JP2019206112A - Photo-fabrication composition set, photo-fabricated article, and production method for photo-fabricated article - Google Patents

Abstract

To provide a photo-fabrication composition set that can mold a photo-fabricated article having high toughness with high accuracy.SOLUTION: A photo-fabrication composition set includes a model material composition and a support material composition. The model material composition includes a polyfunctional monomer having at least one ethylenically polymerizable group, with the polyfunctional monomer at least including a first monomer that includes at least one functional group selected from the group consisting of aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and primary and secondary amide groups and has a molecular weight of 1000 or less, and a second monomer that does not include aromatic hydrocarbon groups, alicyclic hydrocarbon groups, or primary and secondary amide groups and has a molecular weight of 1000 or less. The model material composition does not substantially include cationically polymerizable compounds. The support material composition includes 19-80 pts.wt. of a water-soluble monofunctional ethylenically unsaturated monomer and 15-75 pts.wt. of a polyalkylene glycol that has a weight average molecular weight of at least 300 and includes an oxybutylene group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an optical modeling composition set used for an inkjet optical modeling method, an optical modeling product modeled using the optical modeling composition set, and an optical modeling product using the optical modeling composition set. It relates to a manufacturing method.

  The photocurable resin composition is discharged from the nozzle, and immediately after that, it is cured by irradiating ultraviolet rays or the like.

Thus, there is known an optical modeling method (hereinafter referred to as an inkjet optical modeling method) using an inkjet method for forming a cured layer having a predetermined shape. 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.

  Inkjet stereolithography is easy to model a complex shape as compared with the conventional method of obtaining a stereolithography by irradiating a liquid photocurable composition with light, curing the irradiated portion, and laminating. In addition, since the amount of the photocurable composition required is small and there are merits such as easy adjustment of mechanical properties by simultaneously emitting photocurable compositions with different properties from multiple nozzles, various prototypes are available. Used for applications.

  In recent years, there has been a growing demand for using a molded article having toughness comparable to ABS for trial use. Patent Document 1 proposes a composition for a model material that can be used for an inkjet stereolithography method having high toughness.

JP, 2006-002703, A

  The composition for a model material is usually used for the inkjet stereolithography together with the composition for a support material. In recent years, from the viewpoint of handling and environment, a water-soluble composition for a support material has been developed, and the above-mentioned patent document also describes the composition for a model material described in the document as a water-soluble composition for a support material. It is described that it can be used in combination with a product. However, the conventionally widely known composition for a support material as exemplified in the above-mentioned patent document contains a water-soluble polymer such as polypropylene glycol having a high hydrophilicity. Depending on the type and content of the contained components, the support material obtained may be less self-supporting, so that there is a problem in that the dimensional accuracy of an optically shaped product formed using such a support material composition decreases. It was. In particular, a model material formed from a composition for a model material having high toughness tends to have low dimensional accuracy, and the composition accuracy for the support material to be combined tends to have a great influence on the modeling accuracy.

  Therefore, the present invention proposes a combination of a composition for a model material having high toughness and a composition for a support material having both high support power and excellent water removability for the composition for model material. It aims at providing the composition set for optical modeling which can model the optical modeling thing to have with high precision.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention provides the following preferred embodiments.

[1] For inkjet optical modeling formed by combining a composition for a model material used for modeling an optical modeling object by an inkjet optical modeling method and a composition for a support material used for modeling a support material A composition set comprising:
The model material composition is a model material composition comprising a monofunctional monomer having an ethylene polymerizable group, a polyfunctional monomer having at least one ethylene polymerizable group, and a photoinitiator,
The polyfunctional monomer has at least one functional group selected from the group consisting of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group, and has a molecular weight of 1000 or less. A composition for a model material, including at least a second monomer having a molecular weight of 1000 or less and having no monomer and any of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group The product is a composition containing substantially no cationically polymerizable compound,
The composition for support material is based on 100 parts by weight of the whole composition for support material,
19 parts by weight or more and 80 parts by weight or less of a water-soluble monofunctional ethylenically unsaturated monomer;
A polyalkylene glycol containing 15 to 75 parts by weight of an oxybutylene group;
Contains a photoinitiator,
The composition set for inkjet optical shaping | molding whose weight average molecular weights of the polyalkylene glycol containing the said oxybutylene group are 300 or more.
[2] The composition set for inkjet optical modeling according to [1], wherein the number average molecular weight of the first monomer is smaller than the number average molecular weight of the second monomer.

  [3] The mass ratio represented by the mass of the first monomer / the mass of the second monomer is 40/60 or more and 80/20 or less, according to [1] or [2] The composition set for inkjet optical modeling described.

  [4] For the inkjet optical modeling according to any one of [1] to [3], the ethylene polymerizable groups of the first monomer and the second monomer are all (meth) acrylic groups. Composition set.

