WO2019230135A1

WO2019230135A1 - Photo-fabrication ink set, and production method for photo-fabricated article

Info

Publication number: WO2019230135A1
Application number: PCT/JP2019/010947
Authority: WO
Inventors: 浩史太田; 圭介奥城
Original assignee: マクセルホールディングス株式会社
Priority date: 2018-05-28
Filing date: 2019-03-15
Publication date: 2019-12-05
Also published as: JP2021130198A

Abstract

The present invention relates to a photo-fabrication ink set that comprises a model material composition and a support material composition. The model material composition: contains an ethylenically unsaturated monomer (A) that has a Tg of 20°C–120°C, an ethylenically unsaturated monomer (B) that has a Tg of at least -65°C but less than 20°C, a bifunctional acrylate oligomer (C) that has a Mw of 800–10,000, and a initiator (D); and has a bi- or higher functional acrylate compound content of no more than 15 parts by mass. The support material composition contains 19–80 parts by mass of a water-soluble monofunctional ethylenically unsaturated monomer (a) and 15–75 parts by mass of a polyalkylene glycol (b) that has a molecular weight of 300–3,000 and includes an oxybutylene group.

Description

Optical modeling ink set and manufacturing method of optical modeling product

The present invention relates to an optical modeling ink set combining a composition for a model material and a composition for a support material used in a material jet optical modeling method, and a method for manufacturing an optical modeling product using the optical modeling ink set. .

Conventionally, a modeling method using a photocurable composition that is cured by irradiating ultraviolet rays or the like is widely known as a method of creating a three-dimensional modeled object. Specifically, in such a modeling method, the cured layer having a predetermined shape is formed by irradiating the photocurable composition with ultraviolet rays or the like to cure. Thereafter, a photocurable composition is further supplied onto the cured layer and cured to form a new cured layer. A three-dimensional model is produced by repeating the above steps.

Among the modeling methods, in recent years, a material jet method (inkjet method) that forms a cured layer having a predetermined shape by discharging a photocurable composition from a nozzle and immediately irradiating it with ultraviolet rays and curing. (Hereinafter referred to as “material jet stereolithography” or “inkjet stereolithography”) has been reported (Patent Documents 1 to 4). Inkjet stereolithography does not require the installation of a large resin bath and a dark room for storing the photocurable composition. Therefore, the modeling apparatus can be reduced in size compared with the conventional method. Inkjet stereolithography is attracting attention as a modeling method realized by a 3D printer that can freely create a three-dimensional model based on CAD (Computer Aided Design) data.

In the ink jet stereolithography method, when modeling a stereolithography product having a complicated shape such as a hollow shape, in order to support the model material, the model material and the support material are formed in combination (Patent Document 1). The support material is created by irradiating the photocurable composition with ultraviolet rays or the like and curing the same as the model material. After the model material is created, the support material can be removed by physically peeling the support material or dissolving the support material in an organic solvent or water.

In addition, there is a demand for modeling an optical modeling product that is soft and excellent in tensile strength in the optical modeling method using the inkjet method. In Patent Document 2, the ink composition includes an acrylate monomer A having a homopolymer glass transition temperature of 25 ° C. or more and 120 ° C. or less, an acrylate monomer B having a glass transition temperature of −60 ° C. or more and less than 25 ° C., and a weight average molecular weight. Is a bifunctional acrylate oligomer C having a molecular weight of 2,000 or more and 20,000 or less, and an acylphosphine oxide compound as a photopolymerization initiator, and the content of the bifunctional or higher acrylate compound relative to the total amount of the ink composition It is disclosed that a cured product obtained by photocuring the ink composition is soft and excellent in tensile strength by defining the value in a specific range.

JP 2012-111226 A International Publication No. 2016/098636

Patent Document 2 discloses a support material ink composition containing a monofunctional acrylamide compound and / or a monofunctional acrylate compound having one or more hydroxy groups, polyethylene glycol and / or polypropylene glycol, and a photopolymerization initiator. Is disclosed. However, even if such an ink composition for a support material is used, it can be obtained by photocuring the ink composition for a support material depending on the type and content of components contained in the ink composition for a support material. In some cases, the support material used was inferior. As a result, there has been a problem that the dimensional accuracy of the optically modeled product modeled using the ink composition for a support material is lowered.

The present invention has been made in view of the above-described present situation, and for optical modeling for obtaining a stereolithographic product having a good dimensional accuracy, softness, and excellent tensile strength using a support material excellent in self-supporting property. It is an object of the present invention to provide an ink set, an optical modeling product modeled using the optical modeling ink set, and a method of manufacturing an optical modeling product using the optical modeling ink set.

The present inventors are excellent in water removability of the support material by defining the content of the non-polymerized component and the water-soluble monofunctional ethylenically unsaturated monomer in the composition for the support material within a predetermined range, Furthermore, it discovered that the support material excellent in independence was obtained. By using the composition for a support material and the composition for a model material capable of obtaining a soft and excellent tensile strength, an optically shaped article having good dimensional accuracy. It was found that can be shaped.

According to the first aspect of the present invention, a composition for a model material that is used in an inkjet optical modeling method and is used for modeling a model material, and a support material that is used for modeling a support material. The model material composition is an optical set ink set comprising a combination of an ethylenically unsaturated monomer (A) having a glass transition temperature of 20 ° C. or higher and 120 ° C. or lower. An ethylenically unsaturated monomer (B) having a glass transition temperature of −65 ° C. or higher and lower than 20 ° C., a bifunctional acrylate oligomer (C) having a weight average molecular weight of 800 to 10,000, and photopolymerization. And a functional initiator (D), and the content of the bifunctional or higher acrylate compound is 15 parts by mass or less with respect to 100 parts by mass of the entire model material composition, and for the support material Composition The polyalkylene glycol containing 19 to 80 parts by mass of the water-soluble monofunctional ethylenically unsaturated monomer (a) and 15 to 75 parts by mass of the oxybutylene group with respect to 100 parts by mass of the whole composition for the support material There is provided an optical modeling ink set, wherein the polyalkylene glycol (b) containing (b) and having an oxybutylene group has a molecular weight of 300 to 3,000.

According to a second aspect of the present invention, there is provided an optical modeling ink set in which the ethylenically unsaturated monomer (A) of the model material composition is a monofunctional ethylenically unsaturated monomer. The

According to a third aspect of the present invention, there is provided an optical modeling ink set in which the ethylenically unsaturated monomer (B) of the model material composition is a monofunctional ethylenically unsaturated monomer. The

According to the fourth aspect of the present invention, there is provided an optical modeling ink set in which the bifunctional acrylate oligomer (C) of the model material composition has a Young's modulus at 25 ° C. of 1 to 100 MPa.

According to the fifth aspect of the present invention, the content of the bifunctional acrylate oligomer (C) in the model material composition is 1 to 15 parts by mass with respect to 100 parts by mass of the model material composition as a whole. The optical modeling ink set is provided.

According to the sixth aspect of the present invention, the ethylenically unsaturated monomer (A) of the composition for model material is isobornyl acrylate, t-butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl. There is provided an ink set for stereolithography that is at least one selected from acrylate and dicyclopentanyl acrylate.

According to the seventh aspect of the present invention, the ethylenically unsaturated monomer (B) of the composition for model material is phenoxyethyl acrylate, n-stearyl acrylate, isodecyl acrylate, ethoxyethoxyethyl acrylate, tetrahydro One or more selected from furfuryl acrylate, n-lauryl acrylate, n-octyl acrylate, n-decyl acrylate, isooctyl acrylate, n-tridecyl acrylate, and 2- (N-butylcarbamoyloxy) ethyl acrylate The optical modeling ink set is provided.

