WO2015049873A1 - Composition d'encre, et procédé de formation d'images ou d'objets moulés tridimensionnels - Google Patents

Composition d'encre, et procédé de formation d'images ou d'objets moulés tridimensionnels Download PDF

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WO2015049873A1
WO2015049873A1 PCT/JP2014/005042 JP2014005042W WO2015049873A1 WO 2015049873 A1 WO2015049873 A1 WO 2015049873A1 JP 2014005042 W JP2014005042 W JP 2014005042W WO 2015049873 A1 WO2015049873 A1 WO 2015049873A1
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ink composition
monomer
acrylate
monofunctional
meth
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PCT/JP2014/005042
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English (en)
Japanese (ja)
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小俣　猛憲
中村　正樹
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コニカミノルタ株式会社
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Priority to JP2015540397A priority Critical patent/JP6662041B2/ja
Publication of WO2015049873A1 publication Critical patent/WO2015049873A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks

Definitions

  • the present invention relates to an ink composition and a method for forming an image or a three-dimensional structure.
  • a liquid photocurable composition is irradiated with laser light or ultraviolet light to cure and laminate the irradiated portion (see Patent Documents 1 and 2), or by an inkjet method.
  • a method in which a photocurable liquid is landed on a base material and the landed liquid is cured by irradiation with ultraviolet rays is widely known.
  • the three-dimensional structure forming method using the ink jet method allows a photocurable liquid to be laminated only at a necessary position as compared with the conventional method, so that a complicated shape can be formed. Easy to do.
  • the amount of use of the modeling material is small, and mechanical characteristics can be easily adjusted by simultaneously emitting a plurality of photocurable liquids having different properties from a plurality of nozzles (see Patent Document 5). Therefore, it is used for various prototype applications.
  • Patent Document 6 discloses an ink based on a monofunctional urethane acrylate monomer and having a polyfunctional component of 0.5 to 10%. According to this ink, although the flexibility is improved, since the base is a urethane monomer, the cohesive force becomes too strong and the desired elongation is not exhibited.
  • JP 62-101408 A Japanese Patent Laid-Open No. 5-24119 JP 2002-067174 A JP 2003-299679 A JP 2010-155926 A JP 2012-7107 A
  • An object of the present invention is to provide an ink composition and an image or three-dimensional structure forming method having an elongation and elasticity like rubber when cured.
  • the first of the present invention relates to the following ink composition.
  • An ink composition containing a photocurable reactive compound containing a monofunctional monomer and a polyfunctional monomer, The molar fraction of the monofunctional monomer and the polyfunctional monomer is the monofunctional monomer / the polyfunctional monomer 92/8 to 99.9 / 0.1, At least one of the monofunctional monomer or the polyfunctional monomer has a hydroxyl group or an amino group, and the total molar fraction of the hydroxyl group and amino group in the total amount of the monofunctional monomer and the polyfunctional monomer is 5 to 30. %, The ink composition.
  • At least one of the monofunctional monomer or the polyfunctional monomer has an amide bond, a urea bond, or a urethane bond
  • At least one of the monofunctional monomer or the polyfunctional monomer is an amide bond in which a hydrogen atom is bonded to a nitrogen atom, a urea bond in which a hydrogen atom is bonded to a nitrogen atom, a urethane bond in which a hydrogen atom is bonded to a nitrogen atom, Or having a carboxyl group,
  • the amide bond in which a hydrogen atom is bonded to a nitrogen atom the urea bond in which a hydrogen atom is bonded to a nitrogen atom
  • the urethane bond in which a hydrogen atom is bonded to a nitrogen atom or a carboxyl group
  • the ink composition according to [1] wherein the total molar fraction of is from 5 to 30%.
  • At least one of the monofunctional monomer or the polyfunctional monomer has a urethane bond
  • the monofunctional monomer includes a monofunctional (meth) acrylate,
  • the polyfunctional monomer is a polyfunctional monomer having a plurality of carbon-carbon double bonds in the molecule;
  • the monofunctional (meth) acrylate contains 65% by mass or more of the monomer represented by the general formula (X) or (Y) with respect to the total mass of the monofunctional (meth) acrylate, and the ink
  • the glass transition temperature of the cured product of the composition is less than 25 ° C.
  • the ink composition according to any one of [1] to [7].
  • R 1 represents H or CH 3
  • R 2 represents an alkyl group having 2 to 22 carbon atoms which may be substituted with an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms
  • R 3 represents H or CH 3
  • R 4 represents a monovalent substituent having an alicyclic hydrocarbon, or an alkyl group having 11 to 22 carbon atoms which may be substituted with an aryl group having 6 to 12 carbon atoms
  • m represents an integer of 2 to 4
  • n represents an integer of 1 or 2.
  • the second aspect of the present invention relates to the following image or three-dimensional structure formation method.
  • An image or tertiary including a step of discharging the ink composition according to any one of [1] to [9] onto a base material or a support material, and a step of photocuring the ink composition.