  [5] The inkjet light according to any one of [1] to [4], wherein at least one of the first monomer and the second monomer includes a vinyl ether group or an allyl group as the ethylene polymerizable group. Composition set for modeling.

  [6] The content of the photopolymerization initiator in the support material composition is 1 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the entire support material composition. Inkjet optical modeling composition set.

  [7] The composition for a support material further contains a surface conditioner, and the content of the surface conditioner is 0.005 parts by weight or more and 3 parts by weight with respect to 100 parts by weight of the entire composition for a support material. The composition set for inkjet photofabrication according to [1] or [6], which is at most parts.

  [8] The support material composition further contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 30 parts by weight or less with respect to 100 parts by weight of the entire support material composition. , [1] or [6] or [7] The composition set for inkjet optical modeling according to [7].

  [9] The composition set for inkjet stereolithography according to any one of [1] or [6] to [8], wherein the composition for support material further contains a storage stabilizer.

  [10] An optically shaped article formed by the inkjet optical modeling method using the inkjet optical modeling composition set according to any one of [1] to [9].

  [11] A method for producing an optically shaped article by an inkjet optical shaping method using the optical shaping ink set according to any one of [1] to [9], wherein the composition for a model material is An optically shaped article comprising: a step of photocuring to obtain a model material, and a step of obtaining the support material by photocuring the composition for support material (I) and a step of removing the support material (II). Production method.

  ADVANTAGE OF THE INVENTION According to this invention, the composition set for optical modeling which can model the optical modeling thing which has high toughness with high precision can be provided.

It is a schematic side view which shows the state which ejects the composition for model materials and the composition for support materials in the manufacturing method of the optical modeling thing which concerns on this embodiment, and has irradiated the energy beam. It is a schematic side view which shows the state which is discharging the composition for model materials and the composition for support materials in the manufacturing method of the optical modeling thing which concerns on this embodiment. It is a schematic side view which shows the state which has irradiated the energy beam to the composition for model materials and the composition for support materials in the manufacturing method of the optical modeling thing which concerns on this embodiment. It is a model side view of the optical modeling product precursor (optical modeling thing) which consists of a support material and a model material. It is a model side view of a stereolithography product.

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

1. Composition for Model Material The composition for model material of the present invention is for a model material containing a monofunctional monomer having an ethylene polymerizable group, a polyfunctional monomer having at least one ethylene polymerizable group, and a photoinitiator. In the composition, the polyfunctional monomer has at least one functional group selected from the group consisting of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group, and has a molecular weight. A first monomer having 1000 or less and at least a second monomer having a molecular weight of 1000 or less and having no aromatic hydrocarbon group, alicyclic hydrocarbon group, primary amide group or secondary amide group The composition is a composition that does not substantially contain a cationically polymerizable compound.

1-1. Monofunctional monomer having an ethylene polymerizable group A monofunctional monomer having an ethylene polymerizable group (hereinafter also simply referred to as a monofunctional monomer of the present invention) is a monomer having one ethylene polymerizable group.

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

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

  The monofunctional monomer of the present invention may be used alone or in combination of a plurality of types.

  The number average molecular weight of the monofunctional monomer of the present invention is 150 to 1000, so that it is possible to improve the ink jetting property at the time of manufacturing a three-dimensional structure by the UV-IJ (ultraviolet-inkjet) method, and SLA (stereolithography) It is possible to prevent liquid convection during the production of a three-dimensional structure by the method, increase the curability, and increase the breaking strength. Further, by setting the molecular weight of the monofunctional monomer to 150 to 600, it is possible to further improve the ink jetting property and curability.

  The ratio of the monofunctional monomer of the present invention contained in the composition for a model material is not particularly limited, but is preferably 50% by mass to 95% by mass, and 65% by mass to 90% by mass with respect to the total mass of the composition. More preferably, it is mass%. When the amount of the monofunctional monomer of the present invention is 50% by mass or more, flexibility is generated and elongation is imparted, and when the amount of the monofunctional monomer of the present invention is 90% by mass or less, crosslinking is not caused. The rigidity can be increased due to the reduction of low-molecular substances.

  Examples of the monofunctional monomer of the present invention having the (meth) acryl group that can be contained in the model material composition of the present invention include butyl acrylate, 2-ethylhexyl acrylate, pentyl acrylate, isoamyl acrylate, octyl acrylate, Isooctyl (meth) acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl acrylate, isostearyl acrylate, n-stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenoxyethyl Acrylate, phenoxyethoxyethyl acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, methoxyethoxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, t -Butylcyclohexyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-ethylhexyl-diglycol acrylate, 4-hydroxybutyl acrylate, methoxytriethylene glycol acrylate, ethoxy Examples include diethylene glycol acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2-ethylhexyl carbitol acrylate, and the like.

