WO1990010254A1 - Production de corps tridimensionnels par photopolymerisation - Google Patents

Production de corps tridimensionnels par photopolymerisation Download PDF

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Publication number
WO1990010254A1
WO1990010254A1 PCT/US1990/000991 US9000991W WO9010254A1 WO 1990010254 A1 WO1990010254 A1 WO 1990010254A1 US 9000991 W US9000991 W US 9000991W WO 9010254 A1 WO9010254 A1 WO 9010254A1
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carbon atoms
activating radiation
group
composition
photoinitiator
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PCT/US1990/000991
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English (en)
Inventor
Oscar Valdes-Aguilera
Krishan S. Raghuveer
Darrell Watson
Douglas C. Neckers
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Bowling Green State University
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Publication of WO1990010254A1 publication Critical patent/WO1990010254A1/fr

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    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • centimeter and parts' 1 refer to percent and parts by weight, and the following terms have the meanings stated: “nm” means nanometer or nanometers; “g” means gram or grams; “kg” means kilogram or kilograms; ⁇ ray", as applied to activating radiation for a photoinitiator refers to such radiation which has negligible dimensions at right angles to its direction of travel; “cm” means centimeter or centimeters; “ ⁇ m” means micrometer or micrometers; “mm” means millimeter or millimeters; “L” means liter or liters; Ml means milliliter or milliliters; “m” means mole or moles; nm / 0 n means mole percent, and equals 100 times the number of moles of the constituent designated in a composition divided by the total number of moles in the composition; “m sec” means millisecond or milliseconds; “mW” means milliwatt
  • This invention relates to a new composition comprising a fluid monomer and a photoinitiator system for the monomer, and to a method for producing three dimensional bodies by photopolymerization of the fluid monomer and, more particularly, to such a method in which a laser is used to provide activating radiation for the photoinitiator system for the monomer.
  • a body of a composition comprising a photopolymerizable monomer, usually an acrylate or an acrylate derivative, and a photoinitiator system therefor can be caused to undergo photopolymerization by subjecting it to activating radiation of a suitable wave length.
  • the photoinitiator system includes a compound, called a "photoinitiator", and, usually, an "accelerator”.
  • Activating radiation causes the photoinitiator to undergo a reaction, producing an intermediate which includes a free radical chain and, as a consequence, causes the monomer to polymerize.
  • the accelerator usually a tertiary amine, acts by ameliorating the effect of oxygen, which is to terminate the free radical chains that are produced by the reaction of the photoinitiator and, as a consequence, to quench the free radical polymerization.
  • photoinitiators that have been used commercially are activated by ultraviolet radiation, i.e., radiation having a wavelength shorter than 400nm, and usually from mercury lamps, for example mercury resonance lamps with output at 313nm and 364nm.
  • An ultraviolet laser is used in the process disclosed by the 3-D Patent, but such a laser, at the present time, is not reliable, has a short lifetime, is expensive and has a high power requirement.
  • photoinitiators that are activated by visible light have also been used, notably in a colored copying process that is available under the trade designation "CYCOLOR".
  • Benzoin ethers and related acetals, Hammond's initiators, diaryliodonium and triaryl sulfonium salts and various photosensitive peroxides and peresters are examples of known photoinitiators that are activated by ultraviolet radiation (see, for example, U.S. patent No. 4,561,951, "Neckers", granted December 31, 1985 to one of the present inventors) .
  • Cyanine dye, borate- so-called (+,-) ion pair initiators, xanthene dye, and onium salt (-,+) ion pair photoinitiators are examples of known photoinitiators that are activated by radiation in the visible spectrum.
  • composition that is comprised of a photopolymerizable monome and a photoinitiator system therefor.
