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WO2019230133A1 - Ensemble de compositions de fabrication par photo-incision - Google Patents

Ensemble de compositions de fabrication par photo-incision Download PDF

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Publication number
WO2019230133A1
WO2019230133A1 PCT/JP2019/010943 JP2019010943W WO2019230133A1 WO 2019230133 A1 WO2019230133 A1 WO 2019230133A1 JP 2019010943 W JP2019010943 W JP 2019010943W WO 2019230133 A1 WO2019230133 A1 WO 2019230133A1
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Prior art keywords
composition
mass
support material
parts
meth
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Ceased
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PCT/JP2019/010943
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English (en)
Japanese (ja)
Inventor
浩史 太田
圭介 奥城
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Maxell Ltd
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Maxell Holdings Ltd
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Publication of WO2019230133A1 publication Critical patent/WO2019230133A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to an optical modeling composition set in which a composition for a model material and a composition for a support material used in a material jet optical modeling method are combined, and a method for manufacturing an optical modeling object using the same.
  • the material jet (inkjet) method for forming a cured layer having a predetermined shape by discharging a photocurable resin composition from a nozzle and immediately irradiating it with ultraviolet rays or the like to cure.
  • material jet stereolithography also known as “material jet stereolithography”.
  • the material jet stereolithography has been 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.
  • the material jet stereolithography method is easy to model complex shapes compared to the conventional method of obtaining stereolithography by irradiating a liquid photocurable composition with light, curing the irradiated part, and laminating it. .
  • the amount of the photocurable composition required is small and there is a merit that it is easy to adjust the mechanical characteristics by simultaneously emitting the photocurable composition having different properties from a plurality of nozzles, It is used for various purposes including trial use.
  • Patent Document 1 a model material composition for producing such a full color three-dimensional modeling has been developed.
  • the model material composition is usually used in the material jet stereolithography together with the support material composition.
  • the above patent document also describes that the composition for a model material described in the document can be used in combination with a support material or a water-soluble support material that can be physically removed by pulverization or the like. .
  • the support material obtained by photocuring the support material composition The independence of was sometimes inferior.
  • the present invention combines a composition for a model material having high formability, concealability and mechanical properties, which is suitable for producing a colored three-dimensional structure, and excellent water removal property and high support force. Proposing a combination with a composition for a support material, suppressing the occurrence of appearance defects that may occur when removing the support material, and providing a composition set for optical modeling capable of modeling a colored optical modeled object with high accuracy Objective.
  • a composition set for stereolithography used in a material jet stereolithography method comprising a composition for model material and a composition for support material,
  • a colorant As the model material composition, a colorant, at least one (meth) acrylate monomer (A) having a glass transition temperature of 25 ° C. or more and 120 ° C. or less as a homopolymer, and a glass transition temperature as a homopolymer of ⁇
  • the support material composition is based on 100 parts by mass of the support material composition.
  • composition set for optical modeling containing a photopolymerization initiator.
  • the support material composition includes a water-soluble monofunctional ethylenically unsaturated monomer and a photopolymerization initiator.
  • the content of the water-soluble monofunctional ethylenically unsaturated monomer is 19 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the support material composition, and the content of the photopolymerization initiator is 2 parts by mass.
  • composition for support material contains 30 parts by mass or less of a water-soluble organic solvent with respect to 100 parts by mass of the composition for support material.
  • Composition set for modeling [6] The stereolithography composition set according to any one of [1] to [5], wherein the support material composition includes a storage stabilizer. [7] The colorant contained in the coloring composition for model material is a pigment selected from the group consisting of white, black, cyan, magenta and yellow, according to any one of [1] to [6] above Stereolithography composition set. [8] The stereolithography composition set according to any one of [1] to [7], further including, as the model material composition, a model material clear composition containing no colorant. [9] A method for producing a three-dimensional modeled object, wherein a three-dimensional modeled object is manufactured by a material jet stereolithography method using the stereolithography composition set according to any one of [1] to [8].
  • the composition for optical modeling which suppresses generation
  • the optical modeling composition set of the present invention includes a model material composition.
  • the composition for optical modeling of the present invention is a model material composition, a colorant, at least one (meth) acrylate monomer (A) having a glass transition temperature of 25 ° C. or more and 120 ° C. or less as a homopolymer, and A coloring composition for a model material containing at least one (meth) acrylate monomer (B) having a glass transition temperature of ⁇ 60 ° C. or more and less than 25 ° C.
  • the total mass of the coloring material for the model material The content of the (meth) acrylate monomer (A) is 5% by mass or more and less than 50% by mass, and the content of the (meth) acrylate monomer (B) is 20% by mass or more and less than 80% by mass.
  • the coloring composition for materials is included.
  • “(meth) acrylate” is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to “(meth) acryloyl”, “(meth) acryl” and the like.
  • the coloring composition for a model material includes at least one (meth) acrylate monomer (A) having a glass transition temperature of 25 ° C. or more and 120 ° C. or less as a homopolymer.
  • the coloring composition for a model material contains the (meth) acrylate monomer (A)
  • an appropriate softness and tensile strength can be imparted to the model material obtained by photocuring the composition, and a support is provided.
  • production of the appearance defect which may arise at the time of material removal can be heightened.
  • the glass transition temperature of the (meth) acrylate monomer (A) is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and preferably 100 ° C. or lower.
  • the glass transition temperature (Tg) of the monomer homopolymer is measured by a dynamic viscoelasticity measuring device (DMA).
  • the glass transition temperature of the homopolymer may depend on the degree of polymerization, but if a homopolymer having a weight average molecular weight of 20,000 or more is prepared and measured, the influence of the degree of polymerization can be ignored.
  • a value measured using a sample polymerized until the influence of the degree of polymerization is negligible is defined as a glass transition temperature (Tg).
  • the (meth) acrylate monomer (A) may be an acrylate compound or a methacrylate compound, but is preferably an acrylate compound.
  • a monofunctional (meth) acrylate monomer or a polyfunctional (meth) acrylate monomer may be used, but a monofunctional (meth) acrylate monomer is preferable.
  • the (meth) acrylate monomer (A) is preferably a (meth) acrylate monomer having a hydrocarbon ring structure.
  • the (meth) acrylate monomer (A) include isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, t-butylcyclohexyl acrylate, and methyl methacrylate.