According to an eighth aspect of the present invention, there is provided an optical modeling ink set in which the photopolymerizable compound contained in the model material composition is an acylphosphine oxide photopolymerizable initiator.

According to the ninth aspect of the present invention, there is provided an optical modeling ink set in which the composition for a support material contains 1 to 20 parts by mass of a photopolymerization initiator (d).

According to the tenth aspect of the present invention, the composition for a support material further contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 100 parts by mass of the total composition for the support material. In contrast, an optical modeling ink set of 30 parts by mass or less is provided.

According to the eleventh aspect of the present invention, the composition for support material further contains a surface conditioner, and the content of the surface conditioner is 100 parts by mass with respect to the total mass of the composition for support material. Thus, an ink set for optical modeling that is 0.005 parts by mass or more and 3.0 parts by mass or less is provided.

According to a twelfth aspect of the present invention, there is provided a method for producing a stereolithographic product by using the optical modeling ink set according to the first to eleventh aspects according to the present invention by a material jet stereolithography method, wherein the model The material material is photocured to obtain a model material, and the support material composition is photocured using an ultraviolet LED to obtain a support material (I), and the support material is removed. There is provided a method for producing an optically shaped article, comprising the step (II).

According to the present invention, the light for obtaining a stereolithography product having excellent dimensional accuracy, softness, and excellent tensile strength by using a support material excellent in water removal property of the support material and further excellent in self-supporting property. An ink set for modeling, an optical modeling product modeled using the optical modeling ink set, and a method for manufacturing an optical modeling product using the optical modeling ink set can be provided.

FIG. 1 is a schematic side view showing a state where an ink for a support material and an ink for a model material are ejected by an ink jet modeling method and are irradiated with energy rays. FIG. 2 is a schematic side view showing a state where the support material ink and the model material ink are discharged by the ink jet modeling method. FIG. 3 is a schematic side view showing a state in which energy rays are applied to the support material ink and the model material ink ejected by the ink jet modeling method. FIG. 4 is a schematic side view of a modeled article precursor composed of a support material and a model material formed by an ink jet modeling method. FIG. 5 is a schematic side view of a model formed by the ink jet modeling method.

Hereinafter, an embodiment of the present invention (hereinafter also referred to as the present embodiment) will be described in detail. The present invention is not limited to the following contents. In the following description, “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to “(meth) acryloyl” and “(meth) acryl”.

1. Model Material Composition <Ethylenically Unsaturated Monomer (A)>
The model material composition included in the optical modeling ink set according to the present embodiment contains an ethylenically unsaturated monomer (A). The ethylenically unsaturated monomer (A) has a glass transition temperature (hereinafter referred to as Tg) of a homopolymer (polymer) of 20 ° C. or higher and 120 ° C. or lower. When the Tg of the ethylenically unsaturated monomer (A) is within the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. In addition, the model material can be improved in formability by becoming difficult to break when removing the support material described later. The Tg of the homopolymer of the ethylenically unsaturated monomer (A) is preferably 30 ° C. or higher, and more preferably 60 ° C. or higher. Moreover, it is preferable that Tg of the homopolymer of the said ethylenically unsaturated monomer (A) is 100 degrees C or less. Tg can be measured by a dynamic viscoelasticity measuring device (DMA).

The ethylenically unsaturated monomer (A) may be an acrylate compound or a methacrylate compound, but is preferably an acrylate compound. The ethylenically unsaturated monomer (A) may be a monofunctional ethylenically unsaturated monomer or a polyfunctional ethylenically unsaturated monomer. A saturated monomer is preferred. Furthermore, the ethylenically unsaturated monomer (A) is preferably an ethylenically unsaturated monomer having a hydrocarbon ring structure.

Examples of the ethylenically unsaturated monomer (A) include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and methyl (meth) acrylate. , Ethyl (meth) acrylate, propyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Methacryloyloxyethyl hexahydrophthalic acid, 3-hydroxypropyl (meth) acrylate, 2-methacryloyloxyethyl phthalic acid, 3,3,5-trimethylcyclohexyl (meth) acrylate, dicyclopenteni (Meth) acrylate, 1,6-hexanediol di (meth) acrylate. These may be used alone or in combination of two or more.

Among these, the ethylenically unsaturated monomer (A) is selected from isobornyl acrylate, t-butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, and dicyclopentanyl acrylate 1 It is preferably a seed or more, and more preferably isobornyl acrylate and / or t-butylcyclohexyl acrylate. Thereby, the tensile strength of the model material obtained by photocuring the said composition for model materials, and the optical modeling article manufactured using this model material can be improved. In addition, the model material can be improved in formability by becoming difficult to break when removing the support material described later.

The content of the ethylenically unsaturated monomer (A) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the entire model material composition. When the content of the ethylenically unsaturated monomer (A) is within the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. In addition, the model material can be improved in formability by becoming difficult to break when removing the support material described later. The content of the ethylenically unsaturated monomer (A) is more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more. In addition, the content of the ethylenically unsaturated monomer (A) is more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less. In addition, when the said (A) component is contained 2 or more types, the said content is the sum total of content of each (A) component.

<Ethylenically unsaturated monomer (B)>
The model material composition contained in the optical modeling ink set according to the present embodiment contains an ethylenically unsaturated monomer (B). The ethylenically unsaturated monomer (B) has a homopolymer Tg of −65 ° C. or more and less than 20 ° C. When the Tg of the ethylenically unsaturated monomer (B) is in the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. In addition, the model material can be improved in formability by becoming difficult to break when removing the support material described later. The Tg of the ethylenically unsaturated monomer (B) homopolymer is preferably −30 ° C. or higher, more preferably −10 ° C. or higher. Moreover, it is preferable that Tg of the homopolymer of the said ethylenically unsaturated monomer (B) is 10 degrees C or less. Tg can be measured by a dynamic viscoelasticity measuring device (DMA).

The ethylenically unsaturated monomer (B) may be an acrylate compound or a methacrylate compound, but is preferably an acrylate compound. The ethylenically unsaturated monomer (B) may be a monofunctional ethylenically unsaturated monomer or a polyfunctional ethylenically unsaturated monomer. A saturated monomer is preferred. Furthermore, the ethylenically unsaturated monomer (B) is preferably an ethylenically unsaturated monomer having an ether bond and / or an alkyl group having 8 or more carbon atoms.

Examples of the ethylenically unsaturated monomer (B) include long-chain alkyl (carbon number 8 or more) acrylate compounds, acrylate compounds having a polyethylene oxide or polypropylene oxide chain, phenoxyethyl acrylate compounds, tetrahydrofurfuryl acrylate, and acrylics. Acid 2- (N-butylcarbamoyloxy) ethyl (1,2-ethanediol 1-acrylate 2- (N-butylcarbamate)) and the like. These may be used alone or in combination of two or more.

Examples of the long-chain alkyl acrylate compound include 2-ethylhexyl acrylate, n-octyl acrylate, n-isononyl acrylate, n-decyl acrylate, isooctyl acrylate, n-lauryl acrylate, n-tridecyl acrylate, and n-cetyl. Examples include acrylate, n-stearyl acrylate, isomyristyl acrylate, and isostearyl acrylate.

