WO2019176144A1 - Composition pour matériau modèle - Google Patents

Composition pour matériau modèle Download PDF

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Publication number
WO2019176144A1
WO2019176144A1 PCT/JP2018/034068 JP2018034068W WO2019176144A1 WO 2019176144 A1 WO2019176144 A1 WO 2019176144A1 JP 2018034068 W JP2018034068 W JP 2018034068W WO 2019176144 A1 WO2019176144 A1 WO 2019176144A1
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composition
model material
model
meth
group
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PCT/JP2018/034068
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English (en)
Japanese (ja)
Inventor
智久 西本
智史 久保
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マクセルホールディングス株式会社
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Publication of WO2019176144A1 publication Critical patent/WO2019176144A1/fr

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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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

Definitions

  • the present invention relates to a model material composition for modeling a model material by a material jet stereolithography method, a material jet stereolithography composition set comprising the model material composition, and the model material composition
  • the present invention relates to a method for producing an optical modeling product using the material or the composition set for material jet optical modeling.
  • a method for producing a three-dimensional structure by widely irradiating a photocurable resin composition with light such as ultraviolet rays to continuously form a cured layer having a predetermined shape is widely known.
  • a photo-curable resin composition is ejected from a material jet nozzle, and immediately after that, the resin composition is cured by irradiating light such as ultraviolet rays, thereby laminating a cured layer having a predetermined shape to form a three-dimensional structure.
  • An optical modeling method (hereinafter also referred to as “material jet stereolithography”) using a material jet method (inkjet method) for producing a small-sized model that can freely create a three-dimensional modeled object based on CAD (Computer Aided Design) data.
  • material jet method inkjet method
  • CAD Computer Aided Design
  • Patent Document 1 discloses a predetermined amount of a monofunctional ethylenically unsaturated monomer, a polyfunctional ethylenically unsaturated monomer that does not contain a urethane group, a urethane-containing ethylenically unsaturated monomer, and a photopolymerization initiator.
  • the resin composition for model materials containing this is disclosed.
  • Patent Document 2 discloses a resin composition for a model material containing a monofunctional ethylenically unsaturated monomer, a polyfunctional ethylenically unsaturated monomer, an oligomer and a photopolymerization initiator.
  • the shape of the composition that has landed earlier tends to collapse due to the weight of the composition overlying, ease of wetting and lack of adhesion.
  • the model material and the model material and the support material are mixed with each other, or the overlying composition for the model material slides down from the composition that has landed first, so that three-dimensional Sagging tends to occur in the three-dimensional shape, and it has been difficult to accurately stack the composition for a model material in the vertical direction.
  • the conventional resin composition for a model material cannot sufficiently cope with the speeding up of the material jet stereolithography, and the composition for a model material that can realize a three-dimensional structure having high modeling accuracy at a high modeling speed. There is a request for.
  • the present invention provides a composition for a model material suitable for a material jet stereolithography method capable of realizing high modeling accuracy and excellent mechanical properties even during high-speed modeling of a three-dimensional structure by a material jet method. For the purpose.
  • a composition for a model material for modeling a model material by a material jet stereolithography method including a polymerizable monomer, a photopolymerization initiator, and a silicone-modified urethane oligomer having a polymerizable group at 25 ° C.
  • the polymerizable group of the silicone-modified urethane oligomer is a group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a vinyl ether group, according to the above [1] or [2] Composition for model materials.
  • Composition Composition.
  • a silicone-modified urethane oligomer having a polymerizable group is represented by the following formula (1): [Where, IP represents an isophorone diisocyanate unit, PAG represents a polypropylene glycol unit and / or a polyethylene glycol unit; HEA represents the acrylic end, n is 0-30, a is 1-50, b is 1-50]
  • composition for model materials [10] The composition for a model material according to [9], including the monofunctional ethylenically unsaturated monomer (A) in an amount of 40% by mass or more based on the total mass of the polymerizable compound. [11] The composition for a model material according to [9] or [10], comprising 1 to 30% by mass of the polyfunctional ethylenically unsaturated monomer (B) with respect to the total mass of the polymerizable compound.
  • the monofunctional ethylenically unsaturated monomer (A) according to any one of [9] to [11], wherein the monofunctional ethylenically unsaturated monomer (A) is a monofunctional ethylenically unsaturated monomer having a cyclic structure in the molecule.
  • Composition for model materials [13] The SP values of the monofunctional ethylenically unsaturated monomer (A) and the polyfunctional ethylenically unsaturated monomer (B) are 11.0 or less, respectively, in the above [9] to [12] The composition for model materials in any one. [14] The composition for model material according to any one of [1] to [13], further including a colorant.
  • a material jet comprising the model material composition according to any one of [1] to [14] and a support material composition for modeling the support material by a material jet stereolithography method.
  • Stereolithography composition set [16] The composition set for material jet stereolithography according to [15], wherein the support material composition is water-soluble.
  • An optically shaped article is manufactured using the model material composition according to any one of [1] to [14] or the material jet stereolithography composition set according to [15] or [16].
  • a model material composition comprising: curing a composition for a model material by irradiating an active energy ray having an accumulated light amount per layer of 300 mJ / cm 2 or more in a wavelength range of 320 to 410 nm. Production method.
  • composition for a model material suitable for a material jet stereolithography method capable of realizing high modeling accuracy and excellent mechanical properties even during high-speed modeling of a three-dimensional structure by a material jet method. be able to.
  • the composition for a model material of the present invention includes a polymerizable monomer, a photopolymerization initiator, and a silicone-modified urethane oligomer having a polymerizable group (hereinafter also referred to as “silicone-modified urethane oligomer (S)”).
  • a silicone-modified urethane oligomer having a polymerizable group hereinafter also referred to as “silicone-modified urethane oligomer (S)”.
  • the composition for a model material of the present invention when the composition for a model material of the present invention is continuously dropped from a material jet nozzle, the composition for the model material on which the outermost surface of the dropped droplet of the composition for a model material and the droplet of the composition land
  • the siloxane group is arranged on any of the outermost surfaces of the cured product, and due to this relative relationship, the contact angle of the dropped model material composition on the cured material surface of the model material composition that has landed earlier Can be increased.
  • the siloxane groups exist as the molecular structure of the urethane oligomer, a compound having a siloxane group is used alone. Compared with the case of blending with siloxane, the siloxane groups are more easily aligned to the outside of the droplets or the cured product. In addition, the intermolecular force due to the siloxane groups can be exerted firmly on the cured product surface and the droplet surface, and the cured material of the model material composition that has landed first and the dropped droplet are firmly bonded. .