  • the (meth) acrylate monomer (A) was selected from the group consisting of isobornyl acrylate, t-butylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, and dicyclopentanyl acrylate. It preferably contains a monomer, and more preferably contains isobornyl acrylate and / or 3,3,5-trimethylcyclohexyl acrylate. By including these compounds, the tensile strength of the resulting model material can be improved, and the effect of suppressing the appearance defects that can occur when the support material is removed can be enhanced.
  • the content of the (meth) acrylate monomer (A) in the coloring composition for model material is 5% by mass or more and less than 50% by mass with respect to the total mass of the coloring composition for model material.
  • the content of the (meth) acrylate monomer (A) is preferably 8% by mass or more, more preferably 10% by mass or more, and preferably 45% by mass with respect to the total mass of the coloring composition for model material. % Or less, more preferably 42% by mass or less.
  • the coloring composition for a model material includes at least one (meth) acrylate monomer (B) having a glass transition temperature of ⁇ 60 ° C. or higher and lower than 25 ° C. as a homopolymer.
  • the coloring composition for a model material contains the (meth) acrylate monomer (B)
  • an appropriate softness and tensile strength can be imparted to the model material obtained by photocuring the composition, and molding is performed. Can be improved.
  • the glass transition temperature of the (meth) acrylate monomer (B) is preferably ⁇ 30 ° C. or higher, more preferably ⁇ 10 ° C. or higher, and preferably 10 ° C. or lower.
  • the (meth) acrylate monomer (B) may be an acrylate compound or a methacrylate compound, but is preferably an acrylate compound.
  • a monofunctional (meth) acrylate monomer or a polyfunctional (meth) acrylate monomer may be used, but a monofunctional (meth) acrylate monomer is preferable.
  • the (meth) acrylate monomer (B) is preferably a (meth) acrylate monomer having an ether bond and / or an alkyl group having 8 or more carbon atoms.
  • the (meth) acrylate monomer (B) preferably include a long-chain alkyl (8 or more carbon atoms) acrylate compound, an acrylate compound having a polyethylene oxide or polypropylene oxide chain, and a phenoxyethyl acrylate compound.
  • Examples of the long-chain alkyl acrylate compound include 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, isooctyl acrylate, n-lauryl acrylate, n-tridecyl acrylate, n-cetyl acrylate, Examples thereof include n-stearyl acrylate, isomyristyl acrylate, and isostearyl acrylate.
  • Examples of the acrylate compound having a polyethylene oxide or polypropylene oxide chain include (poly) ethylene glycol monoacrylate, (poly) ethylene glycol acrylate methyl ester, (poly) ethylene glycol acrylate ethyl ester, (poly) ethylene glycol acrylate phenyl ester, (Poly) propylene glycol monoacrylate, (poly) propylene glycol monoacrylate phenyl ester, (poly) propylene glycol acrylate methyl ester, (poly) propylene glycol acrylate ethyl ester, methoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, ethoxydiethylene glycol Acrylate (Ethoxy Butoxyethyl acrylate), methoxy polyethylene glycol acrylate.
  • phenoxyethyl acrylate compound examples include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and nonylphenol ethylene oxide adduct acrylate.
  • Examples of the (meth) acrylate monomer (B) include tetrahydrofurfuryl acrylate and 2- (N-butylcarbamoyloxy) ethyl acrylate (1,2-ethanediol 1-acrylate 2- (N-butylcarbamate) ) Is also preferred.
  • the (meth) acrylate monomer (B) phenoxyethyl acrylate, n-stearyl acrylate, isodecyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, n-lauryl acrylate, n-octyl acrylate, n- It preferably contains a monomer selected from the group consisting of decyl acrylate, isooctyl acrylate, n-tridecyl acrylate, and 2- (N-butylcarbamoyloxy) ethyl acrylate, and includes phenoxyethyl acrylate and / or n-stearyl.
  • acrylate is included, and it is further preferable that phenoxyethyl acrylate is included.
  • phenoxyethyl acrylate is included.
  • the said compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the (meth) acrylate monomer (B) in the colored composition for model material is 20% by mass or more and less than 80% by mass with respect to the total mass of the colored composition for model material.
  • the content of the (meth) acrylate monomer (B) is less than 20% by mass, it becomes difficult to impart appropriate flexibility.
  • the glass transition temperature (Tg) is lowered, so that the surface of the model material becomes sticky, and the tackiness is easily developed.
  • the content of the (meth) acrylate monomer (A) is preferably 25% by mass or more, more preferably 30% by mass or more, and preferably 75% by mass with respect to the total mass of the coloring composition for model material. % Or less, more preferably 70% by mass or less.
  • the coloring composition for a model material preferably contains a bifunctional (meth) acrylate oligomer (C) having a weight average molecular weight of 2,000 or more and 20,000 or less.
  • the (meth) acrylate oligomer (C) is an oligomer having a total of two acryloyloxy groups and / or methacryloyloxy groups, and preferably has an acryloyloxy group.
  • the tensile strength of the resulting model material tends to be inferior, and when only a trifunctional or higher (meth) acrylate oligomer is used, the resulting model material is obtained. Is inferior in softness, but by including the bifunctional (meth) acrylate oligomer (C), appropriate softness and tensile strength can be imparted to the obtained model material in a balanced manner.
  • the weight average molecular weight of the (meth) acrylate oligomer (C) is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and preferably 20,000 or less.
  • the weight average molecular weight of the (meth) acrylate oligomer (C) can be measured by gel permeation chromatography (GPC).
  • the Young's modulus at 25 ° C. of the (meth) acrylate oligomer (C) is preferably 1 to 100 MPa, more preferably 2 to 80 MPa, further preferably 3 to 50 MPa, and 10 to 30 MPa. It is particularly preferred that If it is the said range, moderate softness and tensile strength can be provided to the model material obtained.
  • the Young's modulus at 25 ° C. of the (meth) acrylate oligomer (C) in the present invention is the Young's modulus at 25 ° C. of the homopolymer (homopolymer) of the (meth) acrylate oligomer (C).
  • the Young's modulus at 25 ° C. in the present invention can be measured, for example, according to the following method: Irgacure 819 (BASF) 2 mass%, Irgacure 184 (BASF) 2 mass%, and oligomer to be measured 96 mass
  • a 100 ⁇ m coating film is formed with a bar coater from the mixed liquid, and cured with an ultraviolet (UV) exposure machine. At this time, curing is performed to such an extent that the influence of the degree of polymerization of the cured film can be ignored.
