WO2022163358A1 - 三次元光造形用樹脂組成物 - Google Patents

三次元光造形用樹脂組成物 Download PDF

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Publication number
WO2022163358A1
WO2022163358A1 PCT/JP2022/000824 JP2022000824W WO2022163358A1 WO 2022163358 A1 WO2022163358 A1 WO 2022163358A1 JP 2022000824 W JP2022000824 W JP 2022000824W WO 2022163358 A1 WO2022163358 A1 WO 2022163358A1
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Prior art keywords
resin composition
pattern
dimensional
cured product
liquid film
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English (en)
French (fr)
Japanese (ja)
Inventor
功治 渡部
達也 渡海
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Nagase Chemtex Corp
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Nagase Chemtex Corp
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Priority to JP2022578217A priority Critical patent/JPWO2022163358A1/ja
Priority to US18/262,686 priority patent/US20240117097A1/en
Publication of WO2022163358A1 publication Critical patent/WO2022163358A1/ja
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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/76—Cores
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/40—Removing or ejecting moulded articles
    • B29C45/44—Removing or ejecting moulded articles for undercut articles
    • B29C45/4457—Removing or ejecting moulded articles for undercut articles using fusible, soluble or destructible cores
    • 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
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/35—Cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y80/00—Products made by 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • 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
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
    • B29C2071/0045—Washing using non-reactive liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0085—Copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/007—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/757—Moulds, cores, dies

Definitions

  • the present invention relates to a resin composition for three-dimensional stereolithography, and further to a method for producing a three-dimensional structure using the resin composition.
  • Three-dimensional printers particularly ink-jet type three-dimensional printers, often use a water-soluble UV curable material as a support material.
  • Such conventional water-soluble UV-curable materials often contain a large amount of water-soluble solvent in order to maintain water-solubility, resulting in problems such as low hardness and heat resistance.
  • problems such as low hardness and heat resistance.
  • the water solubility is impaired.
  • Patent Documents 1 and 2 disclose resin compositions containing reactive monomers and water-soluble polymers. However, since it is assumed to be used as a support material to be molded together with model materials, it contains a large amount of water-soluble organic solvent and the glass transition temperature of the cured product is low, so the hardness and heat resistance of the cured product are low. It was something.
  • An object of the present invention is to provide a resin composition that is water-soluble and yet capable of producing a three-dimensional stereolithographic article with high heat resistance.
  • the present inventors have investigated the contradictory characteristics of high heat resistance despite high water solubility, and found that a highly crosslinked polymer containing a reactive monomer, a water-soluble polymer, and a photopolymerization initiator can be obtained.
  • the present inventors have found that a resin composition for three-dimensional stereolithography that gives a cured product that is easily soluble in water can be obtained by increasing the main peak temperature of tan ⁇ of the cured product.
  • the present invention provides a three-dimensional stereolithography resin composition
  • a three-dimensional stereolithography resin composition comprising a reactive monomer, a water-soluble polymer and a photopolymerization initiator, wherein the cured product has a main peak temperature of tan ⁇ of 80° C. or higher and a thickness of 1 mm.
  • the resin composition for three-dimensional stereolithography has a remaining thickness of 0.7 mm or less after immersing the cured product in water at room temperature for 5 hours.
  • the reactive monomer is preferably a reactive monomer having a glass transition temperature of 80° C. or higher when converted into a homopolymer.
  • the Shore D hardness after curing is preferably 60 or more.
  • it preferably contains a divalent metal salt of a carboxylic acid having a polymerizable functional group.
  • the present invention also relates to a cured product of the resin composition for three-dimensional stereolithography.
  • the cured product is preferably a core for injection molding.
  • the present invention provides (i) forming a first liquid film made of the resin composition and curing the first liquid film to form a first pattern; (ii) It relates to a method for manufacturing a three-dimensional structure, including the step of forming a second liquid film made of the resin composition so as to be in contact with the first pattern, curing the second liquid film, and laminating the second pattern. .
