.

  The liquid film forming step is preferably performed by either an ink jet method or a dispenser method.

<Curing process and curing means>
The curing step is a step of curing the liquid film.
The curing means is means for curing the liquid film.
The curing step can be preferably performed by the curing means.
Examples of the curing means include an ultraviolet irradiation device.

-Ultraviolet irradiation device-
Examples of the ultraviolet (UV) irradiation device include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide.
The high-pressure mercury lamp is a point light source, but the Deep UV type with high light utilization efficiency combined with an optical system can irradiate in a short wavelength region.
Since the metal halide has a wide wavelength range, it is effective as a colored product. A metal halide such as Pb, Sn, or Fe is used, and can be selected according to the absorption spectrum of the polymerization initiator. There is no restriction | limiting in particular as a lamp | ramp used for hardening, According to the objective, it can select suitably, For example, what is marketed like H lamp, D lamp, or V lamp made from Fusion System, etc. is also used. be able to.

  The manufacturing apparatus for the three-dimensional structure is preferably heaterless, and can be formed at room temperature.

Hereinafter, specific embodiments for three-dimensional modeling using the shape supporting liquid of the present invention will be described.
First, three-dimensional shape designed by three-dimensional CAD, or three-dimensional surface data or solid data captured by a three-dimensional scanner or digitizer is converted into an STL format and input to an additive manufacturing apparatus.

  Next, the modeling direction of the three-dimensional shape to be modeled is determined based on the input data. The modeling direction is not particularly limited, but usually the direction in which the Z direction (height direction) is the lowest is selected.

  When the modeling direction is determined, the projection area of the three-dimensional shape on the XY plane, XZ plane, and YZ plane is obtained. The obtained block shape is cut into slices (slices) in the Z direction with a single layer thickness. The thickness of one layer depends on the material used, but is usually about 20 μm to 60 μm. When there is one model to be modeled, the block shape is arranged so as to be in the middle of the Z stage (a table on which a model that descends one layer at a time for each model) is placed. In addition, when a plurality of models are formed simultaneously, the block shape is arranged on the Z stage, but the block shapes can be stacked. These block shaping, circular cut data (slice data: contour data), and arrangement on the Z stage can be automatically created by specifying the material to be used.

  Next, a modeling process is carried out. The different heads 1 and 2 (FIG. 1) are moved in both directions to discharge the model material precursor liquid α and the shape support liquid β to form dots. Furthermore, a liquid film can be produced at a desired position by forming continuous dots. The liquid film is cured by irradiating ultraviolet (UV) light, and the model material film and the support material film can be formed at desired positions.

  After the model material film and the support material film are formed in one layer, the stage (FIG. 1) is lowered by a height of one layer. Again, continuous dots are formed on the model material film and the support material film, and a liquid film is produced at a desired position. The liquid film is cured by irradiating ultraviolet (UV) light to form a model material film and a support material film at desired positions. By repeating these laminations, three-dimensional modeling becomes possible as shown in FIG.

  Thus, the three-dimensional modeled object can remove a support part with the said solution, and can obtain a desired three-dimensional modeled object (model part).

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
The viscosity was measured as follows.

<Viscosity>
The viscosity was measured in a 25 ° C. environment using a rotational viscometer (VISCOMATE VM-150III, manufactured by Toki Sangyo Co., Ltd.).

Example 1
50.0 parts by mass of acryloylmorpholine (manufactured by KJ Chemicals), 50.0 parts by mass of 1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, BASF shares 3.0 parts by mass of company) and 0.1 parts by mass of phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and mixed by stirring to obtain the shape supporting liquid of Example 1.

(Examples 2 to 15 and Comparative Examples 1 to 9)
In Example 1, the shape supporting liquids of Examples 2 to 15 and Comparative Examples 1 to 9 were obtained in the same manner as Example 1 except that the composition was changed to Tables 1 to 5 below.

  Next, using each of the obtained shape-supporting liquids, a “cured product (support part)” is formed in the following manner, the support part removability (water disintegration), and the support part support force. (Compressive stress at 1% compression) was evaluated. The results are shown in Tables 1 to 5 below.

[Production of cured product (support part)]
A shape supporting liquid is poured into a silicone rubber mold having a length of 20 mm, a width of 20 mm, and a height of 5 mm, and an ultraviolet ray irradiation amount (apparatus name: SubZero-LED, manufactured by Integration Technology Co., Ltd.) is used to emit an ultraviolet ray of 500 mJ / cm ² ( Irradiation was performed at an illuminance of 100 mW / cm ² and an irradiation time of 5 seconds to obtain a support part that is a cured product of 20 mm long × 20 mm wide × 5 mm high.