  • Original model formation method
  • [11] Convert CAD data into STL data which is data for three-dimensional modeling, Creating a plurality of plane data including first plane data and second plane data based on the STL data; Based on the first plane data, either the model material ink composition or the support material ink composition is ejected onto a stage to form a first film, Photocuring the first film to form a first layer; Based on the second plane data, either the model material ink composition or the support material ink composition is ejected onto the first layer to form a second film, The second film is photocured to form a second layer; Until the final layer is laminated, repeating the step of forming the second film and the step of obtaining the second layer, A step of removing the support material, A three-dimensional structure formation method, wherein the ink composition for a model material is the ink composition according to any one of [1] to [9].
  • an ink composition in which the cured product of the ink composition has rubber-like elongation and elasticity, and an image or three-dimensional structure forming method using the ink composition.
  • FIG. 1 is a diagram illustrating an aspect of a three-dimensional modeling system.
  • FIG. 2 is a flowchart of the three-dimensional modeling method.
  • FIG. 3 is a side view of the process (part 1) of the three-dimensional modeling method.
  • FIG. 4A is a side view of the process (part 2) of the three-dimensional modeling method, and FIG. 4B is a top view thereof.
  • FIG. 5A is a side view of the step (part 3) of the three-dimensional modeling method, and FIG. 5B is a top view thereof.
  • FIG. 6A is a side view of the step (part 4) of the three-dimensional modeling method, and FIG. 6B is a top view thereof.
  • FIG. 7A is a side view of the step (part 5) of the three-dimensional modeling method, and FIG. 7B is a top view thereof.
  • FIG. 8 is a perspective view of a model material obtained by the three-dimensional modeling method.
  • the ink composition contains a photocurable reactive compound and a photopolymerization initiator.
  • a photocurable reactive compound contains a monofunctional monomer and a polyfunctional monomer.
  • Monofunctional monomer is a compound having a monovalent radical polymerizable group.
  • the radical polymerizable group refers to, for example, an ethylene group ((meth) acryl group, vinyl ether group, allyl ether group, styrene group, (meth) acrylamide group, acetyl vinyl group, vinyl amide group), acetylene group, and the like.
  • (meth) acrylate includes acrylate monomer and / or acrylate oligomer, methacrylate monomer and / or methacrylate oligomer.
  • the specific monofunctional monomer refers to a monofunctional monomer having a hydroxyl group or an amino group.
  • the hydroxyl group includes an alcoholic hydroxyl group, a carboxyl group, and the like. In addition to normal amino groups, it contains amide bonds, urea bonds, urethane bonds, and the like.
  • a preferred first embodiment of the specific monofunctional monomer has any partial structure represented by the following (General Formula 1). That is, it has an amide bond, a urea bond or a urethane bond.
  • the specific monofunctional monomer having the partial structure represented by the general formula 1 two or more sites to be polarized are close to each other. Therefore, mutual interaction becomes strong, and the polymer chains can be pseudo-crosslinked when they are contained in the polymer chain.
  • a more preferable embodiment of the specific monofunctional monomer has any partial structure represented by the following (General Formula 2). That is, it has an amide bond in which a hydrogen atom is bonded to an N atom, a urea bond in which a hydrogen atom is bonded to an N atom, a urethane bond or a carboxyl group in which a hydrogen atom is bonded to an N atom.
  • the specific monofunctional monomer having a partial structure represented by General Formula 2 has both a proton donor and an acceptor. Therefore, mutual interaction becomes strong, and the polymer chains can be pseudo-crosslinked when they are contained in the polymer chain.
  • the molecular weight of the specific monofunctional monomer is preferably 200 or more and 1000 or less. This is because the ejection stability of the ink composition is improved by adjusting the ink viscosity of the ink composition.
  • the glass transition temperature of the cured product obtained by polymerizing the specific monofunctional monomer is preferably 0 ° C. or lower. This is because the cured product of the ink composition is given rubber-like elongation and elasticity.
  • Examples of monofunctional monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyl Monofunctional monomers containing alcoholic hydroxyl groups such as loxyethyl-2-hydroxyethyl-phthalic acid, caprolactone acrylate; 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, Examples thereof include a carboxyl group-containing monofunctional monomer such as 2- (meth) acryloyloxyethylphthalic acid.
  • Examples of monofunctional monomers having amino groups include (meth) acrylamides such as dimethylacrylamide, acryloylmorpholine, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, hydroxyethylacrylamide, dimethylaminopropylacrylamide, hydroxyethylacrylamide; acrylic acid Urethane compounds such as 2- (butylcarbamoyloxy) ethyl and compounds represented by the following formula ( ⁇ ); N-vinylformamide, N-vinylcaprolactam, N-vinylpyrrolidone, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. Can be mentioned. In addition, various amine-modified acrylates are included.
  • the monofunctional monomer may contain other monofunctional monomers other than the specific monofunctional monomer.
  • examples of other monofunctional monomers include a monofunctional monomer having a (meth) acryl group, a monofunctional monomer having a vinyl ether group, a monofunctional monomer having an allyl ether group, and a monofunctional monomer having an acetylene group.
