WO2000067981A1 - Method of post-treatment of photofabricated object and mold - Google Patents

Method of post-treatment of photofabricated object and mold Download PDF

Info

Publication number
WO2000067981A1
WO2000067981A1 PCT/NL2000/000290 NL0000290W WO0067981A1 WO 2000067981 A1 WO2000067981 A1 WO 2000067981A1 NL 0000290 W NL0000290 W NL 0000290W WO 0067981 A1 WO0067981 A1 WO 0067981A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
post
photofabricated
treatment
photofabricated object
Prior art date
Application number
PCT/NL2000/000290
Other languages
French (fr)
Inventor
Tetsuya Yamamura
Yoshikazu Yamaguchi
Yukitoshi Kato
Toyokazu Tanabe
Takashi Ukachi
Original Assignee
Dsm N.V.
Jsr Corporation
Japan Fine Coatings Co. Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm N.V., Jsr Corporation, Japan Fine Coatings Co. Ltd. filed Critical Dsm N.V.
Publication of WO2000067981A1 publication Critical patent/WO2000067981A1/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/20—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. moulding inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • 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
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • 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
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/001—Shaping in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0072—Roughness, e.g. anti-slip
    • B29K2995/0073—Roughness, e.g. anti-slip smooth

Definitions

  • the present invention relates to a method of post-treatment of photofabricated object and a mold, and, more particularly, to a method of post-treatment of photofabricated object comprising a step of removing level differences on the surface of photofabricated object to smooth the surface, and a mold made of such a photofabricated object.
  • a method of photofabrication of a three- dimensional object (hereinafter called a photofabricated object) consisting of cured resin layers integrally laminated by repeating a step of selectively irradiating a photocurable liquid resin composition has been proposed (see Japanese Patent Application Laid-open Nos. 247515/1985, 35966/1987, 101408/1987, and 24119/1993) .
  • a photofabricated object used as a mold must satisfy the conditions of mechanical strength, pressure resistance, heat resistance, and durability which are required for a mold.
  • a resin composition capable of producing a photofabricated object (a cured product) which can withstand under such conditions is required.
  • the inventors of the present invention have proposed methods for easily manufacturing resin molds exhibiting excellent durability in repeated use (Japanese Patent Application Laid-open Nos. 137027/1996 and 250584/1996). Fig.
  • A indicates a photofabricated object
  • B is an original design curve (for example, a virtual curve based on CAD design data) .
  • level differences which originate from the laminated layer structure are inevitably formed on the surface (the surface with a gradient in the direction of the lamination layers) of the photofabricated object A.
  • a mold with such level differences on the molded surface has the following problems.
  • the present invention has been achieved in view of this situation.
  • a first object of the present invention is to provide a method of post-treatment of a photofabricated object which can remove the level differences on the surface of the photofabricated object and can form a smooth surface which is precisely in accord with design data.
  • a second object of the present invention is to provide a mold made of a photofabricated object having a smooth fabricated surface without level differences originating from laminated layers.
  • the method of post -treatment of the present invention comprises a step of smoothing the difference in levels on the surface of the photofabricated object by coating the surface with a photocurable resin composition and curing the photocurable resin composition.
  • the method of post-treatment of the present invention comprises a step of smoothing the difference in levels on the surface of the photofabricated object by filling the level differences with a photocurable resin composition and curing the photocurable resin composition.
  • coating with a resin composition indicates not only applying a liquid resin composition, but also providing a film of a resin composition.
  • Preferred embodiments of the post -treatment method of the present invention include: (1) Using the same photocurable resin composition as used for fabrication of the photofabricated object; (2) Using a photocurable resin composition which comprises (1) a cationically polymerizable compound and a cationic polymerization photoinitiator or (2) a radically polymerizable compound and a radical polymerization photoinitiator, or (3) a combination of (1) and (2) ; and (3) in the above embodiment (2) , using a photocurable resin composition further comprising a filler.
  • the mold of the present invention is made of a photofabricated object, with at least part of the fabricated surface thereof having been subjected to the above post-treatment and forming the treated surface with a roughness of 20 ⁇ m or less.
  • the method of the present invention shows the advantage that level differences originating from laminated layers can be removed by a cured resin composition, which brings the surface of photofabricated object precisely in accordance with the design data. In addition, a very smooth surface free from scratches due to a grinding operation, or exposure of fillers, can be formed.
  • the surface of the mold obtained by the post-treatment is smooth without the level differences originating from a laminated layer structure.
  • Photofabrication objects precisely in accord with the design data can be formed over a long period of time using a mold having such a smooth surface on at least part of the molding surface .
  • the present invention will now be described in more detail .
  • level differences originating from a laminated layer structure can be removed not only by shaving protruding parts, but also by coating the level differences with a photocurable resin composition and curing the resin composition.
  • a photocurable or heat -curable resin composition (a liquid composition) is applied to the surface of the photofabricated object 1 so as to fill up the level differences and form a coating layer 2.
  • the coating layer 2 is then cured by light or heat, thereby smoothing the surface of the photofabricated object.
  • a film of photocurable or heat-curable resin composition is placed so as to fill up the level differences on the surface of the photofabricated object.
  • the film is then cured by light or heat , thereby smoothing the surface of the photofabricated object.
  • the level differences on the surface of photofabricated object are not necessarily filled up completely.
  • the manner of coating to the extent that a smooth surface (a surface with a roughness of 20 ⁇ m or less) can be obtained, is included in the post- treatment method of the present invention.
  • the photocurable resin composition used for obtaining such a photofabricated object may be either a composition comprising a cationically polymerizable compound (e.g. epoxy resin) or a composition comprising a radically polymerizable compound (e.g. urethane acrylate resin) , or a composition comprising a mixture of these compounds .
