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WO1995001257A1 - Procede d'elaboration d'un article en couleur et en trois dimensions - Google Patents

Procede d'elaboration d'un article en couleur et en trois dimensions Download PDF

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Publication number
WO1995001257A1
WO1995001257A1 PCT/GB1994/001427 GB9401427W WO9501257A1 WO 1995001257 A1 WO1995001257 A1 WO 1995001257A1 GB 9401427 W GB9401427 W GB 9401427W WO 9501257 A1 WO9501257 A1 WO 9501257A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
infra red
colour
developer
photopolymerisable
Prior art date
Application number
PCT/GB1994/001427
Other languages
English (en)
Inventor
Colin Henry Mclean
Peter Gregory
Original Assignee
Zeneca Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to AU70072/94A priority Critical patent/AU7007294A/en
Priority to JP7503370A priority patent/JPH08512001A/ja
Priority to EP94918984A priority patent/EP0706451A1/fr
Publication of WO1995001257A1 publication Critical patent/WO1995001257A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • 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
    • 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
    • B29C64/129—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 characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—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 characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
    • 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
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0833—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using actinic light
    • 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
    • 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
    • B29K2105/0047—Agents changing thermal characteristics
    • B29K2105/005—Heat sensitisers or absorbers
    • 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
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/002—Coloured