Examples of the acrylate compound having a polyethylene oxide or polypropylene oxide chain include (poly) ethylene glycol monoacrylate, (poly) ethylene glycol acrylate methyl ester, (poly) ethylene glycol acrylate ethyl ester, and (poly) ethylene glycol acrylate phenyl ester. , (Poly) propylene glycol monoacrylate, (poly) propylene glycol monoacrylate phenyl ester, (poly) propylene glycol acrylate methyl ester, (poly) propylene glycol acrylate ethyl ester, methoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, ethoxy Diethylene glycol acrylate (Etoki Ethoxyethyl acrylate), methoxy polyethylene glycol acrylate.

Examples of the phenoxyethyl acrylate compound include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and nonylphenol ethylene oxide adduct acrylate.

Among these, the ethylenically unsaturated monomer (B) includes phenoxyethyl acrylate, n-stearyl acrylate, isodecyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, n-lauryl acrylate, n-octyl acrylate, It is preferably at least one selected from n-decyl acrylate, isooctyl acrylate, n-tridecyl acrylate, and 2- (N-butylcarbamoyloxy) ethyl acrylate, such as phenoxyethyl acrylate and / or n- More preferred is stearyl acrylate. Thereby, the tensile strength of the model material obtained by photocuring the said composition for model materials, and the optical modeling article manufactured using this model material can be improved. In addition, the model material can be improved in formability by becoming difficult to break when removing the support material described later.

The content of the ethylenically unsaturated monomer (B) is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the entire model material composition. When the content of the ethylenically unsaturated monomer (B) is in the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. In addition, the model material can be improved in formability by becoming difficult to break when removing the support material described later. The content of the ethylenically unsaturated monomer (B) is more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more. The content of the ethylenically unsaturated monomer (B) is more preferably 85 parts by mass or less, further preferably 80 parts by mass or less, and particularly preferably 75 parts by mass or less. . In addition, when the said (B) component is contained 2 or more types, the said content is the sum total of content of each (B) component.

Further, the content M (A) of the ethylenically unsaturated monomer (A) and the content M (B) of the ethylenically unsaturated monomer (B) are M (A) <M (B (M (A) is smaller than M (B)), and 2 × M (A) <M (B) is satisfied (a value obtained by doubling M (A) is greater than M (B). Is preferably smaller), and more preferably 3 × M (A) <M (B) (a value obtained by multiplying M (A) by 3 is smaller than M (B)). Thereby, the tensile strength of the model material obtained by photocuring the said composition for model materials, and the optical modeling article manufactured using this model material can be improved. In addition, the model material can be improved in formability by becoming difficult to break when removing the support material described later.

Further, the content M (A) of the ethylenically unsaturated monomer (A) and the content M (B) of the ethylenically unsaturated monomer (B) are 10 × M (A)> M It is preferable that (B) is satisfied (the value obtained by multiplying M (A) by 10 is larger than M (B)), and 7 × M (A)> M (B) is satisfied (M (A) is multiplied by 7) It is more preferable that the value is larger than M (B), and it is more preferable that 5 × M (A)> M (B) is satisfied (a value obtained by multiplying M (A) by 5 is larger than M (B)). preferable.

<Bifunctional acrylate oligomer (C)>
The composition for model materials contained in the optical modeling ink set according to this embodiment contains a bifunctional acrylate oligomer (C). The bifunctional acrylate oligomer (C) has a weight average molecular weight (hereinafter referred to as Mw) of 800 or more and 10,000 or less. When the Mw of the bifunctional acrylate oligomer (C) is within the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. The Mw of the bifunctional acrylate oligomer (C) is preferably 5,000 or more, and more preferably 10,000 or more.

Mw can be measured by gel permeation chromatography (GPC) analysis. More specifically, using Tosoh Corporation HLC-8220 GPC, three columns of TSK gel SuperAWM-H are connected and used, solvent: tetrahydrofuran (10 mM LiBr), flow rate: 0.5 mL / min, sample It can be measured under the conditions of concentration: 0.1% by mass, injection amount: 60 μL, measurement temperature: 40 ° C. A UV or RI detector (differential refractometer) can be used as the detector.

The bifunctional acrylate oligomer (C) may have an acryloyloxy group or a methacryloyloxy group, but preferably has an acryloyloxy group. The bifunctional acrylate oligomer (C) is an oligomer having a total of two acryloyloxy groups and / or methacryloyloxy groups. When the composition for model material contains only the monofunctional acrylate oligomer, the tensile strength of the model material and the stereolithographic product is inferior. On the other hand, if the composition for model material contains only trifunctional or higher acrylate oligomers, the softness of the model material and the stereolithographic product is inferior.

The Young's modulus at 25 ° C. of the bifunctional acrylate oligomer (C) is preferably 1 to 100 MPa. When the Young's modulus of the bifunctional acrylate oligomer (C) is within the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. The Young's modulus of the bifunctional acrylate oligomer (C) is more preferably 2 MPa or more, further preferably 3 MPa or more, and particularly preferably 10 MPa or more. On the other hand, the Young's modulus of the bifunctional acrylate oligomer (C) is more preferably 80 MPa or less, further preferably 50 MPa or less, and particularly preferably 30 MPa or less.

Here, the Young's modulus at 25 ° C. of the bifunctional acrylate oligomer (C) is the Young's modulus at 25 ° C. of the homopolymer (monopolymer) of the bifunctional acrylate oligomer (C). The Young's modulus can be measured by, for example, the following method. A liquid in which 2% by mass of Irgacure 819 (manufactured by BASF), 2% by mass of Irgacure 184 (manufactured by BASF), and 96% by mass of the oligomer to be measured was formed with a bar coater to form a coating film of 100 μm, and ultraviolet (UV) exposure Cured with a machine. At this time, the cured film was cured to such an extent that the influence of the degree of polymerization of the cured film was negligible. This cured film is cut into a 15 mm × 50 mm strip and the Young's modulus is measured with a tensile tester (Autograph AGS-X, 5KN, manufactured by Shimadzu Corporation). The value of Young's modulus is measured at the 1% elongation. Moreover, in a test, it pulls to a major axis direction and grasps about 10 mm part up and down with a clamp.

Examples of the bifunctional acrylate oligomer (C) include olefin-based (ethylene oligomer, propylene oligomer, butene oligomer, etc.), vinyl-based (styrene oligomer, vinyl alcohol oligomer, vinyl pyrrolidone oligomer, acrylic resin oligomer, etc.), diene-based ( Butadiene oligomer, chloroprene rubber, pentadiene oligomer, etc.), ring-opening polymerization system (di-, tri-, tetraethylene glycol, polyethylene glycol, polyethylimine, etc.), polyaddition system (oligoester acrylate, polyamide oligomer, polyisocyanate oligomer) And addition condensation oligomers (phenol resin, amino resin, xylene resin, ketone resin, etc.). Among these, a urethane acrylate oligomer, a polyester acrylate oligomer, or an epoxy acrylate oligomer is preferable, and a urethane acrylate oligomer is more preferable. As the urethane acrylate oligomer, the polyester acrylate oligomer, and the epoxy acrylate oligomer, an oligomer handbook (supervised by Junji Furukawa, Chemical Industries Daily Co., Ltd.) can be referred to. Examples of the bifunctional acrylate oligomer (C) include Shin-Nakamura Chemical Co., Ltd., Sartomer Japan Co., Ltd., Daicel Cytec Co., Ltd., Rahn A.I. G. What is marketed by the company etc. can be used.

The content of the bifunctional acrylate oligomer (C) is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the entire model material composition. When the content of the bifunctional acrylate oligomer (C) is in the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. The content of the bifunctional acrylate oligomer (C) is more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. In addition, when the said (C) component is contained 2 or more types, the said content is the sum total of content of each (C) component.

Among the components (A), (B), and (C), the content of the bifunctional or higher acrylate compound is 15 parts by mass or less with respect to 100 parts by mass of the entire model material composition.