  • the composition for a model material of the present invention can be accurately stacked in the vertical direction even when continuously discharged from a material jet nozzle, and can ensure high modeling accuracy during high-speed modeling.
  • the “model material” means a cured product of the model material composition, and a product finally obtained from the cured product is referred to as an “optically shaped product”.
  • the number average molecular weight of the silicone-modified urethane oligomer (S) contained in the model material composition is preferably 1,000 to 10,000, more preferably 1,200 or more, and even more preferably 1, It is 400 or more, particularly preferably 1,600 or more, more preferably 9,000 or less, further preferably 8,000 or less, and particularly preferably 7,000 or less.
  • the number average molecular weight of the silicone-modified urethane oligomer (S) is within the above range, when a composition for a model material is dropped from a material jet nozzle, a sufficient amount of siloxane groups is formed on the outermost surface of the dropped droplet.
  • the number average molecular weight of the silicone-modified urethane oligomer (S) can be determined using gel permeation chromatography (GPC) or matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF-MS).
  • the polymerizable group of the silicone-modified urethane oligomer (S) is polymerized in the model material composition by active radicals or acids generated from the photopolymerization initiator contained in the model material composition.
  • Any group that can participate in a crosslinking reaction with a compound (polymerizable monomer) is not particularly limited, and acryloyl group, methacryloyl group, vinyl group, allyl group, vinyl ether group, acrylamide group, methacrylamide group, epoxy group, oxetanyl group Etc.
  • a group selected from the group consisting of acryloyl group, methacryloyl group, vinyl group, allyl group and vinyl ether group is preferable, and acryloyl group or methacryloyl group is more preferable.
  • the alkoxy group used as the hydrolyzable group with poor photopolymerizability is not regarded as the polymerizable group which is the subject of the present invention.
  • the polymerizable group possessed by the silicone-modified urethane oligomer (S) is a polymerizable group having a slower reaction rate than the polymerizable group possessed by the polymerizable compound (polymerizable monomer) constituting the composition for a model material.
  • the polymerizable group possessed by the silicone-modified urethane oligomer (S) is polymerized with a slower reaction rate than the polymerizable group possessed by the polymerizable compound (polymerizable monomer) constituting the model material composition. It is preferably a sex group.
  • the polymerizable group that the silicone-modified urethane oligomer (S) has is preferably, for example, a methacryloyl group, and the polymerizable group that the silicone-modified urethane oligomer (S) has is methacryloyl. More preferably, the polymerizable group (polymerizable monomer) of the polymerizable compound (polymerizable monomer) constituting the model material composition is an acryloyl group.
  • the structure of the silicone-modified urethane oligomer (S) contained in the model material composition of the present invention is not particularly limited, and a conventionally known silicone-modified urethane oligomer having a polymerizable group can be used.
  • S) has two or more polymerizable groups in one molecule, the silicone-modified urethane oligomer (S) and the polymerizable compound (polymerizable) in the droplet of the model material composition dropped from the material jet nozzle Monomer)).
  • the silicone-modified urethane oligomer (S) is present on the outermost surface of the droplet, and the siloxane group of the silicone-modified urethane oligomer (S) is liquid. If it is located on the outermost side of the droplet, the modeling accuracy at the time of high-speed modeling can be effectively improved.
  • the silicone-modified urethane oligomer (S) contained in the model material composition of the present invention preferably has one polymerizable group in one molecule.
  • One polymerizable group in one molecule may be present at one end or side chain of the silicone-modified urethane oligomer (S), and it is easier to take the above preferred arrangement, so that it is at the end of the oligomer molecular chain. More preferably it is present.
  • the terminal part of the oligomer molecular chain means the terminal part (one terminal) of the main chain and the terminal part of the side chain of the silicone-modified urethane oligomer (S).
  • the silicone-modified urethane oligomer (S) contained in the model material composition is preferably a silicone-modified urethane (meth) acrylate oligomer, and more preferably a silicone-modified urethane acrylate oligomer.
  • a silicone-modified urethane (meth) acrylate oligomer preferably a silicone-modified urethane (meth) acrylate oligomer.
  • isocyanate used for the urethane component which comprises silicone modified urethane acrylate Aliphatic type, aromatic type, alicyclic type etc.
  • tolylene diisocyanate (TDI), xylylene diisocyanate ( XDI) 4,4-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate (H6XDI), naphthalene diisocyanate (NDI), norbornene diisocyanate (NBDI), 1,5- It may be pentamethylene diisocyanate (PDI) or the like.
  • TDI tolylene diisocyanate
  • XDI xylylene diisocyanate
  • MDI 4,4-diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • H6XDI hydrogenated xylylene diisocyanate
  • NDI naphthalene diiso
  • silicone-modified urethane oligomer (S) examples include a silicone-modified urethane oligomer having a structure represented by the following formula (1).
  • silicone modified urethane oligomer (S) only 1 type may be used and it may be used in combination of 2 or more type.
  • siloxane compound having a structure represented by the following formula (1) the modeling accuracy at the time of high-speed modeling can be effectively increased.
  • IP represents an isophorone diisocyanate unit
  • PAG represents a polypropylene glycol unit and / or a polyethylene glycol unit
  • HEA represents an acrylic terminal.
  • n is 0 to 30, preferably 1 to 20, and more preferably 5 to 15. Further, a is 1 to 50, preferably 2 to 40, more preferably 3 to 30, and b is 1 to 50, preferably 2 to 40, more preferably 3 to 30. is there.
  • the silicone-modified urethane oligomer (S) can be prepared by a conventionally known method. For example, it can be prepared by a method described in JP-A No. 2004-160932 or Japanese Patent No. 6035325. That is, an isocyanate component, a polyhydric alcohol having a polysiloxane skeleton, and a compound having a hydroxyl group and a (meth) acryloyl group are reacted at an appropriate molar ratio using a catalyst such as dibutyltin laurate or dibutyltin acetate. It can prepare by the usual urethanation reaction.
  • a commercially available product may be used as the silicone-modified urethane oligomer (S) contained in the model material composition.
  • the content of the silicone-modified urethane oligomer (S) in the model material composition of the present invention is preferably 0.1% by mass or more, more preferably 0.8% by mass relative to the total mass of the model material composition. It is 5 mass% or more, More preferably, it is 1 mass% or more, Most preferably, it is 2 mass% or more. Moreover, it is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.
  • the content of the silicone-modified urethane oligomer (S) is within the above upper and lower limits, a sufficient amount of siloxane groups are uniformly present on the outermost surface of the model material composition dropped from the material jet nozzle. It is possible to improve the modeling accuracy during high-speed modeling.
  • the range of the said content is defined as the sum total of the content.
