JP6269339B2 - 3D modeling composition, 3D modeling ink set, and 3D manufacturing method - Google Patents

Description

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

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

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

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

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

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

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

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

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

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

In view of the above problems, the first of the present invention relates to a 3D modeling composition liquid.
[1] A 3D modeling composition liquid comprising a monofunctional monomer having an ethylene polymerizable group, a polyfunctional monomer having at least one ethylene polymerizable group, and a photoinitiator, wherein the polyfunctional monomer is A first monomer having 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 having a molecular weight of 1000 or less, and an aromatic The composition liquid contains at least a second monomer having a molecular weight of 1000 or less, which does not have any of a hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group. A composition liquid substantially not contained.
[2] The composition liquid 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 liquid described.
[4] The composition liquid according to any one of [1] to [3], wherein each of the ethylene polymerizable groups of the first monomer and the second monomer is a (meth) acryl group.
[5] The composition liquid according to any one of [1] to [3], 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. .
[6] The composition liquid according to any one of [1] to [5], further containing a release agent.

The second aspect of the present invention relates to an ink set for 3D modeling.
[7] A 3D modeling ink set comprising the composition liquid according to any one of [1] to [6] and a support material composition liquid.

Moreover, the 3rd of this invention is related with the manufacturing method of 3D modeling thing.
[8] A method for producing a 3D structure, comprising a step of irradiating the composition liquid according to any one of [1] to [6] with actinic rays.

  By modeling a 3D model using the 3D modeling composition liquid or ink set for 3D modeling of the present invention, a 3D model that can be cured by ultraviolet irradiation and has high toughness and is not easily broken is obtained. It is done. Moreover, according to this invention, it can provide the manufacturing method of the 3D modeling thing which has high toughness and can obtain the 3D modeling thing which is hard to break.

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

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

1.3D modeling composition liquid The 3D modeling composition liquid of the present invention contains a monofunctional monomer having an ethylene polymerizable group, a polyfunctional monomer containing at least one ethylene polymerizable group, and a photoinitiator. A modeling composition liquid, wherein 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. A first monomer having a molecular weight of 1000 or less, and a second monomer having a molecular weight of 1000 or less, which does not have any of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group. At least, the composition liquid is a composition liquid 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 enhance the ink jetting property at the time of manufacturing a 3D shaped article by UV-IJ (ultraviolet-inkjet) method, and SLA (stereolithography) It is possible to prevent liquid convection during the production of a 3D 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 3D modeling composition liquid 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 liquid. 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 3D modeling composition liquid 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 the allyl ether group that can be contained in the composition liquid for 3D modeling 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 composition liquid for 3D modeling of the present invention include butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, ethyl hexyl 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 3D modeling composition liquid 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 3D modeling composition liquid of the present invention include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N- Examples include ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-butyl (meth) acrylamide and the like.

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. In the 3D modeling composition liquid of the present invention, as the polyfunctional monomer of the present invention, 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 is used. 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 liquid for 3D modeling 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 based on the mass of the entire composition liquid. When the content of the polyfunctional monomer of the present invention with respect to the total amount of the composition liquid is 5% by mass or more, there is an effect of improving the breaking strength. When the content of the polyfunctional monomer of the present invention is 50% by mass or less with respect to the mass of the entire composition liquid, there is an effect of improving elongation. The content of the polyfunctional monomer of the present invention is preferably 10% by mass to 30% by mass, and more preferably 15% by mass to 25% by mass.

  By including the first monomer and the second monomer, the 3D modeling composition liquid of the present invention can enhance the toughness of the 3D modeled product manufactured by curing the first monomer and the second 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 denatured. 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 by 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 is well extended due to weak intermolecular interaction remains, so that elongation after yielding can be obtained. It is thought that the toughness became higher.