  • Monofunctional monomers having a (meth) acryl group include isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isomyristyl (meth) acrylate, iso Stearyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurf Le (meth) acrylate, isoborny
  • Monofunctional monomers having a vinyl ether group include butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, ethyl hexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, cyclohexyl vinyl ether, adamantyl vinyl ether, and the like. Can be mentioned.
  • Monofunctional monomers having an allyl ether group include phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, Examples include cyclohexyl allyl ether and cyclohexane methanol monoallyl ether.
  • Examples of the monofunctional monomer having an acetylene group include acetylene.
  • the monofunctional monomer is not limited to those described above.
  • a monofunctional monomer may contain a monofunctional (meth) acrylate.
  • the monofunctional (meth) acrylate may be represented by the general formula (X) or (Y).
  • the monofunctional (meth) acrylate represented by the general formula (X) or (Y) may be a specific monofunctional monomer or another monofunctional monomer.
  • R 1 represents H or CH 3
  • R 2 represents an alkyl group having 2 to 22 carbon atoms which may be substituted with an aryl group having 6 to 12 carbon atoms, or 6 carbon atoms.
  • R 3 represents H or CH 3
  • R 4 is a carbon that may be substituted with a monovalent substituent having an alicyclic hydrocarbon, or an aryl group having 6 to 12 carbon atoms.
  • Examples of the monofunctional (meth) acrylate represented by the general formula (X) include isoamyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, and decyl (meth) acrylate.
  • Examples of the monofunctional (meth) acrylate represented by the general formula (Y) include methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, Examples include isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate.
  • the content of the monofunctional (meth) acrylate represented by the general formula (X) or (Y) is preferably 65% by mass or more based on the total mass of the monofunctional (meth) acrylate. Moreover, as for content of the monofunctional (meth) acrylate represented by general formula (X), it is more preferable that they are 80 to 98 mass% with respect to the total mass of monofunctional (meth) acrylate.
  • the monofunctional monomer contained in the ink composition is “(meth) acrylate having a molecular weight of 160 or more and less than 400 and a Tg of the cured product of ⁇ 20 ° C. or less” based on 85% by mass with respect to the total mass of the monofunctional monomer. It is preferable to contain above.
  • the “(meth) acrylate having a molecular weight of 160 or more and less than 400 and a Tg of the cured product of ⁇ 20 ° C. or less” may be a specific monofunctional monomer or another monofunctional monomer.
  • (meth) acrylate having a molecular weight of 160 to less than 400 and a Tg of the cured product of ⁇ 20 ° C. or less include isoamyl acrylate, lauryl acrylate, octyl acrylate, decyl acrylate, isomyristyl acrylate, Stearyl acrylate, 2-ethylhexyl-diglycol acrylate, 2-hydroxybutyl acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxypropylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl ( And (meth) acrylate.
  • a polyfunctional monomer is a compound which has a bivalent radically polymerizable group.
  • the polyfunctional monomer is a polyfunctional monomer having a plurality of carbon-carbon double bonds in the molecule, for example, a function selected from (meth) acryl group, vinyl ether group, allyl ether group, styrene group and (meth) acrylamide group in the molecule. It is preferable to use a monomer having a plurality of groups.
  • the polymerizable functional groups contained in one polyfunctional monomer may be the same as or different from each other.
  • the polyfunctional monomer contained in the ink composition may be one type or a combination of different types of polyfunctional monomers. Among them, it is preferable to use a polyfunctional monomer having a functional group selected from an acryl group, a methacryl group, a vinyl ether group, and an allyl ether group because of high photopolymerization sensitivity.
  • the specific polyfunctional monomer may include a “specific polyfunctional monomer”.
  • the specific polyfunctional monomer refers to a polyfunctional monomer having a hydroxyl group or an amino group.
  • the hydroxyl group includes a carboxyl group in addition to an alcoholic hydroxyl group.
  • the amino group includes an amide bond, a urea bond, a urethane bond and the like in addition to a normal amino group.
  • a preferred embodiment of the specific monofunctional monomer has a partial structure represented by the following (General Formula 1). That is, it has an amide bond, a urea bond or a urethane bond.
  • the specific monofunctional monomer having the partial structure represented by the general formula 1 two or more sites to be polarized are close to each other. Therefore, mutual interaction becomes strong, and the polymer chains can be pseudo-crosslinked when they are contained in the polymer chain.
  • a more preferable embodiment of the specific monofunctional monomer has a partial structure represented by the following (General Formula 2). That is, it has an amide bond in which a hydrogen atom is bonded to an N atom, a urea bond in which a hydrogen atom is bonded to an N atom, a urethane bond or a carboxyl group in which a hydrogen atom is bonded to an N atom.
  • the specific monofunctional monomer having a partial structure represented by General Formula 2 has both a proton donor and an acceptor. Therefore, mutual interaction becomes strong, and the polymer chains can be pseudo-crosslinked when they are contained in the polymer chain.
  • the molecular weight of the specific polyfunctional monomer is preferably 200 or more and 1000 or less. This is because the ejection stability of the ink composition is improved by adjusting the ink viscosity of the ink composition.
  • the glass transition temperature of the cured product obtained by polymerizing the specific polyfunctional monomer is preferably 0 ° C. or lower. This is because the cured product of the ink composition is given rubber-like elongation and elasticity.