The content of the bifunctional acrylate oligomer (C) is preferably 50 parts by mass or more with respect to 100 parts by mass of the entire bifunctional or higher acrylate compound. When the content of the bifunctional acrylate oligomer (C) is in the above range, the softness and tensile strength of the model material and the stereolithographic product can be further improved. The content of the bifunctional acrylate oligomer (C) is more preferably 80 parts by mass or more, further preferably 90 parts by mass or more, based on 100 parts by mass of the entire bifunctional or higher acrylate compound. It is particularly preferable that the amount is at least part by mass.

<Photopolymerization initiator (D)>
It is preferable that the composition for model materials of this invention contains a photoinitiator. The photopolymerization initiator is a compound that promotes a radical reaction when irradiated with light having a wavelength in the ultraviolet, near ultraviolet, or visible light region. The photopolymerization initiator is not particularly limited as long as the polymerization can be initiated with low energy, but is not limited to acylphosphine oxide compounds, α-aminoalkylphenone compounds, α-hydroxyquinone compounds, thioxanthone compounds, benzoin compounds, anthraquinone compounds. It is preferable to use a photopolymerization initiator containing at least one compound selected from the group consisting of and ketal compounds. Among these, acylphosphine oxide compounds are particularly preferable.

Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide. 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 4-methylbenzoyldiphenylphosphine oxide, 4-ethylbenzoyldiphenylphosphine oxide, 4-isopropylbenzoyl Diphenylphosphine oxide, 1-methylcyclohexanoylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoylphenylphosphinic acid isopropyl ester, bis (2,6-dimethoxybenzoyl) -2,4 Examples include 4-trimethylpentylphosphine oxide. These may be used alone or in combination. Examples of the acylphosphine oxide compound available in the market include “DAROCURE TPO” manufactured by BASF.

Specific examples of the α-aminoalkylphenone compound include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butanone-1,2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropan-2-one and the like. These may be used alone or in combination. Examples of commercially available α-aminoalkylphenone compounds include “IRGACURE 369” and “IRGACURE 907” manufactured by BASF.
Specific examples of the α-hydroxyquinone compound include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-phenylpropan-1-one, 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propan-1-one and the like can be mentioned. These may be used alone or in combination. Examples of commercially available α-hydroxyquinone compounds include “IRGACURE 184”, “DAROCURE 1173”, “IRGACURE 2959”, “IRGACURE 127”, and the like.

Specific examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. These may be used alone or in combination. Examples of commercially available thioxanthone compounds include “MKAYACURE DETX-S” manufactured by Nippon Kayaku Co., Ltd. and “Chivacure ITX” manufactured by Double Bond Chemical.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.

Specific examples of the anthraquinone compound include 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone and the like.

Specific examples of the ketal compound include, for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like, benzophenone compounds having 13 to 21 carbon atoms (for example, benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4 And '-bismethylaminobenzophenone.

The content of (D) is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the entire model material composition. When the content of (D) is in the above range, the softness and tensile strength of the model material and the stereolithographic product can be improved. The content of (D) is more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more. The content of (D) is more preferably 13 parts by mass or less. In addition, when the said (D) component is contained 2 or more types, the said content is the sum total of content of each (D) component.

<Other additives>
The composition for a model material included in the optical modeling ink set according to the present embodiment can contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include a sensitizer, a colorant, a dispersant, a surface conditioner, a polymerization inhibitor, a storage stabilizer, a photopolymerization initiator other than the acylphosphine oxide compound (D), and co-sensitization. Agent, ultraviolet absorber, antioxidant, anti-fading agent, conductive salt, solvent, polymer compound, basic compound, leveling additive, matting agent, polyester resin for adjusting film properties, polyurethane resin, Examples include vinyl resins, acrylic resins, rubber resins, and waxes.

Examples of the sensitizer include polynuclear aromatics (for example, pyrene, perylene, triphenylene, 2-ethyl-9,10-dimethoxyanthracene), thioxanthones (for example, isopropylthioxanthone), thiochromanones (for example, Thiochromanone, etc.). These may be used alone or in combination of two or more. Among these, thioxanthones are preferable, and isopropylthioxanthone is more preferable.

The content of the sensitizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the entire model material composition. When the content of the sensitizer is within the above range, the model material is excellent in curability and curing sensitivity. The content of the sensitizer is more preferably 0.5 parts by mass or more, and more preferably 3 parts by mass or less. In addition, when the said sensitizer is contained 2 or more types, the said content is the sum total of content of each sensitizer.

As the colorant, various known pigments and dyes can be appropriately selected and used depending on the application. Among these, a pigment is preferable from the viewpoint of excellent light resistance. The pigment is not particularly limited, and all commercially available organic pigments, inorganic pigments, pigments obtained by dyeing resin particles with a dye, and the like can be used. Further, commercially available pigment dispersions, surface-treated pigments, for example, pigments dispersed in an insoluble resin or the like using a dispersion medium, and those obtained by grafting a resin on the pigment surface do not impair the effects of the present invention. As long as it can be used.

Examples of the organic pigment and the inorganic pigment that exhibit a yellow color include C.I. I. Pigment Yellow 1 (Fast Yellow G, etc.), C.I. I. Monoazo pigments such as CI Pigment Yellow 74; I. Pigment Yellow 12 (disaji yellow AAA, etc.), C.I. I. Disazo pigments such as CI Pigment Yellow 17; I. Non-benzidine type azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100 (eg Tartrazine Yellow Lake); I. Condensed azo pigments such as CI Pigment Yellow 95 (Condensed Azo Yellow GR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Yellow 115 (quinoline yellow lake, etc.); I. Basic dye lake pigments such as CI Pigment Yellow 18 (thioflavin lake, etc.); anthraquinone pigments such as Flavantron Yellow (Y-24); isoindolinone pigments such as Isoindolinone Yellow 3RLT (Y-110); quinophthalone yellow Quinophthalone pigments such as (Y-138); isoindoline pigments such as isoindoline yellow (Y-139); I. Nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.); I. And metal complex salt azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow and the like). These may be used alone or in combination of two or more.

Examples of the organic pigment and the inorganic pigment that exhibit red or magenta color include C.I. I. Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.), C.I. I. Azo lake pigments such as CI Pigment Red 57: 1 (Brilliant Carmine 6B); I. Condensed azo pigments such as C.I. Pigment Red 144 (condensed azo red BR and the like); I. Acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Red 81 (Rhodamine 6G 'lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as C.I. Pigment Red 88 (such as Thioindigo Bordeaux); I. Perinone pigments such as C.I. Pigment Red 194 (perinone red, etc.); I. Perylene pigments such as CI Pigment Red 149 (perylene scarlet, etc.); I. Pigment violet 19 (unsubstituted quinacridone), C.I. I. Quinacridone pigments such as C.I. Pigment Red 122 (quinacridone magenta, etc.); I. CI indolinone pigments such as C.I. Pigment Red 180 (Isoindolinone Red 2BLT and the like); I. And alizarin lake pigments such as CI Pigment Red 83 (Madder Lake, etc.). These may be used alone or in combination of two or more.

Among the organic pigment and the inorganic pigment, examples of the pigment exhibiting blue or cyan include C.I. I. Disazo pigments such as CI Pigment Blue 25 (dianisidine blue and the like); I. Phthalocyanine pigments such as C.I. Pigment Blue 15 (phthalocyanine blue, etc.); I. Acidic dye lake pigments such as C.I. Pigment Blue 24 (peacock blue lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Blue 1 (Viclotia Pure Blue BO Lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. And alkaline blue pigments such as CI Pigment Blue 18 (Alkali Blue V-5: 1). These may be used alone or in combination of two or more.

