Classifications

• • 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
• • 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
  • B29C64/307—Handling of material to be used in additive manufacturing
  • B29C64/314—Preparation
• • 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
  • B33Y40/10—Pre-treatment
• • 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
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • 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
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
• • 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
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • 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
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • 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
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0032—Pigments, colouring agents or opacifiyng agents

Definitions

• the invention belongs to the technical field of three-dimensional molding, and in particular relates to a photocurable transparent ink composition for three-dimensional molding, a preparation method and application thereof.
• the three-dimensional molding ink can be classified into a photocurable ink and a temperature-curable ink depending on the curing source.
• the temperature-curing ink usually contains a wax component which cures the ink by lowering the ambient temperature below the melting temperature of the wax; however, the temperature-curing ink needs to be strictly controlled for the ink-jet printing temperature, and the printed article is easily melted at a high temperature. Defects such as deformation, so that it is limited in application range.
• the photocurable ink usually contains a photoinitiator and a photocuring agent (such as an oligomer/oligomer, a monomer, etc.), and the photoinitiator is excited to generate a radical or a cation under the irradiation of light, and the radical or cation promotes photocuring.
• a photoinitiator such as an oligomer/oligomer, a monomer, etc.
• the photoinitiator is excited to generate a radical or a cation under the irradiation of light, and the radical or cation promotes photocuring.
• the polymerization takes place to cure the ink.
• the three-dimensional molding ink can be classified into cyan ink, magenta ink, yellow ink, black ink, white ink, and clear ink (ie, no or basic). Inks containing no dyes and/or pigments, etc. Transparent ink printing products are prone to yellowing.
• the main triggers of yellowing include: 1) the quinone structure produced by the photoinitiator in the ink after decomposition causes yellowing of the printed product; 2) the photoinitiator itself has yellow color, In the photocuring process, the photoinitiator does not completely react, and the residual photoinitiator causes yellowing of the printed product; 3) the photoactive initiator has a higher activity of free radicals generated after the light irradiation, resulting in the molecular chain breakage of the polymerized polymer in the ink.
• Conjugated structure of the substance, thereby causing yellowing of the printed article 4) aging of the main resin component in the ink to produce a conjugated double bond, a carbonyl group, a nitrogen-containing group, etc., a certain number of conjugated double bonds, and a carbonyl group or
• the leucoamines produced by the decomposition of the nitrogen group material cause the printed article material to yellow.
• Transparent inks have long been a difficult point in the research of three-dimensional molding inks due to various factors that cause yellowing of transparent ink printing products.
• the invention provides a photocurable transparent ink composition for three-dimensional molding, a preparation method and application thereof, and the photocurable transparent ink composition for three-dimensional molding can avoid yellowing of a printed product, and make the printed product whiter, more transparent and more Bright appearance.
• the invention provides a photocurable clear ink composition for three-dimensional molding, comprising the following components by weight: 60-125 parts of photocuring agent, 0.01-5 parts of yellowing regulator, 0.5-5 parts of photoinitiator and auxiliary agent 0.5 to 5 parts; wherein the yellowing modifier is capable of absorbing light in a wavelength range of 560 nm to 650 nm to make the photocurable clear ink composition for three-dimensional molding transparent.
• the light in the wavelength range of 560 nm to 650 nm is yellow light and light similar to yellow light (for example, yellow-green light, etc.); the yellowing modifier can absorb light in the wavelength range of 560 nm to 650 nm, that is, can reflect the wavelength range of 560 nm to 650 nm. Complementary light of light (such as blue light and violet light).
• the photocurable clear ink composition for three-dimensional molding of the present invention overcomes the yellowing problem of a printed product by adding a yellowing modifier capable of absorbing light in a wavelength range of 560 nm to 650 nm, which is not subject to yellowing.
• the limitation of the triggering factor can not only solve the yellowing problem caused by various triggering factors, but also has low color requirements for the components of the ink composition, and expands the selection range of raw materials of the ink composition.