  • the system is one wherein a ray of activating radiation which enters the body through a surface thereof activates the photoinitiator system and causes polymerization at each of a succession of points, the first such point being immediately adjacent the surface and subsequent points being successively farther from the surface in the direction of travel of the ray of activating radiation; the distance from the surface to the point of the succession farthest therefrom varies as a function of at least one of (a) the intensity of the activating radiation and
  • Loss of the dye color also occurs as a consequence of the eosin reaction with th triethanol amine, enabling subsequent radiation from the argo ion laser to penetrate farther into the composition and to caus reaction of eosin with triethanol amine and activation of th trimethylolpropane triacrylate at the level of greate penetration, and still greater penetration by subsequen radiation with consequent reaction and activation at the leve of the still greater penetration.
  • the invention is also based upon the discovery that suc photoinitiators as eosin lactone, methylene violet, methylen blue, methylene green, ethyl eosin ester, RB lactone, ethyl RB, RB peroxide and erythrosin Bd, usually in the presence of a accelerator such as triethanolamine, can be used i comparatively high concentrations with a photopolymerizabl monomer to produce a composition wherein a high intensity ra of activating radiation in the visible or infra red spectru will cause polymerization to a desired extend in a short perio of time.
  • suc photoinitiators as eosin lactone, methylene violet, methylen blue, methylene green, ethyl eosin ester, RB lactone, ethyl RB, RB peroxide and erythrosin Bd, usually in the presence of a accelerator such as triethanolamine, can be used
  • the invention in one aspect, is a method which comprises the steps of directing a ray of activating radiation for the photoinitiator system to and through a point in a given plane and into a body of the foregoing trimethylolpropane triacrylate composition, or an equivalent, and controlling at least one of
  • the invention involves a method for polymerizing a body of a composition comprised of a photopolymerizable monomer and a photoinitiator system for the monomer which system includes any one of a number of dyes which are broadly classified as xanthene, thionine, cyanine, stryllium ion, pyrrilium salt, oxazone, azinium ion, and triphenylmethane dyes.
  • the photoinitiator system for the monomer includes one of the following, for example: eosin lactone, methylene violet, methylene blue, methylene green, ethyl eosin ester, eosin ester, RB lactone, ethyl RB, RB peroxide, eosin peroxide or erythrosin Bd.
  • the photopolymerization is carried out by directing visible or infra red spectrum ray of activating radiation fo the photoinitiator system into the body, and controlling th intensity of the activating radiation so that the desired exten of polymerization occurs in an acceptable time.
  • the visible o infra red spectrum ray has a wavelength of from 400 to lOOOn .
  • the ray of activating radiation preferably has a wavelength fro 600 to lOOOnm because available lasers which emit radiatio having such a wavelength are markedly less expensive than laser which emit radiation having shorter wavelengths.
  • the invention is a photochemica method for applying a polymeric coating to a metal, glass, o other substrate, or for welding, laminating or sealing tw bodies, at least one of which is transparent, to one another.
  • the invention is a method fo initiating photopolymerization with an inexpensive diode laser
  • SUBSTITUTE SHEET for example one which emits radiation having a frequency of 682 nm.
  • the invention is a photo ⁇ polymerizable which contains a xanthene dye derivative having a Y2•substituent which makes the derivative more soluble than the dye in the composition.
  • the xanthene dye derivative has the structure of Fig. 1 of the attached drawing.
  • the invention is a method for photo- polymerizing which involves the use, as an activator, of a xanthene dye derivative having a Y2' substituent which makes the derivative more soluble than the dye in the composition.
  • the xanthene dye derivative has the structure of Fig. 1 of the attached drawing.
  • the invention is a photopolymerizable composition which contains one of a family of dyes o derivatives which have the structure of Fig. 2, 3 or 4 of th attached drawing.
  • the invention is a method fo photopolymerizing which involves the use of a dye or dy derivative having the structure of Fig. 1, 2 or 3 of th attached drawing as an initiator.
  • Fig. 1 is a structural formula for a family of xanthene dy derivatives which are initiators in photopolymerizabl compositions according to the invention.
  • Fig. 2 is a structural formula for a family of derivative of 7-hydroxy-3H-phenoxazin-3one, sodiumsalt ("resorutim") whic are initiators in photopolymerizable compositions according t the invention.