Among the organic pigments and the inorganic pigments, examples of the green pigment include C.I. I. Pigment green 7 (phthalocyanine green), C.I. I. Phthalocyanine pigments such as CI Pigment Green 36 (phthalocyanine green); I. And azo metal complex pigments such as CI Pigment Green 8 (Nitroso Green). These may be used alone or in combination of two or more.

Among the organic pigments and the inorganic pigments, examples of the orange pigment include C.I. I. CI indoline pigments such as CI Pigment Orange 66 (isoindoline orange); I. And anthraquinone pigments such as CI Pigment Orange 51 (dichloropyrantron orange). These may be used alone or in combination of two or more.

Among the organic pigment and the inorganic pigment, examples of the black pigment include carbon black, titanium black, and aniline black. These may be used alone or in combination of two or more.

Among the organic pigments and the inorganic pigments, white pigments include, for example, basic lead carbonate (2PbCO ₃ Pb (OH) ₂ , so-called silver white), zinc oxide (ZnO, so-called zinc white), and titanium oxide. (TiO ₂ , so-called titanium white), strontium titanate (SrTiO ₃ , so-called titanium strontium white), and the like. These may be used alone or in combination of two or more. Among these, titanium oxide is preferable from the viewpoint of high hiding power and coloring power as a pigment and excellent durability to acids, alkalis, and other environments.

The content of the colorant is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the entire model material composition from the viewpoint of colorability and storage stability. The content of the colorant is more preferably 0.1 parts by mass or more, and further preferably 0.2 parts by mass or more. Further, the content of the colorant is more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less. In addition, when the said coloring agent is contained 2 or more types, the said content is the sum total of content of each coloring agent.

The dispersant is preferably a polymer dispersant having an Mw of 1,000 or more. Examples of the polymer dispersant include DISPERBYK-101, DISPERBYK-102 and the like (manufactured by BYK Chemie); EFKA4010 and EFKA4046 and the like (above, manufactured by Fuka Additive); As described above, manufactured by San Nopco); various Solsperse dispersants such as SOLPERSE 3000, 5000 (hereinafter, manufactured by Noveon); Adeka Pluronic L31, F38, etc. (hereinafter, manufactured by ADEKA); Manufactured by the company); Disparon KS-860, 873SN, etc. (above, manufactured by Enomoto Kasei Co., Ltd.). These may be used alone or in combination of two or more.

The content of the dispersant is preferably 0.05 to 15 parts by mass with respect to 100 parts by mass of the entire model material composition. In addition, when the said dispersing agent is contained 2 or more types, the said content is the sum total of content of each dispersing agent.

Examples of the surface conditioner (E) include a PEG-type nonionic surfactant [nonylphenol ethylene oxide (hereinafter abbreviated as EO) 1 to 40 mol adduct, stearin having a molecular weight of 264 or more and Mn of 5,000 or less. Acid EO 1-40 mol adducts, etc.], polyhydric alcohol type nonionic surfactants (sorbitan palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactants (perfluoroalkyl EO1) ˜50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), modified silicone oils [polyether-modified silicone oil, (meth) acrylate-modified silicone oil, etc.] and the like. These may be used alone or in combination of two or more. Of the surface conditioners, silicone-based surface conditioners are preferable, and surface conditioners having a polydimethylsiloxane structure are particularly preferable.

The content of the surface conditioner is 3 parts by mass or less with respect to 100 parts by mass of the entire model material composition, from the viewpoint of adding effects and improving the physical properties of the model material and the optically shaped article. It is preferably 2 parts by mass or less, more preferably 0.1 parts by mass or more. In addition, when 2 or more types of the said surface conditioning agents are contained, the said content is the sum total of content of each surface conditioning agent.

The model material composition preferably contains a polymerization inhibitor. When the composition for a model material contains a polymerization inhibitor, it is possible to suppress excessive polymerization at a temperature (about 50 to 90 ° C.) at which the shaped article is molded. As a result, since the monomer can be stabilized, the model material composition is easily cured.

The polymerization inhibitor enhances the storage stability of the model material composition and improves the ejection stability from the inkjet head. Examples of the polymerization inhibitor include nitroso polymerization inhibitors, hydroquinone, methoxyhydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL (HO-TEMPO), cuperon Al, hindered amine and the like.

The content of the polymerization inhibitor is preferably 0.001 to 1.5 parts by mass with respect to 100 parts by mass of the entire model material composition. When the content of the polymerization inhibitor is in the above range, the storage stability of the model material composition is further improved, and the ejection stability from the inkjet head is further improved. The content of the polymerization inhibitor is more preferably 0.01 parts by mass or more, and further preferably 0.05 parts by mass or more. The content of the polymerization inhibitor is more preferably 1.0 part by mass or less, and further preferably 0.8 part by mass or less. In addition, when the said polymerization inhibitor is contained 2 or more types, the said content is the sum total of content of each polymerization inhibitor.

The method for producing the model material composition included in the optical modeling ink set according to the present embodiment is not particularly limited. For example, the components (A) to (D) and, if necessary, the other additives can be produced by uniformly mixing them using a mixing and stirring device or the like.

The composition for a model material thus produced preferably has a viscosity at 25 ° C. of 70 mPa · s or less from the viewpoint of improving dischargeability from an inkjet head. In addition, the measurement of the viscosity of the composition for model materials is performed using R100 type | mold viscosity meter based on JISZ8803.

2. Support Material Composition A support material composition is a photocurable composition for a support material that provides a support material by photocuring. After the model material is created, it can be removed from the model material by physically peeling the support material from the model material or by dissolving the support material in an organic solvent or water. The composition for a model material of the present invention can be used in combination with various conventionally known compositions as a composition for a support material, but does not damage the model material when the support material is removed, and the environment. It is preferable that the support material composition constituting the stereolithography composition set of the present invention is water-soluble because the support material can be removed easily and cleanly in detail.

In the present invention, the water-soluble support material composition comprises at least one water-soluble monofunctional ethylenically unsaturated monomer (a), at least one polyalkylene glycol (b) containing an oxybutylene group, and photopolymerization. It is preferable to contain an initiator (c).

Examples of the water-soluble monofunctional ethylenically unsaturated monomer (a) contained in the support material composition of the present invention include a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms [for example, hydroxyethyl (meta ) Acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.], hydroxyl group-containing (meth) acrylate having a number average molecular weight (Mn) of 200 to 1,000 [for example, polyethylene glycol mono (meth) acrylate, mono Alkoxy (1 to 4 carbon atoms) polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, monoalkoxy (1 to 4 carbon atoms) polypropylene glycol mono (meth) acrylate, mono (meta) of PEG-PPG block polymer Acrylate ], (Meth) acrylamide derivatives [eg (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N ′ -Dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, etc.], (meth) Examples include acryloyl morpholine. These may be used alone or in combination of two or more.

The content of the water-soluble monofunctional ethylenically unsaturated monomer (a) contained in the support material composition is preferably 19 to 80 parts by mass with respect to 100 parts by mass of the support material composition. More preferably, it is 22 parts by mass or more, more preferably 25 parts by mass or more, more preferably 76 parts by mass or less, and further preferably 73 parts by mass or less. When the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is within the above range, the removability of the support material with water can be improved without reducing the support power of the support material.

The polyalkylene glycol (b) containing an oxybutylene group contained in the support material composition may be either a linear type or a multi-chain type. Moreover, as long as it melt | dissolves in water, the alkyl group may be included in the terminal, for example, Preferably it may contain the C6 or less alkyl chain. These may be used alone or in combination of two or more.