  • polyfunctional monomer having a hydroxyl group examples include 2-hydroxy-3-acryloyloxypropyl methacrylate, 1,6-hexanediol diglycidyl ether acrylate, and polyethylene glycol diglycidyl ether acrylate.
  • polyfunctional monomer having an amino group examples include phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (AH-600 manufactured by Kyoeisha Chemical Co., Ltd.), urethane acrylate oligomer (CN9002 manufactured by Sartomer Co.), and the following formula ( ⁇ ): And the like.
  • the polyfunctional monomer may contain other polyfunctional monomers other than the specific polyfunctional monomer.
  • examples of other polyfunctional monomers include polyfunctional (meth) acrylate compounds and polyfunctional vinyl ether compounds.
  • bifunctional (meth) acrylate compounds as other polyfunctional monomers include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, bisphenol A PO adduct di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polytetra Such as Chi glycol di (meth) acrylate.
  • tri- or higher functional (meth) acrylate compounds as other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate and the like are included.
  • the polyfunctional (meth) acrylate compound as another polyfunctional monomer may be a modified product.
  • modified products include ethylene oxide-modified (meth) acrylate compounds such as ethylene oxide-modified trimethylolpropane tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetraacrylate; caprolactone such as caprolactone-modified trimethylolpropane tri (meth) acrylate Modified (meth) acrylate compounds; and caprolactam-modified (meth) acrylate compounds such as caprolactam-modified dipentaerythritol hexa (meth) acrylate.
  • Examples of the other bifunctional vinyl ether compound as the polyfunctional monomer include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol vinyl ether, butylene divinyl ether, dibutylene glycol divinyl ether. And neopentyl glycol divinyl ether, cyclohexanediol divinyl ether, cyclohexane dimethanol divinyl ether, norbornyl dimethanol divinyl ether, isovinyl divinyl ether, divinyl resorcin, and divinyl hydroquinone.
  • Examples of other trifunctional vinyl ether compounds as polyfunctional monomers include glycerin trivinyl ether, glycerin ethylene oxide adduct trivinyl ether (addition mole number of ethylene oxide 6), trimethylolpropane trivinyl ether, trivinyl ether ethylene oxide adduct trivinyl ether (ethylene oxide). The number of added moles of 3) may be mentioned.
  • tetrafunctional or higher functional vinyl ether compounds as other polyfunctional monomers include pentaerythritol trivinyl ether, ditrimethylolpropane hexavinyl ether, and their oxyethylene adducts.
  • Allyl ether group diallyl phthalate, diallyl isophthalate and the like.
  • Styrene group examples include divinylbenzene.
  • (Meth) acrylamide group N, N-ethylenebisacrylamide and the like.
  • Preferred compounds include those having the above-mentioned acrylic group, methacryl group, vinyl ether group, and allyl ether group.
  • composition of a photocurable reactive compound contains a monofunctional monomer and a polyfunctional monomer.
  • the monofunctional monomer is a specific monofunctional monomer, or at least a part of the polyfunctional monomer is a specific polyfunctional monomer.
  • the total number of moles of hydroxyl groups and amino groups (mole fraction) with respect to the total number of moles of the monofunctional monomer and polyfunctional monomer is preferably 5 to 30%.
  • the cured product of the ink composition has rubber-like elongation and elasticity.
  • the mechanism is not particularly limited, but may be inferred as follows.
  • the polyfunctional monomer is polymerized into a polymer chain obtained by polymerizing the monofunctional monomer grown as a linear polymer. Is moderately incorporated to crosslink the polymer chains. Thereby, a rubber-like substance having high extensibility is obtained.
  • a rubbery material undergoes plastic deformation and rebound decreases when a high stress is applied.
  • the monofunctional monomer or polyfunctional monomer is a monomer having a hydroxyl group or an amino group. Hydroxyl or amino groups are polarized to ⁇ + or ⁇ . For this reason, a substituent that interacts electrostatically is introduced into the cured ink, and the cured ink is imparted with extensibility and resilience. That is, when stress is applied to the ink cured product, the electrostatic interaction in the cured product is released, and it behaves like a cured product with a low cross-linking rate, so that it greatly expands. When the stress is released, an electrostatic interaction occurs again, and a high resilience is exhibited like a cured product having a high crosslinking rate. As a result, a cured product having high elongation and resilience is obtained. Based on such knowledge, the ink composition of the present invention has been completed.
  • the ink composition of the present invention may further contain a photopolymerization initiator.
  • a photopolymerization initiator may ordinarily not be included.
  • a photopolymerization initiator is preferably contained.
  • the photopolymerization initiator includes a cleavage type and a hydrogen abstraction type.
  • the ink composition of the present invention preferably contains at least an open type photopolymerization initiator. That is, the ink composition of the present invention may contain (a) both a cleavage type and a hydrogen abstraction type photopolymerization initiator, and (b) contains only a cleavage type photopolymerization initiator. Also good. What is necessary is just to use properly the aspect of a photoinitiator according to the desired effect.