  • This cured film is cut into a 15 mm ⁇ 50 mm strip and the Young's modulus is measured with a tensile tester (Autograph AGS-X, 5KN, manufactured by Shimadzu Corporation). The value of Young's modulus is measured at the 1% elongation. For example, it may be pulled in the long axis direction and the upper and lower portions of about 10 mm may be grasped by the clamp.
  • the (meth) acrylate oligomer (C) is not particularly limited as long as it is an oligomer having an Mw of 2,000 or more and 20,000 or less having a total of two acryloyloxy groups and / or methacryloyloxy groups.
  • Olefin ethylene oligomer, propylene oligomer butene oligomer, etc.
  • vinyl styrene oligomer, vinyl alcohol oligomer, vinyl pyrrolidone oligomer, acrylic resin oligomer, etc.
  • diene butadiene oligomer, chloroprene rubber, pentadiene oligomer, etc.
  • ring opening Polymerization system di-, tri-, tetraethylene glycol, polyethylene glycol, polyethylimine, etc.
  • polyaddition system oligoester acrylate, polyamide oligomer, polyisocyanate oligo
  • Chromatography addition-condensation oligomer (a phenolic resin, amino resins, xylene resins, ketone resins, etc.) and the like.
  • a urethane acrylate oligomer, a polyester acrylate oligomer, or an epoxy acrylate oligomer is preferable, a urethane acrylate oligomer or a urethane acrylate oligomer having a polyester chain is more preferable, and a urethane acrylate oligomer is more preferable.
  • the oligomer handbook (supervised by Junji Furukawa, Chemical Industry Daily Co., Ltd.) can be referred to.
  • examples of the (meth) acrylate oligomer (C) include Shin-Nakamura Chemical Co., Ltd., Sartomer Japan Co., Ltd., Daicel Cytec Co., Ltd., Rahn A.C. G. Those that are commercially available from companies and the like and that meet the above conditions can be used.
  • (Meth) acrylate oligomer (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the coloring composition for model materials contains the (meth) acrylate oligomer (C), the content thereof is preferably 5% by mass or more and less than 30% by mass with respect to the total mass of the coloring composition for model materials. More preferably, it is 8 mass% or more and less than 25 mass%.
  • the coloring composition for model materials used for this invention is polymerizable compounds other than (meth) acrylate monomer (A), (meth) acrylate monomer (B), and (meth) acrylate oligomer (C) (henceforth " It may also be referred to as “other polymerizable compounds”. As other polymerizable compounds, acrylate compounds are preferred.
  • Other oligomers and polymers included in other polymerizable compounds include monofunctional or trifunctional or higher functional (meth) acrylate compounds having a weight average molecular weight of 2,000 to 20,000, and molecular weights exceeding 20,000 (meth).
  • An acrylate compound etc. are mentioned.
  • the coloring composition for a model material contains a monomer other than the (meth) acrylate monomer (A), the (meth) acrylate monomer (B) and the (meth) acrylate oligomer (C), the content thereof is (meth)
  • the content is preferably smaller than any of the contents of the acrylate monomer (A), the (meth) acrylate monomer (B), and the (meth) acrylate oligomer (C).
  • the coloring composition for model materials contains a photoinitiator. It does not specifically limit as a photoinitiator used in this invention, A well-known photoinitiator can be used. A photoinitiator may be used individually by 1 type and may use 2 or more types together.
  • the photopolymerization initiator that can be used in the present invention is a compound that generates a polymerization initiating species by absorbing external energy by irradiation with actinic rays.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • radical photopolymerization initiators aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, Examples thereof include active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
  • photo radical polymerization initiators may be used alone or in combination. Further, for example, a plurality of types can be used in combination from the same type.
  • the radical photopolymerization initiator in the present invention is preferably used alone or in combination of two or more. Details of the photo radical polymerization initiator are described in JP-A-2009-185186.
  • a photopolymerization initiator selected from the group consisting of an ⁇ -hydroxyketone compound and an acylphosphine oxide compound (hereinafter also referred to as “specific photopolymerization initiator”).
  • specific photopolymerization initiator By containing these specific photopolymerization initiators, the resulting model material is excellent in softness and tensile strength, and coloring derived from a residue or decomposition product of the photopolymerization initiator can be reduced.
  • the acyl phosphine oxide compound may be either a monoacyl phosphine oxide compound or a bisacyl phosphine oxide compound, but is preferably a bisacyl phosphine oxide compound.
  • the coloring composition for a model material preferably contains one or more ⁇ -hydroxyketone compounds and one or more acylphosphine oxide compounds.
  • ⁇ -hydroxyketone compounds include 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.
  • Acylphosphine oxide compounds include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- 2-methoxyphenylphosphine oxide, bis (2,6-dimethylbenzoyl) -2-methoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis ( 2,6-Dimethylbenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dipentyloxyphenylphosphine oxide, bis (2,6-dimethylbenzoyl) -2, -Dipentyloxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)
  • the content of the specific photopolymerization initiator in the colored composition for model material is preferably 1 to 20% by mass, more preferably 2 to 15% by mass with respect to the total mass of the colored composition for model material. More preferably, the content is 5 to 15% by mass.
  • the content of the specific photopolymerization initiator is in the above range, a model material that is superior in softness and tensile strength can be obtained.
  • the coloring composition for a model material as a photopolymerization initiator, absorbs a specific active energy ray and promotes the decomposition of the polymerization initiator, so that it functions as a sensitizer (hereinafter simply referred to as “sensitizer”). May also be included.
  • the sensitizer examples include polynuclear aromatics (eg, pyrene, perylene, triphenylene, 2-ethyl-9,10-dimethoxyanthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose Bengal etc.), cyanines (eg thiacarbocyanine, oxacarbocyanine etc.), merocyanines (eg merocyanine, carbomerocyanine etc.), thiazines (eg thionine, methylene blue, toluidine blue etc.), acridines (eg , Acridine orange, chloroflavin, acriflavine, etc.), anthraquinones (eg, anthraquinone, etc.), squariums (eg, squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin, etc.
  • the content thereof is preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass with respect to the total mass of the coloring composition for model material. 3% by mass.
  • the content of the sensitizer is within the above range, the curability and curing sensitivity of the coloring composition for model material can be improved.
  • the coloring composition for model material contains a coloring agent.