Definitions

  • This invention relates to a process and more particularly to a method for the production of three-dimensional articles in which selected parts are coloured in order to provide visible differentiation from other parts of the article.
  • Methods are known for generating three-dimensional models by the selective application of programmed beams of electromagnetic radiation to a fluid medium comprising a photopolymerisable resin composition which becomes selectively cured to form the desired structure.
  • stereolithography is a method for making solid articles by successively “printing” thin layers of a radiation-curable material, one on top of the other.
  • a programmed movable spot beam of electromagnetic radiation for example a laser beam, focused into a surface or layer of radiation curable liquid is used to form a solid cross-section of the article at the surface of the liquid.
  • the cross-section so obtained is then moved, in a programmed manner, away from the liquid surface and into the liquid by the thickness of one layer and the next cross-section is then formed and adhered to the immediately preceding layer.
  • the technique allows the rapid construction of complex shaped, three-dimensional articles without the need for expensive tooling equipment or moulds, especially objects containing voids or having irregular shapes.
  • a three-dimensional model is constructed in a computer file (CAD/CAM), sliced into cross-sectional elements or layers, and a computer then directs a light source to image each cross-sectional element, one on top of the other, in a resin tank to produce a solid laminated model of the computer image.
  • CAD/CAM computer file
  • a computer then directs a light source to image each cross-sectional element, one on top of the other, in a resin tank to produce a solid laminated model of the computer image.
  • CT or MRI scanning can be used to generate the initial data as proposed in EP-A-0348061.
  • parts of a three- dimensional article obtained by stereolithography could be visually differentiated from other parts thereof.
  • This could be especially useful in anatomical and medical models for teaching purposes and more particularly in models of parts of the anatomy of human patients in order to differentiate between different tissue types, for example between bone and tumour tissue and thereby assist in the interpretation of the model prior to invasive surgery. It has now been found that such visual differentiation can be provided by carrying out the stereolithographic process on a polymerisable resin composition containing an infra red absorber which, in conjunction with a colour former and developer, causes colour development or colour change on activation by infra red light.
  • a method of forming a three-dimensional article having at least one selectively coloured zone comprising the steps of:
  • the electromagnetic radiation referred to in Step (1) above is preferably ultraviolet or visible electromagne ic radiation.
  • Step (2) may be performed before, during or after Step (1) , preferably after Step (1) .
  • the article is preferably a model, more preferably an anatomical or medical model.
  • a method of forming a three-dimensional model having at least one selectively coloured zone corresponding to at least one physically differentiated zone present in an original three-dimensional article comprising the steps of:
  • the present invention is particularly useful for preparing three- dimensional models of joints and bones, e.g. those found in toes, feet, legs, hips, pelvis, ribs, the spinal column, arms, hands, fingers, head (particularly the cranium, jaw and teeth) and of organs, e.g. the heart, lungs, kidney and liver.
  • joints and bones e.g. those found in toes, feet, legs, hips, pelvis, ribs, the spinal column, arms, hands, fingers, head (particularly the cranium, jaw and teeth) and of organs, e.g. the heart, lungs, kidney and liver.
  • the three-dimensional model or reproduction formed in the method of the invention may be substantially identical in size with the original three- dimensional article or it may be smaller or larger according to convenience.
  • the "physically differentiated" zones present in the original three dimensional article are zones which should differ in some physically detectable property, for example density or X-ray absorptivity, from other parts of the article.
  • these physically differentiated zones should be detectable and distinguishable by the original data collection/production apparatus, for example CT or MRI scanning.
  • the selectively coloured zones present in the reproduction may be such that parts of the resultant model or article are coloured whilst other parts are substantially uncoloured or such that parts have one colour whilst the other parts have another colour. Differences in colour intensity are also possible.
  • the photopolymerisable resin composition used in the method of the invention may, apart from the presence of a colour former, developer and infra red absorber, be of a conventional type, such compositions having been fully described in the prior art.
  • Suitable compositions contain a photopolymerisable compound or a mixture of such compounds, the term "photopolymerisable compound” embracing monomeric, oligomeric and polymeric compounds which can be photopolymerised under the influence of a photoinitiator.
  • Examples of photopolymerisable compounds are organic compounds containing groups polymerisable by free radicals and/or cationically polymerisable groups.
  • Compounds polymerisable by free radicals include compounds containing at least one ethylenically unsaturated group per molecule, especially the acrylate and/or methacrylate group. Such compounds may be used in conjunction with free radical generating photoinitiators, for example aromatic ketones, o-diketones, thioxanthones, acylphosphine oxides, onium salts and the like. In many cases, the efficiency of the free radical photoinitiators may be improved by the inclusion of an amine, especially a tertiary amine such as dimethylaminoethyl methacrylate or ethyl p- dimethylaminobenzoate.
  • free radical photoinitiators for example aromatic ketones, o-diketones, thioxanthones, acylphosphine oxides, onium salts and the like.
  • the efficiency of the free radical photoinitiators may be improved by the inclusion of an amine, especially a ter
  • the photopolymerisable resin comprises (apart from the colour former, developer and infra red absorber) the resins described in Canadian Patent Application 2028541A1, particularly Claim 1 which is incorporated herein by reference thereto.
  • the liquid photopolymerisable resin composition has a viscosity of 200 to 2000 mPas at 30°c.