  • the composition for a model material of the present invention preferably contains a polymerizable monomer, and preferably contains a monofunctional ethylenically unsaturated monomer (A) as the polymerizable monomer.
  • the monofunctional ethylenically unsaturated monomer (A) is a component having a property of being polymerized and cured by irradiation with active energy rays such as ultraviolet rays, and a polymerizable monomer having one ethylenic double bond in the molecule. It is.
  • active energy rays such as ultraviolet rays
  • a polymerizable monomer having one ethylenic double bond in the molecule It is.
  • (meth) acrylate” represents both and / or acrylate and methacrylate
  • “(meth) acrylamide” represents both and / or acrylamide and methacrylamide. Only one type may be used as the monofunctional ethylenically unsaturated monomer (A), or two
  • the monofunctional ethylenically unsaturated monomer (A) includes an alkyl (meth) acrylate having a linear or branched alkyl group, an alicyclic structure, an aromatic ring structure or Examples thereof include (meth) acrylates having a cyclic structure such as a heterocyclic structure, and monofunctional ethylenically unsaturated monomers containing nitrogen atoms such as (meth) acrylamide and N-vinyl lactams.
  • an alicyclic structure is an aliphatic cyclic structure in which carbon atoms are cyclically bonded
  • an aromatic ring structure is an aromatic cyclic structure in which carbon atoms are cyclically bonded
  • a heterocyclic structure is a carbon atom.
  • a structure in which one or more heteroatoms are bonded in a cyclic manner is
  • alkyl (meth) acrylate having a linear or branched alkyl group preferably include a linear or branched alkyl group having preferably 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms.
  • Alkyl (meth) acrylates having Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (Meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl-dig
  • Examples of the (meth) acrylate having an alicyclic structure include (meth) acrylates preferably having an alicyclic structure having 6 to 20 carbon atoms, more preferably 8 to 15 carbon atoms. Specifically, for example, cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 3, 3, 5 -Trimethylcyclohexanol (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and the like.
  • Examples of the (meth) acrylate having an aromatic ring structure include (meth) acrylates preferably having an aromatic ring structure having 6 to 20 carbon atoms, more preferably 8 to 15 carbon atoms. Specifically, for example, phenoxyethyl (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, nonylphenol ethylene oxide adduct (meth) acrylate, 2- (meth) acrylate And acryloyloxyethyl-phthalic acid, neopentyl glycol-acrylic acid-benzoic acid ester and the like.
  • Examples of the (meth) acrylate having a heterocyclic structure include (meth) acrylates preferably having a heterocyclic structure having 5 to 20 carbon atoms, more preferably 7 to 15 carbon atoms. Specifically, for example, tetrahydrofurfuryl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4 -(Meth) acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane and the like.
  • monofunctional ethylenically unsaturated monomers containing nitrogen atoms which are different from the above (meth) acrylates, include, for example, (meth) acrylamide [eg, N, N-dimethylacrylamide, N, N-diethylacrylamide] N-isopropylacrylamide, hydroxyethylacrylamide, hydroxypropylacrylamide, N, N-acryloylmorpholine, etc.], N-vinyl lactams (eg, N-vinylpyrrolidone, N-vinylcaprolactam, etc.), N-vinylformamide, etc. Can be mentioned.
  • (meth) acrylamide eg, N, N-dimethylacrylamide, N, N-diethylacrylamide] N-isopropylacrylamide, hydroxyethylacrylamide, hydroxypropylacrylamide, N, N-acryloylmorpholine, etc.
  • N-vinyl lactams eg,
  • the monofunctional ethylenically unsaturated monomer (A) contained in the model material composition is preferably a monofunctional ethylenically unsaturated monomer having a cyclic structure in the molecule.
  • the monofunctional ethylenically unsaturated monomer (A) has a cyclic structure in the molecule, compared with other monomers having no cyclic structure, It is excellent in compatibility with the resulting silicone-modified urethane oligomer (S), the glass transition temperature (Tg) of the model material molded article is high, and is excellent in hardness and heat resistance.
  • the content of the monofunctional ethylenically unsaturated monomer having a cyclic structure in the molecule is based on the total mass of the monofunctional ethylenically unsaturated monomer (A). Preferably it is 50% by mass or more, more preferably 80% by mass or more, and all monofunctional ethylenically unsaturated monomers (A) contained in the model material composition have a cyclic structure in the molecule It may be.
  • the monofunctional ethylenically unsaturated monomer (A) is preferably a (meth) acrylate monomer.
  • a (meth) acrylate monomer having a cyclic structure in the molecule is preferable, and isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, 3,3,5-trimethylcyclohexanol (meth) acrylate And at least one selected from the group consisting of cyclic trimethylolpropane formal (meth) acrylate, more preferably isobornyl (meth) acrylate and phenoxyethyl (meth) acrylate, particularly isobornyl acrylate. preferable.
  • the composition for a model material compared to other monomers having an aromatic ring structure or a heterocyclic structure
  • S silicone-modified urethane oligomer
  • Tg glass transition temperature
  • the content of the monofunctional ethylenically unsaturated monomer (A) in the model material composition of the present invention is preferably 40% by mass or more based on the total mass of the polymerizable compound contained in the model material composition. More preferably, it is 45 mass% or more, and still more preferably 50 mass% or more.
  • the content of the monofunctional ethylenically unsaturated monomer (A) is not less than the above lower limit value, it becomes easy to be compatible with the silicone-modified urethane oligomer (S) that is an essential component of the model material composition, and the curing step
  • the silicone-modified urethane oligomer (S) can be quickly arranged on the surface of the shaped article.
  • the content of the monofunctional ethylenically unsaturated monomer (A) is preferably 95% by mass or less, more preferably 90% by mass with respect to the total mass of the polymerizable compound contained in the model material composition. % Or less, and more preferably 80% by mass or less.
  • the silicone-modified urethane oligomer (S) is also included in the polymerizable compound.
  • the model material composition of the present invention preferably contains a polyfunctional ethylenically unsaturated monomer (B) as a polymerizable monomer.
  • the polyfunctional ethylenically unsaturated monomer (B) is a component having a property of being polymerized and cured by irradiation with active energy rays, and a polymerizable monomer having two or more ethylenic double bonds in the molecule. . Only one type may be used as the polyfunctional ethylenically unsaturated monomer (B), or two or more types may be used in combination.
  • Examples of the polyfunctional ethylenically unsaturated monomer (B) include linear or branched alkylene glycol di (meth) acrylate or alkylene glycol tri (meth) acrylate, alkylene glycol tetra (meth) having 10 to 25 carbon atoms.
  • acrylates As acrylates, cyclohexanedimethanol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, bisphenol A ethylene oxide Id adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, vinyl ether group-containing (meth) acrylic acid esters, bifunctional or more amino acrylates.