  • a coloring agent Since the coloring composition for model materials of this invention is non-aqueous, the pigment which is easy to disperse
  • the pigment either an inorganic pigment or an organic pigment can be used.
  • the white pigment (white) is not particularly limited, but basic lead carbonate (2PbCO 3 Pb (OH) 2 , so-called silver white), zinc oxide (ZnO, so-called zinc white), titanium oxide (TiO 2 , so-called , Titanium white), strontium titanate (SrTiO 3 , so-called titanium strontium white) and the like can be used.
  • a white pigment may be used individually by 1 type, and may use 2 or more types together.
  • titanium oxide has a smaller specific gravity than other white pigments, a large refractive index, and is chemically and physically stable, so that it has a large hiding power and coloring power as a pigment. Excellent durability against other environments. Therefore, it is preferable to use titanium oxide as the white pigment.
  • other white pigments may be other than the white pigments listed above) may be used as necessary.
  • pigments exhibiting colors such as black, cyan, magenta, and yellow, and all organic pigments and inorganic pigments that are generally commercially available, and those in which resin particles are dyed with a dye, etc. Can be used.
  • commercially available pigment dispersions and surface-treated pigments for example, pigments dispersed in an insoluble resin or the like as a dispersion medium, or those obtained by grafting a resin on the pigment surface, etc., impair the effects of the present invention. It can be used as long as it is not.
  • examples of these pigments include, for example, “Pigment Dictionary” (2000), edited by Seijiro Ito. Herbst, K.M. Hunger “Industrial Organic Pigments”, JP 2002-12607 A, JP 2002-188025 A, JP 2003-26978 A, and JP 2003-342503 A3.
  • organic pigments and inorganic pigments that can be used in the present invention include C.I. I. Pigment Yellow 1 (Fast Yellow G, etc.), C.I. I. A monoazo pigment such as C.I. Pigment Yellow 74; I. Pigment Yellow 12 (disaji yellow AAA, etc.), C.I. I. Disazo pigments such as C.I. Pigment Yellow 17; I. Non-benzidine type azo pigments such as CI Pigment Yellow 180; I. Azo lake pigments such as C.I. Pigment Yellow 100 (eg Tartrazine Yellow Lake); I. Condensed azo pigments such as CI Pigment Yellow 95 (Condensed Azo Yellow GR, etc.); I. Acidic dye lake pigments such as C.I.
  • Pigment Yellow 115 (such as quinoline yellow lake);
  • Basic dye lake pigments such as CI Pigment Yellow 18 (Thioflavin Lake, etc.), anthraquinone pigments such as Flavantron Yellow (Y-24), isoindolinone pigments such as Isoindolinone Yellow 3RLT (Y-110), and quinophthalone yellow Quinophthalone pigments such as (Y-138), isoindoline pigments such as isoindoline yellow (Y-139), C.I.
  • Nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.);
  • I. And metal complex salt azomethine pigments such as CI Pigment Yellow 117 (copper azomethine yellow, etc.).
  • Monoazo pigments such as CI Pigment Red 3 (Toluidine Red, etc.); I. Disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); I. Pigment Red 53: 1 (Lake Red C, etc.) and C.I.
  • Azo lake pigments such as C.I. Pigment Red 57: 1 (Brilliant Carmine 6B); I. Condensed azo pigments such as C.I. Pigment Red 144 (condensed azo red BR, etc.); I. Acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.); I. Basic dye lake pigments such as C.I.
  • Pigment Red 81 (Rhodamine 6G 'lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Red 177 (eg, dianthraquinonyl red); I. Thioindigo pigments such as C.I. Pigment Red 88 (Thioindigo Bordeaux, etc.); I. Perinone pigments such as C.I. Pigment Red 194 (perinone red, etc.); I. Perylene pigments such as C.I. Pigment Red 149 (perylene scarlet, etc.); I. Pigment violet 19 (unsubstituted quinacridone), C.I. I.
  • Quinacridone pigments such as CI Pigment Red 122 (quinacridone magenta, etc.); I. Isoindolinone pigments such as CI Pigment Red 180 (isoindolinone red 2BLT, etc.); I. And alizarin lake pigments such as CI Pigment Red 83 (Mada Lake, etc.).
  • C.I. I. Disazo pigments such as C.I. Pigment Blue 25 (Dianisidine Blue, etc.); I. Phthalocyanine pigments such as C.I. Pigment Blue 15 (phthalocyanine blue, etc.); I. Acidic dye lake pigments such as C.I. Pigment Blue 24 (Peacock Blue Lake, etc.); I. Basic dye lake pigments such as C.I. Pigment Blue 1 (Viclotia Pure Blue BO Lake, etc.); I. Anthraquinone pigments such as C.I. Pigment Blue 60 (Indantron Blue, etc.); I. And alkali blue pigments such as CI Pigment Blue 18 (Alkali Blue V-5: 1).
  • C.I. I. Pigment green 7 phthalocyanine green
  • C.I. I. Phthalocyanine pigments such as C.I. Pigment Green 36 (phthalocyanine green)
  • I. And azo metal complex pigments such as CI Pigment Green 8 (Nitroso Green).
  • An isoindoline pigment such as C.I. Pigment Orange 66 (isoindoline orange); I. And anthraquinone pigments such as CI Pigment Orange 51 (dichloropyrantron orange).
  • black pigments examples include carbon black, titanium black, and aniline black.
  • the colorant contained in the coloring composition for model material is preferably at least one selected from the group consisting of white, black, cyan, magenta and yellow.
  • the composition set for optical modeling of the present invention may include a plurality of coloring compositions for model materials. For example, in order to perform full-color printing, it is possible to obtain a set in which the coloring compositions for model materials of five colors including yellow, magenta, and cyan subtractive three primary colors and white and black are combined.
  • the composition set for stereolithography of the present invention may be a set in which a coloring composition for a model material containing a colorant as described above and a clear composition for a model material not containing a coloring agent are combined. .
  • the colorant may be directly added together with each component when preparing the coloring composition for model material. Further, in order to improve dispersibility, it may be added to a dispersion medium such as a solvent or a monomer in advance and uniformly dispersed or dissolved, and then blended.
  • a solvent may be added as a dispersion medium for various components such as a colorant, and a polymerizable compound described below which is a low molecular weight component without a solvent may be used as a dispersion medium. Is hardened by irradiation with actinic rays, and is preferably solvent-free.