• the yellowing modifier can absorb light in the wavelength range of 560 nm to 650 nm, that is, the maximum absorption peak of the yellowing modifier is 560 nm to 650 nm; in the present invention, the maximum absorption peak is the Shimadzu UV-2450 ultraviolet light.
• the spectrophotometer was measured, wherein the test sample cell had an optical path of 10 mm.
• the present invention does not strictly limit the specific type of the yellowing modifier.
• it may be selected from a photocurable oligomer having a maximum absorption peak of 560 nm to 650 nm capable of photocuring reaction with a photocuring agent, and may not be photocured with a photocuring agent.
• the maximum absorption peak of the reaction is one or more of a colorant of 560 nm to 650 nm and a compound having a maximum absorption peak of reducing property of 560 nm to 650 nm.
• the photocurable oligomer having a maximum absorption peak of 560 nm to 650 nm may be a blue phase (ie, blue) acrylate oligomer; for example, CNUVE 151NS of Sartomer Corporation, DR-W402, DR-W403 of Changxing Company, DR-W406HV and so on.
• the colorant having a maximum absorption peak of from 560 nm to 650 nm may be one or more of a dye and a pigment, and the weight fraction of the ink composition is ⁇ 0.02 parts; and the content of the colorant in the present invention is a solid of the colorant itself Calculated by content; preferably, the colorant may be a self-dispersing nano-scale organic pigment paste, such as azo lake red PR57: 1, Jinguanghong PR21, Jinguanghong PR53: 1, fast-light red PR 48: 1, resistant Sun Red PR48: 2, Lisol Red PR49: 1, Lisol Red PR49: 2, Pigment Red G (PR37), Pigment Red 171 (PR171), Pigment Red PR122, Pigment Purple PL (PV23), Phthalocyanine Blue (PB15:3, PB15:4), anthrone (PB60), and the like.
• azo lake red PR57 1, Jinguanghong PR21, Jinguanghong PR53: 1, fast-light red PR 48: 1, resistant
• the compound having a maximum absorption peak of reducing property of from 560 nm to 650 nm may be, for example, methylene blue, Co water or the like.
• the photocuring agent may have no absorption peak between 350 nm and 700 nm, and the photocuring agent is colorless and transparent.
• the photocuring agent may also have a weak absorption peak, and when the photocuring agent has a weak absorption peak, the light transmittance of the photocuring agent is ⁇ 80%; at this time, the photocuring agent may be slightly yellow or a color similar to yellow light.
• the photocuring agent may be selected from one or more of a photocurable oligomer and a photocurable monomer; preferably, the photocuring agent includes a photocurable oligomer and a photocurable monomer, and the light
• the mass ratio of the photocurable oligomer to the photocurable monomer in the curing agent may be (35-65): (25-60).
• the photocurable oligomer may be a transparent photocurable oligomer
• the photocurable monomer may be a transparent photocurable monomer.
• the photocuring agent is in an amount of from 90 to 95 parts by weight in the photocurable clear ink composition for three-dimensional molding.
• the mass content of the photocurable oligomer can be controlled to be more than 35% of the total mass of the ink composition, and the ink composition has a small shrinkage of the printed article during the photocuring reaction, thereby avoiding polymerization when a large amount of monomers are used. The resulting contraction.
• the transparent photocurable oligomer may be a transparent acrylate oligomer, a transparent epoxy oligomer, or the like.
• the transparent acrylate oligomer may be an aliphatic urethane acrylate oligomer, an epoxy acrylate oligomer, a pure acrylate oligomer, a silicone acrylate oligomer, or the like.
• the aliphatic urethane acrylate oligomer refers to an oligomer having a linear structure and a urethane bond-NHCOO- in a molecular structure, which is capable of forming a plurality of hydrogens between the polymer chains.
• the bond so that the cured film has excellent wear resistance, flexibility and elongation at break, and the overall performance is better.
• the aliphatic urethane acrylate oligomer may be, for example, CN966J75 NS, CN8007 NS, CN8011 NS, CN9006 NS, CN9007, CN9010 NS, CN9178 NS, CN963B80, CN985B88, etc.