  • vinyl ether group-containing (meth) acrylic acid esters examples include 2- (vinyloxyethoxy) ethyl (meth) acrylate.
  • Bifunctional or higher aminoacrylates are considered to be able to suppress polymerization inhibition due to oxygen in the air, and can improve the curing rate when irradiated with ultraviolet rays, particularly when irradiated with low energy ultraviolet rays using a light emitting diode (LED).
  • bifunctional or higher functional amino acrylates for example, amino (meth) acrylate, amine-modified polyether (meth) acrylate, amine-modified polyester (meth) acrylate, amine-modified epoxy (meth) acrylate, amine-modified urethane (meth) acrylate, etc. Is mentioned.
  • the composition for a model material it is preferably a (meth) acrylate monomer, such as dipropylene glycol di (meth) acrylate or tripropylene glycol di (meth) acrylate.
  • Glycerin propoxy tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate and bifunctional or higher amino acrylate are more preferable, and dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, glycerin propoxy tri (meth) acrylate and bifunctional or higher functional amino acrylates are more preferable, dipropylene glycol diacrylate, tripropylene glycol dia It relates and bifunctional or more amino acrylates are particularly preferred.
  • the content of the polyfunctional ethylenically unsaturated monomer (B) in the composition for model material of the present invention is preferably 1 to 30 mass relative to the total mass of the polymerizable compound contained in the composition for model material. %, More preferably 3% by mass or more, further preferably 5% by mass or more, and more preferably 28% by mass or less.
  • content of the polyfunctional ethylenically unsaturated monomer (B) is within the above upper and lower limits, both high modeling accuracy and excellent mechanical properties can be achieved even during high-speed modeling.
  • the content of the hydrophilic (water-soluble) ethylenically unsaturated monomer is preferably as small as possible.
  • the compatibility with the silicone-modified urethane oligomer (S), which is an essential component of the composition for the model material is increased. Since the siloxane group is quickly arranged on the surface of the modeled object, the modeling accuracy can be increased. Further, swelling deformation of the model material (finally, an optically modeled product) due to water or moisture absorption after photocuring or after curing can be suppressed.
  • the content of the hydrophilic ethylenically unsaturated monomer in the composition for a model material of the present invention is such that the monofunctional ethylenically unsaturated monomer (A) and the polyfunctional ethylenically unsaturated monomer (B ) Is preferably 50% by mass or less, more preferably 25% by mass or less, and still more preferably 10% by mass or less.
  • the model material composition does not contain a hydrophilic ethylenically unsaturated monomer (ie, 0% by mass), in other words, a monofunctional ethylenically unsaturated monomer ( A) and the polyfunctional ethylenically unsaturated monomer (B) are all hydrophobic (water-insoluble) monomers.
  • hydrophilic (water-soluble) ethylenically unsaturated monomer means an ethylenically unsaturated monomer having an SP value of more than 11.0.
  • hydrophilic ethylenically unsaturated monomers include hydroxyl group-containing (meth) acrylates, (meth) acrylamide derivatives, (meth) acryloylmorpholines, N-vinyl lactams, N-vinylformamide, and the like. More specifically, the compound illustrated as a water-soluble monofunctional ethylenically unsaturated monomer which the composition for support materials mentioned later can contain is mentioned.
  • the ethylenically unsaturated monomer contained in the model material composition is preferably hydrophobic, and the monofunctional ethylenically unsaturated monomer (A) and the polyfunctional ethylenically unsaturated monomer
  • the SP value of the body (B) is preferably 11.0 or less, more preferably 10.5 or less, and still more preferably 10.0 or less.
  • the lower limit value of the SP value of the monofunctional ethylenically unsaturated monomer (A) and the polyfunctional ethylenically unsaturated monomer (B) is preferably 7.0 or more, more preferably 7.2. It is above, More preferably, it is 7.5 or more.
  • the ratio of the saturated monomer (B) By increasing the ratio of the saturated monomer (B), the surface property of the resulting shaped article can be improved.
  • the SP value is a solubility parameter
  • the SP value of each monomer is obtained by calculation from the molecular structure.
  • the solubility parameter of each ethylenically unsaturated monomer in the present specification is obtained by calculation from the molecular structure of the solubility parameter of the acrylic monomer, and for each (meth) acrylic monomer in this specification,
  • the solubility parameter means a value at 25 ° C. obtained by the Fedors method (Yuji Harasaki, “Basic Science of Coating”, Chapter 3, page 35, 1977, published by Tsuji Shoten).
  • the composition for a model material of the present invention preferably contains a monofunctional ethylenically unsaturated monomer (A) and a polyfunctional ethylenically unsaturated monomer (B) as the polymerizable monomer.
  • A monofunctional ethylenically unsaturated monomer
  • B polyfunctional ethylenically unsaturated monomer
  • the composition for a model material of the present invention is a polymerizable compound other than the silicone-modified urethane oligomer (S), the monofunctional ethylenically unsaturated monomer (A), and the polyfunctional ethylenically unsaturated monomer (B).
  • S silicone-modified urethane oligomer
  • A monofunctional ethylenically unsaturated monomer
  • B polyfunctional ethylenically unsaturated monomer
  • other polymerizable compounds include polymerizable oligomers other than the silicone-modified urethane oligomer (S) [hereinafter also referred to as “oligomer (C)”].
  • the oligomer (C) is a component having a property of being polymerized and cured by irradiation with active energy rays.
  • oligomer refers to those having a weight average molecular weight Mw of 800 to 10,000. More preferably, the lower limit of the weight average molecular weight Mw is more than 1,000.
  • the weight average molecular weight Mw means a weight average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography). Only one type may be used as the oligomer (C), or two or more types may be used in combination.
  • oligomer (C) examples include an epoxy (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, a non-silicone-modified urethane (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, and an aminoacrylate.
  • the oligomer (C) is preferably a bifunctional or higher polyfunctional oligomer, and more preferably a bifunctional oligomer.
  • an oligomer having a urethane group is preferable, more preferably a non-silicone-modified urethane (meth) acrylate oligomer, and still more preferably. It is a non-silicone modified urethane acrylate oligomer.
  • composition for model materials of this invention contains an oligomer (C), it is 30 mass% or less with respect to the gross mass of the polymeric compound contained in the composition for model materials, More preferably, it is 25 mass% or less. More preferably, it is 20 mass% or less.
  • the composition for a model material of the present invention may not contain the oligomer (C), but when the oligomer (C), particularly a non-silicone modified urethane oligomer, is used in combination with the silicone modified urethane oligomer, both hardness and toughness can be achieved. More preferable.