(Removability of support part (water disintegration))
The obtained support part 20 mm long × 20 mm wide × 5 mm high was placed in 20 g of warm water at 25 ° C. and allowed to stand for 1 hour. Thereafter, the silicone rubber mold was taken out, the support part was visually observed, and “removability of the support part (water disintegration)” was evaluated based on the following evaluation criteria. The volume of the remaining solid was measured by Archimedes method.
-Evaluation criteria-
○: The support part is less than 30% by volume Δ: The support part is 30% by volume or more and 50% by volume or less ×: The support part remains more than 50% by volume

(Supporting force of support part (compressive stress at 1% compression))
The obtained support part of 20 mm long x 20 mm wide x 5 mm high is provided with a universal testing machine (device name: AG-I, manufactured by Shimadzu Corporation), a load cell 1 kN, a compression jig for 1 kN, A support part shaped in a shape of 20 mm in length × 20 mm in width × 5 mm in height is installed, the stress against compression applied to the load cell is recorded in a computer, the stress against displacement is plotted, and the compression stress at 1% compression is measured did.

In the said Tables 1-5, it is as follows about the brand name of a component, and a manufacturing company name.
Acrylylmorpholine: manufactured by KJ Chemicals, molecular weight: 141.17
N-hydroxyethylacrylamide: manufactured by KJ Chemicals, molecular weight: 115.15
1,3-propanediol: manufactured by Tokyo Chemical Industry Co., Ltd.1,4-butanediol: manufactured by Tokyo Chemical Industry Co., Ltd.1,5-pentanediol: manufactured by Tokyo Chemical Industry Co., Ltd.1,6-hexanediol: Tokyo Chemical Industry Co., Ltd., Butanoic Acid: Tokyo Chemical Industry Co., Ltd., L-lactic acid: Tokyo Chemical Industry Co., Ltd., Methylamine: Tokyo Chemical Industry Co., Ltd., Dimethyl Adipate: Tokyo Chemical Industry Co., Ltd., Acetylacetone : Tokyo Chemical Industry Co., Ltd. Trimethylurea: Tokyo Chemical Industry Co., Ltd. 1-Hexanol: Tokyo Chemical Industry Co., Ltd. 1-Dodecanol: Tokyo Chemical Industry Co., Ltd. 1,2-ethanediol: Tokyo Chemical Industry 1,7-heptanediol manufactured by Tokyo Chemical Industry Co., Ltd., 1,3,5-triol-3-methylpentane manufactured by Tokyo Chemical Industry Co., Ltd. Industry Co., Ltd., ethylene glycol dimethyl ether: Tokyo Chemical Industry Co., Ltd. 1-hydroxy phenyl ketone, manufactured by BASF Corporation, trade name: Irgacure 184
-Phenothiazine: Tokyo Chemical Industry Co., Ltd.-Polypropylene glycol (diol type, 400): Wako Pure Chemical Industries, Ltd.

From the results of Tables 1 to 5, Examples 1 to 3 and 8 are all good in viscosity, support part removability (water disintegration), and support part support force (compression stress at 1% compression). It turns out that it is.
Example 4 is an example in which a diol having 5 carbon atoms and a diol having 6 carbon atoms are used in combination, but it can be seen that the removability (water disintegration property) of the support portion is slightly inferior.
Example 5 is an example in which a diol having 6 carbon atoms is used as the component (B), but it can be seen that the removability (water disintegration property) of the support portion is slightly inferior.
Although Example 6 is an example whose mass ratio (A / B) is less than 0.5, it turns out that the support force (compression stress at the time of 1% compression) of a support part is a little inferior.
Example 7 is an example using N-hydroxyethylacrylamide, which is excellent in the removability (water disintegration) of the support part, but the support force of the support part (compression stress at 1% compression) is slightly inferior, It can be seen that the viscosity is also high.
Examples 9 to 15 are examples using the component (B) other than the diol having 3 to 6 carbon atoms, but high viscosity, support part removability (water disintegration), and support part support force ( It can be seen that any one of the compression stresses at the time of 1% compression is inferior.
Comparative Examples 1 to 8 are examples that do not contain the component (B), but either the support part removability (water disintegration) and the support part support force (compression stress at 1% compression) are inferior. I understand that.