  • Fig. 3 is a structural formula for another family o resorutim derivatives which are initiators in photopolymerizabl compositions according to the invention.
  • Fig. 4 is a structural formula for still another family o resorutimderivatives which are initiators inphotopolymerizabl compositions according to the invention.
  • a photopolymerizable composition prepared by mixing trimethylolpropane triacrylate with 0.0669g eosin lactone and
  • 16g triethanolamine, per kg triacrylate was placed in a glass vessel that was square in horizontal cross section, each side of the square being substantially 1 cm in length.
  • a shutter was then positioned closely adjacent one of the walls of the vessel, and a beam of light having a wavelength of 514nm was directed from an argon ion laser toward the shutter and one of the walls of the vessel.
  • the shutter was so positioned that, when closed, it prevented light from the laser from impinging on the vessel and, when open, a beam of light that was circular in cross section and had a radius substantially less than 1mm traveled through one of the glass walls of the vessel, at substantially a right angle thereto, and into the photopolymerizable composition.
  • the shutter was opened for 125 m sec while the laser was set to deliver a light beam which had a power varying from 25 to 250 W, and the position of the glass vessel was changed after each shutter opening, so that different parts of the photopolymerizable composition were activated by light having a wavelength of 514 nm and of diverging intensities.
  • the depth to which photopolymerization occurred at each of four intensities is shown in the following table:
  • Example 2 The laser used as described above in Example 1 was one tha is commercially available under the trade designation "Spectr Physics argon ion laser Model 2016-05". As indicated above, i was tuned to emit light having a wavelength of 514 nm.
  • EXAMPLE 2 The laser used as described above in Example 1 was one tha is commercially available under the trade designation "Spectr Physics argon ion laser Model 2016-05". As indicated above, i was tuned to emit light having a wavelength of 514 nm.
  • the depth to whi photopolymerization occurred at each of three different exposu times is shown in the following table: Exposure time, m sec Depth of photopolymerization, mm
  • Laser 2 The helium/neon laser (hereafter "Laser 2") used as described above in Example 2 is commercially available under the trade designation "Nelles-Griot He/Ne Laser". As used in the present
  • Exposure time m sec Depth of photopolymerization, mm 125 1.44 250 2.81
  • the depth of polymerization when photopolymerizable compositions according to the instant invention are subjected to photon initiation of suitable, constant intensity, is directly proportional to log T, where T is the time of exposure, which is conveniently measured in seconds.
  • T the time of exposure
  • S the slope of the straight line relationship between log time and depth
  • photopolymerizations have also been carried out usin a monomer system composed of 12.Ig diacrylate of an ethoxylated bisphenol and 12.Ig acrylic monomer, using an Ar(+) laser wavelength 514nm, intensity SOOirfW.
  • the monomer composition also containe 0.02g eosin Y lactone dissolved in 0.48g 2-hydroxyethyl methacrylate and 0.8g triethanolamine. I was found to be 0.480m and S was found to be 3.26.
  • the monome composition also contained O.lg eosin Y lactone dissolved i 0.4g 2-hydroxyethylmethacrylate and 0.8g triethanolamine. I wa found to be 0.450mm and S was found to be 1.90.
  • the ethoxylatedbisphenol diacrylate used as described abo in Example 30 is available from Sartomer Company under the tra designation SR349.
  • the acrylic monomer used as described above in Example 30 is available under the trade designation "NOVACURE C3700" from Radcure Company.
  • a xanthate dye derivative for use according to the invention as an initiator in a polymerizable composition was produced from 42.00 g rose bengal (structure of Fig. 1 where X2, X4, X5 and X7 are iodo, Y2'is COONa, Y3', Y4', Y ⁇ 'and Y6' are chloro, and R is Na) which was dissolved in 350 mL dimethyl formamide. The solution was refluxed under an argon blanket for about 16 hours, with stirring, and was then concentrated to 80 mL by distillation of dimethyl formamide. An addition of 200 mL 2M hydrochloric acid was then made to the concentrated solution, after which a pasty red solid was recovered by vacuum filtration.