  • Compounds capable of cationic polymerisation include epoxy compounds, especially compounds containing at least two epoxy groups per molecule, cyclic ethers, lactones, cyclic acetals, cyclic thioethers, vinyl compounds and the like.
  • Cationic photoinitiators which may be used in conjunction with such compounds include onium salts which are double salts capable of releasing a Lewis acid when irradiated by an energy beam.
  • photopolymerisable resin to which the colour former, developer and infra red absorber are added are described in patent specifications EP 425441, EP 525578, EP 492953, WO 92/15620, WO 89/08021, EP 430992, EP 378144, EP 425440, EP 562826, EP 554215, EP 536086 and EP 506616.
  • Substantially colourless colour formers used in conjunction with solid developers which, when caused to melt, for example by exposure to infrared radiation, react with the colour formers to produce coloured substances. Melting of the developer is facilitated by incorporating an infrared absorber which converts the radiation energy into thermal energy.
  • the colour change is irreversible thus allowing the model to be stored without fear of loss of colour from the coloured zones.
  • the colour former is colourless or weakly coloured.
  • Suitable colour formers are basic dyes which, when heated with a developer, change colour or produce colour.
  • Especially preferred colour formers include triaryl methane-, diphenyl methane-, thiazine-, spiro-, lactam- and fluoran- based colour formers.
  • Triarylmethane-based colour formers include, 3-3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis(p- dimethylaminophenyDphthalide, 3- (p-dimethylaminophenyl) -3- (1,2- dimethylindole-3-yl)phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole-3- yDphthalide, 3,3-bis (1,2-dimethylindole-3-yl) -5-dimethylaminophthalide, 3,3- bis (l,2-dimethylindole-3-yl> - -dimethylaminophthalide, 3,3-bis (9- ethylcarbazole-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindole-3-yl) - 6-dimethylaminophthalide, 3-p-p
  • Diphenylmethane-based colour formers include 4,4' -bis- dimethylaminobenzhydryl benzyl ether, N-halophenyl-leucoauramine and N-2,4,5- trichlorophenyl-leucoauramine.
  • Thiazine-based colour formers include benzoyl-leucomethylene blue and p-nitrobenzoyl-leucomethylene blue.
  • Spiro-based colour formers include 3-methyl-spiro-dinaphthopyran, 3- ethyl-spiro-dinaphthopyran, 3-phenyl-spirodinapthopyran, 3-benzyl-spiro- dinaphthopyran, 3-methyl-naphtho- (6' -methoxybenzo)spiropyran and 3-propyl- spiro-dibenzopyran.
  • Lactam-based colour formers include rhodamine- ⁇ -anilinolactam, rhodamine- (p-nitroanilino) lactam and rhodamine- (o-chloroanilino) lactam.
  • Fluoran-based colour formers include 3,6-dimethoxyfluoran, 3,6- diethoxyfluoran, 3,6-dibutoxyfluoran, 3-dimethylamino-7-methoxyfluoran, 3- dimethylamino-6-methoxylfluoran, 3-dimethylamino-7-methoxyfluoran, 3- diethyla ino-7-chlorofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3- diethylamino-6,7-dimethylfuoran, 3- (N-ethyl-p-toluidino) -7-methylfluoran, 3- diethylamino-7- (N-acetyl-N-methylamino) fluoran, 3-diethylamino-7-N- methylaminofluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-5- methyl-7-dibenzylamin
  • Colour formers permitting the production of a wide range of colours are known and have been described, for example, by Peter Gregory in High- Technology Applications of Organic Colourants, Plenum Press, pages 124-134.
  • suitable colour formers include triphenylmethane derivatives such as Crystal Violet Lactone and various xanthene type compounds.
  • Preferred developers have a melting point above 40°C, more preferably above 60°C.
  • the developers which assist the colour formation are preferably inorganic or organic acidic materials.
  • Inorganic acidic materials include activated clay, acidic clay, attapulgite, bentonite, colloidal silica and aluminum silicate,
  • Organic acidic materials include phenolic compounds, especially 4-tert-butyl-phenol, bisphenol A, 4-tert-octylphenol, 4- phenylphenol, 4-acetylphenol, ⁇ -naphthol, ⁇ -naphthol, hydroquinone, 2,2'- dihydroxydiphenyl, 2,2' -methylenebis- (4-methyl-6-tert-butylphenol) , 2,2'- methylenebis- (4-chlorophenol) , 4,4' -dihydroxy-diphenylmethane, 4,4'- isopropylidenediphenol, 4,4 ' -isopropylidenebis
  • the infra red absorber preferably has an absorbtion maximum at above 700nm, more preferably above 750nm, especially in the range 750nm-2000nm.
  • the infra-red absorber may be inorganic but it is preferably organic.
  • Inorganic infra red absorbers include aluminium oxide and hydroxide; silicate minerals such as the olivine group; including olivine, garnet group including almandine and spessartine, pyroxene group including enstatite, amphibole group including tremolite and actinolite, mica group including muscovite and biotite, feldspar group including oligoclase and anorthite, silica mineral group including quartz and cristobalite, clay minerals including kaolinite and montmorillonite, etc.; zinc silicate, magnesium silicate, calcium silicate barium silicate, zinc phosphate, trisilicon tetranitride & boron nitride, barium sulfate, calcium sulfate, and strontium sulfate; calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate and potassium nitrate.
  • silicate minerals such as the olivine group; including olivine,
  • Suitable organic infra red absorbers include metal dithienes, metal dithiolenes, metal mercaptophenols, benzoquinones, naphthoquinones, anthraquinones, phthalocyanines (especially aryloxy and aryl thio phthalocyanines) and triarylphosphates and compounds of the nitroso, cyanine, nigrosine, imminium, diiminium, squarilium, croconium, quinone, azo, indoaniline, azulenium, pyrilium, thiapyrilium series.
  • organic infra red absorbers examples include the following :
  • infra red absorber The function of the infra red absorber is to absorb radiation from the beam of infra red light and, as a result, heat the colour former and developer thereby causing a chemical reaction to occur which effects colour development or colour change.
  • an infra red absorber which strongly absorbs the frequency of infra red light which is used.
  • Table 1 shows the absorbtion wavelengths of various inorganic infra red absorbers and is a useful guide for selecting compatible absorbers and light sources.
  • the photopolymerisable resin may also contain a sensitiser which improves the sensitivity of the colour former for the developer resulting in a stronger coloration.
  • sensitisers include dimethyl terephthalate and O-chloro-N-propionamido aniline which work particularly well when the developer is bisphenol A.