  • the average particle diameter of the colorant is preferably 0.01 to 0.4 ⁇ m, and more preferably 0.02 to 0.2 ⁇ m, because the finer the color, the better the color developability.
  • the colorant, the below-mentioned dispersant and dispersion medium selection, dispersion conditions, and filtration conditions are set so that the maximum particle size is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less.
  • a uniform and stable dispersion can be obtained even when a particulate colorant is used by using the above-described dispersant having excellent dispersibility and stability.
  • the particle size of the colorant can be measured by a known measurement method. Specifically, it can be measured by, for example, a centrifugal sedimentation light transmission method, an X-ray transmission method, a laser diffraction / scattering method, or a dynamic light scattering method. In the present invention, a value obtained by measurement using a laser diffraction / scattering method is employed.
  • a dispersing device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet jet mill is used.
  • a dispersing device such as a ball mill, a sand mill, an attritor, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet jet mill is used. be able to.
  • the colorant When dispersing the colorant, it may contain a dispersant.
  • a dispersant when a pigment is used, a dispersant is preferably contained in order to stably disperse the pigment in the coloring composition for model material.
  • a polymer dispersant is preferable.
  • the “polymer dispersing agent” in the present invention means a dispersing agent having a weight average molecular weight of 1,000 or more.
  • Polymer dispersing agents include DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-166, DISPERBYK-166 -168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-182 (manufactured by BYK Chemie); EFKA4010, EFKA4046, EFKA4080, EFKA5010, EFKA5207, EFKA6745, EFKA 7462, EFKA 7500, EFKA 7570, EFKA 7575, EFKA 7580 (manufactured by Efka Additive); Disperse Aid 6, Disperse Aid 8, Disperse
  • the content of the dispersant with respect to the total mass of the coloring composition for a model material can be appropriately determined according to the purpose of use and the like, but is preferably 0.05 to 15% by mass.
  • a coloring agent it is also possible to use the synergist according to various coloring agents as a dispersing aid as needed.
  • the dispersion aid is preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the colorant.
  • the content of the colorant may be appropriately determined according to the desired color of the model material and the purpose of use, but is preferably 0.01 to 40% by mass with respect to the total mass of the color composition for the model material. More preferably, it is 0.1 to 30% by mass, and further preferably 0.2 to 20% by mass.
  • the coloring composition for model material may contain a surface conditioner.
  • the surface conditioner is a component that adjusts the surface tension of the coloring composition for model material to an appropriate range, and the type thereof is not particularly limited.
  • 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.
  • surface conditioners other than silicone compounds for example, fluorine-based surface conditioners, dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts and other anionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene Nonionic surfactants such as alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts may be used. These may be used alone or in combination of two or more.
  • the coloring composition for a model material contains a surface conditioner
  • the content can be appropriately selected depending on the purpose of use and the like, but is preferably 0.0001 based on the total mass of the coloring composition for a model material. To 3% by mass.
  • the coloring composition for model materials used for this invention may contain other components other than said each component as needed.
  • other components include storage stabilizers, photopolymerization initiators other than specific photopolymerization initiators, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, solvents, and polymer compounds.
  • the coloring composition for model material preferably contains a storage stabilizer from the viewpoint of improving storage stability.
  • the coloring composition for model material is preferably discharged in the range of 40 ° C to 80 ° C with heating and low viscosity, and a storage stabilizer is added to prevent head clogging due to thermal polymerization. Is preferred.
  • the storage stabilizer include hindered amine compounds (HALS), phenolic antioxidants, phosphorus antioxidants, nitrosamine compounds, and the like.
  • the content thereof is preferably 0.001 to 1.5% by mass, more preferably based on the total mass of the coloring composition for a model material.
  • the content is 0.01 to 1.0% by mass, and more preferably 0.05 to 0.8% by mass.
  • the viscosity of the coloring composition for a model material of the present invention is preferably 20 to 150 mPa ⁇ s at 25 ° C., preferably 40 to 100 mPa ⁇ s, from the viewpoint of improving dischargeability from a material jet nozzle and moldability. More preferably.
  • the above-mentioned viscosity can be measured using a rotational viscometer in accordance with JIS Z 8803.
  • the surface tension of the coloring composition for a model material of the present invention is preferably 20 to 40 mN / m at 25 ° C., and 20 to 30 mN / m from the viewpoint of improving dischargeability from a material jet nozzle and moldability. It is more preferable that The surface tension can be measured according to a du Nouey method or a Wilhelmy method based on JIS K2241.
  • the manufacturing method of the coloring composition for model materials of this invention is not specifically limited, For example, it manufactures by mixing uniformly the component which comprises the composition for coloring model materials using a mixing stirrer, a disperser, etc. be able to.
  • the stereolithography composition set of the present invention may contain only one kind of coloring material for a model material as a composition for model material, or may contain two or more kinds of coloring composition for model material. Moreover, you may contain combining the coloring composition for 1 or more types of model materials, and the clear composition for model materials which does not contain a coloring agent.
  • a model material composition containing a colorant is referred to as a “model material color composition”
  • a model material composition not containing a colorant is referred to as a “model material clear composition”.
  • the colorant contained in the model material coloring composition is mainly a white colorant (pigment) is referred to as a “model material white composition”, and the colorant is mainly used.
  • a colorant (pigment) exhibiting a color other than white is referred to as a “model material color composition”.
  • the ratio of the white colorant with respect to the total mass of the coloring material for model material is 0.1% by mass or more is called “white composition for model material”
  • the coloring material for model material What has the ratio of the coloring agent which has colors other than white with respect to gross mass is 0.05 mass% or more is called "the color composition for model materials.”
  • the composition for a model material is formed on a white composition for a model material containing a white pigment constituting an inner layer of the model material, and a white shaped object formed from the white composition for a model material. And one or more color compositions for model materials for forming a color layer.
  • the white composition for a model material contains, as a white pigment, and a polymerizable compound, a (meth) acrylate monomer (A) having a glass transition temperature of 25 ° C. or more and 120 ° C.
  • the content of the white pigment is preferably 0.5% by mass to 10% by mass and the content of the (meth) acrylate monomer (A) is preferably 40% with respect to the total mass of the white composition for model material.
  • It may be a composition [hereinafter also referred to as a white composition for model material (1)] that is not less than 80% by mass.
  • a white composition for model material may have the structure of the colored composition for model material described above, and contains a white pigment as a colorant in the colored composition for model material [hereinafter, for model material] Also referred to as a white composition (2)].