  • the red solid was washed with 500 mL of water and then with 300 mL of hexanes, and was then dried for 48 hours under vacuum.
  • the yield was 31.72 g decarboxylated rose bengal (structure of Fig. 1 where X2, X4, X5 and X7 are iodo, Y2' is H, Y3', Y4 1 , Y5'and Y6' are chloro and R is Na) , 82.63 percent of theory.
  • the compound was identified by NMR and IR.
  • O-trichloroa ⁇ etyl decarboxylated rose bengal (structure o Fig. 2 where X2, X4, X5 and X7 are iodo, Y2'is H, Y3' , Y4' , Y5 f and Y6'are chloro, and R is trichloroacetyl) was produced fro 5.24 g decaraboxylated rose bengal prepared as described i Example 33, and dissolved in 20 mL trichloroacetyl chloride. Th solution was refluxed under an argon blanket, with stirring, fo forty hours, after which time the solution was found to b almost completely free of the starting dye.
  • O-methyl decarboxylated rose bengal (structure of Fig. where X2, X4, X5 and X7 are iodo, Y2• is H, Y3' , Y4', Y5 1 an Y6* are chloro, and R is methyl) was produced from 1.17 decarboxylated rose bengal produced as described in Example 33 2.0 mL dimethyl sulfate, and 4.0 g sodium carbonate dissolve in 30 mL 1,2-dimethoxyethane. The solution was refluxed, wit stirring, under an argon blanket for 5 hours and was cooled t room temperature of about 22 * . Solids which formed were separated from the liquid by filtration and washed with 50 dichloromethane.
  • 0-(3,5-dinitrobenzoyl) decarboxylated rose bengal (structure of Fig. 1 where X2, X4, X5 and X7 are iodo, Y2' is H, Y3' , Y4', R5* and Y6* are chloro, and R is 3,5-dinitrobenzoyl) was produced from 3.00 g decarboxylated rose bengal produced as described in Example 33 and 0.88 g 3,5-dinitrobenzoyl chloride dissolved in 40 L toluene. The solution was refluxed, with stirring, under a nitrogen atmosphere for 48 hours. 0-(3,5- dinitrobenzoyl) decarboxylated rose bengal, whichwas identified by NMR, was recovered by concentrating the reaction mixture under vacuum. EXAMPLE 37
  • O-acetyl ethyl eosin (structure of Fig. 1 where X2, X4, X5 and X7 are bromo, Y2'is -COOCH 2 CH 3 , Y3', Y4', Y5' and Y6' are H, and R is acetyl) was produced from a solution of 5.00 g ethyl eosin (structure of Fig.
  • the composition was placed in a quart cuvette which had a square base 1 cm on a side and four side at right angles to the base, each, 1 cm by 4 cm, and severa portions of the composition were exposed to light from the argo laser at a power of lOOmW in the manner described in Example 1.
  • the unreacted solution was then decanted from the cuvette, an the lengths of spikes attached to the interior of the cuvett which had been formed by polymerization of the solution were measured.
  • the lengths of the spikes at various exposure time are given in the following table:
  • Example 38 The procedure described above in Example 38 was repeated t polymerize a solution which contained 20 percent o tetrahydrofuran in the dipenta-erythritol hydroxy penta acrylate, and, per 1000 g of the solution, 0.0090 g O-acety decarboxylated rose bengal and 0.08 g triethanolamine. Th lengths of the spikes at various exposure times are given in th following table:
  • Example 38 The procedure described above in Example 38 was also repeate to polymerize a solution which contained 20 percent o tetrahydrofuran in the dipenta-erythritol hydroxy penta acrylate, and, per 1000 g of the solution, 0.0876 g O-acety decarboxylated rose bengal and 0.16 g triethanolamine. Th lengths of the spikes at various exposure times are given in th following table:
  • Example 38 1.096 0.0167 The procedure described above in Example 38 was repeated, except that the wavelength of the radiation was 488 nm, t polymerize a solution which contained 20 percent o tetrahydrofuran in the dipenta-erythritol hydroxy penta acrylate, and, per 1000 g of the solution, 0.07650 g O-acetyl decarboxylated rose bengal and 0.09 g triethanolamine. Th lengths of the spikes at various exposure times are given in th following table:
  • Example 38 the procedure described above in Example 38 wa repeated to polymerize a solution which contained 20 percent o tetrahydrofuran in the dipenta-erythritol hydroxy penta acrylate, and, per 1000 g of the solution, 0.04900 g O-acety decarboxylated rose bengal and 0.40 g tetramethylammonium n butyl borate.