  • the content of the silicone-modified urethane oligomer is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on the total mass of the non-silicone-modified urethane oligomer.
  • the content thereof is preferably 30% by mass or less, more preferably based on the total mass of the polymerizable compounds contained in the composition for model materials. Is 25% by mass or less, more preferably 20% by mass or less.
  • the composition for a model material of the present invention may not contain other polymerizable compounds, but the lower limit of the content of the other polymerizable compound is the value of the polymerizable compound contained in the composition for a model material. It is 1 mass% or more normally with respect to the total mass, Preferably it is 2 mass% or more.
  • the model material composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it is a compound that promotes a radical reaction when irradiated with light having a wavelength in the ultraviolet, near ultraviolet, or visible light region.
  • photopolymerization initiator examples include benzoin compounds having 14 to 18 carbon atoms (for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.), acetophenone compounds having 8 to 18 carbon atoms [for example, Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc.], anthraquinone compounds having 14 to 19 carbon atoms [for example, 2-ethyl ant Quinone, 2-t-butylanthraquinone, 2-chloroanth
  • acetophenone compounds and acylphosphine oxide compounds. At least one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, or 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one and the like are preferable.
  • a photoinitiator you may use the product marketed, for example, DAROCURE TPO, IRGACURE184, IRGACURE907, etc. made from BASF.
  • the content of the photopolymerization initiator in the composition for model material is preferably 2 to 15% by mass, more preferably 3 to 10% by mass, based on the total mass of the composition for model material.
  • the content of the photopolymerization initiator is not less than the above lower limit, unreacted polymerization components can be sufficiently reduced, and the curability of the model material can be sufficiently increased.
  • the content of the photopolymerization initiator is not more than the above upper limit, the amount of the photopolymerization initiator remaining unreacted in the model material can be reduced, and the unreacted photopolymerization initiator remains. It is possible to suppress yellowing of the optically shaped product generated by doing so.
  • composition for model material can contain other additives as necessary within the range not impairing the effects of the present invention.
  • other additives include storage stabilizers, surface conditioners, antioxidants, colorants, ultraviolet absorbers, light stabilizers, polymerization inhibitors, chain transfer agents, fillers, diluent solvents, thickeners, and the like. Is mentioned.
  • the surface conditioner is a component that adjusts the surface tension of the model material composition to an appropriate range, and the type thereof is not particularly limited. By making the surface tension of the model material composition within an appropriate range, it is possible to stabilize the ejection properties and to suppress interfacial mixing between the model material composition and the support material composition. As a result, it is possible to obtain a shaped article with good dimensional accuracy.
  • 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.
  • the content thereof is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, based on the total mass of the model material composition. Yes, preferably 3.0% by mass or less, more preferably 1.5% by mass or less.
  • the content of the surface conditioner is within the above range, the surface tension of the model material composition is easily adjusted to an appropriate range.
  • the storage stabilizer is a component that can enhance the storage stability of the model material composition. Further, clogging of the head caused by polymerization of the polymerizable compound by thermal energy can be prevented.
  • Examples of the storage stabilizer include hindered amine compounds (HALS), phenolic antioxidants, phosphorus antioxidants, and the like.
  • the content thereof is preferably 0.05 to 3% by mass based on the total mass of the model material composition from the viewpoint of easily obtaining the above effect. .
  • the model material composition of the present invention may further contain a colorant.
  • a colorant is not included.
  • the colorant is not particularly limited.
  • the model material composition of the present invention is non-aqueous, a pigment that is easily dispersed uniformly in a water-insoluble medium and a dye that is easily dissolved are preferable.
  • an inorganic pigment or an organic pigment can be used.
  • inorganic pigments include titanium oxide, zinc oxide, zinc oxide, lithopone, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silica, alumina, cadmium red, red rose, molybdenum Red, chrome vermilion, molybdate orange, yellow lead, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chrome oxide, pyridian, cobalt green, titanium cobalt green, cobalt chrome green, ultramarine blue, ultramarine blue, bitumen, Examples include cobalt blue, cerulean blue, manganese violet, cobalt violet, and mica.
  • organic pigments examples include organic pigments such as azo, azomethine, polyazo, phthalocyanine, quinacridone, anthraquinone, indigo, thioindigo, quinophthalone, benzimidazolone, and isoindoline. Carbon black made of acidic, neutral or basic carbon may be used. Furthermore, crosslinked acrylic resin hollow particles or the like may be used as the organic pigment.
  • black and pigments of three primary colors of cyan, magenta, and yellow are usually used, but pigments having other hues, metallic luster pigments such as gold and silver, colorless Alternatively, a light-colored extender pigment can also be used depending on the purpose.
  • the above colorants may be used alone or in combination of two or more.
  • two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination.
  • a different colorant may be used for each droplet and liquid to be ejected, or the same colorant may be used.
  • the dispersion of the colorant for example, bead mill, ball mill, sand mill, attritor, roll mill, jet mill, homogenizer, paint shaker, kneader, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, etc.
  • An apparatus can be used, and a mixer such as a line mixer may be used.
  • classification may be performed using a centrifuge, a filter, a cross flow, or the like for the purpose of removing coarse particles of the colorant.
  • a dispersant When dispersing the colorant, a dispersant can be added.
  • the type of the dispersant is not particularly limited, but a known polymer dispersant is preferably used.
  • the content of the dispersant is appropriately selected depending on the purpose of use, and can be set to 0.01 to 5% by mass with respect to the total mass of the model material composition, for example.
  • the content of the colorant is appropriately selected depending on the color and purpose of use, but is 0.05 to 30% by mass with respect to the total mass of the composition for model material from the viewpoint of image density and storage stability. It is preferably 0.1 to 10% by mass.
  • the angle (hereinafter also referred to as “contact angle MM”) is preferably 40 ° or more, more preferably 45 ° or more, still more preferably 48 ° or more, and particularly preferably 50 ° or more.
  • the contact angle refers to an angle formed by the droplet surface and the solid surface at a portion where the droplet contacts the solid surface, and is an index representing the so-called wettability of the droplet.
  • the contact angle MM of the model material composition was measured 0.3 seconds after the composition (droplet) landed on the cured product (solid surface) because the composition was landed by irradiation with energy rays. The standard time until curing is set. If the contact angle MM of the model material composition is equal to or greater than the above lower limit, the excess between the cured material of the model material composition that has landed first and the model material composition that forms the next layer overlapping therewith It is possible to suppress the spread of wetting, and it is difficult for distortion and displacement to occur, and the repair capability when distortion or displacement occurs is high, and even when discharging continuously from the material jet nozzle, it can be stacked accurately in the vertical direction. It is possible to ensure high modeling accuracy during high-speed modeling.