  Examples of the monofunctional monomer of the present invention having an allyl ether group that can be contained in the model material composition of the present invention include phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl- 2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, cyclohexane methanol monoallyl ether and the like are included.

  Examples of the monofunctional monomer of the present invention having the vinyl ether group that can be contained in the model material composition of the present invention include butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, ethylhexyl vinyl ether, and phenyl vinyl ether. Benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, cyclohexyl vinyl ether, adamantyl vinyl ether and the like.

  Examples of the monofunctional monomer of the present invention having the maleimide group that can be contained in the model material composition of the present invention include phenylmaleimide, cyclohexylmaleimide, n-hexylmaleimide and the like.

Examples of the monofunctional monomer of the present invention having the (meth) acrylamide group that can be contained in the model material composition of the present invention include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-butyl (meth) acrylamide and the like are included.
1-2. Polyfunctional monomer containing at least one ethylene polymerizable group Polyfunctional monomer containing at least one ethylene polymerizable group (hereinafter, also simply referred to as the polyfunctional monomer of the present invention) is a polyfunctional monomer, and the polymerization As the functional group, it means one having at least one ethylene polymerizable group. The composition for a model material of the present invention contains at least one selected from the group consisting of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group as the polyfunctional monomer of the present invention. A first monomer having a functional group and a molecular weight of 1000 or less (hereinafter also simply referred to as a first monomer), an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group; It contains at least a second monomer having a molecular weight of 1000 or less (hereinafter also simply referred to as a second monomer).

  The composition for model materials of the present invention can contain 5% by mass or more and 50% by mass or less of the polyfunctional monomer of the present invention with respect to the mass of the entire composition. When the content of the polyfunctional monomer of the present invention with respect to the total amount of the composition is 5% by mass or more, there is an effect of improving the breaking strength. There exists an effect of improving elongation that content of the polyfunctional monomer of this invention with respect to the mass of the whole composition is 50 mass% or less. Content of the polyfunctional monomer of this invention becomes like this. Preferably it is 10 to 30 mass%, More preferably, it is 15 to 25 mass%.

  The composition for model materials of this invention can improve the toughness of the three-dimensional molded item manufactured by hardening | curing this by including a 1st monomer and a 2nd monomer. High toughness means that when the stress is applied, the yield stress is high when the yield point is reached via the elastic region that the polymer chain can withstand without being modified, and in addition, when the stress is further applied This means that the elongation at break and the strength at break when the polymer chain breaks without being able to endure through the ductile region where the polymer chain undergoes deformation and extends are large.

  Since fracture is caused by concentration of stress in the deformed local area, the fracture elongation and the fracture strength can be increased by dispersing the stress in a plurality of locations.

  Since the first monomer has an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group, intermolecular interactions such as hydrogen bonds, π-π bonds, steric hindrance, etc. A cross-linked portion having a large action can be formed. Since the cross-linked portion cross-linked by the first monomer acts as a strong resistance due to a strong intermolecular interaction when the polymer chain is pulled by a stress load, the yield stress can be increased. Moreover, even if the polymer chain after yielding shifts, when the first monomers come close to each other, the cross-linked portion due to the first monomer is easily re-formed, so that the stress is easily dispersed.

  On the other hand, since the second monomer does not have a functional group having intermolecular interaction such as an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group, the second monomer At the cross-linked point cross-linked by (1), the polymer chain is likely to be displaced when stress is applied. In the cross-linked portion of the second monomer, the stress is easily dispersed even when the polymer chain is displaced.

  In the present invention, it is considered that the toughness can be improved because the stress is widely dispersed by using these two monomers together by the above mechanism.

  At this time, the toughness can be further improved by selecting the first monomer and the second monomer so that the number average molecular weight of the first monomer is smaller than the number average molecular weight of the second monomer. . By making the length of the first monomer having a strong intermolecular interaction shorter than the length of the second monomer having a small intermolecular interaction, the first molecule having a strong intermolecular interaction when stress is applied. The cross-linked portion due to the monomer is likely to break preferentially. At this time, after the cross-linked portion by the first monomer is cut and yielding occurs, the cross-linked portion by the second monomer that extends well because the intermolecular interaction is weak remains, so that elongation after yielding can be obtained. It is thought that the toughness became higher.

  Further, the mass ratio of the mass of the first monomer and the mass of the second monomer contained in the composition for model material of the present invention (the mass of the first monomer / the mass of the second monomer). Is preferably 40/60 or more and 80/20 or less. By setting this mass ratio to 40/60 or more, the amount of the first monomer can be increased to increase the yield strength, and by setting this mass ratio to 80/20 or less, The amount can be increased to increase the elongation.