  • the lengths of the spikes at various exposur times are given in the following table:
  • Examples of known xanthen dyes include rose bengal (the starting material in Example 33) , fluorescein, eosin, phloxin, erythrosin, dichloro eosin (tw compounds, one where Y3• and Y6• are Cl and one where X2 and X are Cl) , dibromo flourescein (two compounds, one where X4 an X5 are Br, and one where X2 and X4 are Br) and diiodofluoroes cein.
  • Many other xanthene dyes are disclosed in the literature commencing with Baeyer, A. (Chemische Berichte. 1871, 4, 555 an 1875, 8, 146 and Anna1en.
  • tha R can be an alkyl group having from 1 to 22 carbon atoms, a alkaryl group having from 7 to 22 carbon atoms, an aryl grou having from 6 to 20 carbon atoms, an aralkyl group having fro 7 to 22 carbon atoms, a 2 to 10 membered carbocyclic o heterocyclic group, an olefinically unsaturated hydrocarbo group having from 2 to 10 carbon atoms, an acyl group havin from 2 to 22 carbon atoms, or a halogenated acyl group havin from 2 to 22 carbon atoms.
  • R is an alkyl group othe than t-butyl having from 1 to 4 carbon atoms, an acyl grou having from 1 to 4 carbon atoms or a halogenated acyl grou having from 1 to 4 carbon atoms.
  • Y2• can be a grou having the formula -C00R' , where R' can be an alkyl group havin from 1 to 22 carbon atoms, an alkaryl group having from 7 to 2 carbon atoms, an aryl group having from 6 to 20 carbon atoms an aralkyl group having from 7 to 22 carbon atoms, a 2 to 1 membered carbocyclic or heterocyclic group, or an olefinicall unsaturated hydrocarbon group having from 2 to 10 carbon atoms
  • R' is an alkyl group other than t-butyl having fro 1 to 4 carbon atoms.
  • M can be oxygen sulfur, selenium, tellurium, S0 2 , SO or NR' , where R' has th meaning set forth above.
  • R' has th meaning set forth above.
  • the sodium salt of tetraiodoresorufim a compound having the structure of Fig. 2 of the drawings where XI, X2, X3, and X4 are I, and R is Na was produced from a mixture of 1.0 g resorufim, 70 mL water, 21 L saturated aqueous sodium carbonate and 4.84 g iodine. The iodine was added slowly to a mixture of the resorufim, water, and sodium carbonate solution, and the reaction mixture which resulted was stirred for about 16 hours at about 20 * .
  • the final reaction mixture which contained the sodium salt of tetraiodoresorufim, was then acidified with concentrated hydrochloric acid; the precipitate which formed was recovered by filtration, washed with dilute hydrochloric acid, and dried under reduced pressure, yielding 1.2 g tetraiodoresorufim, which was identified by IR and NMR.
  • Tetraiodoresorufim acetate (the acetate of a compound having the structure of Fig. 2 of the drawings where XI, X2, X3, and X4 are I, and R is H) was then produced by stirring a mixture of 500 mg tetraiodoresorufim produced as described in the preceding paragraph, 20 mg 4-dimethylaminopyridine, and 3 ml acetic anhydride in 40 ml dry tetrahydrofuran at about 20 * for about 16 hours. The solvent was then removed from the reaction mixture under reduced pressure, and the residue which remained was dissolved in 100 mL diethyl ether.