  • a cationically polymerizable compound e.g. epoxy resin
  • a composition comprising a radically polymerizable compound e.g. urethane acrylate resin
  • Desolite SCR 801 and Desolite SCR 802 which are commercially available as photofabrication resins for direct molding are given as examples of preferable resin compositions used for obtaining such a photofabricated object.
  • a photocurable resin composition is supplied onto a support stage to form a thin layer (1) , which is selectively irradiated with light to form a solid cured resin layer (1) .
  • the liquid resin composition is provided on this cured resin layer (1) to form a thin layer (2) .
  • This thin layer (2) is selectively irradiated to form a cured resin layer (2) integrally laminated on the cured resin layer (1) .
  • This step is repeated for a certain number of times while using either the same or different irradiation patterns to form a three-dimensional object consisting of integrally laminated cured resin layers (n) .
  • the laminated cured resin layers (n) have a thickness of about 5-300 ⁇ m, for example, and can be appropriately selected taking into consideration the gradient of the photofabricated object (the surface gradient in the direction of the lamination layers) , the fabrication time, and the like. This thickness corresponds to the size of level differences in the photofabricated object.
  • Resin compositions which are preferably used in the post -treatment method of the present invention are those having almost the same heat resistance (e.g. a resin composition having 60°C or higher, preferably 100°C or higher heat distortion temperature according to JIS K7207A) as the photofabricated object which is the substrate, exhibiting strong adhesion to the photofabricated object, and capable of forming cured products having a coefficient of thermal expansion which is approximately the same as that of the photofabricated object.
  • a resin composition having 60°C or higher, preferably 100°C or higher heat distortion temperature according to JIS K7207A e.g. a resin composition having 60°C or higher, preferably 100°C or higher heat distortion temperature according to JIS K7207A
  • Such a resin composition may be either photocurable or heat-curable, with a photocurable resin composition being preferred.
  • compositions comprising a cationically polymerizable compound and a cationic polymerization photoinitiator
  • compositions comprising a radically polymerizable compound and a radical polymerization photoinitiator
  • compositions comprising a cationically polymerizable compound and a cationic polymerization photoinitiator, and a radically polymerizable compound and a radical polymerization photoinitiator
  • Compositions comprising a cationically polymerizable compound, a cationic polymerization photoinitiator, and a filler.
  • Compositions comprising a radically polymerizable compound, a radical polymerization photoinitiator, and a filler.
  • compositions comprising a cationically polymerizable compound and a cationic polymerization photoinitiator, a radically polymerizable compound and a radical polymerization photoinitiator, and a filler.
  • Resin compositions (1) - (6) can ensure excellent photocurability and favorable processability .
  • the cationically polymerizable compound in the resin composition is a compound which polymerizes or crosslinks by irradiation in the presence of a cationic photopoly ⁇ nerization initiator.
  • epoxy resins such as bisphenol epoxy resins, novolak epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins can be given as examples .
  • the cationic photopolymerization initiator used in the resin composition is a compound which generates a substance to initiate cationic photopolymerization on being irradiated with light.
  • Aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and the like can be given as examples of the cationic photopolymerization initiator.
  • the "radically polymerizable compound” which is a component of the resin composition is a monofunctional or polyfunctional compound having an ethylenically unsaturated bond in the molecule.
  • Acrylic resins such as polyester acrylate, polyurethane acrylate, and epoxy acrylate can be given as examples of the radically polymerizable compound.
  • the "radical polymerization photoinitiator” which is a component of the resin composition is a compound which decomposes and generates radicals by light energy and initiates a radical polymerization reaction by these radicals.
  • Acetophenone-type photoinitiators, benzoin ether-type photoinitiators, benzyl ketal-type photoinitiators, ketone-type photoinitiators, and the like can be given as examples of the radical photopoly ⁇ nerization initiator.
  • Fillers preferably used in the resin composition of the present invention are selected from those increasing heat resistance and strength of the resulting cured products.
  • Spherical silica particles can be given as preferable fillers.
  • Sunsphere NP-100, NP-200 (manufactured by Tokai Chemical Co., Ltd.), Silstar MK-08, MK-15 (manufactured by Nippon Chemical Industrial Co., Ltd.), FB-48 (manufactured by Denki Kagaku Kogyo K.K.) can be given as examples of commercially available spherical silica particles.
  • various optional components may be added to the resin composition for post-treatment insofar as its curability is not adversely affected.
  • a resin composition which is suitably selected from conventionally known heat-curable resin compositions is used in the post-treatment method of the present invention.
  • the same photocurable resin composition used for preparing the photofabricated object is preferably used in the method of post-treatment of the present invention. This increases the strength of adhesion to the surface of photofabricated objects (substrates) of cured products of the resin composition, which, in turn, increases durability of the mold made of the photofabricated object.
  • the resin composition may be in the form of either a liquid or a solid (film) .
  • the viscosity at 25°C of the liquid resin composition is preferably from 1 to 50,000 cp, and more preferably from 10 to 20,000 cp.
  • the resin composition may partially flow along the level differences on the surface of the photofabricated objects, failing to bury those level differences adequately.
  • the viscosity is too large, on the other hand, it is difficult to provide a smooth surface. Coating traces by brush and the like may be left on the coated surface, making it difficult to obtain high precision photofabricated objects.
  • the thickness of films made from the resin composition is in the range from 10 to 1,000 ⁇ m, and preferably from 50 to 500 ⁇ m.
  • the method of coating the liquid resin composition there are no specific limitations to the method of coating the liquid resin composition inasmuch as difference in levels can be buried and a smooth coating can be produced.
  • a method of using a brush or spatula, a method of spraying the composition, and the like can be used, for example.
  • the liquid resin composition need not be applied to the entire surface of the photofabricated objects.
  • the composition may be applied so as to bury the level differences on the whole or part of the surface which is to become a molding surface (i.e. the surface for which glossiness or releasability is required) .
  • one or more sheet of film may be placed on the surface of photofabricated object where a level difference exists.
