CA2035779A1 - Process for the preparation of photostructured layers with improved mechanical properties - Google Patents
Process for the preparation of photostructured layers with improved mechanical propertiesInfo
- Publication number
- CA2035779A1 CA2035779A1 CA2035779A CA2035779A CA2035779A1 CA 2035779 A1 CA2035779 A1 CA 2035779A1 CA 2035779 A CA2035779 A CA 2035779A CA 2035779 A CA2035779 A CA 2035779A CA 2035779 A1 CA2035779 A1 CA 2035779A1
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- Canada
- Prior art keywords
- layer
- light
- thermally
- accordance
- sensitive
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- 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
-
- 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
-
- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
PROCESS FOR THE PREPARATION OF PHOTOSTRUCTURED
LAYERS WITH IMPROVED MECHANICAL PROPERTIES
ABSTRACT OF THE DISCLOSURE
The invention involves a process for the preparation of a photostructured layer or of three dimensional objects.
Structured materials with higher mechanical stability can be prepared by the use of light-sensitive mixtures with a thermally fusible polymer/plasticizer dispersion, at least one monomer, a photoinitiator, and a thermally active compound, such mixtures being photopolymerized imagewise as well as also thermally fused and thermally polymerized.
LAYERS WITH IMPROVED MECHANICAL PROPERTIES
ABSTRACT OF THE DISCLOSURE
The invention involves a process for the preparation of a photostructured layer or of three dimensional objects.
Structured materials with higher mechanical stability can be prepared by the use of light-sensitive mixtures with a thermally fusible polymer/plasticizer dispersion, at least one monomer, a photoinitiator, and a thermally active compound, such mixtures being photopolymerized imagewise as well as also thermally fused and thermally polymerized.
Description
hJ ~ t~ a 7 7 ~
PROCESS FOR THE PREPARATION OF PHOTOSTRVCTURED
LAYERS WITH IMPROVED MECHANICAL PROPERTIES
BACKGROUN~ OF THE_INVENTION
The subject of the present invention is a process for the preparation of strucutred layers and three-dimensional objects. In this process, one or more layers of a light-sensitive mixture from a photo-polymerizable and also thermally hardenable plastisol dispersion are exposed imagewise and the photo-polymerized area are thermally posthardened.
Many processes are used today for the preparation of structured layers. In these processes, light-sensitive layers are exposed imagewise and the exposedor unexposed areas are removed, for example, by washoff.
In particular, the production of printing plates, etching or plating resists, and solder resists uses so-called negative-working mixtures that polymerize or crosslink under the influence of light ~for example, DE-C 22 15 090) and optionally, can be posthardened thermally (~or example, EP-B 00 73 444 and EP-B 00 63 304).
This type of photostructuring is also being used increasingly in the preparation of three-dimensional objects. Various processes that produce three-dimensional models by the stepwise assembly of many individual photohardened layers are known. (U.S.
4,575,330; EP-A 02 50 121; U.S. 4,752,498 and Imaain~
TechnQl 15 (4), 186-190 ~1989) and the literature cited therein.) These processes use technologies that operate with different exposure masks for each individual layer, as well as those that write the desired structure directly on the photopolymerizable layers with a laser.
However, publications to date are concerned not with ~ ~ 3 .) ~ 7 9 special light-sensitive mixtures for three-dimensional objects, but rather only with the process technology for using known light-sensitive materials for other products.
These materials usually consist of a polymeric binder, a liquid photopolymerizable monomer and a photoinltiator, with possible additives, such as fillers, thermal polymerization inhibitors, dyes, etc.
However, materials prepared with these mixtures often have unsatisfactory mechanical properties. The processing of such polymerizable mixtures is also difficult, because their viscosity is very high.
Plasticizers are usually added to lower viscosity.
However, these have the disadvantage of easily exuding from the finished materials.
Plastisols or organosols are a special type of polymer/plasticizer mixtures. These are 90-80% by weight dispersions of polymers in liquid, non-volatile plasticizers, which, when the dispersion is heated above a certain temperature ~the gel or plastisol temperature), are able to dissolve the polymers. Solid, transparent materials are produced when this phase is cooled to roorn temperature. These dispersions can also include volatile solvents. If their content is under 10% ~y weight, the product is called a plastisol; with a higher solvent content, the product is called an ; organosol.
Plastisols, to which monomers and photoinitiators or thermal initiators are added and which can be posthardened after thermal fusion of the polymer/plasticizer mixture, as known. Such reactive plastisols are described, for example, in U.S.
PROCESS FOR THE PREPARATION OF PHOTOSTRVCTURED
LAYERS WITH IMPROVED MECHANICAL PROPERTIES
BACKGROUN~ OF THE_INVENTION
The subject of the present invention is a process for the preparation of strucutred layers and three-dimensional objects. In this process, one or more layers of a light-sensitive mixture from a photo-polymerizable and also thermally hardenable plastisol dispersion are exposed imagewise and the photo-polymerized area are thermally posthardened.
Many processes are used today for the preparation of structured layers. In these processes, light-sensitive layers are exposed imagewise and the exposedor unexposed areas are removed, for example, by washoff.
In particular, the production of printing plates, etching or plating resists, and solder resists uses so-called negative-working mixtures that polymerize or crosslink under the influence of light ~for example, DE-C 22 15 090) and optionally, can be posthardened thermally (~or example, EP-B 00 73 444 and EP-B 00 63 304).
This type of photostructuring is also being used increasingly in the preparation of three-dimensional objects. Various processes that produce three-dimensional models by the stepwise assembly of many individual photohardened layers are known. (U.S.
4,575,330; EP-A 02 50 121; U.S. 4,752,498 and Imaain~
TechnQl 15 (4), 186-190 ~1989) and the literature cited therein.) These processes use technologies that operate with different exposure masks for each individual layer, as well as those that write the desired structure directly on the photopolymerizable layers with a laser.
However, publications to date are concerned not with ~ ~ 3 .) ~ 7 9 special light-sensitive mixtures for three-dimensional objects, but rather only with the process technology for using known light-sensitive materials for other products.