  • Polymerizations were carried out using tetraiodoresorufi acetate produced as described above as an initiator for the polymerization of Monomer 1, cetylpyridinium triphenyl butyl borate as an accelerator, and activating radiation from an argon ion laser which had a wavelength of 514 nm.
  • the composition polymerized was a solution of 8.7 mg tetraiodoreserufim acetate and 60.7 mg cetylpyridinium triphenyl butyl borate in 10 m Monomer 1.
  • the polymerizations were carried out as described i Example 38.
  • the weight of the polymer spike that was formed whe the composition was exposed to light from the argon laser at power of HOmW are given in the following table.
  • Tetrabromoresorufim, tetrachlororesorufim and tetrafluoro resorufim can be produced by bubbling bromine, ejilorine o fluorine through a stirred reaction mixture composed o resorufim, water and sodium carbonate, and other compound having the structure of Fig. 2 can be produced by the method o Example 39 by substituting other starting materials for th resorufim. Lacmoid, a compound having the structure of Fig.
  • X2, X4, X5 and X7 are H F, Cl, Br or I.
  • a beam of activating radiation for example, from an argon ion laser having a wavelength of 514nm, entering the composition causes the eosin to react with the triethanolamine, with the result that the dye color is lost, and two moieties are formed, one of which serves as an activator fo the trimethylolpropane triacrylate; as a consequence of the loss of the dye color, subsequent radiation can penetrate deeper in the photopolymerizable composition.
  • compositions specifically disclosed above are suitably activated. It will be appreciated, however, that other photopolymerizabl compositions, in addition to those specifically disclosed, will react in a similar manner, and that such compositions can b used in practicing the method of the instant invention, as ca still other compositions, so long as they are ones in which a entering ray of activating radiation activates th photoinitiator system thereof at each of a succession of points, the first such point being immediately adjacent the surfac through which the ray enters and subsequent points bein successively farther from the surface in the direction of trave of the ray of activating radiation, the distance from th surface to the point of the succession farthest therefro varying as a function of at least one of
  • concentrations in which photoinitiators are used for thi film photopolymerizations are so high that activating light ca not penetrate the monomer/photoinitiator mixture to a sufficien depth, and polymerization stops on or near the surface throug which the light enters.
  • concentration of the photoinitiato must be sufficiently high that the induction period is no excessive, and the concentration of the activator and the photo density must both be sufficiently high that the rates o bleaching and polymerization are appropriately matched t achieve polymerization to a desired depth in photopolymerizable composition.
  • compositions composed of a trimethylolpropane triacrylat monomer, a vinyl 2-pyrollidone and dipentaerythritol hydrox penta acrylate monomer system, and a monomer system composed o a diacrylate of an ethoxylated-bisphenol and an acrylic monomer one of several dyes which are photoinitiators an triethanolamine or another accelerator.
  • Othet monomers photoinitiators and accelerators that can be used will b apparent to one skilled in the art from the foregoin disclosure.
  • the monomer should be one which has a electron starved double bond that is subject to additio polymerization, acrylic monomers, generally, being suitable
  • other accelerators can be used, tertiary amines bein preferred when visible light is used for activation and th photoinitiator is eosin lactone, methylene violet, methylene blue, methylene green or another photoinitiator which is a dye in the conventional sense.
  • the invention can also be practiced with activating radiation that is outside the visible spectrum and a suitable activator, for example, one that, prior to activation is opaque to the activating radiation but, upon activation, undergoes a reaction which causes it to be transparent to the activating radiation.
  • the photopolymerizable composition be one wherein a ray of activating radiation which enters a body of the composition through a surface thereof activates the photoinitiator system and causes polymerization at each of a succession of points, the first such point being immediately adjacent the surface and subsequent points being successively farther from the surface in the direction of travel of the ray of activating radiation, and the distance from the surface to the point of the succession farthest therefrom varies as a function of at least one of
  • the method of the invention can also be used to produce a colored body.