  Moreover, the mass ratio of the mass of the first monomer and the mass of the second monomer contained in the 3D modeling composition liquid 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 3D modeling composition liquid 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 3D modeling composition liquid 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 3D modeling composition liquid 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 liquid for 3D modeling 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 3D modeling composition liquid of the present invention include bismethylene acrylamide, di (ethyleneoxy) bispropylacrylamide, and tri (ethyleneoxy) bis. Examples thereof include propylacrylamide and polymerizable monomers 2 described in JP2013-208890A 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 may be another monomer (monofunctional monomer of the present invention, first monomer, second monomer, or other monomer contained in the 3D modeling composition liquid of the present invention) by one ethylene polymerizable group. 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 liquid for 3D modeling of the present invention include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and 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 3D modeling composition liquid 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 3D modeling composition liquid 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 3D structure. . This is thought to be because the vinyl ether group or allyl group is slow to polymerize, and the polymerization of the monofunctional monomer proceeds, so that the distance between the cross-linking portions becomes long and the elongation becomes large.

1-3. Photoinitiator As the photoinitiator, a photoradical initiator can be used.

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

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

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

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

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

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

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

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

1-4. Release agent The 3D modeling composition liquid of the present invention may further contain a release agent in order to facilitate the release of the cured product and the cured product of the support material composition liquid described below. The release agent is preferably contained in an amount of 0.01% by mass to 3.0% by mass with respect to the total mass of the ink. If it is less than 0.01% by mass, the releasability from the substrate is lowered, and if it exceeds 3.0% by mass, the droplets of the 3D modeling composition liquid before curing are likely to coalesce and cause ink bleeding. Sometimes.

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

1-5. Other ink components The composition liquid for 3D modeling of the present invention may further contain a photoinitiator auxiliary agent or a polymerization inhibitor, if necessary. The photoinitiation assistant may be, for example, a tertiary amine compound, and is preferably an aromatic tertiary amine compound. Examples of aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included. Of these, N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. Only 1 type of these compounds may be contained in the composition liquid for 3D modeling, and 2 or more types may be contained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Example 1
(Preparation of model material composition)
Phenoxyethyl acrylate 68.4 parts by mass Isobornyl acrylate 10 parts by mass Tricyclodecane dimethanol diacrylate (molecular weight 304) 7 parts by mass polyethylene glycol (n = 9) diacrylate (molecular weight 542) 13 parts by mass Silicon oil KF-969 (Shin-Etsu Chemical Co., Ltd.) 0.1 part by mass 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) 1 part by mass 2,4-diethylthioxanthen-9-one (DETX) 0.5 part by mass The mixture was dissolved by heating to obtain a model material composition liquid.

(Preparation of support material composition)
Support by mixing and dissolving 40 g of polyoxyethylene (n≈9) diacrylate, 60 g of water, 5 g of photoinitiator irgacure 2959 ′ (BASF), and 0.1 g of silicon surfactant (TSF-4442) A material composition solution was obtained.

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

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

(Examples 2-11, Comparative Examples 1-7)
The composition of the model material composition liquid was changed as described in Table 1, Table 2, and Table 3, and 3D objects were manufactured by the same procedure for each.

[Measurement of yield strength, breaking elongation and breaking 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.

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

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

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

DESCRIPTION OF SYMBOLS 1 Inkjet part 2 Arithmetic control part 3 Storage device 4 Input device 5 Output device 6 Display apparatus 11 Stage 12 Inkjet apparatus 13 Inkjet head for model material composition liquid 14 Inkjet head for support material composition liquid 16 Light source

Claims (7)

A 3D modeling composition liquid comprising a monofunctional monomer having an ethylene polymerizable group, a polyfunctional monomer having at least one ethylene polymerizable group, a photoinitiator, and a release agent ,
The polyfunctional monomer is
A first monomer having 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, having a molecular weight of 1000 or less, and
At least a second monomer having a molecular weight of 1000 or less, which does not have any of an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a primary amide group, and a secondary amide group,
The composition liquid is a composition liquid in which the content ratio of the cationic polymerizable compound to the total mass of the composition liquid is 1% by mass or less .   The composition liquid 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.   The composition liquid according to claim 1 or 2, 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.   The composition liquid 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 liquid according to claim 1, 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. A 3D modeling ink set comprising the composition liquid according to any one of claims 1 to 5 and a support material composition liquid. The manufacturing method of 3D modeling thing which has the process of irradiating an ultraviolet-ray to the composition liquid of any one of Claims 1-5 .

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