  • a model material having both moderate softness and tensile strength can be formed.
  • Whichever white composition for model materials is used it is preferable that the color composition for model materials has the structure of the coloring composition for model materials demonstrated previously.
  • the model material composition includes a colorant that constitutes the inner layer of the model material or can be used to dilute the model material color composition during modeling of the model material.
  • a clear composition for a model material and one or more color compositions for a model material for forming a color layer on the clear modeled object formed from the clear composition for a model material.
  • a clear composition for model materials what is comprised from the component remove
  • the optical modeling composition set of the present invention includes a support material composition.
  • the composition for support material constituting the composition set for optical modeling of the present invention is based on 100 parts by mass of the composition for support material. 15 to 75 parts by mass of a polyalkylene glycol (a) containing an oxybutylene group and having a weight average molecular weight of 300 or more, and 19 parts by weight or more and 80 parts by weight or less of a water-soluble monofunctional ethylenically unsaturated monomer (b) It is a composition containing this.
  • the composition for a support material contains the polyalkylene glycol (a) containing an oxybutylene group in the above content, a support material having both excellent water removal property and support capability can be provided. Moreover, the support material composition excellent in low-temperature stability can be provided. While the polyalkylene glycol (a) containing the oxybutylene group is water-soluble, it does not have hydrophilicity to reduce the support force of the support material when the support material is formed, while the oxybutylene group is Since the polyalkylene glycol (a) contained is water-soluble, the support material is excellent in water removability when the support material is formed.
  • water-soluble means a property that can be dissolved in water or dispersed in water. Moreover, the composition for a support material is not easily solidified (solidified) at low temperatures, and the fluidity is not easily lowered.
  • the support material composition comprises the above polyalkylene glycol (a) containing an oxybutylene group, a water-soluble monofunctional ethylenically unsaturated monomer (b), and a photopolymerization initiator. Contains. Thereby, it is possible to provide a support material that has both excellent water removability and support capability, and is excellent in low-temperature stability.
  • the polyalkylene glycol (a) containing an oxybutylene group that can be included in the support material composition may be either a linear type or a multi-chain type.
  • the alkyl group may be included in the terminal, for example, Preferably it may contain the C6 or less alkyl chain. These may be used alone or in combination of two or more.
  • the polyalkylene glycol (a) containing an oxybutylene group is a water-soluble resin for imparting appropriate hydrophilicity to a support material, and by adding this, a support material having both water removability and support power Can be obtained.
  • the polyalkylene glycol containing an oxybutylene group is not particularly limited as long as it contains an oxybutylene group.
  • the polyalkylene glycol having only an oxybutylene group (oxytetramethylene group) is a single polybutylene glycol.
  • it may be a polybutylene polyoxyalkylene glycol (for example, polybutylene polyethylene glycol) having both an oxybutylene group and another oxyalkylene group.
  • polybutylene glycol is represented by the following chemical formula (1)
  • polybutylene polyethylene glycol is represented by the following chemical formula (2).
  • m is preferably an integer of 5 to 300, and n is preferably an integer of 2 to 150. More preferably, m is 6 to 200, and n is 3 to 100.
  • the oxybutylene group in the chemical formula (1) and the chemical formula (2) may be a straight chain or may be branched. These may be used alone or in combination of two or more.
  • the support material composition contains the polyalkylene glycol (a) containing an oxybutylene group, it is possible to further improve the removability by water without reducing the support power of the support material, and to support the model material. It becomes a support material suitable for modeling a model material with high accuracy.
  • the support material can sufficiently support the model material during the optical modeling, it is possible to improve the modeling accuracy at the stage of optical modeling by suppressing a decrease in dimensional accuracy during molding. Furthermore, since the support material can be easily removed at the stage of removing the support material after that, the support material can be used while suppressing the decrease in accuracy even in the microstructure of the three-dimensional model molded with high accuracy during stereolithography. Can be removed. This not only prevents the reduction of dimensional accuracy when removing the support material by improving the removability of the support material with water, but also improves the dimensional accuracy of the model material during stereolithography by improving the self-supporting property of the support material. By increasing the height, an optically shaped object having better modeling accuracy can be obtained.
  • the weight average molecular weight (M w ) of the polyalkylene glycol (a) containing an oxybutylene group is 300 or more.
  • the weight average molecular weight of the polyalkylene glycol (a) containing an oxybutylene group is more preferably 400 or more, and even more preferably 500 or more.
  • the upper limit of the weight average molecular weight of the polyalkylene glycol (a) containing an oxybutylene group is not particularly limited, but is usually 3000 or less, preferably 2000 or less.
  • the weight average molecular weight is within the above range, the water-soluble monofunctional ethylenically unsaturated monomer (b) is easily compatible in the composition before curing, while the water-soluble monofunctional ethylenic monomer after light irradiation is easily compatible. It becomes difficult to be compatible with the cured product of the saturated monomer, and the support material can be easily removed with water or a water-soluble solvent.
  • the content of the polyalkylene glycol (a) containing an oxybutylene group in the support material composition is preferably 15 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the support material composition. Is 17 parts by mass or more, more preferably 20 parts by mass or more, preferably 72 parts by mass or less, more preferably 70 parts by mass or less.
  • the content of the polyalkylene glycol (a) containing an oxybutylene group is less than 15 parts by mass, the hydrophilicity of the support material decreases, so the water removability of the support material decreases, and the content is 75 masses.
  • the amount of the water-soluble monofunctional ethylenically unsaturated monomer (b) that is a polymerizable component is reduced, and the support material is softened and the self-supporting property is lowered. To do.
  • the water-soluble monofunctional ethylenically unsaturated monomer (b) contained in the support material composition includes, for example, 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 Acry Etc.], (meth) acrylamide derivatives [eg (meth)
  • Content of the water-soluble monofunctional ethylenically unsaturated monomer (b) contained in the composition for support material is 19 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the composition for support material.
  • the amount is preferably 22 parts by mass or more, more preferably 25 parts by mass or more, preferably 76 parts by mass or less, and more preferably 73 parts by mass or less.
  • composition for support material may contain a water-soluble organic solvent.
  • a water-soluble organic solvent is a component which improves the solubility to water of the support material obtained by photocuring the composition for support materials. Moreover, it has the function to adjust the composition for support materials to low viscosity.