These materials usually consist of a polymeric binder, a liquid photopolymerizable monomer and a photoinltiator, with possible additives, such as fillers, thermal polymerization inhibitors, dyes, etc.
However, materials prepared with these mixtures often have unsatisfactory mechanical properties. The processing of such polymerizable mixtures is also difficult, because their viscosity is very high.
Plasticizers are usually added to lower viscosity.
However, these have the disadvantage of easily exuding from the finished materials.
Plastisols or organosols are a special type of polymer/plasticizer mixtures. These are 90-80% by weight dispersions of polymers in liquid, non-volatile plasticizers, which, when the dispersion is heated above a certain temperature ~the gel or plastisol temperature), are able to dissolve the polymers. Solid, transparent materials are produced when this phase is cooled to roorn temperature. These dispersions can also include volatile solvents. If their content is under 10% ~y weight, the product is called a plastisol; with a higher solvent content, the product is called an ; organosol.
Plastisols, to which monomers and photoinitiators or thermal initiators are added and which can be posthardened after thermal fusion of the polymer/plasticizer mixture, as known. Such reactive plastisols are described, for example, in U.S.
2,518,621; DE-A 30 06 3q9; U.S. 9,523,983 or U.S.
4,623,558. Mixtures of a plastisol, a polyfunctional monomer and/or an epoxy resin, a photoinitiator, and a i~ ~ 3 3 7 7 9 thermal initiator, which can be used as sealing compounds and adhesives, are described in J. Radiat.
Curing 10 ~9), 8~ 1983) and DE-A 33 14 896. These plastisol mixtures are solidified by short, overall light exposure ~as described also in U.S. 4,634,562 for mixtures without thermal initiators) and then are hardened completely by thermal treatment. Thermal polymerization is used to harden the adhesive when photopolymerization is not possible. The process for printing plate production in U.S. 9,176,028 uses plastisols that are photohardenable only and whose thermal fusion is utilized to form a photopolymerizable layer. This is then laminated onto a support, exposed imagewise by the usual process, and washed off. In this case, plastisols containing thermal initiators and forming very hard layers in the assembly of photopolymerizable layers, should not be used, because the removal of the unexposed areas is adversely affected.
Another process for the preparation of printing plates, using the combination of a plastisol and a photopolymerizable mixture, is described in U.S.
4,623,558. Mixtures of a plastisol, a polyfunctional monomer and/or an epoxy resin, a photoinitiator, and a i~ ~ 3 3 7 7 9 thermal initiator, which can be used as sealing compounds and adhesives, are described in J. Radiat.
Curing 10 ~9), 8~ 1983) and DE-A 33 14 896. These plastisol mixtures are solidified by short, overall light exposure ~as described also in U.S. 4,634,562 for mixtures without thermal initiators) and then are hardened completely by thermal treatment. Thermal polymerization is used to harden the adhesive when photopolymerization is not possible. The process for printing plate production in U.S. 9,176,028 uses plastisols that are photohardenable only and whose thermal fusion is utilized to form a photopolymerizable layer. This is then laminated onto a support, exposed imagewise by the usual process, and washed off. In this case, plastisols containing thermal initiators and forming very hard layers in the assembly of photopolymerizable layers, should not be used, because the removal of the unexposed areas is adversely affected.
Another process for the preparation of printing plates, using the combination of a plastisol and a photopolymerizable mixture, is described in U.S.
3,615,448 and by W. J. Nebe in the advance printing of summaries for the "Symposium on Photopolymer Systems", 25 Washington, 1978, p. 75-56. Here, a layer consisting of a plastisol, a light-sensitive compound, such as a monomer, a crosslinkable polymer or a polymerizable plasticizer, and a photoinitiator are exposed imagewise and heated. The unexposed areas melt and, on cooling, form solid, non-tacky areas. The exposed portions can then be washed off or toned. In this process, plastisol fusion and photohardening occur in different areas, thus differentiating imagewise between thermally fusible and non-fusible areas by photopolymerization of the monomers, polymers, or plasticizers.
., .:
,:
9 ~'(3'3`3779 Summaxy of -the Invention The problem involved in the present invention is to develop a process that starts with a liyht-sensitive mixture to produce structured layers or three dimensional objects with high mechanical stability. The products should have high tensi:Le strength, high shore hardness, low elongation, high rigidity and low shrinkage as a result of the hardening process. In addition, the plasticizer should not exude, and the light-sensitive mixtures should be easy to handle and process. At the same time, an exact reproduction should be assured for the image or model to be represented.
~his problem is solved by a process for the preparation of photostructured layers comprising the steps of:
a) forming a layer from a light-sensitive mixture containing 1. a thexmally fusible polymer and plasticizer dispersion, 2. at least one addition-polymerizable, ethylenically unsaturated compound, 3. a photoinitiator or a photoinitiator system, and 9. a thermally reactive compound, b) imagewise exposing the light-sensitive layer, c) removing the unexposed areas of the layer, and d) thermally treating the exposed layer.
With the present process, it is possible to use the advantages of reactive plastisols for imagewise photo-structuring. None of the known processes for converting reactive plastisols suggest the process of the invention. It is astonishing that adverse effects do not occur either in the imagewise exposure and removal of the unexposed areas or in the thermal fusion or thermal hardening. Although it is known from the i current state of the art that thermally fusible areas can be differentiated from non~fusible areas by imagewise exposure of plastisols containing monomers and photoinitiators, it was most unexpected that thermal fusion is still possible despite prior photo-polymerization.
Detaile~ Description Qf the Inv~ention ~ he use of a light-sensitive mixture that is photo~
polymerizable as well as thermally fusible and hardenable is essential to the invention. The binder system of the light-sensltive mixture of the invention uses a polymer/plasticizer dispersion that, on heating, melts to one phase, which, on cooling, hardens to a solid, transparent composition. At the same time, because a plastisol is used, the high plasticizer proportion means a low viscosity and with it, good processibility of the light-sensitive mixture. The combination of a monomer or monomer mixture with a photoinitiator and a thermally reactive compound implies the possibility of imagewise photopolymerization and associated thermal posthardening. Astonishingly, the addition of a thermally reactive compound does not significantly degrade the stability and processibility of the light-sensitive mixture, although thermal polymerization inhibitors must be added to conventional light-sensitive mixtures. It was also astonishing that the stability of the structuxed materials was highest for short exposure times.