  • the manufacturing method preferably further includes the step of washing the first pattern and the second pattern with a solvent having a Hansen solubility parameter of 25 MPa 0.5 or less.
  • the present invention relates to a method for preserving a cured product, comprising the step of allowing the cured product to stand at a relative humidity of 40 to 60%.
  • the resin composition for three-dimensional stereolithography of the present invention it is possible to obtain a three-dimensional stereolithographic object that has both the contradictory properties of water solubility and high heat resistance.
  • FIG. 2 is a schematic diagram for explaining the process of forming a modeled object by stereolithography using the resin composition for three-dimensional modeling according to one embodiment of the present invention.
  • the resin composition for three-dimensional stereolithography of the present invention contains a reactive monomer, a water-soluble polymer and a photopolymerization initiator, has a main peak temperature of tan ⁇ of the cured product of 80° C. or higher, and has a thickness of 1 mm. and a remaining thickness of 0.7 mm or less after being immersed in water at room temperature for 5 hours.
  • the reactive monomer is preferably a monomer whose homopolymer has a glass transition temperature of 80° C. or higher.
  • the glass transition temperature is preferably 85°C or higher, more preferably 100°C or higher. If it is less than 80°C, the heat resistance will be poor.
  • the glass transition temperature may be obtained by actually polymerizing a homopolymer and measuring the glass transition temperature, or by calculation using the atomic group contribution method.
  • a reactive monomer is a photocurable monomer that can be cured or polymerized by the action of radicals or ions generated by light irradiation.
  • a monomer having a polymerizable functional group is preferred.
  • the number of polymerizable functional groups in the photocurable monomer is preferably 1 to 8.
  • the polymerizable functional group include a group having a polymerizable carbon-carbon unsaturated bond such as a vinyl group and an allyl group, and an epoxy group.
  • radically polymerizable monomers such as (meth)acrylic monomers, cationic polymerizable monomers such as epoxy-based monomers, vinyl-based monomers, and diene-based monomers are included.
  • (meth)acrylic monomers and vinyl monomers are preferred from the viewpoint of reaction rate, and monofunctional (meth)acrylic monomers and monofunctional vinyl monomers are preferred so as not to increase the crosslink density.
  • (Meth)acrylic monomers include monomers having a (meth)acryloyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, (meth) ) cyclohexyl acrylate, benzyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, ethyl carbitol (meth) acrylate, (Meth)acrylic esters such as hydroxyethyl methacrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, methoxyethyl (me
  • (meth)acrylic acid amide is preferable in terms of reaction rate.
  • (meth)acrylic acid amides (meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and dimethylaminopropylacrylamide are preferred.
  • acrylic acid and methacrylic acid are referred to as (meth)acrylic acid
  • acrylic acid ester (or acrylate) and methacrylic acid ester (or methacrylate) are referred to as (meth)acrylic acid ester (or (meth)acrylate).
  • vinyl-based monomers examples include vinyl ethers such as polyol poly(vinyl ether), aromatic vinyl monomers such as styrene, and vinylalkoxysilanes.
  • polyols constituting polyol poly(vinyl ether) examples include polyols (butanediol) exemplified for acrylic monomers.
  • diene-based monomers include isoprene and butadiene.
  • Epoxy-based monomers include compounds having two or more epoxy groups in the molecule.
  • Epoxy-based monomers include, for example, compounds containing an epoxycyclohexane ring or a 2,3-epoxypropyloxy group.
  • the content of the reactive monomer in the three-dimensional stereolithography resin composition of the present invention is not particularly limited, but is preferably 99.5 to 1% by mass, more preferably 90 to 60% by mass. If it is less than 1% by mass, the resin tends to have high viscosity, and if it exceeds 99.5% by mass, curing shrinkage tends to increase.