• the epoxy acrylate oligomer can be obtained by ring-opening esterification of an epoxy resin with acrylic acid, which has high rigidity, strength and thermal stability; preferably, epoxy acrylate
• the polymer may be bisphenol A epoxy acrylate, such as CN104 NS, CN104A80 NS, CN101 NS, CN115 NS of Sartomer Corporation; 621A-80, 6219-100, 624B-80, etc. of Changxing Company of Taiwan.
• the pure acrylate oligomer has good flexibility and solvent resistance, and has good adhesion to various substrates.
• the pure acrylate oligomer may be, for example, 6530B-40, DR-A815, DR-A830, DR-A845, DR-A870, etc. of Changxing Company of Taiwan.
• the silicone acrylate oligomer is an acrylate polymer having a Si-O bond as a main chain structure, and has characteristics of low yellowing, low viscosity, low odor, and the like.
• the silicone acrylate oligomer may be EB350, EB1360 of Cytec; 6225 of Changxing Company; B-816, B-818 of Boxing Technology; EB350, EB1360 of Eusby.
• the transparent epoxy oligomer is an oligomer used in a cationic system, preferably an aliphatic epoxy resin, which has low odor, low viscosity and shrinkage, and has good flexibility and abrasion resistance. It has the advantages of good transparency and excellent adhesion to plastics and metals.
• the transparent epoxy oligomer may be Dow Chemical's UVR6110, UVR6105, UVR6128, UVR6100, UVR6216; Eusper's UVACURE 1500, UVACURE 1534, UVACURE 156, and the like.
• the transparent photocurable monomer may be a transparent acrylate monomer, a cationic monomer or the like.
• the transparent acrylate monomer may be an acrylate monomer having no benzene ring structure, thereby avoiding yellowing and aging of the printed product.
• the transparent acrylate monomer may be an aliphatic acrylate monomer, and the number of conjugated bonds contained in the acrylate monomer is preferably not more than 5, and the acrylate monomer may not contain 5 or more.
• the aliphatic acrylate monomer may be selected from one of a monofunctional aliphatic acrylate monomer, a difunctional aliphatic acrylate monomer, a polyfunctional aliphatic acrylate monomer, and a cycloalkane acrylate monomer. kind or more.
• the monofunctional aliphatic acrylate monomer may be the following monomers: isodecyl acrylate, such as EM219, EM2191, EM309, etc. of Taiwan Changxing Co., Ltd.; lauryl acrylate, such as EM215 of Changxing, Taiwan; ethoxy ethoxylate B Oxyethyl esters, such as EOEOEA of DSM Corporation, EM211 of Changxing, and the like.
• the difunctional aliphatic acrylate monomer may be the following monomers: a difunctional propylene glycol diacrylate such as dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA); other glycol diacrylates
• a difunctional propylene glycol diacrylate such as dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA); other glycol diacrylates
• DPGDA dipropylene glycol diacrylate
• TPGDA tripropylene glycol diacrylate
• 1,6-hexanediol diacrylate (HDDA) may be SR238 NS of Sartomer, EM221 of Changxing, HDDA of DSM, and the like.
• the trifunctional aliphatic acrylate monomer may be ethoxylated trimethylolpropane triacrylate (TMPTA), propoxyglycerol triacrylate, etc.; wherein ethoxylated trimethylolpropane triacrylate (TMPTA) may be Changxing For EM2382, etc., propoxyglycerol triacrylate can be Changxing EM2387 and the like.
• TMPTA trimethylolpropane triacrylate
• TMPTA ethoxylated trimethylolpropane triacrylate
• propoxyglycerol triacrylate can be Changxing EM2387 and the like.
• the polyfunctional aliphatic acrylate monomer may be dipentaerythritol pentaacrylate, such as SR399 LV NS of Sartomer, etc.; in particular, the polyfunctional aliphatic acrylate monomer is preferably an aliphatic acrylate monomer not exceeding five functional groups. Otherwise, it will affect the volume shrinkage of the printed 3D product.