An essential aspect of the process of the invention is that the thermal treatment takes place only after removal of the unexposed areas.
Consequently, the thermal treatment affects only the exposed areas, whose mechanical properties can be significantly improved thereby. Stabilization of the materials structured by imagewise photopolymerization is ~3~rl79 indeed effected partially by the plastisol fusion of the binder system, but more extensive reinforcement is accomplished only by an additional thermal hardening.
Structured materials that have been subjected to this two-fold reinforcement by a thermal treatment have adequa~e mechanical stability and resistance to high stress, and in addition, show long service life. A
structure material that was hardened only by plastisol fusion shows lower tensile strength, higher elongation and plasticizer migration.
For the thermal hardening essential to the invention, the light-sensitive mixture contains preferably a thermal initiator and an addition-polymerizable, ethylenically unsaturated compound. The latter can be photopolymerizable monomer or monomer mixture that was not completely reacted in the photo-polymerization step. This can be accomplished by short exposure times, limiting photoinitiation by the selection of a high optical density, preferably D>1.3, or adding less reactive monomers. Monomer mixtures containing monomers of different reactivities are preferred. The more reactive monomer is photo-polymerized by imagewise exposure to structure the material, and the less reactive monomer is thermally polymerized during subsequent treatment to reinforce the material. Moreover, the monomers must be compatible with the polymers. Above all, the less reactive monomer must be compatible with the polymers, particularly at higher temperatures. On the other hand, the monomers should not swell the polymer at room temperature.
Suitable monomers wiih different reactivities are, for example, acrylates and methacrylates. Examples of suitable monomers are ethyl acrylate and methacrylate, 1,4-butanediol diacrylate and methacrylate, isodecyl acrylate and methacrylate, dicyclopentenyl diacrylate ~ ~ 3 r3 7 7 9 and methacrylate, 2-ethyl hexyl acrylate and methacrylate, and lauryl acrylate an~ methacrylate.
Particularly advantageous are trimethylol propane triacrylate and methacrylate, l,6-hexanediol acrylate and methacrylate, or ethoxylated trimethylol propane triacrylate and N-vinyl pyrrolidone. Thermal polymerization should not take place below the plastisol temperature, but rather at or preferably above this temperature. This means that thermal polymerization should take place only after plastisol fusion within the phase formed thereby. This is achieved by the use of a thermal initiator that decomposes at or preferably above the plastisol temperature. Examples of suitable thermal initiators are t-butyl hydroperoxide, t-butyl perbenzoate, and cumene hydroperoxide.
Another version of the invention comprises thermal hardening by means of compounds that are thermally crosslinkable with themselves and/or with one or more other components of the mixture. Suitable examples are compounds with epoxy, hydroxy, alkyl ether and hydroxy alkyl groups. Particularly suitable are compounds with at least two epoxy groups and melamine derivatives.
Preferred compounds are hexamethoxy melamine, 3,4-epoxy-cyclohexyl carboxylic acid-3,4-epoxycyclohexyl methyl ester and 2,2-bis(glycidoxyphenyl)propane.
The photopolymerization initiators can be known photoinitiators or initiator systems, such as, for example, benzoin, benzoin alkyl ether, alpha-methyl benzoin or its ether, benzil dimethyl ketal, and systems, such as, for example, benzophenone/Michler's ketone and thioxanthones/amines. In the invention, polymer/plasticizer dispersions that fuse at elevated temperature are used as the binder system. Suited for this purpose are plastisols and organosols with 40 to 80 percent by weight, preferably 50 to 70 percent by 7 ~ ~
weight, of a homopolymer or copolymers of vinyl chloride, vinyl acetate, vinyl propionate, vinyl stearate, vinyl ether, vinyl pyridine, styrene, acrylic acid and methacrylic acid or its esters, such as, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, (meth)-acrylonitrile, etc. Mixtures of more than one of the cited homopolymers or copolymers or core/shell polymers can also be used. The molecular weight of the polymers should be between 10,000 and 200,000, preferably between 50,000 and 180,000. Polymers with a molecular weight between 70,000 and 150,000 are particularly preferred.
Examples of suitable plasticizers, which are 20 to 60 percent by weight pre~erably 30 to 50 percent by weight, of the plastisol dispersions, are phosphates, phthalates, and esters of sebacic acid or adipic acid.
Especially suitable are dibutyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, tricresyl phosphate, tributyl phosphate, particularly diethyl hexyl phthalate and triethylene glycol diacetate. Thermally polymerizable plasticizers, such as triallyl phosphate and diallyl phthalate can also be used.
The light-sensitive mixtures of the invention usually contain 40 to 90 percent by weight binder system, 5 to 30 percent by weight monomer, 0.01 to 5 percent by weight photoinitiator, and 0.1 to 5, preferably 0.5 to 2, percent by weight thermal initiator, or 1 to 30, preferably 10 to 20, percent by weight of a compound thermally crosslinkable with itself and/or with one or more other components of the mixture.
Furthermore, the light-sensitive mixture can contain the usual additives, such as, for example, thickeners like SiO2, fillers! dyes, and stabilizers.
Particularly advantageous is the addition of compounds that release water, CO2, N2, etc. on heating at the :~ ~3 .~ ~ ~ 7 ~
plastisol temperature, for example, potassium hydrogen carbonate. As a rule, this can reduce shrinkage that occurs on hardening. The present process for the preparation of structures layers comprises formation of a layer of the light-sensitive mixture essential to the invention, optionally on a support, imagewise exposure of this layer, removal of unexposed areas and thermal posttreatment. Suitable support materials are, for example, glass, metal supports, metal-coated supports, and synthetic resin sheets, such as, for example, polyester sheets.