  • Photoinitiators are activated by the action of light to initiate polymerization of reactive monomers.
  • the photopolymerization initiator for example, in addition to radical polymerization initiators that generate radicals by the action of light, those that generate base (or anion) or acid (or cation) by the action of light (specifically, anion generator, cation generator).
  • the photoinitiator can be selected according to the type of photocurable monomer, for example, whether it is radically polymerizable or ionically polymerizable.
  • radical polymerization initiators include alkylphenone-based photopolymerization initiators and acylphosphine oxide-based photopolymerization initiators.
  • alkylphenone polymerization initiators examples include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane.
  • acylphosphine oxide polymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
  • the amount of the photopolymerization initiator added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the reactive monomer. If it is less than 0.01 part by weight, it tends to cause poor curing, and if it exceeds 10 parts by weight, it tends to cause poor storage stability and poor curing due to absorption.
  • the water-soluble polymer is a polymer that swells or dissolves in water, such as polyalkylene glycol, polyvinyl alcohol, modified polyvinyl alcohol (polyvinyl alcohol/polyacrylate block copolymer, grafted polyvinyl alcohol, etc.), polyester, hydroxymethyl cellulose, Hydroxyethylcellulose, hydroxypropylcellulose, polyvinylpyrrolidone, vinylpyrrolidone-vinylimidazole copolymer, water-soluble alkyd resin, salt of copolymer containing (meth)acrylic acid (sodium salt, amine salt, etc.), ethylenic side chain Examples include water-soluble polymers having double bonds.
  • the weight average molecular weight of the water-soluble polymer is not particularly limited, but is preferably from 500 to 1,000,000, more preferably from 500 to 100,000. If it exceeds 1,000,000, the water solubility of the cured product tends to be impaired, or the solubility in monomers tends to decrease significantly.
  • the weight ratio of the reactive monomer to the water-soluble polymer is preferably 99.5/0.5 to 1/99, more preferably 60/40 to 95/5. If the reactive monomer is more than 99.5, curing shrinkage tends to increase, and if it is less than 1, the resin tends to have high viscosity.
  • the content of the water-soluble polymer in the three-dimensional stereolithography resin composition of the present invention is not particularly limited, but is preferably 0.5 to 99% by mass, more preferably 5 to 40% by mass. If it is less than 0.5% by mass, curing shrinkage tends to increase, and if it exceeds 99% by mass, the viscosity of the resin tends to be high.
  • the resin composition preferably further contains a divalent metal salt of a carboxylic acid having a polymerizable functional group. Heat resistance is improved by containing the metal salt.
  • a (meth)acryl group etc. are mentioned as a polymerizable functional group.
  • Metal salts include magnesium salts, zinc salts, calcium salts and the like. Specific examples include magnesium (meth)acrylate, zinc (meth)acrylate and calcium (meth)acrylate.
  • the amount of the divalent metal salt of carboxylic acid having a polymerizable functional group to be added is preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, per 100 parts by weight of the total of the reactive monomer and the water-soluble polymer. If it is less than 1 part by weight, the heat resistance may be insufficient, and if it exceeds 10 parts by weight, the monomer solubility tends to deteriorate.
  • the resin composition may further contain other known curable resins.
  • the curable resin composition can contain known additives such as dyes, UV sensitizers, polymerization inhibitors, plasticizers, UV absorbers, pigments and surfactants.
  • the resin composition is preferably liquid at room temperature. Since the resin composition is liquid at room temperature, stereolithography can be easily performed using a 3D printer or the like.
  • the viscosity of the curable resin composition at 25° C. is preferably 5000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less.
  • the viscosity of the resin composition can be measured using a cone-plate E-type viscometer at a rotational speed of 20 rpm.
  • the main peak temperature of tan ⁇ of the cured product is 80° C. or higher, preferably 100° C. or higher, more preferably 120° C. or higher. If it is less than 80°C, the heat resistance becomes insufficient.