  • the upper limit value of the contact angle MM of the model material composition is not particularly limited, but is usually 70 ° or less, and preferably 65 ° or less from the viewpoint of achieving both high modeling accuracy and excellent mechanical properties. .
  • the contact angle MM of the model material composition can be controlled by adjusting the type and blending amount of the silicone-modified urethane oligomer (S) described above. For example, adjusting the number average molecular weight of the silicone-modified urethane oligomer (S) in the range of 1,000 to 10,000, and the content of the silicone-modified urethane oligomer (S) with respect to the total mass of the model material composition By adjusting to the range of 0.1 to 20% by mass, the contact angle MM can be increased.
  • the contact angle MM in the present invention is a contact angle formed by the droplets of the model material composition with respect to the cured product of the model material composition droplets, and the measurement method will be described in Examples described later.
  • the surface tension of the composition for a model material of the present invention is preferably 24 to 30 mN / m, more preferably 24.5 mN / m or more, further preferably 25 mN / m or more, more preferably 29. 5 mN / m or less, more preferably 29 mN / m or more.
  • the surface tension is within the above range, droplets ejected from the nozzle can be formed normally even during high-speed ejection of material jets, ensuring adequate droplet volume and landing accuracy, and generating satellites. It is possible to suppress, and it becomes easy to improve modeling accuracy.
  • the surface tension of the composition for a model material can be controlled by adjusting the type and blending amount of the silicone-modified urethane oligomer (S) described above and the type and blending amount of the surface modifier. it can.
  • the surface tension of the composition for model materials can be measured according to the method as described in an Example.
  • the composition for a model material of the present invention has a viscosity of 20 to 500 mPa ⁇ s at 25 ° C. because it is used for material jet stereolithography. From the viewpoint of improving dischargeability from the material jet nozzle, the viscosity at 25 ° C. is preferably 20 to 400 mPa ⁇ s, and more preferably 20 to 300 mPa ⁇ s.
  • the viscosity can be measured according to JIS Z 8803 using an R100 viscometer.
  • the viscosity of the composition for a model material can be controlled by adjusting the type of the polymerizable compound and the blending ratio thereof, the type of the diluent solvent and the thickener, the amount of addition thereof, and the like.
  • the method for producing the composition for model material of the present invention is not particularly limited. For example, it can be produced by uniformly mixing the components constituting the model material composition using a mixing and stirring device or the like.
  • composition set for material jet stereolithography The composition for a model material of the present invention is excellent in modeling accuracy at the time of high-speed modeling, and can be accurately stacked in the height direction even when discharged continuously from a material jet nozzle. For this reason, it is possible to form a three-dimensional structure only with the composition for the model material, but by using it in combination with a support material for supporting the model material during the three-dimensional modeling, a complicated shape or a dense shape is higher. It can be modeled with accuracy. Therefore, the present invention also covers a composition set for material jet stereolithography comprising the composition for model material of the present invention and a composition for support material for modeling a support material by a material jet stereolithography method. To do.
  • composition for a support material is a photocurable composition for a support material that provides the support material by photocuring. After the model material is created, it can be removed from the model material by physically peeling the support material from the model material or by dissolving the support material in an organic solvent or water.
  • the composition for a model material of the present invention can be used in combination with various conventionally known compositions as a composition for a support material, but does not damage the model material when the support material is removed, and the environment. It is preferable that the support material composition that constitutes the stereolithography composition set of the present invention is water-soluble because the support material can be easily removed cleanly and easily in detail.
  • Such a water-soluble composition for a support material preferably contains a water-soluble monofunctional ethylenically unsaturated monomer, a water-soluble resin, and a photopolymerization initiator.
  • the water-soluble monofunctional ethylenically unsaturated monomer is (
  • the water-soluble resin contains at least one selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxytetramethylene group
  • the photopolymerization initiator is an acylphosphine oxide-based derivative. It is preferable to include a photopolymerization initiator.
  • Examples of the water-soluble monofunctional ethylenically unsaturated monomer contained in the support material composition include, for example, a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms [for example, hydroxyethyl (meth) 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, monoalkoxy (from 1 to carbon atoms) 4) Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, monoalkoxy (1 to 4 carbon atoms) polypropylene glycol mono (meth) acrylate, mono (meth) acrylate of PEG-PPG block polymer, etc.], carbon Number 3 15 (meth) acrylamide derivatives [e
  • the content of the water-soluble monofunctional ethylenically unsaturated monomer contained in the support material composition is 19% by mass to 80% by mass with respect to 100% by mass of the total mass of the support material composition. It is preferable. When the content is within the above range, the removability of the support material with water can be improved without reducing the support force of the support material.
  • the water-soluble resin contained in the composition for the support material is for imparting moderate hydrophilicity to the support material, and by adding this, a support material having both water removability and support power is obtained. be able to.
  • the water-soluble resin preferably contains at least one selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxytetramethylene group. This is because the water removability can be further improved without reducing the support force of the support material.
  • Specific examples of the water-soluble resin include oxyethylene such as polyethylene glycol, polypropylene glycol, poly (oxytetramethylene) glycol, polyoxytetramethylene polyoxyethylene glycol, and polyoxytetramethylene polyoxypropylene glycol.
  • a polyoxyalkylene glycol containing at least one selected from the group consisting of a group, an oxypropylene group and an oxytetramethylene group a polyoxyalkylene glycol containing at least one selected from the group consisting of a group, an oxypropylene group and an oxytetramethylene group.
  • the said water-soluble resin may be used individually by 1 type, and may use 2 or more types together.
  • the content of the water-soluble resin in the support material composition of the present invention is preferably 15% by mass or more and 75% by mass or less with respect to 100% by mass of the total mass of the support material composition. If the content is within the above range, the removability by water can be improved without reducing the support force of the support material.
  • the number average molecular weight Mn of the water-soluble resin is preferably 100 to 5,000.
  • the number average molecular weight Mn of the water-soluble resin is preferably 200 to 3,000, more preferably 400 to 2,000.
  • the support composition may contain other additives as necessary.
  • additives include a photopolymerization initiator, a water-soluble organic solvent, an antioxidant, a colorant, a pigment dispersant, a storage stabilizer, a surface conditioner, an ultraviolet absorber, a light stabilizer, and a polymerization inhibitor. , Chain transfer agents, fillers and the like.
  • the compounds described above as photopolymerization initiators that can be contained in the model material composition may be used in the same manner.
  • the photopolymerization initiator is excellent in curability with an LED light source, and the molded article is colored. From the viewpoint of being small, it is preferable to include an acyl phosphine oxide-based photopolymerization initiator.