• the cycloalkane acrylate monomer may be 3,3,5-trimethylcyclohexane acrylate, isobornyl acrylate IBOA, tricyclodecane dimethanol diacrylate, etc.; among them, 3,3,5-trimethyl
• the cyclohexane acrylate may be SR420 of Sartomer, EM2104 of Changxing, etc.
• isobornyl acrylate IBOA may be SR506NS of Sartomer, EM70 of Changxing, IBXA of Osaka Chemical, etc.
• the ester may be SR833S of Sartomer, EM2204 of Changxing, and the like.
• the cationic monomer may be an oxetane compound or a vinyl ether compound; wherein the vinyl ether compound has a carbon-carbon double bond which is an electron-rich double bond, and has high reactivity and can be carried out.
• the radical polymerization, cationic polymerization and charge transfer complex are alternately copolymerized, and thus can be applied to various radiation curing systems.
• the oxetane compound may be 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxalate Cyclobutane, 3,3-(oxybisbismethylene-bis-(3-ethyl)oxetane, 1,4-bis[(3-ethyl-3-oxymethyleneoxy) Cyclobutane)toluene]benzene, 3-ethyl-3-(phenoxy)methyloxetane, 3-ethyl-3-(p-fluorophenoxy)methyloxetane,
• MOX-101, MOX-102, MOX-103, MOX-104, etc. developed by Changzhou Power Company.
• the vinyl ether compound may be triethylene glycol divinyl ether DVE-3, 1,4-cyclohexyl dimethanol divinyl ether CHVE, 4-hydroxybutyl vinyl ether HBVE, dodecyl vinyl ether DDVE and so on.
• the photocuring agent of the present invention is selected from a plurality of transparent photocurable monomers, that is, when the photocuring agent is a mixture of a plurality of transparent acrylate monomers and/or a plurality of cationic monomers.
• the viscosity of a monomer must be less than 15 cps at 25 °C.
• the transparent photocurable monomer component in the present invention is a compound selected from a plurality of transparent photocurable monomers, it is a compound of a plurality of acrylate monomers and/or a plurality of cationic monomers.
• the viscosity of the monomer compound having the highest content is less than 15 cps at 25 °C.
• the photoinitiator may be an ultraviolet photoinitiator; wherein the ultraviolet photoinitiator may be one or more of a radical photoinitiator and a cationic photoinitiator.
• the radical photoinitiator may be an initiator: an acylphosphine oxide such as 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide (trade name TEPO), 2, 4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: 819);
• An ⁇ -hydroxyketone initiator such as 2-hydroxy-2-methyl-1-phenylacetone (trade name: 1173), 1-hydroxy-cyclohexyl benzophenone (trade name: 184), 2-hydroxy- 2-methyl-1-p-hydroxyethylether phenylacetone (trade name: 2959); oxime ester initiators such as Irgacure OXE 01 and Irgacure OXE 02 of BASF, respectively, have the structural formula:
• the cationic photoinitiator may be a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, an aromatic ferrocenium salt or the like.
• the diaryliodonium salt may be, for example, a dodecylbenzene iodonium salt, a long-chain alkoxydiphenyliodonium salt or the like; the triarylsulfonium salt is thermally stable to a diaryl iodonium salt. Well, it does not decompose when heated to 300 ° C, and the photoinitiating activity is high.
• the ferrocene iron salt is ⁇ 6 -isopropyl Ferrocene hexafluorophosphate, such as Irgacure 250, Irgacure 261, etc. of BASF Corporation.
• the auxiliary agent may be selected from one or more of a toughening agent, an antifoaming agent, a stabilizer, and a surfactant.
• the toughening agent may be a polycaprolactone triol and a polyol product, such as 305T, 205N of the company, and the Greatech GT8003 of the Gudi company.