  • tan ⁇ is the Tg measured using a dynamic viscoelasticity measurement device (DMA). Measurement can be performed while the cured product is heated from a low temperature side to a high temperature side (for example, from -100°C to +200°C). If there are multiple peaks, the peak temperature of the larger peak (main peak) is used.
  • DMA dynamic viscoelasticity measurement device
  • the deformation start temperature of the cured product is preferably 30° C. or higher, more preferably 50° C. or higher, and even more preferably 80° C. or higher. If it is less than 30°C, the heat resistance becomes insufficient.
  • the deformation start temperature is the temperature at 1% strain measured using a dynamic viscoelasticity measurement device (DMA). Measurement can be performed while the cured product is heated from a low temperature side to a high temperature side (for example, from -100°C to +200°C).
  • DMA dynamic viscoelasticity measurement device
  • the remaining thickness after immersing a cured product having a thickness of 1 mm in water at room temperature for 5 hours is 0.7 mm or less, preferably 0.5 mm or less. 0 mm or less (that is, complete dissolution) is more preferable. If it exceeds 0.7 mm, the water solubility will be insufficient.
  • the Shore D hardness of the cured product is 60 or more, preferably 70 or more, more preferably 80 or more. If it is less than 60, the strength tends to be insufficient.
  • the Shore D hardness is measured using a type D durometer in accordance with JIS K7215:1986.
  • the elastic modulus Er of the cured product at 80° C. is preferably 0.01 GPa or more, more preferably 0.1 GPa or more, and even more preferably 1 GPa or more. If it is less than 0.01 GPa, the strength is insufficient.
  • the elastic modulus Er at 25° C. is preferably 0.1 GPa or more, more preferably 1 GPa or more. If the elastic modulus Er of the cured product at 25°C is less than 0.1 GPa, the strength is insufficient.
  • the elastic modulus Er can be measured by a viscoelasticity measuring device.
  • the resin composition for three-dimensional stereolithography of the present invention can form a two-dimensional or three-dimensional model (or pattern) by various modeling methods, and is particularly suitable for stereolithography. Since the resin composition for three-dimensional stereolithography is liquid at room temperature, it may be used for, for example, vat-type stereolithography or inkjet-type stereolithography.
  • the method for manufacturing a three-dimensional structure of the present invention includes: (i) a step of forming a first liquid film made of the three-dimensional stereolithography resin composition of the present invention and curing the first liquid film to form a first pattern; (ii) Forming a second liquid film made of the three-dimensional stereolithography resin composition of the present invention so as to be in contact with the first pattern, and curing the second liquid film to laminate the second pattern. characterized by
  • FIG. 1 shows an example of forming a three-dimensional structure using a stereolithography apparatus (patterning apparatus) having a resin tank (bat).
  • the hanging type modeling is shown, but the method is not particularly limited as long as the method is capable of three-dimensional stereolithography using a resin composition.
  • the method of light irradiation (exposure) is not particularly limited, and point exposure or surface exposure may be used.
  • the stereolithography apparatus 1 includes a platform 2 having a pattern forming surface 2a, a resin tank 3 containing a curable resin composition 5, and a projector 4 as a surface exposure type light source.
  • step (i) Step of forming a first liquid film and curing it to form a first pattern
  • step (i) as shown in FIG.
  • the pattern formation surface 2a of the platform 2 is immersed in the composition 5 in a state facing the projector 4 (bottom surface of the resin bath 3).
  • the height of the pattern formation surface 2a (or the platform 2) is adjusted so that the liquid film 7a (liquid film a) is formed between the pattern formation surface 2a and the projector 4 (or the bottom surface of the resin tank 3). to adjust.
  • the liquid film 7a is irradiated with light L from the projector 4 (surface exposure), thereby photocuring the liquid film 7a and forming a first pattern 8a (pattern a).
  • the resin tank 3 serves as a supply unit for the curable resin composition 5 .