The light-sensitive mixture can be applied onto the support by current coating methods, such as, for example, casting, immersion, spraying, etc. The layer thickness is usually 2 to 750 microns, preferably 25 to 400 microns. The actinic radiation needed for imagewise exposure can be ultraviolet, visible or infrared light, ultraviolet light being preferred. Exposure is accomplished, for example, with mercury vapor lamps, xenon lamps or carbon arc lamps. The use of lasers is especially advantageous. ~on-photopolymerized areas can be removed by a stream of air or by treatment with liquid or vapor solvents. If required, a suitable solvent, such as, for example, trichloroethane, can be used for a rewash treatment. Non-photopolymerized areas can also be removed directly by washoff with any of the usual development solvents. Subsequently, thermal posthardening is accomplished in an electric oven or by an infrared lamp. The temperature should be 80 to 200C, preferably 100 to 180C. The duration of the thermal treatment depends on the light-sensitive mixture used and is between 15 and 60 minutes.
The light-sensitive mixtures essential to the invention are used preferably for the production of three-dimensional objects. They are particularly ~1~3 ~77~
suitable for the layerwise construction of these objects by coating the individual layers of the liqht-sensitive mixtures over each other and exposing them imagewise individually. For this purpose, the use of laser beams for direct recording on the light-sensitive layers, as described in U.S. 4,575,330 or EP-A 02 50 121, is particularly advantageous. The individual layers of the light-sensitive mixture can be formed by conventional methods, in which the light-sensitive mixture is applied stepwise for the preparation of each layer. However, it is also possible to put the entire light-sensitive mixture in a vessel that contains a vertically mobile support plate. At the beginning of the process, this support plate is located on the surface of the light-sensitive mlxture and is covered with a layer of thismixture. The layer is exposed imagewise. Then the plate is lowered to receive a new, light-sensitive layer. The newly formed light-sensitive layer is then also exposed imagewise. These process steps are repeated until the three-dimensional object is complete.
Furthex processing follows as in the one-layer process.
To further illustrate the present invention the following examples are presented.
Example 1 A dispersion A of 10 g of polyvinyl chloride (molecular weight 110,000), 5 g bis-~2-ethylhexyl)-phthalate, 3 g trimethylol propane txiacrylate, 3 g hexanediol diacrylate, 0.5 g benzil dimethyl ketal, and 0.2 g dibenzoyl peroxide was applied as a 0.3 mm thick layer onto a copper plate and exposed thro~gh a circuit pattern by an argon laser ~360 nm, 250 mJ/cm2) controlled by a screen scanner. The unexposed areas were washed off with a mixture of ethanol and trichloroethane (1:1 by volume). The resulting ~O'.:~i77~
structured layer was heated 5 minutes at 180C. An exact reproduction of the original circuit was obtained.
Exam~l~_~
A 0.3 mm thick layer of Dispersion A and a Dispersion B (like A, but without dibenzoyl peroxide) was exposed overall with an argon laser (360 nm, 250 mJ/cm2) and then heated 5 minutes at 180~C. The tensile strength F and elongation L were measured with a Zwick apparatus 1435.
F EN/mm2] L [%]
Dispersion A 43 6 Dipersion B 31 10 E~mPl~ 3 Two samples of Dispersion A in 0.3 mm thick layers were exposed with an argon laser (360 nm). The exposure energy was:
a) 50 mJ/cm2 b) 500 mJ/cm2 Then the layers were heated 3 minutes at 180C.
The tensile strength of the samples was measured as in Example 2:
a) 49 N/mm2 b) 40 N/mm2 The test shows that, to increase tensile strength, a diffusible monomer residue must be present before thermal treatment.
Example 4 A dispersion of 10 g powdered polymethyl methacrylate (molecular weight 150,000), 4 g ethoxylated trimethylol propane triacrylate, 5.5 g dimethyl phthalate, 2 g N-vinyl pyrrolidone, 0.4 g benzil dimethyl ketal, and 0.2 g 2,2 -azo-bis-isobutyric acid nitrile was coated as a 0.4 mm thick layer on a copper plate and exposed through a circuit pattern with an argon laser (360 nm, 60 mJ/cm2) controlled by a screen ~ ~3 3 ~ ~ 7 9 scanner. The unexposed areas were washed off with a mixture of 1,1,1-trichloroethane and ethanol. Then, the sample was heated 5 minutes at 140C. An exact reproduction of the original circuit was obtained.
E~m~
For the preparation of a cube-shaped object with edges 1.5 cm long, the dispersion of Example 4 was put into a vessel ~ontaining a vertically mobile support plate. At the beginning of the process, this support plate was positioned so that it was covered with a layer of the dispersion. This layer was exposed with an argon laser at about 360 nm through a square. ~he diameter of the laser beam was 150 microns. The laser was controlled by a screen scanner. The exposure energy per unit of area was 90 m~/cm2. ~fter the exposure of the first layer, the support plate was lowered ~ar enough for the formation of a new layer of the light-sensitive dispersion. These process steps were repeated until the cubic object ~as completely formed. Altogether, 50 layers were used. Layer thickness was 300 microns in each case. The photopolymerized object was removed from the vessel, the residual, non-photopolymerized dispersion was removed by a stream of air and the cubic object was heated 10 minutes at 140C. A solid, flexible object, an exact reproduction of the original, was obtained.
Exampl~_~
A dispersion of 30 g polyvinyl chloride (molecular weight 110,000), 16 g bis-~2-ethylhexyl)phthalate, 9 g 7,7,9-trimethyl-4,13-dioxo~3,19-dioxa-5,12-diaza hexadecane-1,16-diol-dimethacrylate, 9 g N-vinyl pyrrolidone ~10 ppm N,N'-di-sec butyl-p-phenylene diamine), 3 g benzil dimethyl ketal and 15 g 3,9-epoxy-cyclohexane carboxylic acid-3,9 epoxycyclohexyl methyl ester was coa~ed as a 0.3 mm thick layer onto a copper 3~77~
plate and exposed through a circuit pattern with an argon laser ~360 nm, 250 mJ/cm2) controlled by a screen scanner. The unexposed portions were removed with trichloroethane vapor. Then, the thus structured layer was heated 5 minutes at 150C. An exact reproduction of the original circuit was obtained.