  • the support material composition contains a photopolymerization initiator, the content thereof is preferably 2 to 20% by mass, more preferably 3 to 10% by mass, based on the total mass of the support material composition. .
  • the content of the photopolymerization initiator is not less than the above lower limit, unreacted polymerization components are sufficiently reduced, and the curability of the support material can be sufficiently increased.
  • the content of the photopolymerization initiator is not more than the above upper limit, it is easy to avoid remaining unreacted photopolymerization initiator in the support material.
  • the water-soluble organic solvent is a component that improves the solubility of the support material obtained by photocuring the support material composition in water. Moreover, it is a component which adjusts the composition for support materials to low viscosity.
  • the content is preferably 35% by mass or less, more preferably 30% by mass or less, based on the total mass of the composition for support material. Further, the content is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the dimensional accuracy of the material may deteriorate.
  • the content of the water-soluble organic solvent is not more than the above upper limit, it is easy to suppress such leaching.
  • the content of the water-soluble organic solvent in the support material composition is equal to or higher than the above lower limit, it is easy to improve the solubility of the support material in water, and the support material composition is adjusted to a low viscosity. It's easy to do.
  • water-soluble organic solvent examples include alkylene glycol monoacetate having a linear or branched alkylene group (for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol).
  • alkylene glycol monoacetate having a linear or branched alkylene group for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol.
  • alkylene glycol monoalkyl ethers having linear or branched alkylene groups [eg ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether , Triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetrapropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, Triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, tetrapropylene glycol monoe
  • the water-soluble organic solvent is triethylene glycol monomethyl ether or dipropylene. More preferred is glycol monomethyl ether acetate.
  • the viscosity of the composition for a support material of the present invention is preferably 20 to 500 mPa ⁇ s at 25 ° C., more preferably 20 to 400 mPa ⁇ s, from the viewpoint of improving dischargeability from the material jet nozzle. preferable.
  • the above-mentioned viscosity can be measured using an R100 viscometer in accordance with JIS Z 8 803.
  • the method for producing the composition for support material of the present invention is not particularly limited.
  • the composition for the support material can be produced by uniformly mixing the components constituting the composition for support material using a mixing and stirring device or the like.
  • This invention manufactures a three-dimensional molded article by the stereolithography method by a material jet system using the composition for model materials of this invention, or the composition set for material jet stereolithography of this invention. A method is also provided.
  • the manufacturing method of the optical modeling product of the present invention is particularly limited as long as it is a method of manufacturing a three-dimensional modeling object by an optical modeling method by a material jet method using the model material composition or the optical modeling composition set of the present invention.
  • the production method of the present invention includes a step of photocuring the model material composition to obtain a model material, and photocuring the support material composition to obtain the support material. And a step of removing the support material from the model material.
  • 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.
  • Examples of the light for curing the composition for the model material and the composition for the support material include active energy rays such as far infrared rays, infrared rays, visible rays, near ultraviolet rays, ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and X rays. It is done. Among these, near ultraviolet rays or ultraviolet rays are preferable from the viewpoint of the ease and efficiency of the curing operation.
  • the light source examples include conventionally known high pressure mercury lamps, metal halide lamps, and UV-LEDs.
  • the LED system is preferable from the viewpoint that the equipment can be downsized and the power consumption is small.
  • the composition for a model material is cured by irradiating an active energy ray having an accumulated light amount per layer of 300 mJ / cm 2 or more in a wavelength region of 320 to 410 nm.
  • an active energy ray having an accumulated light amount per layer of 300 mJ / cm 2 or more in a wavelength region of 320 to 410 nm By irradiating active energy rays with a high integrated light amount in the wavelength range of 320 to 410 nm, the cross-linking reaction of a component having a polymerizable group (for example, acryloyl group) having a relatively high reaction rate is promoted.
  • a component having a polymerizable group for example, acryloyl group
  • a material jet Since the crosslinking reaction of the polymerizable monomer is first accelerated and the crosslinking of the silicone-modified urethane oligomer (S) is delayed in the time until the droplet of the composition for the model material discharged from the nozzle lands and cures, the silicone is delayed.
  • the integrated light amount is more preferably 300 mJ / cm 2 or more, and further preferably 500 mJ / cm 2 or more.
  • the upper limit of the peak illuminance is not particularly limited, but is usually 2,000 mJ / cm 2 or less from the viewpoint of preventing energy saving and substrate damage.
  • 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 obtained shaped product is a combination of model material and support material.
  • the support material is removed from the modeled product to obtain an optical modeled product that is a model material.
  • the removal of the support material is preferably performed by, for example, immersing a shaped article 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.
  • 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.
  • a stereolithography product is obtained by the above process.
  • the optical modeling product manufactured using such a model material composition or optical modeling composition set of the present invention has good dimensional accuracy.
  • Model Material Composition Table 1 shows the details and abbreviations of the components constituting the model material composition used in the examples.
  • the SP value of the monofunctional ethylenically unsaturated copolymer (A) and the polyfunctional ethylenically unsaturated monomer (B) is the Fedors method (written by Yuji Harasaki, “Basic Science of Coating”, No. (Chapter 3, p. 35, 1977, published by Sakai Shoten) means a value at 25 ° C., calculated according to the following method.
  • Fedors considers that both the cohesive energy density and the molar volume depend on the type and number of substituents, and proposes the following formula and a constant corresponding to each substituent.
  • ⁇ is the SP value (cal / cm 3 ) 1/2
  • ⁇ E is the cohesive energy density
  • V is the molar volume
  • ⁇ ei is the evaporation energy (cal / mol) of each atom or atomic group
  • ⁇ vi is each atom.
  • the molar volume of the atomic group (cm 3 / mol).
  • Tg 25 ° C. or higher, the following value is added to the molar volume.
  • n is the number of main chain skeleton atoms in the repeating unit in the compound
  • 4n is added to ⁇ vi when n ⁇ 3
  • 2n is added to ⁇ vi when n ⁇ 3.
  • Model Material Composition According to the composition shown in Table 2, the components constituting each model material composition were uniformly mixed using a mixing and stirring device, and after stirring, a glass filter (Kiriyama Seisakusho) was prepared. The mixture was subjected to suction filtration using the above-mentioned product, and the compositions 1 and 2 for model materials of Examples 1 and 2 were prepared.
  • ⁇ Wettability (pipette droplet diameter)>
  • the model material composition produced in Example 1 was applied onto a 188 ⁇ m thick polyethylene terephthalate film (white PET film manufactured by Teijin DuPont Films, trade name “U292W”) using a bar coater (# 14). Then, a printing film having a thickness of 3 ⁇ m was formed.