• defoamer is mainly used to eliminate bubbles generated during filtration and printing, to avoid the occurrence of bubbles affecting print fluency; defoamer can be a silicone-free polymer, such as Digo's silicone-free defoaming Agent TEGO Airex 920, TEGO Airex 921, etc.
• a stabilizer i.e., a polymerization inhibitor
• the stabilizers may be, for example, GENORAD 16, GenoRAD 18, GENORAD 20, GENORAD 22 from Jingan, PM acrylic acid phosphate PM2010 from Jingde Chemical, polymerization inhibitor ZJ-701 from TCI, Tinuvin 234, Tinuvin 770, Irganox 245 from BASF. Cytec S100, Cytec 130, etc., Ciba's Irgastab UV10, Irgastab UV 22 and the like.
• the surfactant may be one or more of a silicone acrylate and a modified polysiloxane-based polymer that are capable of radiation crosslinking.
• the silicone acrylate which can be cross-linked by radiation can be TEGO RAD2010, 2011, 2100, 2200N, 2250, etc.
• the modified polysiloxane polymer may be BYK-333, BYK-371, BYK-377 of BYK, Tego wet 270, Tego Glide 450 of Digo Company, and the like.
• the photocurable clear ink composition for three-dimensional molding comprises, as a total weight of the ink composition, 100% by weight, 35-65% of a transparent photocurable oligomer, and 25-60% of a transparent photocurable monomer.
• Yellowing modifier 0.01-5%, photoinitiator 0.5-5%, auxiliary 0.5-5%; wherein the yellowing modifier can absorb light in the wavelength range of 560 nm-650 nm to make light curing transparent ink for three-dimensional molding
• the composition is transparent.
• the photocurable clear ink composition for three-dimensional molding of the present invention has a viscosity at room temperature (for example, 25 ° C) of 25 to 70 cps, a surface tension of 20 to 30 dyn, and a viscosity at a spray temperature (40 to 60 ° C). 9-14 cps, surface tension is 20-35 dyn.
• the photocurable clear ink composition for three-dimensional molding of the present invention may contain no volatile solvent; in particular, all components in the photocurable clear ink composition for three-dimensional molding of the present invention may participate in a photocuring reaction. At this time, the ink composition is free of VOC emissions and does not cause environmental pollution.
• the photocurable clear ink composition for three-dimensional molding of the present invention has wide application conditions, and is applicable not only to a high-viscosity photocurable resin composition (for example, SLA resin) but also to a photocurable ink for three-dimensional inkjet printing; in particular, the present invention
• the three-dimensional forming photocurable clear ink composition can be ink-jet printed at a low temperature (for example, 40-60 ° C), which has good print fluency and prolongs the life of the print head.
• the present invention also provides a method for preparing the above-mentioned photocurable clear ink composition for three-dimensional molding, comprising the following steps:
• the present invention does not strictly limit the order of addition of the components in the step 1); in particular, the present invention can perform secondary filtration on the third mixture by using a microporous membrane; wherein the first stage filtration adopts a pore diameter of 0.45 ⁇ m.
• the glass fiber membrane was used, and the second-stage filtration was carried out using a polypropylene film (abbreviated as PP film) having a pore diameter of 0.22 ⁇ m.
• PP film polypropylene film
• the preparation method of the present invention may further comprise degassing the filtrate to obtain the photocurable clear ink composition for three-dimensional molding.
• the operation mode of the degassing treatment may be selected from one of vacuum degassing, atmospheric degassing, and heated degassing; in addition, the degassing treatment may be performed for not less than 1 h, for example, may be 1-3 h.
• the preparation of the photocurable clear ink composition for three-dimensional molding needs to be carried out in an environment outside the range of the initiation wavelength of the selected photoinitiator, thereby avoiding light-induced ink composition in the environment.
• the components are polymerized.
• the method for preparing the photocurable clear ink composition for three-dimensional molding of the present invention can be completed by mixing and filtering, and the operation is simple and easy, and not only a stable ink composition but also liquefaction and ejection of the ink composition can be ensured.