1-2-1. First monomer The first monomer is a polyfunctional monomer having at least one polymerizable group, and has at least one ethylene polymerizable group as the polymerizable group, and includes an aromatic hydrocarbon group and an alicyclic ring. A monomer having a molecular weight of 1000 or less, further having at least one functional group selected from the group consisting of a formula hydrocarbon group, a primary amide group, and a secondary amide group. The alicyclic hydrocarbon group may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.

  In the ethylene polymerizable group, like the monofunctional monomer of the present invention, ethylene group, propenyl group, butenyl group, vinylphenyl group, (meth) acryl group, allyl ether group, vinyl ether group, maleyl group, maleimide group, (Meth) acrylamide group, acetylvinyl group, vinylamide group and the like are included. Of these, (meth) acryl groups, allyl ether groups, vinyl ether groups and (meth) acrylamide groups are preferred. The ethylene polymerizable group possessed by the first monomer may be the same functional group as the ethylene polymerizable group possessed by the monofunctional monomer of the present invention, or may be a different functional group.

  The first monomer is composed of the above-mentioned ethylene polymerizable group and another monomer (monofunctional monomer of the present invention, first monomer, second monomer, or other monomer contained in the composition for model material of the present invention). Can be polymerized. The aromatic hydrocarbon group, alicyclic hydrocarbon group, primary amide group or secondary amide group contained in the first monomer forms a cross-linked portion by the first monomer during polymerization.

  Moreover, the first monomer can increase the rigidity by setting the molecular weight to 150 or more and 1000 or less. The molecular weight of the first monomer is preferably 160 or more and 600 or less, and more preferably 160 or more and 400 or less.

  Examples of the first monomer having a (meth) acryl group that can be contained in the composition for a model material of the present invention include tricyclodecane dimethanol di (meth) acrylate, bisphenol A EO adduct di ( (Meth) acrylate, bisphenol A PO adduct di (meth) acrylate, hydrogenated bisphenol A EO adduct di (meth) acrylate, hydrogenated bisphenol A PO adduct di (meth) acrylate, cyclohexanedi (meth) acrylate And cyclohexanedimethanol di (meth) acrylate and the like.

  Examples of the first monomer having an allyl ether group which can be contained in the model material composition of the present invention include phthalic acid diallyl ether, isophthalic acid diallyl ether, dimethanol tricyclodecane diallyl ether and 1,4. -Cyclohexanedimethanol diallyl ether and the like are included.

  Examples of the first monomer having a vinyl ether group that can be contained in the composition for a model material of the present invention include cyclohexane dimethanol divinyl ether and tricyclodecane dimethanol divinyl ether. Examples include EO adduct divinyl ether of bisphenol A, cyclohexanediol divinyl ether, norbornyl dimethanol divinyl ether, divinyl resorcin, and divinyl hydroquinone.

  Examples of the first monomer having a (meth) acrylamide group that can be contained in the composition for a model material of the present invention include bismethyleneacrylamide, di (ethyleneoxy) bispropylacrylamide, and tri (ethyleneoxy) bis. Examples thereof include propylacrylamide and polymerizable monomer 2 described in JP-A-2013-208890 exemplified below.

1-2-2. Second monomer The second monomer is a polyfunctional monomer having at least one polymerizable group, and has at least one ethylene polymerizable group as the polymerizable group, and includes an aromatic hydrocarbon group and an alicyclic ring. It is a monomer having a molecular weight of 1000 or less, which does not have any of the formula hydrocarbon group, primary amide group and secondary amide group.

  The ethylene polymerizable group includes an ethylene group, a propenyl group, a butenyl group, a vinylphenyl group, a (meth) acryl group, an allyl ether group, a vinyl ether group, a maleyl group, and an acetyl vinyl group, as in the monofunctional monomer of the present invention. Etc. are included. The ethylene polymerizable group possessed by the second monomer may be the same functional group as the ethylene polymerizable group possessed by the monofunctional monomer of the present invention, or may be a different functional group. Further, the ethylene polymerizable group of the second monomer may be the same functional group as the ethylene polymerizable group of the first monomer, or may be a different functional group.

  The second monomer preferably has two or more ethylene polymerizable groups. The second monomer has one ethylene polymerizable group and another monomer (monofunctional monomer of the present invention, first monomer, second monomer, or other monomer contained in the model material composition of the present invention). Can be polymerized. A 2nd monomer forms the bridge | crosslinking part by said 2nd monomer at the time of superposition | polymerization by another ethylene polymeric group.

  In addition, the second monomer having a molecular weight of 150 or more and 1000 or less can prevent elongation from occurring even with a weak force, and can improve toughness. The molecular weight is preferably 160 or more and 600 or less, and more preferably 180 or more and 500 or less.