  • a glycol-based solvent is preferably used. Specifically, for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate, triethylene glycol monoacetate, and the like.
  • Glycol ester solvents such as propylene 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 Ethyl 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, ethylene Glycol ether solvents such as glycol dipropyl ether, propylene glycol dipropyl ether, ethylene glycol dibut
  • examples of the water-soluble organic solvent include triethylene glycol monomethyl ether, diethylene glycol diethyl ether and Dipropylene glycol monomethyl ether acetate is preferred.
  • the content of the water-soluble organic solvent in the support material composition is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, further preferably 100 parts by mass of the support material composition. 25 parts by mass or less.
  • the content of the water-soluble organic solvent 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 contains a water-soluble organic solvent
  • the content thereof is preferably 3 masses with respect to 100 parts by mass of the composition for a support material from the viewpoint that the composition for a support material can be adjusted to a low viscosity. More than a part.
  • 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 composition for support material is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the composition for support material. Moreover, More preferably, it is 18 mass parts or less, More preferably, it is 15 mass parts or less.
  • a composition for a support material that has both excellent water solubility and support ability can be obtained.
  • 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.
  • the support material composition may contain other additives as necessary.
  • additives include surface conditioners, antioxidants, colorants, pigment dispersants, storage stabilizers, ultraviolet absorbers, light stabilizers, chain transfer agents, and fillers.
  • 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.
  • 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 previous model material composition can be used, the content of which is the composition for the support material It is preferable that it is 0.005 mass part or more and 3 mass parts or less with respect to 100 mass parts of things.
  • the storage stability can be improved by blending a storage stabilizer into the support material composition.
  • a storage stabilizer that can be contained in the support material composition
  • those exemplified as the storage stabilizer that can be used in the previous model material composition can be used, and the content thereof can be determined by the support material composition. It is preferable that they are 0.05 mass part or more and 3 mass parts or less with respect to 100 mass parts.
  • the viscosity of the composition for a support material is preferably 30 to 200 mPa ⁇ s at 25 ° C., more preferably 35 mPa ⁇ s or more, from the viewpoint of improving dischargeability from a material jet nozzle.
  • it is 40 mPa * s or more, More preferably, it is 170 mPa * s or less, More preferably, it is 150 mPa * s or less.
  • the measurement of the said viscosity can be performed using R100 type
  • 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.
  • 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.
  • 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.
  • composition set for stereolithography In the composition set for optical modeling of the present invention, since the support material is excellent in self-supporting property and removability, the dimensional accuracy of the optical modeling object is not impaired, so that the three-dimensional modeled object (model material) can be modeled with excellent accuracy. And a model material excellent in appearance can be provided.
  • the manufacturing method of the optical modeling thing of this invention is a manufacturing method of the optical modeling thing using the composition set for optical modeling of this invention, and is a composition for model materials, and a support material using a material jet (inkjet) type printer.
  • the model material composition is photocured to obtain a model material
  • the water soluble support material composition is photocured to obtain a water soluble support material
  • the manufacturing method of the present invention uses the optical modeling composition set of the present invention, it is possible to form an optical modeling object that is excellent in colored appearance with high modeling accuracy.
  • FIG. 1 is a schematic side view showing a state in which a support material composition and a model material composition are ejected by a material jet modeling method and irradiated with energy rays.
  • 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.
  • the optical modeling ink unit 11a includes a model material inkjet head 11aM filled with the model material composition 13, and a support material inkjet head 11aS filled with the support material composition 14.
  • 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
  • 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.
  • 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 head for model material is used.
  • the composition 13 for model material is discharged from 11aM
  • the composition 14 for support material is discharged from the inkjet head 11aS for support material.
  • the layer which consists of the model material precursor 13M, and the layer which consists of the support material precursor 14S are arrange
  • 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.
  • 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.
  • the modeling table 12 is lowered by one layer in the Z direction, and the same process as described above is performed to form a second layer of model material and support material. Thereafter, by repeating the above steps, as shown in FIG. 4, an optically shaped product precursor 16 composed of the model material 13PM and the support material 14PS is formed.
  • 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.
  • a high pressure mercury lamp, a metal halide lamp, a UV-LED, or the like can be used as the light source.
  • 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.
  • a UV-LED 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.
  • ultraviolet rays 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, ⁇ rays, ⁇ rays, X-rays, and the like can be used. And from a viewpoint of efficiency, ultraviolet rays or near ultraviolet rays are preferable.
  • 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.
  • the photo-curing treatment is repeated for each layer to produce an optically shaped article composed of a cured product of the model material composition (model material) and a cured product of the composition for support material (support material). it can.
  • each layer constituting the three-dimensional model is preferably thin from the viewpoint of modeling accuracy, but is preferably 5 to 30 ⁇ m from the balance with the modeling speed.
  • the stereolithography composition set includes two or more model material compositions as the model material composition
  • the white composition for model material containing a white pigment constituting the inner layer of the model material or A color layer is formed on a clear composition for a model material that does not contain a colorant and a white shaped article that is shaped from the white composition for a model material or a clear shaped article that is shaped from the clear composition for a model material
  • the color composition for the model material on the white shaped article or the clear shaped article according to the cross-sectional data corresponding to the three-dimensional shape of the desired three-dimensional shaped article.
  • the obtained stereolithography is a combination of a model material and a support material.
  • the support material is removed from the stereolithography product to obtain a stereolithography product as a model material.
  • the support material can be removed by, for example, immersing an optical modeling object obtained in a removal solvent that dissolves the support material, softening the support material, and then removing the support material from the model material surface with a brush or the like.
  • 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.
  • Water or a water-soluble solvent such as a glycol solvent or an alcohol solvent may be used as the solvent for removing the support material. These may be used alone or in combination.
  • the above-mentioned stereolithography product has suppressed water absorption and swelling when contacted with water, and is less likely to cause breakage and deformation of the fine structure portion. Further, the stereolithographic product is excellent in water and oil repellency and hardly contaminated.
  • the stereolithographic product obtained by the above steps has a relatively high surface hardness in an embodiment.
  • the stereolithographic product has a surface hardness of Shore-D hardness of 50 or more, preferably 60 or more, more preferably 70 or more.
  • the optically shaped article has a high dimensional accuracy because water absorption and swelling are suppressed because it takes a short time to contact water when removing the support material.
  • Model Material Composition Table 1 shows the details of the components constituting the model material composition used in the examples.