• the ink composition is more convenient to use and is particularly suitable for printing on 3D objects.
• the present invention also provides a three-dimensional molding method for performing three-dimensional inkjet printing using the above-described photocurable clear ink composition for three-dimensional molding to obtain a printed article; wherein the ejection temperature at the time of three-dimensional inkjet printing is 40 to 60 °C.
• the printed article (having a size of, for example, 50 mm ⁇ 50 mm ⁇ 2 mm) formed by the three-dimensional molding method of the present invention has a hue range of L value of 80-90, a value of -1.00 to 2.00, and b value of -10.00-0.
• the three-dimensional molding method of the present invention is formed by using the above-mentioned photocurable clear ink composition for three-dimensional molding, in which the interface layer ink composition is irradiated with ultraviolet light, and the yellowing modifier in the ink composition is the maximum absorption peak.
• the yellowing modifier participates in the photocuring reaction, and photocuring in the ink composition
• the chemical reaction of the agent causes the ink composition to solidify, and the blue or violet light reflected by the yellowing modifier superimposes with the yellow light or the approximate light of the object formed after curing, and complements to form white light, thereby causing the object to be reflected to the human
• the white light of the eye increases, and the printed object observed by the naked eye becomes obviously white and transparent; when the yellowing modifier in the ink composition is a colorant having a maximum absorption peak at 560 nm to 650 nm, the colorant does not participate in photocuring.
• the blue or violet light reflected by the colorant is superimposed with the yellow light or the approximate light of the object formed after solidification.
• Complementary white light the white light reflected by an object so that the human eye is increased, this time to the printing object visually observed becomes clear transparent white.
• the third mixture was subjected to first-stage filtration using a 0.45 ⁇ m glass fiber membrane, followed by second-stage filtration using a 0.22 ⁇ m PP membrane to obtain a filtrate.
• the filtrate was filtered under reduced pressure for 1 hour under a vacuum of 0.1 MPa to remove bubbles in the filtrate to obtain a photocurable clear ink composition for three-dimensional molding.
• the maximum absorption peak of the yellowing regulator mixture i.e., a mixture of gold red (PR21) and phthalocyanine blue (PB15:4) was measured by an ultraviolet spectrophotometer, and the results are shown in Table 1.
• the third mixture was subjected to first-stage filtration using a 0.45 ⁇ m glass fiber membrane, followed by second-stage filtration using a 0.22 ⁇ m PP membrane to obtain a filtrate.
• the filtrate was filtered under reduced pressure for 2 hours under a vacuum of 0.1 MPa to remove bubbles in the filtrate to obtain a photocurable clear ink composition for three-dimensional molding.
• the third mixture was subjected to first-stage filtration using a 0.45 ⁇ m glass fiber membrane, followed by second-stage filtration using a 0.22 ⁇ m PP membrane to obtain a filtrate.
• the filtrate was degassed at 50 ° C for 30 min to remove bubbles in the filtrate to obtain a photocurable clear ink composition for three-dimensional molding.
• the maximum absorption peak of the yellowing regulator mixture i.e., a mixture of pigment violet PL (PV23) and phthalocyanine blue (PB15:3) was measured by an ultraviolet spectrophotometer, and the results are shown in Table 1.
• the third mixture was subjected to first-stage filtration using a 0.45 ⁇ m glass fiber membrane, followed by second-stage filtration using a 0.22 ⁇ m PP membrane to obtain a filtrate.
• the filtrate was allowed to stand under normal pressure for 3 hours to remove bubbles in the filtrate to obtain a photocurable clear ink composition for three-dimensional molding.
• the third mixture was subjected to first-stage filtration using a 0.45 ⁇ m glass fiber membrane, followed by second-stage filtration using a 0.22 ⁇ m PP membrane to obtain a filtrate.
• the filtrate was filtered under reduced pressure for 3 hours under a vacuum of 0.1 MPa to remove bubbles in the filtrate to obtain a photocurable clear ink composition for three-dimensional molding.