Examples of the second monomer having a (meth) acryl group that can be contained in the composition for model material of the present invention include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, Bifunctional monomers such as 9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate; Tyrolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate and Trifunctional or higher polyfunctional monomers such as pentaerythritol ethoxytetra (meth) acrylate are included.

  Examples of the second monomer having a vinyl ether group that can be contained in the composition for a model material of the present invention include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, and dipropylene. Glycol vinyl ether, butylene divinyl ether, dibutylene glycol divinyl ether, neopentyl glycol divinyl ether, glycerin trivinyl ether, glycerin ethylene oxide adduct trivinyl ether (addition mole number of ethylene oxide 6), trimethylolpropane trivinyl ether, trivinyl ether ethylene oxide adduct tri Vinyl ether (addition mole number of ethylene oxide 3), pentaerythritol tri Vinyl ether include such ditrimethylolpropane hexa ether and their oxyethylene adduct.

Examples of the second monomer having an allyl ether group that can be contained in the model material composition of the present invention include alkylene (2 to 5 carbon atoms) glycol diallyl ether, polyethylene glycol diallyl ether, and the like. . Also, glyceryl diallyl ether, trimethylolpropane diallyl ether, pentaerythritol diallyl ether and polyglycerol (degree of polymerization 2-5) diallyl ether, trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether and tetraallyloxy Includes ethane. Also included are pentaerythritol triallyl ether, diglycerol triallyl ether, sorbitol triallyl ether, polyglycerol (degree of polymerization 3 to 13) polyallyl ether, and the like.
1-2-3. Combination of the first monomer and the second monomer The combination of the first monomer and the second monomer is not particularly limited and may be any combination.

  When the ethylene polymerizable group of the first monomer and the ethylene polymerizable group of the second monomer are both (meth) acrylic groups, photocuring sensitivity is high and modeling can be performed with less energy. .

  On the other hand, when at least one of the first monomer and the second monomer is a compound containing a vinyl ether group or an allyl group as the ethylene polymerizable group, it is possible to further increase the elongation of the manufactured three-dimensional structure. . This is presumably because the vinyl ether group or allyl group is slow to polymerize, so that the polymerization of the monofunctional monomer proceeds, so that the distance between the cross-linking portions becomes long and the elongation becomes large.

<Photopolymerization initiator>
It is preferable that the composition for model materials of this invention contains a photoinitiator. The photopolymerization initiator is not particularly limited as long as it 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. It is preferable to use a photopolymerization initiator containing at least one compound selected from the group consisting of and ketal compounds.

  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 α-aminoalkylphenone compounds available on the market 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 the α-hydroxyquinone compound available on the market 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, and 2-amylanthraquinone.

  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 Examples include '-bismethylaminobenzophenone.

  Content of the said photoinitiator is 1-15 weight part with respect to 100 weight part of the whole resin composition. When the content of the component is within the above range, the curability of the model material composition is improved, and the dimensional accuracy of the optically shaped object is improved. The content of the above components is preferably 2 parts by weight or more, and preferably 13 parts by weight or less. In addition, when the said component is contained 2 or more types, the said content is defined as the sum total of content of each photoinitiator.

<Surface conditioner>
The surface conditioner is contained in order to adjust the surface tension of the resin composition to an appropriate range. By adjusting the surface tension of the resin composition to an appropriate range, the model material composition and the support material composition can be prevented from being mixed at the interface. As a result, an optically shaped article with good dimensional accuracy can be obtained using these resin compositions. In order to acquire this effect, content of the said component shall be 0.005-3.0 weight part with respect to 100 weight part of the whole resin composition.

  Examples of the surface conditioner include silicone compounds. Examples of the silicone compound include a silicone compound having a polydimethylsiloxane structure. Specific examples include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyaralkyl-modified polydimethylsiloxane. As these, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (above, manufactured by BYK Chemie), TEGO-Rad2100 , TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700 (above, manufactured by Degussa), Granol 100, Granol 115, Granol 400, Grano Le 410, Granol 435, Granol 440, Granol 450, B-1484, Polyflow ATF-2, KL-600, UCR-L72, UCR-L93 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like may be used. Moreover, other than silicone compounds (for example, fluorine-based surface conditioners and nonionic surface conditioners) can also be used. These may be used alone or in combination of two or more. In addition, when the said component is contained 2 or more types, the said content is defined as the sum total of content of each surface modifier.

<Storage stabilizer>
The model material composition according to this embodiment preferably further contains a storage stabilizer. The storage stabilizer can increase the storage stability of the resin composition. Further, clogging of the head caused by polymerization of the polymerizable compound by thermal energy can be prevented. In order to acquire these effects, it is preferable that content of the said component is 0.05-3.0 weight part with respect to 100 weight part of the whole resin composition.