The polyalkylene glycol (b) containing an oxybutylene group contained in the support material composition is a water-soluble resin for imparting appropriate hydrophilicity to the support material. Support material that combines strength can be obtained. The polyalkylene glycol containing an oxybutylene group is not particularly limited as long as it contains an oxybutylene group. For example, the polyalkylene glycol having only an oxybutylene group (oxytetramethylene group) is a single polybutylene glycol. Alternatively, it may be a polybutylene polyoxyalkylene glycol (for example, polybutylene polyethylene glycol) having both an oxybutylene group and another oxyalkylene group. For example, the polybutylene glycol is represented by the following chemical formula (1), and the polybutylene polyethylene glycol is represented by the following chemical formula (2).

In the above chemical formula (2), m is preferably an integer of 5 to 300, and n is preferably an integer of 2 to 150. More preferably, m is 6 to 200, and n is 3 to 100. Further, the oxybutylene group in the chemical formula (1) and the chemical formula (2) may be a straight chain or may be branched. These may be used alone or in combination of two or more.

Since the composition for the support material contains the polyalkylene glycol (b) containing an oxybutylene group, the removability by water can be further improved without reducing the support power of the support material, and a soft model material can be obtained. It is a support material that is suitable for supporting and modeling a highly accurate model material. In particular, since the support material can sufficiently support the model material during the optical modeling, the modeling accuracy at the optical modeling stage can be improved with respect to the soft model material whose dimensional accuracy is likely to be lowered during molding. Furthermore, since the support material can be easily removed at the stage of removing the support material after that, the support material can be used while suppressing the decrease in accuracy even in the microstructure of the three-dimensional model molded with high accuracy during stereolithography. Can be removed. This not only prevents the reduction of dimensional accuracy when removing the support material by improving the removability of the support material with water, but also improves the dimensional accuracy of the model material during stereolithography by improving the self-supporting property of the support material. By increasing the height, it is possible to obtain an optically shaped article having better dimensional accuracy.

The weight average molecular weight of the polyalkylene glycol (b) component containing an oxybutylene group is 300 or more, preferably less than 3000, more preferably 800 or more, and more preferably less than 2000. When the weight average molecular weight of the component (b) is smaller than 300, bleeding of the support material tends to occur when the support material composition is cured. Bleeding is a phenomenon in which a liquid component oozes from the inside of a cured support material to the support material surface. Moreover, when the weight average molecular weight of the polyalkylene glycol containing an oxybutylene group is smaller than 3000, the discharge stability of the support material composition is excellent. When the weight average molecular weight is in the above range, the water-soluble monofunctional ethylenically unsaturated monomer (a) is easily compatible in the composition before curing, while the water-soluble monofunctional ethylenic monomer after light irradiation is easily compatible. It becomes difficult to be compatible with the cured product of the saturated monomer, and the support material can be easily removed with water or a water-soluble solvent. (B) Two or more types of components may be used. When two or more types of polyalkylene glycol are used, the content of polyalkylene glycol having a weight average molecular weight of less than 300 or greater than 3000 is preferably small.

The content of the polyalkylene glycol (b) containing an oxybutylene group in the support material composition is preferably 15 to 75 parts by mass, more preferably 17 parts by mass with respect to 100 parts by mass of the support material composition. Part or more, more preferably 20 parts by weight or more, more preferably 72 parts by weight or less, and even more preferably 70 parts by weight or less. When the content of the polyalkylene glycol (b) containing an oxybutylene group is within the above range, the removability of the support material with water or a water-soluble solvent can be improved without reducing the support power of the support material. .

The support material composition may contain a water-soluble organic solvent (c). The water-soluble organic solvent (c) is a component that improves the solubility of the support material obtained by photocuring the support material composition in water. Moreover, it has the function to adjust the composition for support materials to low viscosity.

As the water-soluble organic solvent (c), it is preferable to use a glycol solvent. Specifically, for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate. Glycol ester solvents such as acetate, tripropylene glycol monoacetate, tetraethylene glycol monoacetate, tetrapropylene glycol monoacetate, ethylene glycol diacetate, propylene glycol diacetate; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, triethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol Monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, Glycol ether solvents such as ethylene glycol dipropyl ether, propylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol Nomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monobutyl ether Examples thereof include glycol monoether acetate solvents such as acetate. These may be used alone or in combination of two or more.

Among them, the low-viscosity support material composition is easy to prepare, and the support material obtained by curing is excellent in water solubility. Therefore, as the water-soluble organic solvent (c), triethylene glycol monomethyl ether, diethylene glycol diethyl Ether and dipropylene glycol monomethyl ether acetate are preferred.

The content of the water-soluble organic solvent (c) in the support material composition is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, with respect to 100 parts by mass of the support material composition. More preferably, it is 25 parts by mass or less. When the content of the water-soluble organic solvent (c) is within the above range, the removability of the support material with water or the water-soluble solvent can be improved without reducing the support power of the support material. When the composition for a support material contains a water-soluble organic solvent, the content thereof is preferably 3 masses with respect to 100 parts by mass of the composition for a support material from the viewpoint that the composition for a support material can be adjusted to a low viscosity. More than a part.

As the photopolymerization initiator (d), the compounds described above as photopolymerization initiators that can be contained in the model material composition can be similarly used. The content of the photopolymerization initiator in the support material composition is preferably 1 to 20 parts by mass and more preferably 2 to 18 parts by mass with respect to 100 parts by mass of the support material composition. When the content of the photopolymerization initiator is within the above range, unreacted polymerization components can be sufficiently reduced, and the curability of the support material can be sufficiently enhanced.

The support material composition may contain other additives as necessary. Examples of other additives include surface conditioners, antioxidants, colorants, pigment dispersants, storage stabilizers, ultraviolet absorbers, light stabilizers, polymerization inhibitors, chain transfer agents, and fillers. .

The surface tension of the support material composition can be controlled within an appropriate range by adding the surface conditioner (e) to the support material composition, and the model material composition and the support material composition Mixing at the interface can be suppressed. Thereby, a stereolithography product with favorable dimensional accuracy can be obtained. As the surface conditioner that can be contained in the support material composition, the same as those exemplified as the surface conditioner that can be used in the model material composition of the present invention can be used. It is preferable that it is 0.005 mass part or more and 3 mass parts or less with respect to 100 mass parts of things.

Further, the storage stability can be improved by blending the storage stabilizer (f) into the support material composition. As the storage stabilizer that can be contained in the support material composition, the same storage stabilizers as those exemplified as the storage stabilizer that can be used in the model material composition of the present invention can be used. It is preferable that they are 0.05 mass part or more and 3 mass parts or less with respect to 100 mass parts of composition for materials.

In the present invention, the viscosity of the support material composition is preferably 30 to 200 mPa · s at 25 ° C., more preferably 35 mPa · s or more, and still more preferably, from the viewpoint of improving dischargeability from the inkjet nozzle. Is 40 mPa · s or more, more preferably 170 mPa · s or less, and still more preferably 150 mPa · s or less. In addition, the measurement of the said viscosity can be performed using R100 type | mold viscosity meter based on JISZ8803.

In the present invention, the surface tension of the support material composition is preferably 24 to 30 mN / m, more preferably 24.5 to 29.5 mN / m, and further preferably 25 to 29 mN / m. When the surface tension is within the above range, it is possible to normally form droplets ejected from the nozzle, to ensure an appropriate droplet amount and landing accuracy, and to suppress the occurrence of satellites, It becomes easy to ensure high modeling accuracy. In addition, the surface tension of the composition for support material can be measured in accordance with the method similar to the measuring method of the surface tension in the composition for model materials.