  • the liquid photopolymerisable resin preferably contains 0.1 to 10%, more preferably 0.1 to 5% colour former (especially 0.2 to 2%); 1 to 25%, more preferably 1 to 16% developer (especially 1.5 to 15%); and 0.01 to 10%, preferably 0.01 to 5% infra red absorber (especially 0.02 to 1%).
  • a sensitiser when used this is preferably present in an amount of up to 2%.
  • Suitable infrared absorbers for inclusion with the colour formers and solid developers have also been described in the prior art, for example in our EP-A-0155780, EP-A-0282181 and EP-A-0282182 and at pages 218-243 of the above mentioned book by Peter Gregory.
  • the photopolymerisable resin composition may also contain other conventional ingredients, for example organic or inorganic fillers for modification of the final physical and/or mechanical properties of the model.
  • Polymerisation of the photopolymerisable resin composition by the application of electromagnetic radiation outside of the infra red, especially ultra violet or visible electromagnetic radiation, may be effected using conventional stereolithographic techniques in a manner fully described in the prior art.
  • electromagnetic radiation outside of the infra red especially ultra violet or visible electromagnetic radiation
  • the photopolymerisation is not sufficiently exothermic to cause solid developer to melt. Suitable operating conditions can be established by appropriate choice of developer and infrared absorber.
  • Suitable light sources for Step (1) include lasers such as argon ion lasers, helium-cadmium lasers and the like and also conventional light sources for generating ultra violet radiation or visible light such as extra high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, metal halide lamps, xenon lamps, tungsten lamps and the like.
  • the infra red light beam may be applied to the photopolymerisable resin composition or "substantially polymerised" resin composition before, during or after photopolymerisation has been effected.
  • the infra red light beam may therefore be applied on a layer by layer basis as the article is formed by scanning the whole or selected parts of each layer or it can follow the first step throughout the curing operation with an appropriate time lag.
  • the infra red light team may be programmed in manner analogous to the known manner so as to be activated only in response to selected physical features present in the original three-dimensional object, for example zones of higher or lower density than the remainder of said object or of different "-aterial composition.
  • data obtained of part of the human anatomy by body-scanning equipment and representative of different tissue types may be converted in known manner into computer data capable of programming the beam of radiation.
  • the present invention also provides use of a photopolymerisable resin composition containing a colour former, a developer and an infra red absorber to form a three-dimensional model having at least one selectively coloured zone corresponding to at least one physically differentiated zone present in an original three-dimensional object.
  • a photopolymerisable resin composition containing a colour former, a developer and an infra red absorber to form a three-dimensional model having at least one selectively coloured zone corresponding to at least one physically differentiated zone present in an original three-dimensional object.
  • the preferred colour former, developer and infra red absorber are as hereinbefore described and the model is preferably a medical or anatomical model as discussed above.
  • the wavelength of the infra red light beam will be such as to effect colour development or colour change and, therefore, will be different from the wavelength of the first programmed beam of electromagnetic radiation used in Step (1) .
  • Suitable infra red lasers include gallium-aluminium- arsenide (GaAlAs) lasers (780-830nm) and the more powerful neodymium yttrium- aluminium-garnet (Nd-YAG) (1064nm) , GaAs lasers (780-905nm) , GaAs x Pl-x (650- 900nm) , InP lasers (900nm) , InGaP Lasers (760nm) , Nd:YLF lasers (1047/1053nm) and Nd:YAP Lasers (1080nm) and C0 2 lasers.
  • GaAlAs gallium-aluminium- arsenide
  • Nd-YAG neodymium yttrium- aluminium-garnet
  • Infra red absorber (IRA) Y had the formula CuPc(-S- [2-naphthyl] ) 1516 and (IRA) Z had the formula CuPc(-S- [4-methylphenyl] ) 10 (-S- [4-methoxyphenyl] ) 5 .
  • PRO-JET 900 NP is an IRA available from ZENECA Limited, Blackley, Manchester, England. Crystal Violet Lactone is a commercially available Colour former and bisphenol A is available from Aldrich Chemical Company Ltd, Gillingham, England.
  • Resin X was prepared by mixing ethoxylated bisphenol A dimethacrylate ester (DIACRYOL 101, obtained from Akzo chemicals, 45g) with NeoRad NR 2720 having a molecular weight of 950 and viscosity of 1200 mPas at 25°C, (24g, obtained from ZENECA Resins, USA), polyethylene glycol (400) diacrylate (SR 344 obtained from Sartomer Company) , alkoxylated triacrylate having a molecular weight of 1000 (SR9035, obtained from Sartomer Company, 10.5g) and 1,1-dimethyl-1-hydroxy acetophenone (5.5g) .
  • Resin X is a clear liquid having a viscosity of 388 mPas at 30°C.
  • compositions A and B were prepared having the ingredients shown in Table 1 below.
  • a film was formed by curing a lOO ⁇ m layer of the composition with an ultra violet light Fusion "D" lamp, (300W, 3J/cm 2 ) and the cured film was irradiated with infra red light (a laser diode from Spectra (Physics) Ltd, 820nm, power lOOmW) .
  • impressions describes, qualitatively, response of the film to the infra red source. Zero means there was no response, 2 and 3 was a good response and 5 means the film burned through (an excessive response) .
  • This example compares the effects of different infra red absorbers on impression and colour.
  • the compositions were prepared, cured with ultraviolet and irradiated with infra red as described in Example 1.
  • Example 1 illustrates the effect of different levels of infra red absorber in the photopolymerisable resin composition.
  • the compositions were prepared, cured with ultra violet and irradiated with infra red as described in Example 1.
  • Example 2 illustrates the effect of different levels of colour former in the photopolymerisable r-esin composition.
  • the compositions were prepared, cured with ultra violet and irradiated with infra red as described in Example 1.
  • This example illustrates the effect of using a sensitiser in the photopolymerisable resin composition which improves colour development.
  • the compositions were prepared, cured with ultra violet and irradiated with infra red as described in Example 1.
  • Table 5