  • the ink composition contains (a) both a cleavage type and a hydrogen abstraction type photopolymerization initiator
  • the ratio of the hydrogen abstraction type initiator in the photopolymerization initiator is preferably 30% by mass or less, and more preferably 20% by mass or more and 30% by mass or less.
  • the curing rate of the inkjet ink composition increases.
  • the cleavage type and the hydrogen abstraction type coexist, it is considered that the polymerization rate is improved because the hydrogen abstraction type initiator functions as a sensitizer. This is important in 3D modeling printing, which takes much longer time than normal printing.
  • both the cleavage type and the hydrogen abstraction type photopolymerization start Compared with the case where an agent is contained, the stretchability or elasticity of the cured product of the ink composition may be improved.
  • the reason for this is not clear, but can be considered as follows.
  • a graft reaction occurs between linear polymers obtained by polymerization of monofunctional monomers with a hydrogen abstraction type initiator, irregular crosslinking may occur. If the cross-linking is regular, a uniform force is applied when the cured product is stretched, so that high stretchability can be maintained.
  • the ink composition contains (a) both of a cleavage type and a hydrogen abstraction type polymerization initiator.
  • a cleavage type photopolymerization initiator substantially no hydrogen abstraction type
  • Examples of the cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethyl) Acetophenones such as phenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 6-trimethylbenzoindiphenylphosphine oxide, etc. Acylphosphine oxide; benzyl and methyl phenylglyoxylate esters include.
  • hydrogen abstraction type photopolymerization initiators examples include benzophenones (benzophenone, N, N-diethylbenzophenone, etc.), thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, isopropoxychlorothioxanthone, etc.) And anthraquinones (ethyl anthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone, etc.), acridines (9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.) and the like.
  • the content of the photopolymerization initiator in the ink composition is preferably 0.01% by mass to 10% by mass, and 1.5% by mass or less, although it depends on the type of actinic ray or actinic ray curable compound. It is more preferable that This is because the monofunctional monomer is easily grown as a linear polymer.
  • the ink composition may further contain a photopolymerization initiator auxiliary agent or a polymerization inhibitor, if necessary.
  • the photopolymerization initiator assistant may be a tertiary amine compound, preferably an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included.
  • N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. Only one kind of these compounds may be contained in the actinic ray curable ink composition, or two or more kinds thereof may be contained.
  • polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone , Nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino- 1,3-Dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime
  • the ink composition may further contain a peeling accelerator in order to facilitate the peeling between the cured ink and the support agent described later.
  • the peeling accelerator is preferably contained in an amount of 0.01% by mass to 3.0% by mass with respect to the total mass of the ink. If it is less than 0.01% by mass, the releasability from the substrate is lowered, and if it exceeds 3.0% by mass, the droplets of the ink composition before curing are likely to coalesce, which may cause ink bleeding. is there.
  • release accelerator examples include silicon surfactants, fluorine surfactants, and higher fatty acid esters such as stearyl sebacate, and silicon surfactants are preferable.
  • the release accelerator may be contained in either the ink-jet ink composition or the support material composition described below, but is preferably contained in both.
  • the viscosity of the ink composition is preferably 150 mPa ⁇ s or less. This is because ink jetting cannot be used when the viscosity is high. It is because it can radiate
  • the glass transition temperature of the cured product (ink cured product) of the ink composition is preferably less than 25 ° C. This is to impart stretchability and resilience to stress, such as a rubber-like substance, to the cured product. In consideration of the temperature in winter, the glass transition temperature of the cured product of the ink composition is preferably 5 ° C. or less, preferably 0 ° C. or less, and more preferably less than ⁇ 25 ° C.
  • the manufacturing method of an image or a three-dimensional structure includes a step of discharging an ink composition onto a substrate or a support material, and a step of photocuring the ink composition. .
  • CAD data is converted into STL data that is data for three-dimensional structure; first plane data and second plane data based on the STL data
  • a plurality of plane data including: a model material ink composition and a support material ink composition are ejected onto a stage to form a first film based on the first plane data Photocuring the first film to form a first layer; based on the second plane data, either the model material ink composition or the support material ink composition is the first layer; Discharging onto one layer to form a second film; photocuring the second film to form a second layer; forming the second film until the final layer is laminated And repeating the step of obtaining the second layer A step of removing the support member.
  • the image or the three-dimensional structure is formed by a model material made of the ink composition according to the embodiment (hereinafter also referred to as “ink composition”).
  • the image or three-dimensional structure formed by the ink composition has rubber-like elongation and elasticity. Therefore, it is used not only for the shape of the prototype but also for confirming the function of the prototype.
  • the ink composition before curing and the ink composition after curing in the formation process (hereinafter also referred to as “cured product”) have different physical and chemical properties. Therefore, when forming an image or a three-dimensional structure, it is more preferable to use a support material, which will be described later, which is relatively easy to peel, in addition to the ink composition.
  • the three-dimensional modeling apparatus using an ink jet includes driving means (not shown) for driving up and down (in the drawing Z direction), and the three-dimensional modeling object is arranged. And an inkjet 12 that discharges the ink composition for the model material and the support material, which is arranged on a rail (not shown) so as to be movable in the left and right (XY direction in the drawing).