  • the dispersion time was 1 to 6 hours.
  • pigment dispersions Cyan 1, Magenta 1, Yellow 1, Black, and White 1 were produced.
  • the numerical value of the mass% described in Table 2 represents content (mass%) of each component with respect to the total mass of a pigment dispersion.
  • model material photocured material
  • evaluation of characteristics Using the coloring compositions for model materials of Examples M1 to M8 and Comparative Examples m1 to m3, model materials (photocured materials) were prepared, The model material was evaluated for film flexibility and film strength according to the following methods and evaluation criteria. Table 4 shows the results.
  • a frame is formed of a frame-shaped silicon rubber having a length of 30 mm, a width of 30 mm, and a thickness of 10 mm on a glass plate, and the composition for each model material shown in Table 3 is placed in the frame.
  • Each was poured and irradiated with ultraviolet rays having an accumulated light amount of 400 mJ / cm 2 by a metal halide lamp, to obtain a model material.
  • the softness was measured with a durometer (GS-779G Tech Rock). (Evaluation criteria) 5: 0 or more but less than 30 4:30 or more but less than 60 3:60 or more but less than 95 2:95 or more but less than 100 1: 100 or more
  • a frame is formed with a frame-shaped silicon rubber having a length of 30 mm, a width of 30 mm, and a thickness of 10 mm on a glass plate, and the composition for each model material shown in Table 3 is placed in the frame.
  • the model material was obtained by pouring and irradiating with a metal halide lamp an ultraviolet ray having an integrated light quantity of 400 mJ / cm 2 .
  • a tensile test Autograph AGS-X 5KN, manufactured by Shimadzu Corporation
  • the model material was formed so that the long direction was horizontal to the table.
  • ⁇ Low temperature stability of support material composition The stability of the composition for the support material at low temperature was evaluated. Each composition for support material was put into a glass bottle, and the glass bottle with the composition for support material was stored in a thermostatic bath set at a temperature of 10 ° C. for 24 hours. Then, the state of the composition for support material after storage was confirmed visually, and the low temperature stability of the composition for support material was evaluated according to the following criteria.
  • composition for the support material When the composition for the support material is maintained in a liquid state: low temperature stability A (excellent) When the support material composition is partially solidified (solidified): Low temperature stability B (good) When the composition for the support material is solidified (solidified): low temperature stability C (poor)
  • a frame is formed on a glass plate with a frame-shaped silicon rubber having a length of 30 mm, a width of 30 mm, and a thickness of 5 mm, each support material composition is poured into the frame, and an ultraviolet ray with an integrated light amount of 500 mJ / cm 2 is obtained by a metal halide lamp.
  • a metal halide lamp was irradiated to produce a cured support material.
  • 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.
  • Support strength A excellent
  • Support strength B good
  • Support force C defect
  • 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.
  • Stereolithographic Composition Set Examples 1 to 6 and Comparative Example 1 were prepared by combining the model material composition and the support material composition as shown in Table 6.
  • a spacer having a thickness of 1 mm was arranged on the four upper surfaces of a glass plate (trade name “GLASS PLATE”, manufactured by ASONE, 200 mm ⁇ 200 mm ⁇ thickness 5 mm), and was partitioned into 10 cm ⁇ 10 cm squares.
  • an ultraviolet LED NCCU001E, manufactured by Nichia Corporation
  • UV rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm 2. And cured to obtain a support material.
  • 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.
  • an ultraviolet LED NCCU001E, manufactured by Nichia Corporation
  • UV rays are irradiated so that the total irradiation light amount becomes 500 mJ / cm 2.
  • cured to obtain a model material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Polymerisation Methods In General (AREA)
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Abstract

La présente invention concerne un ensemble de compositions de fabrication par photo-incision qui est destiné à être utilisé dans la fabrication par photo-incisions par jet de matériau et comprend une composition de matériau de modèle et une composition de matériau de support. La composition de matériau de modèle est une composition colorée de matériau de modèle qui comprend un colorant, au moins un (méth)acrylate monomère (A) qui, en tant qu'homopolymère, a une température de transition vitreuse de 25 °C à 120 °C, et au moins un (méth)acrylate monomère (B) qui, en tant qu'homopolymère, a une température de transition vitreuse d'au moins -60 °C mais inférieure à 25 °C, le (méth)acrylate monomère (A) étant d'au moins 5 % en masse mais inférieur à 50 % en masse de la masse totale de la composition colorée de matériau de modèle, et le (méth)acrylate monomère (B) étant d'au moins 20 % en masse mais inférieur à 80 % en masse de la masse totale de la composition colorée de matériau de modèle. La composition de matériau de support contient, pour 100 parties en masse de la composition de matériau de support, 15 à 75 parties en masse d'un glycol de polyalkylène (a) qui comprend un groupe oxybutylène et a un poids moléculaire moyen en poids d'au moins 300, 19 à 80 parties en masse d'un monomère monofonctionnel éthyléniquement insaturé hydrosoluble (b), et un initiateur de photopolymérisation.
PCT/JP2019/010943 2018-05-29 2019-03-15 Ensemble de compositions de fabrication par photo-incision Ceased WO2019230133A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006307203A (ja) * 2005-03-30 2006-11-09 Dainippon Ink & Chem Inc ジェットプリンター用インキ組成物
JP2010180308A (ja) * 2009-02-04 2010-08-19 Fujifilm Corp ジヒドロペリミジンスクアリリウム化合物を含む印刷インク、トナー、及びそれらを用いた情報検出方法
JP2015183103A (ja) * 2014-03-25 2015-10-22 ジェイエムエス・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング サポート部形成用の光硬化性樹脂組成物
JP2016078284A (ja) * 2014-10-14 2016-05-16 花王株式会社 三次元造形用可溶性材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006307203A (ja) * 2005-03-30 2006-11-09 Dainippon Ink & Chem Inc ジェットプリンター用インキ組成物
JP2010180308A (ja) * 2009-02-04 2010-08-19 Fujifilm Corp ジヒドロペリミジンスクアリリウム化合物を含む印刷インク、トナー、及びそれらを用いた情報検出方法
JP2015183103A (ja) * 2014-03-25 2015-10-22 ジェイエムエス・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング サポート部形成用の光硬化性樹脂組成物
JP2016078284A (ja) * 2014-10-14 2016-05-16 花王株式会社 三次元造形用可溶性材料

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