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  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
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  • Automatic Analysis And Handling Materials Therefor (AREA)

Abstract

Procédé d'élaboration d'un article en trois dimensions dont une partie au moins est colorée de manière sélective; cette méthode comprend les étapes suivantes: (1) on soumet des couches successives d'une composition de résine liquide photopolymérisable contenant une substance chromogène, un révélateur et un absorbeur infrarouge à un faisceau programmé d'ondes électromagnétiques dont la longueur n'est pas comprise dans la partie infrarouge du spectre. En procédant ainsi à la polymérisation de cette composition de résine, on obtient des couches successives d'une composition de résine solide essentiellement polymérisée; les couches adjacentes s'intègrent les unes dans les autres à mesure qu'elles sont constituées, et définissent de la sorte la structure de l'article en trois dimensions; (2) on soumet la résine photopolymérisable ou chaque couche de la composition de résine solide essentiellement polymérisée à un faisceau programmé de lumière infrarouge afin de révéler ou modifier la couleur d'une ou de plusieurs parties de l'article.
PCT/GB1994/001427 1993-07-02 1994-07-01 Procede d'elaboration d'un article en couleur et en trois dimensions WO1995001257A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU70072/94A AU7007294A (en) 1993-07-02 1994-07-01 Method of forming a three-dimensional coloured article
JP7503370A JPH08512001A (ja) 1993-07-02 1994-07-01 方 法
EP94918984A EP0706451A1 (fr) 1993-07-02 1994-07-01 Procede d'elaboration d'un article en couleur et en trois dimensions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9313723.0 1993-07-02
GB939313723A GB9313723D0 (en) 1993-07-02 1993-07-02 Process

Publications (1)

Publication Number Publication Date
WO1995001257A1 true WO1995001257A1 (fr) 1995-01-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1994/001427 WO1995001257A1 (fr) 1993-07-02 1994-07-01 Procede d'elaboration d'un article en couleur et en trois dimensions

Country Status (5)

Country Link
EP (1) EP0706451A1 (fr)
JP (1) JPH08512001A (fr)
AU (1) AU7007294A (fr)
GB (1) GB9313723D0 (fr)
WO (1) WO1995001257A1 (fr)