  • the film may be applied to coated surfaces after the application of the liquid resin composition.
  • the resin composition coated or placed so as to fill out the level differences existing on the surface of a photofabricated object is subjected to a curing treatment .
  • a method of curing the photocurable resin composition (1) a method of curing by irradiating said resin composition with light and (2) a method of curing by irradiating said resin composition with light, followed by heating (post-cure) the resin composition can be given.
  • the photocure of (1) and (2) above can be carried out, for example, by irradiating the coated surface of the resin composition with ultraviolet light at a dose of 0.1-5 J/cm 2 using UV irradiation equipment.
  • the post-cure (heat curing) in (2) above can be carried out by heating the photofabricated object after photocure in a thermostat at 60-250°C for 0.5-24 hours.
  • the heat -cure (heat curing) in (3) above can be carried out by heating the photofabricated object with a covered layer of the resin composition in a thermostat at a temperature of 60-100°C for 0.5-24 hours, then at a higher temperature of 80-250°C for another 0.5-24 hours.
  • the surface of photofabricated objects treated by the post -treatment method of the present invention has no level differences which originate from the laminated layer structure and has a configuration strictly in accordance with a design data (CAD data) .
  • CAD data design data
  • the surface is very smooth with no roughening problems such as scratches due to a grinding operation or exposure of particulate fillers.
  • surface conditions with a roughness of 20 ⁇ m or less can be obtained.
  • surface roughness means a surface roughness value measured by a surface roughness meter, Surfcom 575A (manufactured by Tokyo Seimitu Co., Ltd.) under the conditions of a scanning speed of 1.5 mm/s .
  • the value represents a degree of level differences or irregularities which are present on the surface.
  • the mold of the present invention is a photofabricated object of which the surface has been treated by the post-treatment method (the surface- smoothing method) of the present invention.
  • the post-treatment of the present invention need not be applied to the entire surface of the fabricated objects. It is sufficient for the mold of the present invention to be post-treated only on part of the mold surface for which glossiness or releasability is required.
  • the mold of the present invention should have a surface roughness of 20 ⁇ m or less, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less, in the area to which the post-treatment has been applied. Fabricated objects with a surface which is smooth (glossy) and strictly in accordance with the design data can be obtained using the mold of the present invention.
  • the mold of the present invention exhibits excellent releasability due to its smooth surface and, as a result, can exhibit superior durability.
  • the mold of the present invention is particularly suitable for use with injection molding, but the use of the mold is not limited to this. It can be suitably used in various other molding operations such as press molding, vacuum molding, blow molding, foam molding, and pulp molding.
  • resin composition (2) 100 parts by weight of the resin composition (1) prepared in the same manner as in Preparation Example 1 and 100 parts by weight of spherical silica particles (average sphericity: 0.97, average particle diameter: 10 ⁇ m) were mixed, placed in a vessel equipped with a high speed stirrer, and stirred at 3000 rpm at room temperature for 10 minutes, to obtain a resin composition with spherical silica particles homogeneously dispersed therein and a viscosity of 1,500 cp at 25°C (hereinafter called "resin composition (2) " ) .
  • Cavity molds and core molds were formed from a photofabrication resin of direct molding "Desolite SCR801" (manufactured by JSR Corporation) using photofabrication equipment "Solid Creator JSC- 2000” (manufactured by SONY Corp.) under the following conditions (1) to (5) .
  • the resin composition adhering to the surface of resulting photofabricated objects (cavity molds and core molds) was wiped off. After washing with a solvent, the products were post-cured in an oven at 160°C for about 2 hours.
  • Figure 3 is a plan view (I) and side view (II) of a core mold.
  • 11 is a pin shape
  • 12 a rib
  • 13 a pin shape
  • 14 a nail
  • 15 a screw hole for securing
  • 16 a pin shape.
  • the resin composition (1) was applied to photofabricated objects (cavity molds and core molds) produced in the above Preparation Examples using a brush to bury level differences existing on the surface.
  • the coated film of the resin composition (1) was then irradiated with ultraviolet radiation at 1 J/cm2 using UV irradiation equipment "SPOTCURE SP-III" (manufactured by Ushio Inc . ) .
  • SPOTCURE SP-III UV irradiation equipment
  • the photofabricated objects were then subjected to a heat-treatment in a thermostat at 80°C for 2 hours to obtain photofabricated object with the smoothing treatment performed on the surface (such photofabricated objects are hereinafter called "molds (1)").
  • Photofabrication objects with the smoothing treatment performed on the surface were obtained by applying the resin composition (2) instead of the resin composition (1) , irradiating with UV light, and performing heat-treatment in the same manner as in Example 1.
  • Injection molding products were prepared from polycarbonate resin "Eupiron S-2000" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) using mold (1) and mold (2) which were processed by the surface- smoothing treatment in Examples 1 or 2 , respectively, a mold without a surface-smoothing treatment (hereinafter called mold (3)) , and a mold processed by sandpaper to remove level differences (hereinafter called mold (4) ) under the conditions of a mold locking force of 75 tons, cylinder temperature of 300°C, mold temperature of 65°C, injection pressure of 200 kg/cm 2 , 1st step pressure of 360 kg/cm 2 (4 seconds) , and 2nd step pressure of 230 kg/cm 2 (6 seconds) .
  • mold (3) a mold without a surface-smoothing treatment
  • mold (4) a mold processed by sandpaper to remove level differences
  • Injection products with an error of less than 0.5% and those with an error of 0.5% or more from the designed size were respectively rated as “Good” and "Bad” .
  • the Surface conditions were evaluated by measuring surface roughness using a surface roughness meter, Surfcom 575A (manufactured by Tokyo Seimitu Co., Ltd.) at a scanning speed of 1.5 mm/s.
  • the products with surface roughness of less than 5 ⁇ m were rated as " ⁇ ", from 5 ⁇ m to 20 ⁇ m as “O” , and more than 20 ⁇ m as “X” .
  • Injection molding was continuously carried out using the molds to identify the number of times that the molds can fabricates the objects (shot number) before the molds were unusable .
  • Figure 1 is a sectional view schematically showing the configuration of part of a photofabricated object.
  • FIG. 2 is a sectional view schematically showing the configuration of part of a photofabricated object.
  • Figure 2 is a sectional view schematically showing an embodiment of the post -treatment of the present invention.
  • Figure 3 is a plan view (I) and side view (II) of a core mold obtained in Preparation Example.