  • the inkjet 12 includes an inkjet head 13 for model material, an inkjet head 14 for support material, a film thickness adjusting roller 15, and a light irradiation means 16.
  • the model material inkjet head 13 communicates with the pump 13b and the ink tank 13c via a pipe 13a
  • the support material inkjet head 14 communicates with the pump 14b and the ink tank 14c via a pipe 14a.
  • the ink composition for a model material and the ink composition for a support material are photocured.
  • the actinic ray for photocuring is ultraviolet rays
  • examples of the actinic ray irradiation part include fluorescent tubes (low-pressure mercury lamps, germicidal lamps), cold cathode tubes, ultraviolet lasers, up to several hundred Pa to 1 MPa.
  • Low pressure, medium pressure, high pressure mercury lamp, metal halide lamp, LED and the like having the following operating pressure.
  • ultraviolet irradiation means for irradiating ultraviolet rays having an illuminance of 100 mW / cm 2 or more; specifically, high-pressure mercury lamps, metal halide lamps, and LEDs are preferable, and LEDs are more preferable from the viewpoint of low power consumption. Specifically, a 395 nm, water-cooled LED manufactured by Phoseon Technology can be used.
  • examples of the active light beam irradiation unit include electron beam irradiation units such as a scanning method, a curtain beam method, and a broad beam method.
  • a curtain beam type electron beam irradiation means is preferable.
  • Examples of electron beam irradiation means include “Curetron EBC-200-20-30” manufactured by Nissin High Voltage Co., Ltd., “Min-EB” manufactured by AIT Co., Ltd., and the like.
  • the acceleration voltage for electron beam irradiation is preferably 30 to 250 kV and more preferably 30 to 100 kV in order to perform sufficient curing.
  • the electron beam irradiation amount is preferably 30 to 100 kGy, and more preferably 30 to 60 kGy.
  • the three-dimensional modeling system is further converted from CAD data by an arithmetic control unit 2, an input device 4 for inputting three-dimensional modeling data such as CAD (Computer Aided Design) data, and the like.
  • CAD Computer Aided Design
  • output device 5 that outputs slice data obtained from STL data
  • display device 6 that displays STL data, virtual three-dimensional structure, and the like
  • a three-dimensional structure It has a storage device 3 for recording various information necessary, for example, a lot number, a CAD data number, an STL data number, an ink set number and the like in association with each other.
  • the calculation control unit 2 drives an STL calculation unit 21 that calculates STL data based on CAD data, an ink set control unit 22 that sends information to select an ink set suitable for a desired three-dimensional structure, and a stage.
  • Stage control means 23 for sending information to be transferred
  • ink jet control means 24 for sending information for discharging the ink composition for model material or support material
  • roller control means 25 for sending information for polishing the layer to a desired thickness.
  • UV light source control means 26 for sending information to irradiate UV to cure the ejected ink.
  • the arithmetic control unit 2 may be configured by an arithmetic device used in a normal computer system such as a CPU.
  • Examples of the input device 4 include pointing devices such as a keyboard and a mouse.
  • Examples of the output device 5 include a printer.
  • Examples of the display device 6 include an image display device such as a liquid crystal display and a monitor.
  • step S101 for example, CAD data is input.
  • step S102 the CAD data is converted into STL data as three-dimensional modeling data. Note that a virtual three-dimensional structure (virtual model material) formed from the STL data is displayed on the monitor to check whether a desired shape is formed. If the desired shape is not formed, the STL data Modifications may be made to.
  • step S103 as shown in FIG. 3, the virtual three-dimensional structure is finely divided into a plurality of lamellar layers in the Z direction of FIG. 3, and the first plane data D1, the second plane data D2, ... X-th plane data DX is obtained.
  • support material arrangement data for supporting or fixing the model material is also created. This is because the support material is disposed around the model material in the X and Y directions, so that a so-called overhang portion, for example, the second image portion of the letter “K” is supported from below by the support material.
  • step S105 an optimal ink composition for a model material and an ink composition for a support material are prepared based on data of a virtual three-dimensional structure and a plurality of plane data.
  • step S108 based on the first plane data D1, the driving means is operated to perform relative alignment between the stage and the inkjet.
  • step S110 the position of the ink jet is controlled based on the first plane data D1, and the ink composition for the model material and the ink composition for the support material are placed at appropriate positions on the stage. Either one of the objects is discharged to form the first film.
  • the amount of droplets ejected from each nozzle is preferably 1 pl to 70 pl, more preferably 2 to 50 pl, although it depends on the resolution of the image.
  • step S112 the first film is cured by irradiating actinic rays to obtain a first layer. Note that it is preferable to check whether or not the thickness of the first layer is uniform, and if it is not uniform, the thick portion is polished to make the thickness of the first layer uniform.
  • the thickness of each layer after curing is preferably about 2 to 25 ⁇ m.
  • Irradiation with actinic rays is performed within 10 seconds, preferably within 0.001 seconds to 5 seconds, more preferably after the ink droplets are deposited on the recording medium, in order to prevent adjacent ink droplets from coalescing. It is preferable to carry out within 0.01 second to 2 seconds.