  Examples of the component include hindered amine compounds (HALS), phenolic antioxidants, phosphorus antioxidants, nitrosamine compounds, and the like. Specifically, hydroquinone, methoquinone, benzoquinone, p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutyl ether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, cupron Al, IRGASTAB UV-10, IRGASTAB UV-22, FIRSTCURE ST- 1 (manufactured by ALBEMARLE), t-butylcatechol, pyrogallol, TINUVIN 111 FDL, TINUVIN 144, TINUVIN 292, TINUVIN XP40, TINUVIN XP60, and TINUVIN 400 manufactured by BASF. These may be used alone or in combination of two or more. In addition, when the said (G) component is contained 2 or more types, the said content is defined as the sum total of content of each storage stabilizer.

  If necessary, the model material composition may contain other additives as long as the effects of the present invention are not impaired. Examples of other additives include an antioxidant, a colorant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, a chain transfer agent, and a filler.

  The composition for model materials of the present invention may further contain a photoinitiator auxiliary as necessary. Examples of photoinitiator aids may be, for example, tertiary amine compounds, with aromatic tertiary amine compounds being preferred. Examples of aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included. Of these, N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. Only one of these compounds may be included in the model material composition, or two or more of these compounds may be included.

  Although the composition for model materials which concerns on this embodiment is not specifically limited, It can manufacture by mixing uniformly using a mixing stirring apparatus, a disperser, etc.

  The composition for a model material of the present invention may contain a polymerizable compound other than the monofunctional monomer, the first monomer, or the second monomer of the present invention. Examples of the polymerizable compound that may be contained include monomers other than those described above, oligomers having a polymerization degree of 2 to 20 and polymerizability, and polymers having polymerizability.

  In addition, it is preferable that the composition for model materials of this invention does not contain substantially cationically polymerizable compounds, such as a compound which has an epoxy group. The vinyl ether group is not included in the cationically polymerizable compound here because it can be either radical polymerization or cationic polymerization. By substantially not containing a cationically polymerizable compound, it is possible to prevent a decrease in photocuring sensitivity and to cure the composition even with ultraviolet rays. The phrase “substantially free of cationically polymerizable compound” means that the content ratio of the cationically polymerizable compound is 1% by mass or less with respect to the total mass of the composition.

  When the model material composition of the present invention is emitted from an inkjet head, the viscosity of the model material composition is 100 mPa.s. It is preferable that it is s or less.

2. Composition for Support Material In the present invention, the water-soluble composition for a support material comprises at least one water-soluble monofunctional ethylenically unsaturated monomer (a), at least one polyalkylene glycol (b) and light. It preferably contains a polymerization initiator.

  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 etc. , (Meth) acrylamide derivatives [e.g. (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) acryloyl And 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) that can be included in the composition for a support material 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. Specific examples of such polyalkylene glycol (b) include polyalkylene glycols containing an oxybutylene group. These may be used alone or in combination of two or more.

  The polyalkylene glycol (b) that can be contained in the support material composition is not particularly limited in the structure of the alkylene portion. For example, even if it is a polybutylene glycol alone having only an oxybutylene group (oxytetramethylene group). Alternatively, it may be a polybutylene polyoxyalkylene glycol having both an oxybutylene group and another oxyalkylene group (for example, polybutylene polyethylene glycol). For example, the polybutylene glycol is represented by the following chemical formula (2), and the polybutylene polyethylene glycol is represented by the following chemical formula (3).

  In the chemical formula (3), 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 (2) and the chemical formula (3) may be a straight chain or may be branched.

  When the composition for a support material contains the polyalkylene glycol (b), the removability by water can be further improved without reducing the support force of the support material. These may be used alone or in combination of two or more.

  The weight average molecular weight of the polyalkylene glycol (b) component is 300 or more, preferably less than 3000, more preferably 800 or more, and more preferably less than 2000. If the weight average molecular weight of component (b) is less than 300, bleeding of the support material occurs 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, since the weight average molecular weight of polyalkylene glycol is smaller than 3000, it is excellent in the discharge stability of the composition for support materials.

  Two or more polyalkylene glycol (b) 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) in the support material composition is preferably 15 to 75 parts by mass, more preferably 17 parts by mass or more, with respect to 100 parts by mass of the support material composition. More preferably, it is 20 mass parts or more, More preferably, it is 72 mass parts or less, More preferably, it is 70 mass parts or less. When the content of the polyalkylene glycol (b) 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 composition for a support material 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 Methyl 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 acetate And glycol monoether acetate solvents such as 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.

  As the photopolymerization initiator, the compounds described above as photopolymerization initiators that can be contained in the model material composition can be used in the same manner. 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.