The method for producing the composition for a support material of the present invention is not particularly limited. For example, the composition for the support material can be produced by uniformly mixing the components constituting the composition for a support material using a mixing stirrer or the like.

3. Optical modeling product and manufacturing method thereof The manufacturing method of the optical modeling object of this embodiment is a manufacturing method of an optical modeling object using the composition set for material jet optical modeling described in the above embodiment, and is a material jet (inkjet). ) After discharging the composition for the model material and the composition for the support material using a method printer, the model material composition is photocured to obtain the model material, and the water soluble support material composition is photocured. A step of obtaining a water-soluble support material, and a step of removing the water-soluble support material by immersing the water-soluble support material in water.

Since the manufacturing method of the optical modeling thing of this embodiment is using the said composition set for material jet optical modeling, it can form the optical modeling thing excellent in modeling precision.

Hereinafter, a method for manufacturing an optically shaped object according to the present embodiment will be described with reference to the drawings. FIG. 1 is a schematic side view showing a state in which a support material composition and a model material composition are ejected by a material jet modeling method and irradiated with energy rays. In FIG. 1, the three-dimensional modeling apparatus 10 includes an inkjet head module 11 and a modeling table 12. The ink jet head module 11 includes an optical modeling ink unit 11a, a roller 11b, and a light source 11c. Further, the optical modeling ink unit 11a includes a model material inkjet head 11aM filled with the model material ink 13 and a support material inkjet head 11aS filled with the support material ink.

The model material composition 13 is ejected from the model material inkjet head 11aM, the support material composition 14 is ejected from the support material inkjet head 11aS, and the energy beam 15 is irradiated and ejected from the light source 11c. The model material composition 13 and the support material composition 14 are cured to form the model material 13PM and the support material 14PS. FIG. 1 shows a state in which the first layer model material 13PM and the support material 14PS are formed.

Next, the method for manufacturing an optically shaped object according to this embodiment will be described in more detail based on the drawings. In the method for manufacturing an optically shaped object according to the present embodiment, first, as shown in FIG. 2, the inkjet head module 11 is scanned in the X direction (right direction in FIG. 2) with respect to the modeling table 12, and the inkjet for model material is used. The model material composition 13 is discharged from the head 11aM, and the support material composition 14 is discharged from the support material inkjet head 11aS. Thereby, on the modeling table 12, the layer which consists of the model material precursor 13M, and the layer which consists of the support material precursor 14S are arrange | positioned adjacently so that each interface may contact.

Next, as shown in FIG. 3, the inkjet head module 11 is scanned in the reverse X direction (left direction in FIG. 3) with respect to the modeling table 12, and the model material precursor 13 </ b> M and the support material precursor 14 </ b> S are scanned by the roller 11 b. After smoothing the surface of the layer made of the material, the energy beam 15 is irradiated from the light source 11c to cure the layer made of the model material precursor 13M and the support material precursor 14S, and the first model material 13PM and the support material 14PS. A layer consisting of is formed.

Subsequently, the modeling table 12 is lowered by one layer in the Z direction, and the same process as described above is performed to form a second layer of model material and support material. Thereafter, by repeating the above steps, as shown in FIG. 4, an optically shaped product precursor 16 composed of the model material 13PM and the support material 14PS is formed.

Finally, the optical modeling product precursor 16 shown in FIG. 4 is immersed in water to dissolve and remove the support material 14PS, thereby forming the optical modeling product 17 as shown in FIG.

In the method for producing an optically shaped object of the present embodiment, for example, a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like can be used as the light source. From the viewpoint that the three-dimensional modeling apparatus 10 can be miniaturized and the power consumption is small, UV-LED is preferable. The amount of light is preferably 200 to 500 mJ / cm ² from the viewpoint of the hardness and dimensional accuracy of the shaped product. When a UV-LED is used as the light source, it is preferable to use a light having a center wavelength of 385 to 415 nm because light easily reaches a deep layer and the hardness and dimensional accuracy of the optically shaped product can be improved. As the energy rays 15 irradiated from the light source 11c, ultraviolet rays, near ultraviolet rays, visible rays, infrared rays, far infrared rays, electron beams, α rays, γ rays, X-rays, and the like can be used. And from a viewpoint of efficiency, ultraviolet rays or near ultraviolet rays are preferable.

In the manufacturing method of the present invention, for example, based on the three-dimensional CAD data of the object to be manufactured, the data of the composition for the model material that forms the three-dimensional structure by stacking by the material jet method, and the three-dimensional modeling in the process of preparation The data of the composition for the support material that supports the object is prepared, and further, the slice data for discharging each composition by the 3D printer of the material jet method is prepared, and each of the model material and the support material is used based on the prepared slice data. After discharging the composition, the photo-curing treatment is repeated for each layer to produce an optically shaped article composed of a cured product of the model material composition (model material) and a cured product of the composition for support material (support material). it can.

The thickness of each layer constituting the three-dimensional model is preferably thin from the viewpoint of modeling accuracy, but is preferably 5 to 30 μm from the balance with the modeling speed.

The obtained stereolithography is a combination of a model material and a support material. The support material is removed from the stereolithography product to obtain a stereolithography product as a model material. The support material can be removed by, for example, immersing an optical modeling object obtained in a removal solvent that dissolves the support material, softening the support material, and then removing the support material from the model material surface with a brush or the like. preferable. Water or a water-soluble solvent such as a glycol solvent or an alcohol solvent may be used as the solvent for removing the support material. These may be used alone or in combination.

The above-mentioned stereolithography product has suppressed water absorption and swelling when contacted with water, and is less likely to cause breakage and deformation of the fine structure portion. Further, the stereolithographic product is excellent in water and oil repellency and hardly contaminated.

Hereinafter, examples that more specifically disclose the present embodiment will be shown. In addition, this invention is not limited only to these Examples.

<Model material composition>
(Manufacture of compositions for model materials)
As shown in Tables 1 and 2, the components were mixed uniformly using a mixing and stirring device to produce compositions for model materials of Examples M1 to M16 and Comparative Examples m1 to m3.

<Composition for support material>
Table 3 summarizes the components used in the support material composition in the following Examples and Comparative Examples.

(Examples S1 to S13)
First, the support material compositions of Examples S1 to S13 and Comparative Example s1 were prepared as follows. That is, each support material composition was prepared by measuring the components (a) to (f) shown in Table 4 at the blending amounts (unit: parts by mass) shown in Table 4 and mixing them in a plastic bottle. .

Next, with respect to the support material compositions of the above Examples and Comparative Examples, the support material composition was cooled at low temperatures and the support material cured product obtained by curing the support material composition was stable under high temperature and high humidity conditions by the following methods. The property (supporting power) and water removal property were evaluated.

<Low temperature stability of support material composition>
The stability of the composition for the support material at low temperature was evaluated. Each support material composition was put in a glass bottle, and the glass bottle containing the support material composition was stored in a thermostatic bath set at a temperature of 10 ° C. for 24 hours. Then, the state of the composition for support material after storage was confirmed visually, and the low temperature stability of the composition for support material was evaluated according to the following criteria.