  • a dye or pigment which imparts a color to a polymer produced from a body of the polymerizable composition can be to the body, and a polymer can be produced as previously described.
  • the polymer can then be immersed in a body of another polymerizable composition containing another dye or pigment which imparts a different color to a polymer produced therefrom, and a second polymer can be produced.
  • the composite polymer can be immersed in a body of a third polymerizable composition containing a dye or pigment which imparts a third color to a polymer produced therefrom, and a third polymer can be produced.
  • the colors of the three polymers of the final composite can complement one another as colored printing inks complement one another in producing colored images.
  • the method of the invention can also be used in surgical procedures, for example to reconstruct a bone or to construct a hip.
  • a photopolymerizable composition according to the invention can be positioned in any suitable way in the region where construction or reconstruction is required, and photopolymerization can be initiated by light of a suitable wavelength conducted to the polymer through optical fibers, the depth of polymerization being controlled by the duration of the activating light, the intensity, or both.
  • data concerning the reconstruction or construction can be input to a computer remote from the surgery, and the output from the computer can be used to control the activating light.
  • Three dimensional objects can be made according to the method of the invention by positioning an appropriate laser and moving a body of the composition to be photopolymerized appropriately relative to the fixed laser.
  • the body of the composition to be polymerized can be moved either vertically or horizontally and then translated in the other direction; by repeating these movements radiation from the laser can be caused to enter the body in a complete two dimensional grid.
  • the depth of polymerization can then be controlled by varying the rate of movement of the body, slower movement causing deeper polymerization, and vice versa.
  • a similar result can be achieved by moving the laser rather than the body of the photopolymerizable composition.
  • a relief map can be made by the method of the instant invention by directing a suitable laser upwardl through a bottom of a container and into a body of a appropriate photopolymerizable composition, moving the body o the polymerizable composition so that the laser enters the bod in a complete two-dimensional grid, as described, and varyin the rate of movement so that the depth of polymerizatio corresponds with the height to be represented at all points o the grid.
  • the bottom of the container can be a material to whic the polymer adheres, so that the relief map, when completed, i mounted on the bottom of the container as a base.
  • the method can also be used to weld two pieces, one of whic is transparent to the radiation from the laser used, b confining a body of a photopolymerizable material in a regio which includes that where the weld is desired, and then initiating photopolymerization with a laser to form the weld.
  • a spacer can be formed between two sheets, one of which is transparent to the radiation, by confining the body of the photopolymerizable material between the sheets, and then initiating photopolymerization with the laser to form the spacer.
  • edges of two sheets can be sealed and supported relative to one another by confining the body of the photopolymerizable material between the sheets, and then initiating photopolymerization with the laser to seal the edges and support them relative to one another.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Composition polymérisable comprenant un monomère photopolymérisable ainsi qu'un système de photoexcitation pour le monomère. Grâce à ce système, un rayon de radiation d'activation qui pénètre un corps de la composition par une de ses surfaces active le système de photoexcitation et provoque la polymérisation de tous les points d'une série de points dont le premier est immédiatement adjacent à la surface, les points suivants étant de plus en plus éloignés de cette surface dans le sens du déplacement du rayon de radiation d'activation, la distance entre la surface et le point de la série qui en est le plus éloigné variant en fonction d'au moins un des deux éléments suivants: (a) l'intensité de la radiation d'activation; et (b) le temps que prend la radiation d'activation pour pénétrer dans le corps à travers la surface. Le procédé consiste à diriger un rayon de radiation d'activation pour le système de photoexcitation sur un point situé dans un plan donné, à travers ce point et dans un corps de la composition, et à contrôler au moins un des deux facteurs suivants: (c) l'intensité de la radiation d'activation du rayon; et (d) le temps pendant lequel le rayon qui pénètre dans l'élement est dirigé à travers la point; cela de manière à déterminer la distance entre une surface à travers laquelle le rayon de radiation d'activation pénètre dans le corps et le point le plus éloigné de cette surface de la série de points dont le rayon active le système de photoexcitation. L'invention porte en outre sur de nouveaux photoexcitants dont les structures sont représentées par les figures 1, 2 et 3.