  By including each of the above components in a content within the above range, a composition for a support material having both excellent water solubility and support ability can be obtained. In particular, since the support power is excellent, there is no concern that the moisture in the air is taken in during modeling and the support power is reduced, and an optical modeling product with good dimensional accuracy can be obtained.

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

  By adding a surface conditioner to the support material composition, the surface tension of the support material composition can be controlled within an appropriate range, and the model material composition and the support material composition are mixed at the interface. Can be suppressed. Thereby, a stereolithography thing 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 0.005-3 mass parts with respect to 100 mass parts of things.

  Moreover, storage stability can be improved by mix | blending a storage stabilizer with the composition for support materials. As the storage stabilizer that can be contained in the support material composition, 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 it is 0.05-3 mass parts with respect to 100 mass parts of things.

  When the support material composition is emitted from the inkjet head, 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 40 mPa · s or more. Yes, more preferably 170 mPa · s or less, 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 a support material can be produced by uniformly mixing the components constituting the composition for a support material using a mixing stirrer, a disperser or the like. it can.
3. Stereolithography product and manufacturing method thereof The fabrication method of the stereolithography object of the present embodiment is a fabrication method of the stereolithography object using the composition set for inkjet stereolithography described in the above embodiment, and uses an inkjet printer. After the model material composition and the support material composition are discharged, the model material composition is photocured to obtain a model material, and the water soluble support material composition is photocured to obtain a water soluble support material. And a step of removing the water-soluble support material by bringing it into contact with water.

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

  Hereinafter, the manufacturing method of the optical modeling thing of this embodiment is explained based on a drawing. FIG. 1 is a schematic side view showing a state in which a support material composition and a model material composition are discharged by an ink 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 manufacturing method of the optical modeling thing of this embodiment is demonstrated still in detail based on drawing. In the method of 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 with 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, the same process as described above is performed, and a second layer of the model material and the support material is formed. 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 brought into contact with water, for example, by immersing in water, the support material 14PS is dissolved and removed to form the optical modeling product 17 as shown in FIG. Is done.

  In the method for manufacturing 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 a 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.

  Since the composition for a model material of the present invention does not substantially contain the content of the cationically polymerizable compound, it can be sufficiently cured even with ultraviolet rays having the least energy load and apparatus load. Therefore, a three-dimensional molded item can be manufactured at a lower cost by using ultraviolet rays.

  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 material jet type 3D printer is prepared, and each of the material for the model material and the support material is based on the prepared slice data. After the composition is discharged, the photocuring 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 support material composition (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 optically shaped object 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 optically shaped article 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.

  In the embodiment described above, the number of inkjet heads for the model material composition is not limited to one. For example, two ink jet heads may be provided for the model material composition, model material compositions having different physical properties may be simultaneously ejected from the nozzles of the respective ink jet heads, and the model material composition may be mixed to form a composite material.

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

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and part by mass.

<Model material composition>
The details of the components constituting the composition for model material used in the examples are shown in Table 1.

<Manufacture of composition for model material>
In the formulation shown in Table 2, each component was uniformly mixed using a mixing and stirring device, and the compositions for model materials of Examples M1 to M7 and Comparative Examples m1 to m3 were produced.

<Manufacture of 3D objects>
A frame is formed on a glass plate with a frame-shaped silicon rubber having a length of 100 mm, a width of 20 mm, and a thickness of 5 mm. Each model material composition is poured into the frame, and an ultraviolet ray with an integrated light amount of 400 mJ / cm ² is obtained by a metal halide lamp. Was irradiated to obtain a model material. The following characteristics were measured and evaluated. The results are shown in Table 3.

<Measurement of yield strength, fracture elongation and fracture strength>
The yield strength, the breaking elongation at break and the breaking strength were measured by applying a constant load at a tensile speed of 20 mm / min in the scanning direction and the laminating direction at room temperature. The results are shown in Table 3.

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

  The three-dimensional structure manufactured using the composition for model materials of the present invention had a good balance of yield strength, fracture strength and fracture elongation, and had high toughness. Further, all of the inks examined in this example had good emission characteristics.

<Composition for support material>
Table 4 summarizes the components used in the support material composition in the following Examples and Comparative Examples.

(Examples S1 to S13 and Comparative Example s1)
First, the support material compositions of Examples S1 to 13 were prepared as follows. That is, each support material composition was prepared by measuring the components (a) to (f) shown in Table 7 at the blending amounts (unit: parts by mass) shown in Table 5 and mixing them in a plastic bottle. .

  Next, with respect to the support material compositions of Examples S1 to 13, the low temperature stability of the support material composition and the high temperature and high humidity condition stability of the cured support material obtained by curing the support material composition ( Support power) and water removability were evaluated.