• the photocurable clear ink composition for three-dimensional molding of this comparative example is composed of the following parts by weight:
• the method for preparing the photocurable clear ink composition for three-dimensional molding described above can be carried out by referring to Example 1 (excluding the step 3 of adding the yellowing modifier in Example 1), and the viscosity and surface of the photocurable clear ink composition for three-dimensional molding.
• the tensile strength measurement results are shown in Table 1.
• the photocurable clear ink composition for three-dimensional molding of this comparative example is composed of the following parts by weight:
• the preparation method of the above-mentioned photocurable clear ink composition for three-dimensional molding can be carried out by referring to Example 2 (excluding the step 3 of adding the yellowing modifier in Example 2), and the viscosity and surface of the photocurable clear ink composition for three-dimensional molding.
• the tensile strength measurement results are shown in Table 1.
• the photocurable clear ink composition for three-dimensional molding of this comparative example is composed of the following parts by weight:
• the above method for preparing the photocurable clear ink composition for three-dimensional molding can be carried out by referring to Example 3 (excluding the step 3 of adding the yellowing modifier in Example 3), and the viscosity and surface of the photocurable clear ink composition for three-dimensional molding.
• the tensile strength measurement results are shown in Table 1.
• the photocurable clear ink composition for three-dimensional molding of this comparative example is composed of the following parts by weight:
• the method for preparing the photocurable clear ink composition for three-dimensional molding described above can be carried out by referring to Example 4 (excluding the step 3 of adding a yellowing modifier in Example 4), and the viscosity and surface of the photocurable clear ink composition for three-dimensional molding.
• the tensile strength measurement results are shown in Table 1.
• the photocurable clear ink composition for three-dimensional molding of this comparative example is composed of the following parts by weight:
• the above method for preparing the photocurable clear ink composition for three-dimensional molding can be carried out by referring to Example 5 (excluding the step 3 of adding the yellowing modifier in Example 5), and the viscosity and surface of the photocurable clear ink composition for three-dimensional molding.
• the tensile strength measurement results are shown in Table 1.
• Example 1-5 and Comparative Examples 1-5 were respectively applied to a 3D photocurable inkjet printer of an industrial head, and the wavelength of the ultraviolet light source was set to 395 nm, respectively at a suitable jetting temperature (see Table 1).
• the accuracy test is mainly reflected by the volume shrinkage rate.
• the test method is:
• the density ⁇ 1 before curing of the ink composition and the density ⁇ 2 after completion of the ink composition were measured at 25 ° C, and the volume shrinkage ratio was calculated according to the following formula:
• the ultraviolet light visible spectrophotometer is used to measure the light transmittance, that is, the luminous flux transmitted through the sample and the sample is incident on the sample.
• the ratio of luminous flux expressed as a percentage.
• the L*a*b of the square article was tested using an X-rite color difference meter.
• the L*a*b value of the block model represents the hue of the block color, ie the color space coordinates of the color.
• L is the brightness, L is from 0 to 100, 0 is black, 100 is white; a is the range from red to green, b is the range from blue to yellow, and the ranges of a and b are both It is +120 to -120, where +120a is red, and it gradually turns green when it transitions to -120a; likewise, +120b is yellow and -120b is blue.
• a photocurable clear ink composition containing a yellowing modifier according to each embodiment of the present invention which is printed with a 50 mm (length) ⁇ 50 mm (width) ⁇ 2 mm (thickness) square article, which satisfies an L value of 80 ⁇ when performing hue measurement. 90, a value of -1.00 to 2.00, b value of -10.00 to 0, thereby indicating that the article printed using the photocurable clear ink composition of the present invention overcomes yellowing defects.
• the light transmittance value of the object printed by the photocurable clear ink composition of the present invention is more than 92%, thereby indicating that the object printed using the photocurable clear ink composition of the present invention has good transparency.
• the photocurable clear ink composition of the present invention has good printing fluency, low viscosity at room temperature, low ejection temperature, and a shrinkage ratio of the printed object of less than 5% with high precision.

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• 2017
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