'. .~ . . .
: ' ~
., .:
,:
9 ~'(3'3`3779 Summaxy of -the Invention The problem involved in the present invention is to develop a process that starts with a liyht-sensitive mixture to produce structured layers or three dimensional objects with high mechanical stability. The products should have high tensi:Le strength, high shore hardness, low elongation, high rigidity and low shrinkage as a result of the hardening process. In addition, the plasticizer should not exude, and the light-sensitive mixtures should be easy to handle and process. At the same time, an exact reproduction should be assured for the image or model to be represented.
~his problem is solved by a process for the preparation of photostructured layers comprising the steps of:
a) forming a layer from a light-sensitive mixture containing 1. a thexmally fusible polymer and plasticizer dispersion, 2. at least one addition-polymerizable, ethylenically unsaturated compound, 3. a photoinitiator or a photoinitiator system, and 9. a thermally reactive compound, b) imagewise exposing the light-sensitive layer, c) removing the unexposed areas of the layer, and d) thermally treating the exposed layer.
With the present process, it is possible to use the advantages of reactive plastisols for imagewise photo-structuring. None of the known processes for converting reactive plastisols suggest the process of the invention. It is astonishing that adverse effects do not occur either in the imagewise exposure and removal of the unexposed areas or in the thermal fusion or thermal hardening. Although it is known from the i current state of the art that thermally fusible areas can be differentiated from non~fusible areas by imagewise exposure of plastisols containing monomers and photoinitiators, it was most unexpected that thermal fusion is still possible despite prior photo-polymerization.
Detaile~ Description Qf the Inv~ention ~ he use of a light-sensitive mixture that is photo~
polymerizable as well as thermally fusible and hardenable is essential to the invention. The binder system of the light-sensltive mixture of the invention uses a polymer/plasticizer dispersion that, on heating, melts to one phase, which, on cooling, hardens to a solid, transparent composition. At the same time, because a plastisol is used, the high plasticizer proportion means a low viscosity and with it, good processibility of the light-sensitive mixture. The combination of a monomer or monomer mixture with a photoinitiator and a thermally reactive compound implies the possibility of imagewise photopolymerization and associated thermal posthardening. Astonishingly, the addition of a thermally reactive compound does not significantly degrade the stability and processibility of the light-sensitive mixture, although thermal polymerization inhibitors must be added to conventional light-sensitive mixtures. It was also astonishing that the stability of the structuxed materials was highest for short exposure times.
An essential aspect of the process of the invention is that the thermal treatment takes place only after removal of the unexposed areas.
Consequently, the thermal treatment affects only the exposed areas, whose mechanical properties can be significantly improved thereby. Stabilization of the materials structured by imagewise photopolymerization is ~3~rl79 indeed effected partially by the plastisol fusion of the binder system, but more extensive reinforcement is accomplished only by an additional thermal hardening.
Structured materials that have been subjected to this two-fold reinforcement by a thermal treatment have adequa~e mechanical stability and resistance to high stress, and in addition, show long service life. A
structure material that was hardened only by plastisol fusion shows lower tensile strength, higher elongation and plasticizer migration.
For the thermal hardening essential to the invention, the light-sensitive mixture contains preferably a thermal initiator and an addition-polymerizable, ethylenically unsaturated compound. The latter can be photopolymerizable monomer or monomer mixture that was not completely reacted in the photo-polymerization step. This can be accomplished by short exposure times, limiting photoinitiation by the selection of a high optical density, preferably D>1.3, or adding less reactive monomers. Monomer mixtures containing monomers of different reactivities are preferred. The more reactive monomer is photo-polymerized by imagewise exposure to structure the material, and the less reactive monomer is thermally polymerized during subsequent treatment to reinforce the material. Moreover, the monomers must be compatible with the polymers. Above all, the less reactive monomer must be compatible with the polymers, particularly at higher temperatures. On the other hand, the monomers should not swell the polymer at room temperature.
Suitable monomers wiih different reactivities are, for example, acrylates and methacrylates. Examples of suitable monomers are ethyl acrylate and methacrylate, 1,4-butanediol diacrylate and methacrylate, isodecyl acrylate and methacrylate, dicyclopentenyl diacrylate ~ ~ 3 r3 7 7 9 and methacrylate, 2-ethyl hexyl acrylate and methacrylate, and lauryl acrylate an~ methacrylate.
Particularly advantageous are trimethylol propane triacrylate and methacrylate, l,6-hexanediol acrylate and methacrylate, or ethoxylated trimethylol propane triacrylate and N-vinyl pyrrolidone. Thermal polymerization should not take place below the plastisol temperature, but rather at or preferably above this temperature. This means that thermal polymerization should take place only after plastisol fusion within the phase formed thereby. This is achieved by the use of a thermal initiator that decomposes at or preferably above the plastisol temperature. Examples of suitable thermal initiators are t-butyl hydroperoxide, t-butyl perbenzoate, and cumene hydroperoxide.
Another version of the invention comprises thermal hardening by means of compounds that are thermally crosslinkable with themselves and/or with one or more other components of the mixture. Suitable examples are compounds with epoxy, hydroxy, alkyl ether and hydroxy alkyl groups. Particularly suitable are compounds with at least two epoxy groups and melamine derivatives.
Preferred compounds are hexamethoxy melamine, 3,4-epoxy-cyclohexyl carboxylic acid-3,4-epoxycyclohexyl methyl ester and 2,2-bis(glycidoxyphenyl)propane.