  • At least a portion of the resin tank (bottom surface in FIG. 1) between the liquid film and the projector 4 is preferably transparent to the exposure wavelength so that the liquid film is irradiated with light from the light source.
  • the shape, material, size, etc. of the platform 2 are not particularly limited.
  • the liquid film a is photo-cured by irradiating the liquid film a with light from a light source.
  • Light irradiation can be performed by a known method.
  • the exposure method is not particularly limited, and may be point exposure or surface exposure.
  • a known light source used for photocuring can be used as the light source.
  • a plotter method, a galvano laser (or galvano scanner) method, an SLA (stereolithography) method, and the like can be used.
  • a projector is preferable as the light source in terms of simplicity.
  • Examples of projectors include an LCD (transmissive liquid crystal) system, an LCoS (reflective liquid crystal) system, and a DLP (registered trademark, Digital Light Processing) system.
  • the exposure wavelength can be appropriately selected according to the constituent components of the curable resin composition (in particular, the type of initiator).
  • step (ii) Forming a second liquid film so as to be in contact with the first pattern, and curing the second liquid film to laminate the second pattern. and a light source to form a liquid film (liquid film b). That is, the liquid film b is formed on the pattern a formed on the pattern forming surface.
  • the supply of the curable resin composition is the same as in step (i).
  • the first pattern forming surface 2a may be lifted together with the platform 2 .
  • the liquid film 7b liquid film b
  • the formed liquid film b is exposed from a light source to photo-cure the liquid film b, and another pattern (pattern b obtained by photo-curing of the liquid film b) is laminated on the first pattern a.
  • pattern b obtained by photo-curing of the liquid film b
  • a three-dimensional fabrication pattern can be formed.
  • the liquid film 7b (liquid film b) formed between the first pattern 8a (pattern a) and the bottom surface of the resin tank 3 is exposed from the projector 4.
  • the liquid film 7b is photo-cured. This photocuring converts the liquid film 7b into a second pattern 8b (pattern b).
  • the second pattern 8b can be laminated on the first pattern 8a.
  • the description of step (i) can be referred to.
  • Step (ii) can be repeated multiple times. By repeating this, a plurality of patterns b are laminated in the thickness direction, and a more three-dimensional modeling pattern is obtained. The number of repetitions can be appropriately determined according to the shape and size of a desired three-dimensional structure (three-dimensional structure pattern).
  • the platform 2 with the first pattern 8a (pattern a) and the second pattern 8b (pattern b) laminated on the pattern forming surface 2a is raised.
  • a liquid film 7b (liquid film b) is formed between the second pattern 8b and the bottom surface of the resin tank 3 .
  • the projector 4 exposes the liquid film 7b to photo-harden the liquid film 7b.
  • another pattern 8b (pattern b) is formed on the first pattern 8b.
  • a plurality of patterns 8b (two-dimensional patterns b) can be stacked.
  • the method for manufacturing a three-dimensional structure of the present invention further includes a step of washing the first pattern and the second pattern with a solvent. Since an uncured curable resin composition adheres to the obtained three-dimensional modeled pattern, this is performed to remove the composition.
  • the solvent preferably has a Hansen solubility parameter of 25 MPa 0.5 or less. Specific solvents include 3-methoxy-3-methyl-1-butanol.
  • the obtained three-dimensional structure pattern may be subjected to post-curing, if necessary.
  • Post-curing can be performed by irradiating the pattern with light.
  • the conditions for light irradiation can be appropriately adjusted according to the type of resin composition and the degree of curing of the obtained pattern.
  • Post-curing may be performed on a part of the pattern or may be performed on the entire pattern.
  • the three-dimensional stereolithographic article obtained from the cured product of the resin composition for three-dimensional stereolithography of the present invention and the three-dimensional article obtained by the method for producing the three-dimensional article of the present invention can be used in various applications. can be used. Since it is excellent in water solubility and heat resistance, it can be suitably used as a model material. Examples include sacrificial molds, injection molds, and casting molds.