Abstract

A method of post-treatment of a photofabricated object of the present invention comprising a step of smoothing level differences on the surface of the photofabricated object by coating the surface with a photocurable resin composition and curing the photocurable resin composition, and a mold consisting a photofabricated object in which at least part of the fabricated surface thereof is subjected to the above post-treatment and the roughness of the treated surface is 20 νm or less.

Description

METHOD OF POST-TREATMENT OF PHOTOFABRICATED OBJECT AND
MOLD
The present invention relates to a method of post-treatment of photofabricated object and a mold, and, more particularly, to a method of post-treatment of photofabricated object comprising a step of removing level differences on the surface of photofabricated object to smooth the surface, and a mold made of such a photofabricated object. A method of photofabrication of a three- dimensional object (hereinafter called a photofabricated object) consisting of cured resin layers integrally laminated by repeating a step of selectively irradiating a photocurable liquid resin composition has been proposed (see Japanese Patent Application Laid-open Nos. 247515/1985, 35966/1987, 101408/1987, and 24119/1993) .
In recent years, a number of trials have been undertaken to produce molds used in various molding operations such as injection molding, press molding, vacuum molding, blow molding, foam molding, and pulp molding by a photofabrication method.
A photofabricated object used as a mold must satisfy the conditions of mechanical strength, pressure resistance, heat resistance, and durability which are required for a mold. In particular, in injection molding of engineering plastics which is carried out under high temperature and high pressure conditions, a resin composition capable of producing a photofabricated object (a cured product) which can withstand under such conditions is required. To respond to such a demand, the inventors of the present invention have proposed methods for easily manufacturing resin molds exhibiting excellent durability in repeated use (Japanese Patent Application Laid-open Nos. 137027/1996 and 250584/1996). Fig. 1 is a cross-sectional view schematically showing the shape of a portion of a photofabricated object, wherein A indicates a photofabricated object and B is an original design curve (for example, a virtual curve based on CAD design data) . As shown in the Figure, level differences which originate from the laminated layer structure are inevitably formed on the surface (the surface with a gradient in the direction of the lamination layers) of the photofabricated object A. A mold with such level differences on the molded surface has the following problems.
(1) Level differences exhibit an adverse effect on flow behavior of the resin to be molded.
(2) Releasability of fabricated objects is impaired. (3) The level differences are transferred onto the objects fabricated by the mold, thereby impairing appearance of the fabricated objects.
(4) Durability of the resulting mold is impaired (e.g. decrease in the shot number) . Conventionally, a grinding operation using a file and sandpaper has been used as a post-treatment means to remove such level differences on the surface of photofabricated objects.
Such a grinding operation, however, produces file and sandpaper scratches on the molded surface and causes particulate fillers, which are added to the photofabricated object to increase heat resistance, to become exposed on the finished surface. As a result, the surface subjected to the post- treatment is roughened, and this roughened surface is copied onto the surface of the fabricated objects.
Because of this, not only is it impossible to obtain fabricated objects with a glossy surface, but also appearance, releasability, and durability of the fabricated objects are impaired. In this way, it has been impossible to obtain a smooth surface which is precisely in accord with design data by a conventional method of post- treatment .
The present invention has been achieved in view of this situation.
A first object of the present invention is to provide a method of post-treatment of a photofabricated object which can remove the level differences on the surface of the photofabricated object and can form a smooth surface which is precisely in accord with design data.
A second object of the present invention is to provide a mold made of a photofabricated object having a smooth fabricated surface without level differences originating from laminated layers. [Means for the Solution of the Problems]
The method of post -treatment of the present invention comprises a step of smoothing the difference in levels on the surface of the photofabricated object by coating the surface with a photocurable resin composition and curing the photocurable resin composition.
The method of post-treatment of the present invention comprises a step of smoothing the difference in levels on the surface of the photofabricated object by filling the level differences with a photocurable resin composition and curing the photocurable resin composition.
It is not essential in the present invention that the entire surface of a photofabricated object be smoothed. The method of smoothing part of the surface of a photofabricated object is also included in the present invention.
In the present invention, "coating with a resin composition" indicates not only applying a liquid resin composition, but also providing a film of a resin composition.
Preferred embodiments of the post -treatment method of the present invention include: (1) Using the same photocurable resin composition as used for fabrication of the photofabricated object; (2) Using a photocurable resin composition which comprises (1) a cationically polymerizable compound and a cationic polymerization photoinitiator or (2) a radically polymerizable compound and a radical polymerization photoinitiator, or (3) a combination of (1) and (2) ; and (3) in the above embodiment (2) , using a photocurable resin composition further comprising a filler.
The mold of the present invention is made of a photofabricated object, with at least part of the fabricated surface thereof having been subjected to the above post-treatment and forming the treated surface with a roughness of 20 μm or less.
[Effect] The method of the present invention shows the advantage that level differences originating from laminated layers can be removed by a cured resin composition, which brings the surface of photofabricated object precisely in accordance with the design data. In addition, a very smooth surface free from scratches due to a grinding operation, or exposure of fillers, can be formed.
Furthermore, the surface of the mold obtained by the post-treatment is smooth without the level differences originating from a laminated layer structure.
Photofabrication objects precisely in accord with the design data can be formed over a long period of time using a mold having such a smooth surface on at least part of the molding surface . The present invention will now be described in more detail .
<Post-treatment method>
Using the method of post-treatment of the present invention, level differences originating from a laminated layer structure can be removed not only by shaving protruding parts, but also by coating the level differences with a photocurable resin composition and curing the resin composition.
In one embodiment of the post-treatment method of the present invention, as shown in Figure 2, a photocurable or heat -curable resin composition (a liquid composition) is applied to the surface of the photofabricated object 1 so as to fill up the level differences and form a coating layer 2. The coating layer 2 is then cured by light or heat, thereby smoothing the surface of the photofabricated object.
In another embodiment of the post-treatment method of the present invention, a film of photocurable or heat-curable resin composition is placed so as to fill up the level differences on the surface of the photofabricated object. The film is then cured by light or heat , thereby smoothing the surface of the photofabricated object.
In the post-treatment method of the present invention, the level differences on the surface of photofabricated object are not necessarily filled up completely. The manner of coating, to the extent that a smooth surface (a surface with a roughness of 20 μm or less) can be obtained, is included in the post- treatment method of the present invention.
[1] Photofabrication object