The photopolymerization initiators can be known photoinitiators or initiator systems, such as, for example, benzoin, benzoin alkyl ether, alpha-methyl benzoin or its ether, benzil dimethyl ketal, and systems, such as, for example, benzophenone/Michler's ketone and thioxanthones/amines. In the invention, polymer/plasticizer dispersions that fuse at elevated temperature are used as the binder system. Suited for this purpose are plastisols and organosols with 40 to 80 percent by weight, preferably 50 to 70 percent by 7 ~ ~
weight, of a homopolymer or copolymers of vinyl chloride, vinyl acetate, vinyl propionate, vinyl stearate, vinyl ether, vinyl pyridine, styrene, acrylic acid and methacrylic acid or its esters, such as, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, (meth)-acrylonitrile, etc. Mixtures of more than one of the cited homopolymers or copolymers or core/shell polymers can also be used. The molecular weight of the polymers should be between 10,000 and 200,000, preferably between 50,000 and 180,000. Polymers with a molecular weight between 70,000 and 150,000 are particularly preferred.
Examples of suitable plasticizers, which are 20 to 60 percent by weight pre~erably 30 to 50 percent by weight, of the plastisol dispersions, are phosphates, phthalates, and esters of sebacic acid or adipic acid.
Especially suitable are dibutyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, tricresyl phosphate, tributyl phosphate, particularly diethyl hexyl phthalate and triethylene glycol diacetate. Thermally polymerizable plasticizers, such as triallyl phosphate and diallyl phthalate can also be used.
The light-sensitive mixtures of the invention usually contain 40 to 90 percent by weight binder system, 5 to 30 percent by weight monomer, 0.01 to 5 percent by weight photoinitiator, and 0.1 to 5, preferably 0.5 to 2, percent by weight thermal initiator, or 1 to 30, preferably 10 to 20, percent by weight of a compound thermally crosslinkable with itself and/or with one or more other components of the mixture.
Furthermore, the light-sensitive mixture can contain the usual additives, such as, for example, thickeners like SiO2, fillers! dyes, and stabilizers.
Particularly advantageous is the addition of compounds that release water, CO2, N2, etc. on heating at the :~ ~3 .~ ~ ~ 7 ~
plastisol temperature, for example, potassium hydrogen carbonate. As a rule, this can reduce shrinkage that occurs on hardening. The present process for the preparation of structures layers comprises formation of a layer of the light-sensitive mixture essential to the invention, optionally on a support, imagewise exposure of this layer, removal of unexposed areas and thermal posttreatment. Suitable support materials are, for example, glass, metal supports, metal-coated supports, and synthetic resin sheets, such as, for example, polyester sheets.
The light-sensitive mixture can be applied onto the support by current coating methods, such as, for example, casting, immersion, spraying, etc. The layer thickness is usually 2 to 750 microns, preferably 25 to 400 microns. The actinic radiation needed for imagewise exposure can be ultraviolet, visible or infrared light, ultraviolet light being preferred. Exposure is accomplished, for example, with mercury vapor lamps, xenon lamps or carbon arc lamps. The use of lasers is especially advantageous. ~on-photopolymerized areas can be removed by a stream of air or by treatment with liquid or vapor solvents. If required, a suitable solvent, such as, for example, trichloroethane, can be used for a rewash treatment. Non-photopolymerized areas can also be removed directly by washoff with any of the usual development solvents. Subsequently, thermal posthardening is accomplished in an electric oven or by an infrared lamp. The temperature should be 80 to 200C, preferably 100 to 180C. The duration of the thermal treatment depends on the light-sensitive mixture used and is between 15 and 60 minutes.
The light-sensitive mixtures essential to the invention are used preferably for the production of three-dimensional objects. They are particularly ~1~3 ~77~
suitable for the layerwise construction of these objects by coating the individual layers of the liqht-sensitive mixtures over each other and exposing them imagewise individually. For this purpose, the use of laser beams for direct recording on the light-sensitive layers, as described in U.S. 4,575,330 or EP-A 02 50 121, is particularly advantageous. The individual layers of the light-sensitive mixture can be formed by conventional methods, in which the light-sensitive mixture is applied stepwise for the preparation of each layer. However, it is also possible to put the entire light-sensitive mixture in a vessel that contains a vertically mobile support plate. At the beginning of the process, this support plate is located on the surface of the light-sensitive mlxture and is covered with a layer of thismixture. The layer is exposed imagewise. Then the plate is lowered to receive a new, light-sensitive layer. The newly formed light-sensitive layer is then also exposed imagewise. These process steps are repeated until the three-dimensional object is complete.
Furthex processing follows as in the one-layer process.
To further illustrate the present invention the following examples are presented.
Example 1 A dispersion A of 10 g of polyvinyl chloride (molecular weight 110,000), 5 g bis-~2-ethylhexyl)-phthalate, 3 g trimethylol propane txiacrylate, 3 g hexanediol diacrylate, 0.5 g benzil dimethyl ketal, and 0.2 g dibenzoyl peroxide was applied as a 0.3 mm thick layer onto a copper plate and exposed thro~gh a circuit pattern by an argon laser ~360 nm, 250 mJ/cm2) controlled by a screen scanner. The unexposed areas were washed off with a mixture of ethanol and trichloroethane (1:1 by volume). The resulting ~O'.:~i77~
structured layer was heated 5 minutes at 180C. An exact reproduction of the original circuit was obtained.
Exam~l~_~
A 0.3 mm thick layer of Dispersion A and a Dispersion B (like A, but without dibenzoyl peroxide) was exposed overall with an argon laser (360 nm, 250 mJ/cm2) and then heated 5 minutes at 180~C. The tensile strength F and elongation L were measured with a Zwick apparatus 1435.
F EN/mm2] L [%]
Dispersion A 43 6 Dipersion B 31 10 E~mPl~ 3 Two samples of Dispersion A in 0.3 mm thick layers were exposed with an argon laser (360 nm). The exposure energy was:
a) 50 mJ/cm2 b) 500 mJ/cm2 Then the layers were heated 3 minutes at 180C.
The tensile strength of the samples was measured as in Example 2:
a) 49 N/mm2 b) 40 N/mm2 The test shows that, to increase tensile strength, a diffusible monomer residue must be present before thermal treatment.