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WO1997009168A1 (fr) * 1995-09-09 1997-03-13 Zeneca Limited Procede de fabrication de couches en polymere a regions colorees selectivement
US5942370A (en) * 1991-10-02 1999-08-24 Ciba Specialty Chemicals Corporation Production of three-dimensional objects
EP1314540A4 (fr) * 2000-07-28 2003-05-28 Ntt Data Corp Procede de production d'articles colores en 3d de resine durcissable, articles ainsi produits, et appareil de formage
GB2410459A (en) * 2004-02-02 2005-08-03 Peter David Hurley Three dimensional model making
US7279266B2 (en) * 2003-09-24 2007-10-09 Fujifilm Corporation Photosensitive composition and lithographic printing plate precursor using the same
WO2015108543A1 (fr) * 2014-01-16 2015-07-23 Hewlett-Packard Development Company, L.P. Procédé d'impression 3d
EP3094475A4 (fr) * 2014-01-16 2017-03-15 Hewlett-Packard Development Company, L.P. Procédé d'impression 3d
US9864274B2 (en) 2010-01-22 2018-01-09 Dsm Ip Assets B.V. Liquid radiation curable resins capable of curing into layers with selective visual effects and methods for the use thereof
CN110650833A (zh) * 2017-05-19 2020-01-03 索尼公司 三维结构和三维结构的制造方法
US10544311B2 (en) 2014-01-16 2020-01-28 Hewlett-Packard Development Company, L.P. Polymeric powder composition for three-dimensional (3D) printing
EP3626431A4 (fr) * 2017-05-19 2020-07-01 Sony Corporation Structure tridimensionnelle et procédé de production pour structure tridimensionnelle

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JP5966938B2 (ja) * 2013-01-15 2016-08-10 コニカミノルタ株式会社 立体物造形装置及び立体物造形方法

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942370A (en) * 1991-10-02 1999-08-24 Ciba Specialty Chemicals Corporation Production of three-dimensional objects
AU710052B2 (en) * 1995-09-09 1999-09-09 Avecia Limited Process for producing polymeric layers having selectively coloured regions
US6133336A (en) * 1995-09-09 2000-10-17 Zeneca Limited Process for forming a colored three-dimensional article
WO1997009168A1 (fr) * 1995-09-09 1997-03-13 Zeneca Limited Procede de fabrication de couches en polymere a regions colorees selectivement
EP1314540A4 (fr) * 2000-07-28 2003-05-28 Ntt Data Corp Procede de production d'articles colores en 3d de resine durcissable, articles ainsi produits, et appareil de formage
US7074354B2 (en) 2000-07-28 2006-07-11 Nabtesco Corporation Process for producing colored shaped article from curable resin, colored shaped article produced from curable resin, and shaping apparatus
US7279266B2 (en) * 2003-09-24 2007-10-09 Fujifilm Corporation Photosensitive composition and lithographic printing plate precursor using the same
GB2410459A (en) * 2004-02-02 2005-08-03 Peter David Hurley Three dimensional model making
US9864274B2 (en) 2010-01-22 2018-01-09 Dsm Ip Assets B.V. Liquid radiation curable resins capable of curing into layers with selective visual effects and methods for the use thereof
US9927704B2 (en) 2010-01-22 2018-03-27 Dsm Ip Assets, B.V. Liquid radiation curable resins capable of curing into layers with selective visual effects and methods for the use thereof
WO2015108543A1 (fr) * 2014-01-16 2015-07-23 Hewlett-Packard Development Company, L.P. Procédé d'impression 3d
EP3094475A4 (fr) * 2014-01-16 2017-03-15 Hewlett-Packard Development Company, L.P. Procédé d'impression 3d
US10544311B2 (en) 2014-01-16 2020-01-28 Hewlett-Packard Development Company, L.P. Polymeric powder composition for three-dimensional (3D) printing
US10583612B2 (en) 2014-01-16 2020-03-10 Hewlett-Packard Development Company, L.P. Three-dimensional (3D) printing method
CN110650833A (zh) * 2017-05-19 2020-01-03 索尼公司 三维结构和三维结构的制造方法
EP3626430A4 (fr) * 2017-05-19 2020-06-10 Sony Corporation Structure tridimensionnelle et méthode de production pour structure tridimensionnelle
EP3626431A4 (fr) * 2017-05-19 2020-07-01 Sony Corporation Structure tridimensionnelle et procédé de production pour structure tridimensionnelle
US11518101B2 (en) 2017-05-19 2022-12-06 Sony Corporation Three-dimensional structure and method of manufacturing three-dimensional structure

Also Published As

Publication number Publication date
EP0706451A1 (fr) 1996-04-17
JPH08512001A (ja) 1996-12-17
AU7007294A (en) 1995-01-24
GB9313723D0 (en) 1993-08-18

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