As an aspect of this invention, it is as follows, for example.
<1> a monomer (A) having hydrogen bonding ability;
A solvent (B) having hydrogen bonding ability;
A shape-supporting liquid comprising a polymerization initiator (C).
<2> The above-mentioned solvent (B) having hydrogen bonding ability is at least one selected from diols having 3 to 6 carbon atoms, carboxylic acid compounds, amine compounds, ester compounds, ketone compounds, and urea compounds. It is a shape support liquid as described in <1>.
<3> The shape supporting liquid according to <1>, wherein the solvent (B) having hydrogen bonding ability is the diol having 3 to 6 carbon atoms.
<4> From the above <1> to <1> in which the compression stress at the time of 1% compression in a 25 ° C. environment becomes a solid of 0.5 kPa or more of the cured product obtained by irradiating the ultraviolet ray with 500 mJ / cm ² by the ultraviolet irradiation device 3> The shape supporting liquid according to any one of 3).
<5> From the above <1> to <4, a cured product obtained by irradiating ultraviolet rays at 500 mJ / cm ² with an ultraviolet irradiation device becomes a solid having a compressive stress at 1% compression in a 25 ° C. environment of 2.0 kPa or more. > The shape supporting liquid according to any one of the above.
<6> The shape supporting liquid according to any one of <1> to <5>, wherein the following condition is satisfied.
<Conditions>
When a cured product having a length of 20 mm, a width of 20 mm and a height of 5 mm obtained by irradiating with ultraviolet rays of 500 mJ / cm ² by an ultraviolet irradiation device is placed in 20 mL of water and allowed to stand at 25 ° C. for 1 hour, at least one direction is It is a solid having a size of 1 mm or less or completely dissolved.
<7> The shape supporting liquid according to any one of <1> to <6>, wherein the following condition is satisfied.
<Conditions>
A cured product obtained by irradiating with ultraviolet rays of 500 mJ / cm ² by an ultraviolet irradiation device is a solid having a compressive stress of 2.0 kPa or more at 1% compression in a 25 ° C. environment,
2 g of the solid is put in 20 mL of water, and the volume of the remaining solid when left at 25 ° C. for 1 hour is 50% by volume or less.
<8> The content of (A) is 30% by mass or more and 60% by mass or less,
The shape support liquid according to any one of <1> to <7>, wherein the content of (B) is 10% by mass or more and 50% by mass or less.
<9> The (A) is a monofunctional monomer,
The shape supporting liquid according to any one of <1> to <8>, wherein the molecular weight of the monofunctional monomer is 100 or more and 500 or less.
<10> The above-mentioned <A> wherein the mass ratio (A / B) of the content (% by mass) of (A) and the content (% by mass) of (B) is 0.5 or more and 2.5 or less. The shape supporting liquid according to any one of <1> to <9>.
<11> The shape supporting liquid according to any one of <1> to <10>, wherein (A) is at least one of acryloylmorpholine and N-hydroxyethylacrylamide.
<12> The shape support liquid according to any one of <1> to <11>, wherein the shape support liquid has a viscosity of 100 mPa · s or less at 25 ° C.
<13> The diol having 3 to 6 carbon atoms is 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. The shape supporting liquid according to any one of <2> to <12>, which is at least one selected.
<14> The shape supporting liquid according to any one of <2> to <13>, wherein the carboxylic acid compound is at least one of butanoic acid and lactic acid.
<15> The shape supporting liquid according to any one of <2> to <14>, wherein the amine compound is ethylenediamine.
<16> The shape support liquid according to any one of <2> to <15>, wherein the ester compound is dimethyl adipate.
<17> The shape supporting liquid according to any one of <2> to <16>, wherein the ketone compound is acetylacetone.
<18> A method for producing a three-dimensional structure, comprising producing a three-dimensional structure using the shape supporting liquid according to any one of <1> to <17>.
<19> A liquid film forming step of forming a liquid film using the model material and the shape supporting liquid (support material) according to any one of <1> to <17>,
By repeating the curing step of curing the liquid film, a three-dimensional model formed of a model part that is a cured product of the model material and a support part that is a cured product of the shape supporting liquid (support material) was produced. Then, it is the manufacturing method of the three-dimensional molded item characterized by removing the said support part.
<20> The method for producing a three-dimensional structure according to <19>, wherein the support part is removed with water or steam.
<21> The method for producing a three-dimensional structure according to any one of <19> to <20>, wherein the liquid film forming unit is one of an inkjet method and a dispenser method.
<22> an accommodating portion that accommodates the shape supporting liquid according to any one of <1> to <17>;
A liquid film forming means for forming a liquid film using the shape supporting liquid;
And a curing means for curing the liquid film.