  • the light source for curing the printed film is an illuminance of 508 mW / cm 2 (UVR-N1 manufactured by UV Checker GS Yuasa Lighting) using a UV-LED curing device (aluminum substrate module NSSU100AT manufactured by Nichia Corporation, LED peak wavelength 365 nm). Irradiation).
  • a transparent PET film having no UV-cut function is bonded to the surface of the print film in order to impart an oxygen inhibition suppressing effect, and the total integrated light amount including precuring is 23 mJ / cm 2 .
  • the model material cured film A was obtained by irradiating with ultraviolet rays so as to be cured, and peeling the bonded PET film. Subsequently, using a micropipette, a drop volume of 5.0 ⁇ 0.2 ⁇ L of the model material was dropped on the surface of the model material cured film A, and 20 seconds later, using the above-described UV-LED curing device.
  • the length of the diameter was measured by irradiating and curing with ultraviolet rays so that the total accumulated light amount was 138 mJ / cm 2 .
  • the measured value of Table 3 evaluated 3 times by the same composition, and displayed the average value.
  • Example 2 Using the model material composition prepared in Example 2, a model material cured film B was prepared in the same manner as in Example 1 above.
  • ⁇ Contact angle MM> A model material that forms each model material cured film on the surface of each model material cured film described above using the contact angle measuring device “PG-X” manufactured by Matsubo Co., Ltd. and setting the dynamic mode to the dropping mode.
  • Each of the compositions was discharged at a drop volume of 1.8 ⁇ 0.1 ⁇ L, and the contact angle of the droplets was measured 0.3 seconds after the droplets of the composition landed on the model material cured film.
  • the contact angle of the model material composition with respect to the model material cured film was expressed as MM.
  • compositions for model materials prepared in Examples 1 and 2 above is a polyethylene terephthalate having a thickness of 100 ⁇ m using an ink jet recording apparatus (Fuji Film Co., Ltd. DMP-2831, head 10 pL specification) equipped with a piezo ink jet nozzle. It was laminated on a film (transparent PET film manufactured by Toray Industries, Inc., trade name “Lumirror QT92”), and the modeling accuracy was evaluated.
  • the head discharge conditions in this ink jet recording apparatus the voltage was 30 V, the frequency was 20 kHz, the head temperature was 40 ° C., and the clearance between the head and the PET film was 2 mm.
  • a UV-LED curing device (aluminum substrate module NVSU119C manufactured by Nichia Corporation, LED peak wavelength 375 nm, illuminance 800 mW / cm 2 ) was installed as a light source so as to run alongside the head. 0.4 seconds after the model material composition landed on the PET film or the model material cured film as the lower layer, the total accumulated light amount was adjusted to 43 mJ / cm 2 and cured by irradiating with ultraviolet rays. As input data of a modeled object, one side of a 0.3 mm square was used as one layer, and 100 layers were stacked in order to produce a quadrangular prism. The height of the column was measured according to the following criteria, and the modeling accuracy was evaluated.
  • the model material compositions prepared in Examples 1 and 2 above were each 75 ⁇ m thick polyethylene terephthalate film (transparent PET film manufactured by Toray Industries, Inc., trade name “Lumirror 75S10”) ) To form a printed film having a thickness of 8 ⁇ m.
  • the light source for curing the printed film is a high-pressure mercury lamp curing device (eye graphics company ECS-151S unit, high-pressure mercury lamp H015-L312, peak wavelength 365 nm), and an illuminance of 330 mW / cm 2 (UV checker GS Yuasa Lighting) Irradiation was performed under the conditions of actual measurement using UVR-N1 manufactured by the manufacturer.
  • This printed film was cured by irradiating with ultraviolet rays so that the total accumulated light amount was 570 mJ / cm 2 , thereby obtaining each model material cured film for evaluating the warpage of the modeled object.
  • the level of warpage was confirmed according to the following criteria. ⁇ Evaluation criteria> Evaluation ⁇ : No warpage Evaluation ⁇ : Slight warpage Evaluation ⁇ : Large warpage

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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne une composition de matériau modèle qui est destinée à former un matériau modèle par stéréolithographie par jet de matériau, qui comprend un monomère polymérisable, un initiateur de photopolymérisation, et un oligomère d'uréthane modifié par silicone contenant un groupe polymérisable, et qui a une viscosité de 20 à 500 mPa·s à 25° C.
PCT/JP2018/034068 2018-03-15 2018-09-13 Composition pour matériau modèle WO2019176144A1 (fr)

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CN115043986A (zh) * 2022-04-29 2022-09-13 广州大学 一种高强度光固化3d打印树脂及其制备方法
EP4324864A1 (fr) * 2022-08-19 2024-02-21 Sumitomo Rubber Industries, Ltd. Composition photodurcissable et produit formé à partir de la composition photodurcissable

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JPH0485314A (ja) * 1990-07-26 1992-03-18 Japan Synthetic Rubber Co Ltd 光学的立体造形用樹脂組成物
JP2001311917A (ja) * 2000-02-24 2001-11-09 Hoya Healthcare Corp 側鎖にポリシロキサン構造を有するマクロマーからなるコンタクトレンズ材料
JP2015208904A (ja) * 2014-04-25 2015-11-24 コニカミノルタ株式会社 三次元造形装置
WO2017047693A1 (fr) * 2015-09-15 2017-03-23 日立マクセル株式会社 Composition de résine de matériau modèle, assortiment d'encre pour façonnage optique et procédé de fabrication d'un article optiquement façonné

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US9873180B2 (en) 2014-10-17 2018-01-23 Applied Materials, Inc. CMP pad construction with composite material properties using additive manufacturing processes

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH0485314A (ja) * 1990-07-26 1992-03-18 Japan Synthetic Rubber Co Ltd 光学的立体造形用樹脂組成物
JP2001311917A (ja) * 2000-02-24 2001-11-09 Hoya Healthcare Corp 側鎖にポリシロキサン構造を有するマクロマーからなるコンタクトレンズ材料
JP2015208904A (ja) * 2014-04-25 2015-11-24 コニカミノルタ株式会社 三次元造形装置
WO2017047693A1 (fr) * 2015-09-15 2017-03-23 日立マクセル株式会社 Composition de résine de matériau modèle, assortiment d'encre pour façonnage optique et procédé de fabrication d'un article optiquement façonné

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115043986A (zh) * 2022-04-29 2022-09-13 广州大学 一种高强度光固化3d打印树脂及其制备方法
EP4324864A1 (fr) * 2022-08-19 2024-02-21 Sumitomo Rubber Industries, Ltd. Composition photodurcissable et produit formé à partir de la composition photodurcissable

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