Although there are no specific restrictions to the photofabricated object to which the post- treatment method of the present invention is applied, the method of the present invention is particularly effective when the cured product is a high heat resistant product comprising particulate fillers. The photocurable resin composition used for obtaining such a photofabricated object may be either a composition comprising a cationically polymerizable compound (e.g. epoxy resin) or a composition comprising a radically polymerizable compound (e.g. urethane acrylate resin) , or a composition comprising a mixture of these compounds .
Desolite SCR 801 and Desolite SCR 802 (manufactured by JSR Corporation) which are commercially available as photofabrication resins for direct molding are given as examples of preferable resin compositions used for obtaining such a photofabricated object.
In a specific example of the photofabrication method, a photocurable resin composition is supplied onto a support stage to form a thin layer (1) , which is selectively irradiated with light to form a solid cured resin layer (1) . The liquid resin composition is provided on this cured resin layer (1) to form a thin layer (2) . This thin layer (2) is selectively irradiated to form a cured resin layer (2) integrally laminated on the cured resin layer (1) . This step is repeated for a certain number of times while using either the same or different irradiation patterns to form a three-dimensional object consisting of integrally laminated cured resin layers (n) .
The laminated cured resin layers (n) have a thickness of about 5-300 μm, for example, and can be appropriately selected taking into consideration the gradient of the photofabricated object (the surface gradient in the direction of the lamination layers) , the fabrication time, and the like. This thickness corresponds to the size of level differences in the photofabricated object.
[2] Resin composition Resin compositions which are preferably used in the post -treatment method of the present invention are those having almost the same heat resistance (e.g. a resin composition having 60°C or higher, preferably 100°C or higher heat distortion temperature according to JIS K7207A) as the photofabricated object which is the substrate, exhibiting strong adhesion to the photofabricated object, and capable of forming cured products having a coefficient of thermal expansion which is approximately the same as that of the photofabricated object.
Such a resin composition may be either photocurable or heat-curable, with a photocurable resin composition being preferred.
The following photocurable resin compositions can be given as examples.
(1) Compositions comprising a cationically polymerizable compound and a cationic polymerization photoinitiator
(2) Compositions comprising a radically polymerizable compound and a radical polymerization photoinitiator
(3) Compositions comprising a cationically polymerizable compound and a cationic polymerization photoinitiator, and a radically polymerizable compound and a radical polymerization photoinitiator (4) Compositions comprising a cationically polymerizable compound, a cationic polymerization photoinitiator, and a filler. (5) Compositions comprising a radically polymerizable compound, a radical polymerization photoinitiator, and a filler.
(6) Compositions comprising a cationically polymerizable compound and a cationic polymerization photoinitiator, a radically polymerizable compound and a radical polymerization photoinitiator, and a filler.
Resin compositions (1) - (6) can ensure excellent photocurability and favorable processability . The cationically polymerizable compound in the resin composition is a compound which polymerizes or crosslinks by irradiation in the presence of a cationic photopolyτnerization initiator. As such a cationically polymerizable compound, epoxy resins such as bisphenol epoxy resins, novolak epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins can be given as examples .
The cationic photopolymerization initiator used in the resin composition is a compound which generates a substance to initiate cationic photopolymerization on being irradiated with light.
Aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and the like can be given as examples of the cationic photopolymerization initiator.
The "radically polymerizable compound" which is a component of the resin composition is a monofunctional or polyfunctional compound having an ethylenically unsaturated bond in the molecule. Acrylic resins such as polyester acrylate, polyurethane acrylate, and epoxy acrylate can be given as examples of the radically polymerizable compound. The "radical polymerization photoinitiator" which is a component of the resin composition is a compound which decomposes and generates radicals by light energy and initiates a radical polymerization reaction by these radicals.
Acetophenone-type photoinitiators, benzoin ether-type photoinitiators, benzyl ketal-type photoinitiators, ketone-type photoinitiators, and the like can be given as examples of the radical photopolyτnerization initiator.
Fillers preferably used in the resin composition of the present invention are selected from those increasing heat resistance and strength of the resulting cured products. Spherical silica particles can be given as preferable fillers. Sunsphere NP-100, NP-200 (manufactured by Tokai Chemical Co., Ltd.), Silstar MK-08, MK-15 (manufactured by Nippon Chemical Industrial Co., Ltd.), FB-48 (manufactured by Denki Kagaku Kogyo K.K.) can be given as examples of commercially available spherical silica particles.
Moreover, various optional components may be added to the resin composition for post-treatment insofar as its curability is not adversely affected. A resin composition which is suitably selected from conventionally known heat-curable resin compositions is used in the post-treatment method of the present invention.
The same photocurable resin composition used for preparing the photofabricated object is preferably used in the method of post-treatment of the present invention. This increases the strength of adhesion to the surface of photofabricated objects (substrates) of cured products of the resin composition, which, in turn, increases durability of the mold made of the photofabricated object.
The resin composition may be in the form of either a liquid or a solid (film) .
The viscosity at 25°C of the liquid resin composition (measured by a Brookfield viscometer) is preferably from 1 to 50,000 cp, and more preferably from 10 to 20,000 cp.
When the viscosity is too small, the resin composition may partially flow along the level differences on the surface of the photofabricated objects, failing to bury those level differences adequately. When the viscosity is too large, on the other hand, it is difficult to provide a smooth surface. Coating traces by brush and the like may be left on the coated surface, making it difficult to obtain high precision photofabricated objects.
The thickness of films made from the resin composition is in the range from 10 to 1,000 μm, and preferably from 50 to 500 μm.
[3] Application of resin composition
There are no specific limitations to the method of coating the liquid resin composition inasmuch as difference in levels can be buried and a smooth coating can be produced. A method of using a brush or spatula, a method of spraying the composition, and the like can be used, for example. In addition, the liquid resin composition need not be applied to the entire surface of the photofabricated objects. For example, in the case of processing a photofabricated object which is used as a mold, the composition may be applied so as to bury the level differences on the whole or part of the surface which is to become a molding surface (i.e. the surface for which glossiness or releasability is required) .
When the resin composition is in the form of films, one or more sheet of film may be placed on the surface of photofabricated object where a level difference exists.
In addition, the film may be applied to coated surfaces after the application of the liquid resin composition.
[4] Curing of resin composition
The resin composition coated or placed so as to fill out the level differences existing on the surface of a photofabricated object is subjected to a curing treatment .
As a method of curing the photocurable resin composition, (1) a method of curing by irradiating said resin composition with light and (2) a method of curing by irradiating said resin composition with light, followed by heating (post-cure) the resin composition can be given.
As a method of curing the heat -curable resin composition, (3) a method of curing the resin composition by heating can be given.
The photocure of (1) and (2) above can be carried out, for example, by irradiating the coated surface of the resin composition with ultraviolet light at a dose of 0.1-5 J/cm2 using UV irradiation equipment.