  • the irradiation with actinic rays is preferably performed after ink is ejected from all the support material inkjet heads 14 accommodated in the head carriage.
  • step S114 the process returns to step S108 prior to the formation of the second layer, and the position of the stage 11 is moved downward (Z direction) by the thickness of the first layer as shown in FIG. Let Thereafter, similarly to the first layer, the second layer is formed on the first layer by steps S110 and S112. Then, as shown in FIGS. 6 and 7, the steps S108, S110, and S112 are repeated to stack a plurality of layers until the final layer (Xth layer) is stacked.
  • step S116 the support material is removed.
  • the support material is removed by swelling with water.
  • the support material may be removed from the model material by performing another removal step, for example, spraying high-pressure water on the support material.
  • a three-dimensional structure M as shown in FIG. 8 can be produced.
  • the ink composition for support material used for the manufacturing method of an image or a three-dimensional structure contains a water-soluble or water-swellable photocurable resin composition.
  • a photocurable resin composition mainly composed of a water-soluble ethylenic polymerizable compound, a water-soluble polymer, a photocleavable initiator, and water, but is not particularly limited.
  • Examples of the water-soluble or water-swellable photocurable resin composition include a water-soluble ethylenic polymerizable compound and a water-soluble acrylamide.
  • Examples of the water-soluble ethylenic polymerizable compound include water-soluble (meth) acrylate compounds, polyoxyethylene diacrylate, polyoxypropylene diacrylate, achloroylmorpholine, and hydroxyalkyl acrylate.
  • Examples of the water-soluble acrylamide include acrylamide, N, N-dimethylacrylamide, N-hydroxyethylacrylamide and the like.
  • water-soluble polymers examples include polyethylene glycol, polypropylene glycol, polyvinyl alcohol and the like.
  • photocleavable initiator examples include 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propan-1-one, but are not particularly limited.
  • the inkjet nozzle for the model material is shown, but the number of inkjet nozzles for the model material is not limited to one.
  • two inkjet nozzles may be provided for a model material, and model materials having different physical properties may be simultaneously discharged from each nozzle, and the model materials may be mixed to form a composite material.
  • Phenoxyethyl A Phenoxyethyl acrylate (Kyoeisha Chemical Co., Ltd. Light Acrylate PO-A) Phenoxy DEGA: Phenoxydiethylene glycol acrylate (Kyoeisha Chemical Co., Ltd.
  • Isodecyl A Isodecyl acrylate (SR-395 manufactured by Sartomer)
  • Isostearyl A Isostearyl acrylate (S-1800A manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Isobornyl A Isobornyl acrylate (SR-506, manufactured by Sartomer)
  • THFA Tetrahydrofurfuryl acrylate (SR-285 manufactured by Sartomer)
  • Benzyl A benzyl acrylate (V # 160, Osaka Organic Chemical Company)
  • HDDA 1,6-hexanediol diacrylate (A-HD-N manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • TEMPO 2,2,6,6-tetramethylpiperidinyl-N-oxyl
  • TPO phosphine oxide photoinitiator (manufactured by BASF)
  • Example 1 Preparation of Ink Composition 1
  • Ink composition 1 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 1 Phenoxyethyl acrylate ... 85.7g 1,6-hexanediol diacrylate ... 1.7g Urethane monomer ... 11.0g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 2 Preparation of Ink Composition 2
  • Ink composition 2 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 2 Phenoxyethyl acrylate ... 90.5g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 1.8g Isopropylacrylamide ... 6.1g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 3 Preparation of Ink Composition 3
  • Ink composition 3 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 3 Phenoxyethyl acrylate ... 89.6g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 1.8g Hydroxypropyl acrylate 7.0g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 4 Preparation of Ink Composition 4
  • Ink composition 4 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 4 Phenoxyethyl acrylate 84.7g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 1.6g Urethane compound 1 ... 12.1g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 5 Preparation of Ink Composition 5
  • Ink composition 5 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 5 Phenoxyethyl acrylate 84.1g Urethane compound 2 ... 14.3g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 6 Preparation of Ink Composition 6
  • Ink composition 6 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 6 Phenoxyethyl acrylate ... 91.2g 1,6-hexanediol diacrylate ... 1.9g Dimethylacrylamide ... 5.4g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 7 Preparation of Ink Composition 7
  • Ink composition 7 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 7 Phenoxyethyl acrylate 74.9g 1,6-hexanediol diacrylate ... 1.7g Urethane monomer ... 21.8g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 8 Preparation of Ink Composition 8
  • Ink composition 8 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 8 Phenoxyethyl acrylate ... 64.4g 1,6-hexanediol diacrylate ... 1.7g Urethane monomer ... 32.3g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 9 Preparation of Ink Composition 9
  • Ink composition 9 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 9 Phenoxyethyl acrylate ... 91.1g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 1.8g Urethane monomer 5.5g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 10 Preparation of Ink Composition 10
  • Ink composition 10 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 10 Phenoxyethyl acrylate ... 82.4g 1,6-hexanediol diacrylate ... 4.7g Urethane monomer ... 11.2g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 11 Preparation of Ink Composition 11
  • Ink composition 11 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 11 Phenoxyethyl acrylate ... 84.4g 1,6-hexanediol diacrylate ... 2.9g Urethane monomer ... 11.1g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 12 Preparation of Ink Composition 12
  • Ink composition 12 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 12 Phenoxyethyl acrylate ... 87.5g 1,6-hexanediol diacrylate ... 0.1g Urethane monomer ... 10.9g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 13 Preparation of Ink Composition 13
  • Ink composition 13 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 13 Phenoxyethyl acrylate 85.6g 1,6-hexanediol diacrylate ... 1.7g Urethane monomer ... 11.0g TEMPO ... 0.1g DAROCURE TPO ⁇ ⁇ ⁇ 1.6g
  • Example 14 Preparation of ink composition 14 The following components were mixed and dissolved to prepare an ink composition 14.