  • the sacrificial mold includes a core for injection molding, a sacrificial mold for thermosetting resin, and the like.
  • a sacrificial mold for thermosetting resin is formed from a cured product of a resin composition for three-dimensional stereolithography and used as a curable resin.
  • the sacrificial mold of curable resin is to be dissolved and removed after the curable resin is cured and molded.
  • Curable resins include urethane resins, epoxy resins, silicone resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, diallyl phthalate resins, acrylic resins, and alkyd resins.
  • the curable resin may be photocurable or thermosetting.
  • the method for preserving a cured product of the present invention is characterized by including the step of allowing the cured product to stand at a relative humidity of 40 to 60%. If it is less than 40%, the moisture in the cured product may escape and cracks may occur in the cured product, and if it is higher than 60%, the material properties may change due to moisture absorption.
  • the storage temperature is not particularly limited, 15 to 40°C is preferable.
  • Examples 1-9 and Comparative Examples 1-3 A reactive monomer, a water-soluble polymer, and a photopolymerization initiator were mixed according to the respective components and blending amounts shown in Table 1.
  • a uniform liquid resin composition was prepared by heating in an oven at 80° C. with stirring to dissolve the solid components. The following evaluation was performed using the obtained resin composition. Table 1 shows the evaluation results.
  • DVA-2000 manufactured by IT Keisoku Co., Ltd.
  • the temperature at which tan ⁇ reached the top peak was determined as the Tg of the cured product of the resin composition.
  • the peak temperature of the larger peak Tg of the matrix polymer
  • the temperature at which the film was elongated by 1% was taken as the deformation start temperature.
  • ⁇ Water solubility> Using the method described in ⁇ tan ⁇ peak temperature, elastic modulus Er, and deformation start temperature>, a glass plate having a thickness of about 1 mm and having a cured product formed on one side thereof was produced. The film thickness was measured after immersion in 100 g of water at room temperature for 5 hours. It was evaluated according to the following evaluation criteria. ⁇ : Film thickness is 0.7 mm or less ⁇ : Film thickness is over 0.7 mm
  • the resin compositions of Examples 1 to 9 had a high tan ⁇ main peak temperature, a high elastic modulus at 80° C., and excellent water solubility.
  • the main peak temperature of tan ⁇ was low, and the elastic modulus at 80° C. could not be measured.
  • the resin compositions of Comparative Examples 2 and 3 had a low main peak temperature of tan ⁇ and a high elastic modulus at 80° C., but were gelled and did not have water solubility.
  • ⁇ Washability> The resin composition prepared in Example 2 was evaluated for washability as follows. 1 g of the composition before curing was immersed in 100 ml each of ethanol or 3-methoxy-3-methyl-1-butanol (Solfit FG, manufactured by Kuraray Co., Ltd.) at room temperature for 10 minutes, and then the composition was dissolved. It was visually evaluated whether or not there was any. In addition, a strip-shaped cured product prepared using the method described in ⁇ Shore D hardness> was immersed in 100 ml each of ethanol or 3-methoxy-3-methyl-1-butanol at room temperature for 10 minutes, and then cured. The stickiness and appearance of the product were evaluated by touch and visual observation, respectively.
  • stereolithography device 2 platform 2a: pattern forming surface 3: resin tank 4: projector 5: curable resin composition 6: release agent layer 7a: liquid film a 7b: liquid film b 8a: First pattern a 8b: second pattern b L: light

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JPH04123834A (ja) * 1990-09-14 1992-04-23 Nissan Motor Co Ltd 鋳造用砂中子の製造方法
JP2012111226A (ja) * 2010-11-01 2012-06-14 Keyence Corp インクジェット光造形法における、光造形品形成用モデル材、光造形品の光造形時の形状支持用サポート材および光造形品の製造方法
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