The post-cure (heat curing) in (2) above can be carried out by heating the photofabricated object after photocure in a thermostat at 60-250°C for 0.5-24 hours.
The heat -cure (heat curing) in (3) above can be carried out by heating the photofabricated object with a covered layer of the resin composition in a thermostat at a temperature of 60-100°C for 0.5-24 hours, then at a higher temperature of 80-250°C for another 0.5-24 hours.
When a liquid resin composition is cured, it is possible to laminate a releasable film such as a PET film over the coated surface of the resin composition, curing the resin composition covered by the laminate film, and removing the laminate film after cure. This procedure can improve smoothness of the treated surface. In the post-treatment method of the present invention, it is possible to repeat the process of applying (placing) the resin composition onto the surface of the photofabricated objects and curing the resin composition, thereby covering the level differences existing on the surface of the photofabricated objects with laminated layers of the cured resin composition. Such a method can surely and easily cover large level differences which otherwise cannot be filled up or covered by one application of the resin composition. [5] Surface conditions after treatment
The surface of photofabricated objects treated by the post -treatment method of the present invention has no level differences which originate from the laminated layer structure and has a configuration strictly in accordance with a design data (CAD data) .
In addition, the surface is very smooth with no roughening problems such as scratches due to a grinding operation or exposure of particulate fillers. Specifically, according to the post- treatment method of the present invention, surface conditions with a roughness of 20 μm or less can be obtained.
The term "surface roughness" as used in the present invention means a surface roughness value measured by a surface roughness meter, Surfcom 575A (manufactured by Tokyo Seimitu Co., Ltd.) under the conditions of a scanning speed of 1.5 mm/s . The value represents a degree of level differences or irregularities which are present on the surface.
<Mold>
The mold of the present invention is a photofabricated object of which the surface has been treated by the post-treatment method (the surface- smoothing method) of the present invention.
The post-treatment of the present invention need not be applied to the entire surface of the fabricated objects. It is sufficient for the mold of the present invention to be post-treated only on part of the mold surface for which glossiness or releasability is required. The mold of the present invention should have a surface roughness of 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less, in the area to which the post-treatment has been applied. Fabricated objects with a surface which is smooth (glossy) and strictly in accordance with the design data can be obtained using the mold of the present invention.
The mold of the present invention exhibits excellent releasability due to its smooth surface and, as a result, can exhibit superior durability.
The mold of the present invention is particularly suitable for use with injection molding, but the use of the mold is not limited to this. It can be suitably used in various other molding operations such as press molding, vacuum molding, blow molding, foam molding, and pulp molding.
[Examples] The present invention will now be described in detail by way of examples, which should not be construed as limiting the present invention.
Preparation Example 1 A reaction vessel with a stirrer was charged with 74 parts by weight of epoxy resin (3,4- epoxycyclohexylmethyl-3 , 4-epoxycyclohexanecarboxylate) shown by the following formula (i) , 25 parts by weight of epoxy resin shown by the following formula (ii) , and 1 part by weight of a cationic polymerization photoinitiator "UVI-6970" (manufactured by Union Carbide Corp.) . The mixture was stirred for 2 hours at 50°C to obtain a resin composition with a viscosity of 180 cp at 25°C (hereinafter called "resin composition (1)").
Figure imgf000018_0001
(ii)
Figure imgf000018_0002
Preparation Example 2
100 parts by weight of the resin composition (1) prepared in the same manner as in Preparation Example 1 and 100 parts by weight of spherical silica particles (average sphericity: 0.97, average particle diameter: 10 μm) were mixed, placed in a vessel equipped with a high speed stirrer, and stirred at 3000 rpm at room temperature for 10 minutes, to obtain a resin composition with spherical silica particles homogeneously dispersed therein and a viscosity of 1,500 cp at 25°C (hereinafter called "resin composition (2) " ) .
[Preparation Example of photofabricated object] Cavity molds and core molds were formed from a photofabrication resin of direct molding "Desolite SCR801" (manufactured by JSR Corporation) using photofabrication equipment "Solid Creator JSC- 2000" (manufactured by SONY Corp.) under the following conditions (1) to (5) . The resin composition adhering to the surface of resulting photofabricated objects (cavity molds and core molds) was wiped off. After washing with a solvent, the products were post-cured in an oven at 160°C for about 2 hours.
Figure 3 is a plan view (I) and side view (II) of a core mold. In this Figure, 11 is a pin shape, 12 a rib, 13 a pin shape, 14 a nail, 15 a screw hole for securing, and 16 a pin shape.
(1) Intensity of laser beam at the liquid surface: 100 mW
(2) Scanning speed: optimum scanning speed at which the cure depth of each composition was 0.3 mm (3) thickness of cured resin layer: 0.2 mm
(4) The number of layers in the cavity mold: 306
(5) The number of layers in the cavity mold: 220
Example 1
The resin composition (1) was applied to photofabricated objects (cavity molds and core molds) produced in the above Preparation Examples using a brush to bury level differences existing on the surface.
The coated film of the resin composition (1) was then irradiated with ultraviolet radiation at 1 J/cm2 using UV irradiation equipment "SPOTCURE SP-III" (manufactured by Ushio Inc . ) . The photofabricated objects (cavity molds and core molds) were then subjected to a heat-treatment in a thermostat at 80°C for 2 hours to obtain photofabricated object with the smoothing treatment performed on the surface (such photofabricated objects are hereinafter called "molds (1)").
Example 2
Photofabrication objects with the smoothing treatment performed on the surface ("molds (2)") were obtained by applying the resin composition (2) instead of the resin composition (1) , irradiating with UV light, and performing heat-treatment in the same manner as in Example 1.
<Evaluation of molds (injection molding) >
Injection molding products were prepared from polycarbonate resin "Eupiron S-2000" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) using mold (1) and mold (2) which were processed by the surface- smoothing treatment in Examples 1 or 2 , respectively, a mold without a surface-smoothing treatment (hereinafter called mold (3)) , and a mold processed by sandpaper to remove level differences (hereinafter called mold (4) ) under the conditions of a mold locking force of 75 tons, cylinder temperature of 300°C, mold temperature of 65°C, injection pressure of 200 kg/cm2, 1st step pressure of 360 kg/cm2 (4 seconds) , and 2nd step pressure of 230 kg/cm2 (6 seconds) .
(1) Dimensional accuracy of the resulting fabricated objects, (2) surface conditions of the resulting fabricated objects, and (3) durability of the molds in repeated use were evaluated as follows. Results are shown in Table 1. [Evaluation of dimensional accuracy of fabricated objects]
Injection products with an error of less than 0.5% and those with an error of 0.5% or more from the designed size were respectively rated as "Good" and "Bad" .
[Surface conditions of fabricated objects]
The Surface conditions were evaluated by measuring surface roughness using a surface roughness meter, Surfcom 575A (manufactured by Tokyo Seimitu Co., Ltd.) at a scanning speed of 1.5 mm/s.
The products with surface roughness of less than 5 μm were rated as "Θ", from 5 μm to 20 μm as "O" , and more than 20 μm as "X" .
[Repeated use durability of molds]
Injection molding was continuously carried out using the molds to identify the number of times that the molds can fabricates the objects (shot number) before the molds were unusable .
Figure imgf000021_0001
[Brief Description of the Drawings] [Fig. 1]
Figure 1 is a sectional view schematically showing the configuration of part of a photofabricated object. [Fig. 2]
Figure 2 is a sectional view schematically showing an embodiment of the post -treatment of the present invention. [Fig. 3] Figure 3 is a plan view (I) and side view (II) of a core mold obtained in Preparation Example.