  • Composition of Ink Composition 14 Phenoxydiethylene glycol acrylate ... 87.8g 1,6-hexanediol diacrylate ... 1.5g Urethane monomer ... 9.2g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 15 Preparation of Ink Composition 15
  • Ink composition 15 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 15 Isodecyl acrylate ... 86.7g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 1.6g Urethane monomer ... 10.1g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 16 Preparation of Ink Composition 16
  • Ink composition 16 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 16 Isostearyl acrylate ... 90.4g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 1.1g Urethane monomer 6.9g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 17 Preparation of Ink Composition 17 An ink composition 17 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 17 Isobornyl acrylate ... 86.5g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 1.6g Urethane monomer ... 10.3g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 18 Preparation of Ink Composition 18 An ink composition 18 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 18 Tetrahydrofurfuryl acrylate ... 83.2g 1,6-hexanediol diacrylate ⁇ ⁇ ⁇ 2.1g Urethane monomer ... 13.2g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • Example 19 Preparation of Ink Composition 19
  • Ink composition 19 was prepared by mixing and dissolving the following components.
  • Composition of Ink Composition 19 Benzyl acrylate ... 83.6g 1,6-hexanediol diacrylate ... 2.0g Urethane monomer ... 12.8g TEMPO ... 0.1g DAROCURE TPO ... 1.5g
  • the ink compositions 1 to 23 of each Example and Comparative Example were applied on a glass substrate so as to have a thickness of 1 mm using an applicator, irradiated with light from a high-pressure mercury lamp at an illuminance of 100 mW / cm 2 for 10 seconds, and then glass. It peeled off from the board
  • Breaking elongation is 200% or more ⁇ : Breaking elongation is 150% or more and less than 200% ⁇ : Breaking elongation is 100% or more and less than 150% ⁇ : Breaking elongation is less than 100%
  • Break strength is 3 MPa or more ⁇ : Break strength is 2 MPa or more and less than 3 MPa ⁇ : Break strength is 1.5 MPa or more and less than 2 MPa ⁇ : Break strength is less than 1.5 MPa
  • Inks 1 to 23 of Examples and Comparative Examples were loaded into a UV curable printer equipped with a piezo head 512L manufactured by Konica Minolta IJ.
  • the head temperature was set to “75 ° C. or lower and the ink viscosity becomes 10 mPa ⁇ s”, or “75 ° C.” when the ink viscosity exceeds 10 mPa ⁇ s even at 75 ° C.
  • 1 L of ink was continuously ejected for 60 minutes under the conditions of a droplet amount of 42 pl and a frequency of 8 kHz. Then, the number of missing nozzles was counted to evaluate ink emission. Evaluation of ink emission was performed according to the following criteria. ⁇ : No missing nozzle occurred ⁇ : One or more missing nozzles occurred less than 3% of the whole ⁇ : Missing nozzles occurred 3% or more and less than 10% of the whole ⁇ : Missing nozzles occurred 10% or more of the whole
  • the ink composition of the present invention has photocurability, and the cured product has elongation and elasticity like rubber. Therefore, unique characteristics can be imparted to the image or three-dimensional structure obtained from the ink composition of the present invention.

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Abstract

　Cette invention concerne une composition d'encre, dont le produit durci possède l'allongement et l'élasticité du caoutchouc. La composition d'encre selon l'invention contient : un composé réactif de type à photodurcissement constitué d'un monomère monofonctionnel et d'un monomère polyfonctionnel ; et un amorceur de photopolymérisation, les fractions molaires du monomère monofonctionnel et du monomère polyfonctionnel, exprimées sous forme du rapport monomère monofonctionnel/ monomère polyfonctionnel, étant égales à 92/8-99,9/0,1. Le monomère monofonctionnel et/ou le monomère polyfonctionnel a des groupes hydroxyle ou des groupes amino, la fraction molaire des structures comportant les fragments précités représentant de 5 à 30 % de la quantité totale du monomère monofonctionnel et du monomère polyfonctionnel.
PCT/JP2014/005042 2013-10-03 2014-10-03 Composition d'encre, et procédé de formation d'images ou d'objets moulés tridimensionnels WO2015049873A1 (fr)

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