PCT/US1990/000991 1989-02-24 1990-02-23 Production de corps tridimensionnels par photopolymerisation WO1990010254A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US31538389A 1989-02-24 1989-02-24
US34806989A 1989-05-05 1989-05-05
US348,069 1989-05-05
US315,383 1994-09-30

Publications (1)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0535984A1 (fr) * 1991-10-02 1993-04-07 Spectra Group Limited Inc Produktion d'objets tridimensionnels
WO1995001257A1 (fr) * 1993-07-02 1995-01-12 Zeneca Limited Procede d'elaboration d'un article en couleur et en trois dimensions
US5395862A (en) * 1992-12-09 1995-03-07 Spectra Group Limited, Inc. Photooxidizable initiator composition and photosensitive materials containing the same
WO1995014689A1 (fr) * 1993-11-19 1995-06-01 Spectra Group Limited, Inc. Derives de la fluorone et de la pyronine y
WO1997009168A1 (fr) * 1995-09-09 1997-03-13 Zeneca Limited Procede de fabrication de couches en polymere a regions colorees selectivement
US5639802A (en) * 1991-05-20 1997-06-17 Spectra Group Limited, Inc. Cationic polymerization
WO2000067073A1 (fr) * 1999-04-29 2000-11-09 Tatiyana Nikolaevna Smirnova Composition photopolymerisable pour enregistrement holographique et variantes

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US4772530A (en) * 1986-05-06 1988-09-20 The Mead Corporation Photosensitive materials containing ionic dye compounds as initiators
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US3244518A (en) * 1960-05-19 1966-04-05 Gen Aniline & Film Corp Process for obtaining multicolor images and a multilayer sheet for use therein
US3203332A (en) * 1962-02-07 1965-08-31 Keuffel & Esser Co Method for measuring photographic exposure time
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US4816379A (en) * 1982-12-28 1989-03-28 Basf Aktiengesellschaft Production of relief plates and printing plates by a positive-working method
US4654378A (en) * 1984-05-02 1987-03-31 Calgon Corporation Process for the manufacture of high solids, free-flowing, granular poly(dimethyldiallyl ammonium chloride)
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US4772530A (en) * 1986-05-06 1988-09-20 The Mead Corporation Photosensitive materials containing ionic dye compounds as initiators

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5451343A (en) * 1991-05-20 1995-09-19 Spectra Group Limited, Inc. Fluorone and pyronin y derivatives
US5623080A (en) * 1991-05-20 1997-04-22 Spectra Group Limited, Inc. Fluorone and pyronin Y derivatives
US5639802A (en) * 1991-05-20 1997-06-17 Spectra Group Limited, Inc. Cationic polymerization
EP0535984A1 (fr) * 1991-10-02 1993-04-07 Spectra Group Limited Inc Produktion d'objets tridimensionnels
US5395862A (en) * 1992-12-09 1995-03-07 Spectra Group Limited, Inc. Photooxidizable initiator composition and photosensitive materials containing the same
WO1995001257A1 (fr) * 1993-07-02 1995-01-12 Zeneca Limited Procede d'elaboration d'un article en couleur et en trois dimensions
WO1995014689A1 (fr) * 1993-11-19 1995-06-01 Spectra Group Limited, Inc. Derives de la fluorone et de la pyronine y
WO1997009168A1 (fr) * 1995-09-09 1997-03-13 Zeneca Limited Procede de fabrication de couches en polymere a regions colorees selectivement
US6133336A (en) * 1995-09-09 2000-10-17 Zeneca Limited Process for forming a colored three-dimensional article
WO2000067073A1 (fr) * 1999-04-29 2000-11-09 Tatiyana Nikolaevna Smirnova Composition photopolymerisable pour enregistrement holographique et variantes

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