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

When the support material composition 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 support material composition is solidified (solidified): low temperature stability C (poor)
<Supporting power of cured support material>
A frame is formed on a glass plate with silicon rubber in a frame shape of 30 mm in length, 30 mm in width, and 5 mm in thickness, each support material composition is poured into the frame, and ultraviolet rays with an integrated light amount of 500 mJ / cm 2 are emitted from a metal halide lamp. 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.

When it takes 30 minutes for the cured product to completely dissolve: Water removability A (excellent)
When it takes 1 hour for the cured product to completely dissolve: Water removability B (good)
When it takes 2 hours for the cured product to completely dissolve: water removability C (poor)
The results are shown in Table 6.

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

<Composition set for inkjet optical modeling>
Examples 1 to 4 and Comparative Examples 1 and 2 were prepared by combining the composition for model material and the composition for support material as shown in Table 7.

  Spacers with a thickness of 1 mm were arranged on the four upper sides of a glass plate (trade name “GLASS PLATE”, manufactured by AS ONE, 200 mm × 200 mm × thickness 5 mm) and 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 the ultraviolet ray is irradiated so that the total irradiation light amount becomes 500 mJ / cm 2. 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 model material composition in the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as the irradiation means, and the total irradiation light quantity is 500.
A model material was obtained by irradiating and curing with ultraviolet rays so as to be mJ / cm 2.

<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 7.
○: The model material and the support material were in close contact.
Δ: The model material and the support material were in close contact with each other, but peeling occurred when the interface between the model material and the support material was scratched with a nail.
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 7, 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, no peeling occurs at the interface between the model material and the support material. 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 and 2 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 composition set for optical modeling of 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 ink 13M Model material precursor 13PM Model material 14 Support material Ink 14S support material precursor 14PS support material 15 energy beam 16 modeled object precursor 17 modeled object

Claims (11)

Inkjet stereolithography composition set comprising a combination of a model material composition used for modeling an optical modeling object by an inkjet stereolithography method and a support material composition used for modeling a support material. Because
The model material composition is a model material composition comprising a monofunctional monomer having an ethylene polymerizable group, a polyfunctional monomer having at least one ethylene polymerizable group, and a photoinitiator,
The polyfunctional monomer has at least one functional group selected from the group consisting of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group, and has a molecular weight of 1000 or less. A composition for a model material, including at least a second monomer having a molecular weight of 1000 or less and having no monomer and any of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group The product is a composition containing substantially no cationically polymerizable compound,
The composition for support material is based on 100 parts by weight of the whole composition for support material,
19 parts by weight or more and 80 parts by weight or less of a water-soluble monofunctional ethylenically unsaturated monomer;
A polyalkylene glycol containing 15 to 75 parts by weight of an oxybutylene group;
Contains a photoinitiator,
The composition set for inkjet optical shaping | molding whose weight average molecular weights of the polyalkylene glycol containing the said oxybutylene group are 300 or more. The composition set for inkjet optical modeling according to claim 1, wherein the number average molecular weight of the first monomer is smaller than the number average molecular weight of the second monomer. 3. The inkjet stereolithography according to claim 1, wherein a mass ratio represented by a mass of the first monomer / a mass of the second monomer is 40/60 or more and 80/20 or less. 4. Composition set. The composition set for inkjet photofabrication according to any one of claims 1 to 3, wherein each of the ethylene polymerizable groups of the first monomer and the second monomer is a (meth) acryl group. . The composition for inkjet photofabrication according to any one of claims 1 to 4, wherein at least one of the first monomer and the second monomer includes a vinyl ether group or an allyl group as the ethylene polymerizable group. Things set. 2. The inkjet according to claim 1, wherein in the support material composition, the content of the photopolymerization initiator is 1 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the entire support material composition. Stereolithography composition set. The composition for support material further contains a surface conditioner, and the content of the surface conditioner is 0.005 part by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the whole composition for support material. The composition set for inkjet optical modeling according to claim 1 or 6. The composition for a support material further contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is 30 parts by weight or less with respect to 100 parts by weight of the entire composition for a support material. The composition set for inkjet optical modeling according to 1 or 6 or 7. The composition set for inkjet optical modeling according to any one of claims 1 or 6 to 8, wherein the composition for support material further contains a storage stabilizer. The optical modeling thing modeled by the inkjet optical modeling method using the composition set for inkjet optical modeling as described in any one of Claims 1-9. It is a method of manufacturing an optical modeling thing using the ink set for optical modeling as described in any one of Claims 1-9 by the inkjet optical modeling method, Comprising: The said model material composition is photocured, and it is a model. A method for producing an optically shaped article, comprising: obtaining a material; and (1) obtaining the support material by photocuring the composition for support material, and (II) removing the support material.

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