Example 4 A dispersion of 10 g powdered polymethyl methacrylate (molecular weight 150,000), 4 g ethoxylated trimethylol propane triacrylate, 5.5 g dimethyl phthalate, 2 g N-vinyl pyrrolidone, 0.4 g benzil dimethyl ketal, and 0.2 g 2,2 -azo-bis-isobutyric acid nitrile was coated as a 0.4 mm thick layer on a copper plate and exposed through a circuit pattern with an argon laser (360 nm, 60 mJ/cm2) controlled by a screen ~ ~3 3 ~ ~ 7 9 scanner. The unexposed areas were washed off with a mixture of 1,1,1-trichloroethane and ethanol. Then, the sample was heated 5 minutes at 140C. An exact reproduction of the original circuit was obtained.
E~m~
For the preparation of a cube-shaped object with edges 1.5 cm long, the dispersion of Example 4 was put into a vessel ~ontaining a vertically mobile support plate. At the beginning of the process, this support plate was positioned so that it was covered with a layer of the dispersion. This layer was exposed with an argon laser at about 360 nm through a square. ~he diameter of the laser beam was 150 microns. The laser was controlled by a screen scanner. The exposure energy per unit of area was 90 m~/cm2. ~fter the exposure of the first layer, the support plate was lowered ~ar enough for the formation of a new layer of the light-sensitive dispersion. These process steps were repeated until the cubic object ~as completely formed. Altogether, 50 layers were used. Layer thickness was 300 microns in each case. The photopolymerized object was removed from the vessel, the residual, non-photopolymerized dispersion was removed by a stream of air and the cubic object was heated 10 minutes at 140C. A solid, flexible object, an exact reproduction of the original, was obtained.
Exampl~_~
A dispersion of 30 g polyvinyl chloride (molecular weight 110,000), 16 g bis-~2-ethylhexyl)phthalate, 9 g 7,7,9-trimethyl-4,13-dioxo~3,19-dioxa-5,12-diaza hexadecane-1,16-diol-dimethacrylate, 9 g N-vinyl pyrrolidone ~10 ppm N,N'-di-sec butyl-p-phenylene diamine), 3 g benzil dimethyl ketal and 15 g 3,9-epoxy-cyclohexane carboxylic acid-3,9 epoxycyclohexyl methyl ester was coa~ed as a 0.3 mm thick layer onto a copper 3~77~
plate and exposed through a circuit pattern with an argon laser ~360 nm, 250 mJ/cm2) controlled by a screen scanner. The unexposed portions were removed with trichloroethane vapor. Then, the thus structured layer was heated 5 minutes at 150C. An exact reproduction of the original circuit was obtained.
'. .~ . . .
: ' ~
Claims (4)
1. A process for the preparation of a photostructured layer, comprising the steps of:
a) forming a layer from a light-sensitive mixture containing 1. a thermally fusible polymer and plasticizer dispersion, 2. at least one addition-polymerizable, ethylenically unsaturated compound, 3. a photoinitiator or a photoinitiator system, and 4. a thermally reactive compound, b) imagewise exposing the light-sensitive layer, c) removing of the unexposed areas of the layer, and d) thermally treating the exposed layer.
2. The process in accordance with claim 1 characterized in that the thermally reactive compound is a thermal initiator.
3. The process in accordance with claim 1 characterized in that the imagewise exposure is accomplished at a wavelength where the optical density of the layer being exposed is at least 1.3.
4. The process in accordance with claim 1 characterized in that at least two addition-polymerizable, ethylenically unsaturated compounds of different reactivities are used.
5. The process in accordance with claim 1 characterized in that the thermal initiator decomposes at or above the temperature at which the polymer/
plasticizer dispersion melts.
6. The process in accordance with claim 1 characterized in that the thermally reactive compound is a compound thermally crosslinkable with itself or with at least one component of the mixture.
7. The process in accordance with claim 6 characterized in that the thermally reactive compound is an epoxy or a melamine compound.
8. The process in accordance with claim 1 characterized in that the polymer/plasticizer dispersion is a plastisol or an organosol.
9. The process in accordance with claim 1 characterized in that the light-sensitive mixture contains at least one compound that releases a gas at an elevated temperature.
10. A process for the preparation of a three-dimensional object comprising the steps of:
a) forming a layer from a light-sensitive mixture containing
1. a thermally fusible polymer and plasticizer dispersion,
2. at least one addition-polymerizable, ethylenically unsaturated compound,
3. a photoinitiator or a photoinitiator system, and
4. a thermally reactive compound, b) imagewise exposing the light-sensitive layer, c) applying a new layer of the light-sensitive mixture onto the layer exposed in accordance with b), d) imagewise exposing the light-sensitive layer, e) successive repeating steps c) and d) until the three-dimensional object is fully formed, f) removing the unexposed areas, and d) thermally treating the three-dimensional object.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4004620.6 | 1990-02-15 | ||
| DE4004620A DE4004620C1 (en) | 1990-02-15 | 1990-02-15 | Photo-structured layer of three=dimensional object prodn. - by using fusible plastisol or organosol contg. unsatd. monomer, photoinitiator and thermally reactive cpd. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2035779A1 true CA2035779A1 (en) | 1991-08-16 |
Family
ID=6400167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2035779A Abandoned CA2035779A1 (en) | 1990-02-15 | 1991-02-06 | Process for the preparation of photostructured layers with improved mechanical properties |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0442071B1 (en) |