When the composition for the support material is maintained in a liquid state: low temperature stability A (excellent)
When the support material composition is partially solidified (solidified): Low temperature stability B (good)
When the composition for the support material is solidified (solidified): low temperature stability C (poor)
<Supporting power of cured support material>
A frame is formed on a glass plate with a frame-shaped silicon rubber having a length of 30 mm, a width of 30 mm, and a thickness of 5 mm, each support material composition is poured into the frame, and an ultraviolet ray with an integrated light amount of 500 mJ / cm ² is obtained by a metal halide lamp. Was irradiated to produce a cured support material. Subsequently, the cured product was placed in a glass petri dish, and the petri dish containing the cured product was left in a thermostatic bath at a temperature of 40 ° C. and a relative humidity of 90% for 2 hours. Thereafter, the state of the cured product after standing was visually confirmed, and the support force of the cured support material was evaluated according to the following criteria.

When there is no generation of liquid substances on the surface of the cured product and no softening of the cured product is confirmed: Support strength A (excellent)
When a slight amount of liquid material is generated on the surface of the cured product and softening of the cured product is confirmed slightly: Support strength B (good)
When a liquid substance is generated on the surface of the cured product and softening of the cured product is confirmed: Support force C (defect)
<Water removability of the cured support material>
A cured support material was produced in the same manner as in the evaluation of the support force of the cured support material. Next, the cured product is placed in a beaker filled with 50 mL of ion exchange water, treated with an ultrasonic cleaner while maintaining the water temperature at 25 ° C., and the time until the cured product is dissolved is measured. The water removal property of the support material cured product was evaluated based on the standard.

The time until the cured product completely dissolved was less than 1 hour: water removability A (excellent)
The time until the cured product was completely dissolved was 1 hour or more and less than 2 hours: Water removability B (good)
The time until the cured product was completely dissolved was 2 hours or more: water removability C (poor)
The results are shown in Table 5.

It can be seen that the support material compositions of Examples S1 to S13 obtained satisfactory results for all evaluation items.

<Optical modeling products>
<Composition set for material jet stereolithography (ink set)>
Examples 1 to 4 and Comparative Examples 1 to 3 were prepared by combining the composition for model material and the composition for support material as shown in Table 6.

A spacer having a thickness of 1 mm was arranged on the four upper surfaces of a glass plate (trade name “GLASS PLATE”, manufactured by ASONE, 200 mm × 200 mm × thickness 5 mm), and was partitioned into 10 cm × 10 cm squares. After casting the composition for the support material in the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as the irradiation means, and ultraviolet rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm ^2. And cured to obtain a support material.

Next, spacers having a thickness of 1 mm were arranged on the four sides of the upper surface of the support material and partitioned into squares of 10 cm × 10 cm. After casting the composition for the model material in the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as the irradiation means, and ultraviolet rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm ^2. And cured to obtain a model material.
(Evaluation of adhesion)
In this state, it was left in a thermostatic bath at 30 ° C. for 12 hours, the state of adhesion between the model material and the support material was visually confirmed, and evaluated according to the following criteria. The results are shown in Table 6.
○: The model material and the support material were in close contact.
X: Peeling occurred at the interface between the model material and the support material, and the model material was peeled off so as to be warped by the curing shrinkage of the model material.

As can be seen from the results in Table 6, in Examples 1 to 4 in which both the composition for the model material and the composition for the support material satisfy the requirements of the present invention, the interface between the model material and the support material does not peel, Model material and support material were more closely attached. Thus, if the model material and the support material are in close contact with each other, an optically shaped product with good dimensional accuracy can be obtained.

On the other hand, in Comparative Examples 1 to 3 in which one or both of the model material composition and the support material composition did not satisfy the requirements of the present invention, peeling occurred at the interface between the model material and the support material. As described above, when the adhesion between the model material and the support material is poor, the dimensional accuracy of the stereolithography product deteriorates.

The ink set for optical modeling according to the present invention can be suitably used when an optical modeling product with good dimensional accuracy is manufactured using an inkjet optical modeling method.

DESCRIPTION OF SYMBOLS 10 3D modeling apparatus 11 Inkjet head module 11a Optical modeling ink unit 11aM Model material inkjet head 11aS Support material inkjet head 11b Roller 11c Light source 12 Modeling table 13 Model material composition 13M Model material precursor 13PM Model material 14 Support Material composition 14S Support material precursor 14PS Support material 15 Energy beam 16 Stereolithography product precursor (Optical fabrication product)
17 Stereolithography

Claims

For optical modeling, which is a combination of a composition for a model material that is used in an inkjet optical modeling method and is used for modeling a model material, and a composition for a support material that is used to model a support material An ink set,
The model material composition is:
An ethylenically unsaturated monomer (A) having a glass transition temperature of 20 ° C. or higher and 120 ° C. or lower of the polymer;
An ethylenically unsaturated monomer (B) having a glass transition temperature of −65 ° C. or higher and lower than 20 ° C. of the polymer;
A bifunctional acrylate oligomer (C) having a weight average molecular weight of 800 or more and 10,000 or less;
A photopolymerizable initiator (D);
Containing, and
The content of the bifunctional or higher acrylate compound is 15 parts by mass or less with respect to 100 parts by mass of the entire model material composition,
The support material composition is based on 100 parts by mass of the support material composition as a whole.
19 to 80 parts by weight of a water-soluble monofunctional ethylenically unsaturated monomer (a) and 15 to 75 parts by weight of a polyalkylene glycol (b) containing an oxybutylene group, An optical modeling ink set in which the molecular weight of the alkylene glycol (b) is 300 to 3000.
The optical modeling ink set according to claim 1, wherein the ethylenically unsaturated monomer (A) of the model material composition is a monofunctional ethylenically unsaturated monomer.
The ink set for stereolithography according to claim 1 or 2, wherein the ethylenically unsaturated monomer (B) of the composition for model material is a monofunctional ethylenically unsaturated monomer.
4. The optical modeling ink set according to claim 1, wherein the bifunctional acrylate oligomer (C) of the model material composition has a Young's modulus at 25 ° C. of 1 to 100 MPa.
The content of the bifunctional acrylate oligomer (C) in the model material composition is 1 to 15 parts by mass with respect to 100 parts by mass of the model material composition as a whole. The ink set for stereolithography described in 1.
The ethylenically unsaturated monomer (A) of the model material composition is selected from isobornyl acrylate, t-butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, and dicyclopentanyl acrylate The ink set for stereolithography according to any one of claims 1 to 5, wherein the ink set is one or more selected from the above.
The ethylenically unsaturated monomer (B) of the model material composition is phenoxyethyl acrylate, n-stearyl acrylate, isodecyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, n-lauryl acrylate, n- 7. One or more selected from octyl acrylate, n-decyl acrylate, isooctyl acrylate, n-tridecyl acrylate, and 2- (N-butylcarbamoyloxy) ethyl acrylate The ink set for stereolithography described in 1.
The optical modeling ink set according to any one of claims 1 to 7, wherein the photopolymerizable compound contained in the model material composition is an acylphosphine oxide photopolymerization initiator.
9. The optical modeling ink set according to claim 1, wherein the support material composition contains 1 to 20 parts by mass of a photopolymerization initiator (d).
The composition for support material further contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 30 parts by mass or less with respect to 100 parts by mass of the total mass of the composition for support material. The optical modeling ink set according to any one of claims 1 to 9.
The support material composition further contains a surface conditioner,
The content of the surface conditioner is 0.005 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the total mass of the support material composition. Ink set for optical modeling.
A method for producing a stereolithography product by using the ink jet for stereolithography according to any one of claims 1 to 11, by a material jet stereolithography method,
Step (I) of obtaining a model material by photocuring the composition for model material, and obtaining a support material by photocuring the composition for support material using an ultraviolet LED;
Removing the support material (II);
A method for manufacturing an optically shaped article.