Claims

1. A method of post-treatment of a photofabricated object comprising a step of smoothing level differences on the surface of the photofabricated object by coating the surface with a photocurable resin composition and curing the photocurable resin composition.
2. A method of post-treatment of a photofabricated object comprising a step of smoothing level differences on the surface of the photofabricated object by filling the level differences with a photocurable resin composition and curing the photocurable resin composition.
3. The method of post-treatment of a photofabricated object according to claim 1 or 2, wherein the resin composition used for smoothing the level differences on the surface is the same photocurable resin composition used for preparing the photofabricated object.
4. The method of post-treatment of a photofabricated object according to claims 1 or 2 , wherein the photocurable resin composition comprises (1) a cationically polymerizable compound and a cationic polymerization photoinitiator or (2) a radically polymerizable compound and a radical polymerization photoinitiator, or (3) a combination of (1) and (2) .
5. The method of post-treatment of a photofabricated object according to claim 4, wherein the photocurable resin composition comprises a filler. A mold made of the photofabricated object, at least part of the fabricated surface thereof having been subjected to the post-treatment according to any one of the methods in claims 1-5 and the surface roughness of the treated surface being 20 μm or less.
PCT/NL2000/000290 1999-05-10 2000-05-04 Method of post-treatment of photofabricated object and mold WO2000067981A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/128352 1999-05-10
JP11128352A JP2000318048A (en) 1999-05-10 1999-05-10 Post-treating method for stereo lithographic matter and forming mold

Publications (1)

Publication Number Publication Date
WO2000067981A1 true WO2000067981A1 (en) 2000-11-16

Family

ID=14982705

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2000/000290 WO2000067981A1 (en) 1999-05-10 2000-05-04 Method of post-treatment of photofabricated object and mold