| JP (1) | JPH04214326A (en) |
| KR (1) | KR910015889A (en) |
| CN (1) | CN1054674A (en) |
| AU (1) | AU7105191A (en) |
| CA (1) | CA2035779A1 (en) |
| DE (2) | DE4004620C1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2503391A2 (en) * | 2011-03-25 | 2012-09-26 | Heraeus Kulzer GmbH & Co. KG | Use of dual-hardening compositions for coating |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5980812A (en) * | 1997-04-30 | 1999-11-09 | Lawton; John A. | Solid imaging process using component homogenization |
| CA2317039C (en) | 1998-01-21 | 2009-09-29 | Takeda Chemical Industries, Ltd. | Lyophilization method for sustained-release preparations |
| CN1304353A (en) * | 1999-03-09 | 2001-07-18 | 李·艾辛格 | Application of a textured or patterned surface to a sample |
| AU2015280283B2 (en) | 2014-06-23 | 2019-05-02 | Carbon, Inc. | Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening |
| BR112017016780A2 (en) | 2015-02-05 | 2018-04-17 | Carbon Inc | intermittent exposure additive manufacturing method |
| US10391711B2 (en) | 2015-03-05 | 2019-08-27 | Carbon, Inc. | Fabrication of three dimensional objects with multiple operating modes |
| WO2017040883A1 (en) | 2015-09-04 | 2017-03-09 | Carbon, Inc. | Cyanate ester dual cure resins for additive manufacturing |
| WO2017044381A1 (en) | 2015-09-09 | 2017-03-16 | Carbon3D, Inc. | Epoxy dual cure resins for additive manufacturing |
| US10647873B2 (en) | 2015-10-30 | 2020-05-12 | Carbon, Inc. | Dual cure article of manufacture with portions of differing solubility |
| US11891485B2 (en) | 2015-11-05 | 2024-02-06 | Carbon, Inc. | Silicone dual cure resins for additive manufacturing |
| US10343331B2 (en) | 2015-12-22 | 2019-07-09 | Carbon, Inc. | Wash liquids for use in additive manufacturing with dual cure resins |
| US10501572B2 (en) | 2015-12-22 | 2019-12-10 | Carbon, Inc. | Cyclic ester dual cure resins for additive manufacturing |
| US10639844B2 (en) * | 2015-12-22 | 2020-05-05 | Carbon, Inc. | Fabrication of compound products from multiple intermediates by additive manufacturing with dual cure resins |
| US10538031B2 (en) | 2015-12-22 | 2020-01-21 | Carbon, Inc. | Dual cure additive manufacturing of rigid intermediates that generate semi-rigid, flexible, or elastic final products |
| US10647054B2 (en) | 2015-12-22 | 2020-05-12 | Carbon, Inc. | Accelerants for additive manufacturing with dual cure resins |
| CN115195104B (en) * | 2015-12-22 | 2023-12-05 | 卡本有限公司 | Dual precursor resin system for additive manufacturing with dual cure resins |
| WO2017112751A1 (en) | 2015-12-22 | 2017-06-29 | Carbon, Inc. | Blocked silicone dual cure resins for additive manufacturing |
| US10500786B2 (en) | 2016-06-22 | 2019-12-10 | Carbon, Inc. | Dual cure resins containing microwave absorbing materials and methods of using the same |
| WO2018094131A1 (en) | 2016-11-21 | 2018-05-24 | Carbon, Inc. | Method of making three-dimensional object by delivering reactive component for subsequent cure |
| US11535686B2 (en) | 2017-03-09 | 2022-12-27 | Carbon, Inc. | Tough, high temperature polymers produced by stereolithography |
| US11458673B2 (en) | 2017-06-21 | 2022-10-04 | Carbon, Inc. | Resin dispenser for additive manufacturing |
| EP3768494B1 (en) * | 2018-08-01 | 2023-04-19 | Carbon, Inc. | Production of low density products by additive manufacturing |
| US11504903B2 (en) | 2018-08-28 | 2022-11-22 | Carbon, Inc. | 1K alcohol dual cure resins for additive manufacturing |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3615448A (en) * | 1969-01-14 | 1971-10-26 | Grace W R & Co | Lithographic printing plate and method of preparation |
| US4309331A (en) * | 1977-03-22 | 1982-01-05 | E. I. Du Pont De Nemours And Company | Surfactant-free acrylic plastisols and organosols compositions |
| US4288527A (en) * | 1980-08-13 | 1981-09-08 | W. R. Grace & Co. | Dual UV/thermally curable acrylate compositions with pinacol |
| CA1194637A (en) * | 1982-04-26 | 1985-10-01 | Charles R. Morgan | Uv and thermally curable, thermoplastic-containing compositions |
| DE3512176A1 (en) * | 1985-04-03 | 1986-10-09 | Winfried 7758 Meersburg Heinzel | METHOD FOR TREATING THE SURFACE OF A PRINTING MACHINE CYLINDER |
| DE3814567A1 (en) * | 1988-04-29 | 1989-11-09 | Du Pont Deutschland | PHOTOPOLYMERIZABLE COMPOSITIONS COMPRISING CARBOXYL GROUPS CONTAINING BINDER |
-
1990
- 1990-02-15 DE DE4004620A patent/DE4004620C1/en not_active Expired - Fee Related
- 1990-12-11 EP EP90123765A patent/EP0442071B1/en not_active Expired - Lifetime
- 1990-12-11 DE DE59010693T patent/DE59010693D1/en not_active Expired - Fee Related
-
1991
- 1991-02-06 CA CA2035779A patent/CA2035779A1/en not_active Abandoned
- 1991-02-11 KR KR1019910002278A patent/KR910015889A/en not_active Withdrawn
- 1991-02-13 CN CN91100915A patent/CN1054674A/en active Pending
- 1991-02-14 JP JP3040794A patent/JPH04214326A/en active Pending
- 1991-02-15 AU AU71051/91A patent/AU7105191A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2503391A2 (en) * | 2011-03-25 | 2012-09-26 | Heraeus Kulzer GmbH & Co. KG | Use of dual-hardening compositions for coating |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4004620C1 (en) | 1991-09-05 |
| EP0442071B1 (en) | 1997-04-02 |
| EP0442071A3 (en) | 1992-04-29 |
| KR910015889A (en) | 1991-09-30 |
| JPH04214326A (en) | 1992-08-05 |
| EP0442071A2 (en) | 1991-08-21 |
| CN1054674A (en) | 1991-09-18 |
| AU7105191A (en) | 1991-08-22 |
| DE59010693D1 (en) | 1997-05-07 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19940806 |