  The shape supporting liquid according to any one of <1> to <17>, the method for producing a three-dimensional structure according to any one of <18> to <21>, and the three-dimensional modeling according to <22>. The product manufacturing apparatus can solve the above-mentioned problems and achieve the object of the present invention.

Special table 2003-535712 gazette JP 2012-111226 A

Claims (17)

A monomer (A) having hydrogen bonding ability;
A solvent (B) having hydrogen bonding ability;
A shape-supporting liquid comprising a polymerization initiator (C).   The solvent (B) having hydrogen bonding ability is at least one selected from diols having 3 to 6 carbon atoms, carboxylic acid compounds, amine compounds, ester compounds, ketone compounds, and urea compounds. The liquid for shape support as described.   The shape support liquid according to claim 2, wherein the solvent (B) having hydrogen bonding ability is the diol having 3 to 6 carbon atoms. The cured product obtained by irradiating ultraviolet rays at 500 mJ / cm ² with an ultraviolet irradiation device becomes a solid having a compressive stress at 1% compression in an environment of 25 ° C of 0.5 kPa or more. Liquid for shape support. The hardened | cured material obtained by irradiating an ultraviolet-ray 500mJ / cm < ² > with an ultraviolet irradiation device turns into a solid whose compressive stress at the time of 1% compression in 25 degreeC environment is 2.0 kPa or more. Liquid for shape support. The shape supporting liquid according to any one of claims 1 to 5, which satisfies the following condition.
<Conditions>
When a cured product having a length of 20 mm, a width of 20 mm and a height of 5 mm obtained by irradiating with ultraviolet rays of 500 mJ / cm ² by an ultraviolet irradiation device is placed in 20 mL of water and allowed to stand at 25 ° C. for 1 hour, at least one direction is It is a solid having a size of 1 mm or less or completely dissolved. The shape supporting liquid according to any one of claims 1 to 6, which satisfies the following conditions.
<Conditions>
A cured product obtained by irradiating with ultraviolet rays of 500 mJ / cm ² by an ultraviolet irradiation device is a solid having a compressive stress of 2.0 kPa or more at 1% compression in a 25 ° C. environment,
2 g of the solid is put in 20 mL of water, and the volume of the remaining solid when left at 25 ° C. for 1 hour is 50% by volume or less. The content of (A) is 30% by mass or more and 60% by mass or less,
The shape support liquid according to claim 1, wherein the content of (B) is 10% by mass or more and 50% by mass or less. (A) is a monofunctional monomer,
The liquid for shape support according to any one of claims 1 to 8, wherein the molecular weight of the monofunctional monomer is 100 or more and 500 or less.   The mass ratio (A / B) of the content (% by mass) of (A) and the content (% by mass) of (B) is 0.5 or more and 2.5 or less. The shape supporting liquid according to any one of the above.   The shape supporting liquid according to claim 1, wherein (A) is at least one of acryloylmorpholine and N-hydroxyethylacrylamide.   The shape supporting liquid according to claim 1, wherein the shape supporting liquid has a viscosity of 100 mPa · s or less at 25 ° C.   A method for producing a three-dimensional structure, comprising producing a three-dimensional structure using the shape supporting liquid according to any one of claims 1 to 12. A liquid film forming step of forming a liquid film using the model material and the shape supporting liquid (support material) according to any one of claims 1 to 12,
By repeating the curing step of curing the liquid film, a three-dimensional model formed of a model part that is a cured product of the model material and a support part that is a cured product of the shape supporting liquid (support material) was produced. Then, the manufacturing method of the three-dimensional molded item characterized by removing the said support part.   The manufacturing method of the three-dimensional molded item of Claim 14 which removes the said support part with water or water vapor | steam.   The manufacturing method of the three-dimensional molded item in any one of Claim 14 to 15 with which the said liquid film formation process is performed by either an inkjet system or a dispenser system. An accommodating portion for accommodating the shape supporting liquid according to any one of claims 1 to 12,
A liquid film forming means for forming a liquid film using the shape supporting liquid;
A three-dimensional object manufacturing apparatus, comprising: a curing unit that cures the liquid film.