Country Status (2)

Country Link
JP (1) JP2000318048A (en)
WO (1) WO2000067981A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1925428A1 (en) * 2006-11-23 2008-05-28 Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO Method and apparatus for making partially coated products
DE102006060720A1 (en) * 2006-12-21 2008-06-26 Qimonda Ag Reducing roughness of surface of resist layer comprises treating layer with e.g. epoxy compound, where surface of the resist layer is modified and the surface roughness is decreased
US8123999B2 (en) 2002-04-17 2012-02-28 Stratasys, Inc. Smoothing method for layered deposition modeling
US8765045B2 (en) 2007-01-12 2014-07-01 Stratasys, Inc. Surface-treatment method for rapid-manufactured three-dimensional objects
US20140332997A1 (en) * 2013-05-08 2014-11-13 Jason Shih Flexible manufacture of polymeric tubing
WO2017062857A1 (en) 2015-10-09 2017-04-13 Indizen Optical Technologies of America, LLC Smoothing of 3d printed lenses
EP3222411A1 (en) * 2016-03-22 2017-09-27 OCE Holding B.V. Method of gloss correction in 3d printing
EP3842221A1 (en) * 2019-12-23 2021-06-30 Essilor International Method for manufacturing an optical component with improved quality surface using additive manufacturing
CN114393751A (en) * 2022-03-22 2022-04-26 中车戚墅堰机车车辆工艺研究所有限公司 Mold preparation method, mold and rail vehicle connecting piece
US11433658B2 (en) 2017-07-26 2022-09-06 3M Innovative Properties Company Method of making a physical object by additive manufacturing
US11786345B2 (en) 2017-11-21 2023-10-17 3M Innovative Properties Company Method of making a physical object

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100472084B1 (en) * 2002-10-25 2005-03-08 이석희 Device for improving the surface roughness of stereolithography parts
US9933632B2 (en) * 2014-03-26 2018-04-03 Indizen Optical Technologies, S.L. Eyewear lens production by multi-layer additive techniques
KR20170110845A (en) * 2016-03-24 2017-10-12 주식회사 캐리마 A Surface Treating Apparatus For A 3-Dimensional Formed Object and A Surface Treating Method Thereof
KR101925415B1 (en) * 2017-11-30 2019-02-26 주식회사 캐리마 A Surface Treating Apparatus For A 3-Dimensional Formed Object and A Surface Treating Method Thereof
US20230210728A1 (en) 2019-12-25 2023-07-06 Kuraray Noritake Dental Inc. Energy ray-curable coating material for three-dimensional shaped articles, energy ray-curable material kit for three-dimensional shaping including same, three-dimensional shaped article using same, and method of production thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427713A (en) * 1983-01-17 1984-01-24 Rca Corporation Planarization technique
US5234636A (en) * 1989-09-29 1993-08-10 3D Systems, Inc. Methods of coating stereolithographic parts
JPH08174679A (en) * 1994-11-14 1996-07-09 Toshiba Ceramics Co Ltd Precise optical shaping method and optical shaped element
EP0831373A2 (en) * 1996-09-20 1998-03-25 Dsm N.V. Photo-curable resin compositions and process for preparing a resin-based mold
US5874041A (en) * 1996-05-30 1999-02-23 Dsm N.V. Photo-curable resin composition and process for preparing resin-based mold

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427713A (en) * 1983-01-17 1984-01-24 Rca Corporation Planarization technique
US5234636A (en) * 1989-09-29 1993-08-10 3D Systems, Inc. Methods of coating stereolithographic parts
JPH08174679A (en) * 1994-11-14 1996-07-09 Toshiba Ceramics Co Ltd Precise optical shaping method and optical shaped element
US5874041A (en) * 1996-05-30 1999-02-23 Dsm N.V. Photo-curable resin composition and process for preparing resin-based mold
EP0831373A2 (en) * 1996-09-20 1998-03-25 Dsm N.V. Photo-curable resin compositions and process for preparing a resin-based mold

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 11 29 November 1996 (1996-11-29) *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8123999B2 (en) 2002-04-17 2012-02-28 Stratasys, Inc. Smoothing method for layered deposition modeling
WO2008063069A1 (en) * 2006-11-23 2008-05-29 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Method and apparatus for making partially coated products
US9242412B2 (en) 2006-11-23 2016-01-26 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Method and apparatus for making partially coated products
EP1925428A1 (en) * 2006-11-23 2008-05-28 Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO Method and apparatus for making partially coated products
DE102006060720A1 (en) * 2006-12-21 2008-06-26 Qimonda Ag Reducing roughness of surface of resist layer comprises treating layer with e.g. epoxy compound, where surface of the resist layer is modified and the surface roughness is decreased
US8765045B2 (en) 2007-01-12 2014-07-01 Stratasys, Inc. Surface-treatment method for rapid-manufactured three-dimensional objects
US20140332997A1 (en) * 2013-05-08 2014-11-13 Jason Shih Flexible manufacture of polymeric tubing
US10086537B2 (en) * 2013-05-08 2018-10-02 Minipumps, Llc Flexible manufacture of polymeric tubing
CN108136667B (en) * 2015-10-09 2021-07-16 美国因迪森光学技术有限责任公司 Smoothing of 3D printed lenses
WO2017062857A1 (en) 2015-10-09 2017-04-13 Indizen Optical Technologies of America, LLC Smoothing of 3d printed lenses
CN108136667A (en) * 2015-10-09 2018-06-08 美国因迪森光学技术有限责任公司 The smoothing of 3D printing lens
EP3359986A4 (en) * 2015-10-09 2019-06-26 Indizen Optical Technologies Of America, LLC Smoothing of 3d printed lenses
EP3222411A1 (en) * 2016-03-22 2017-09-27 OCE Holding B.V. Method of gloss correction in 3d printing
US11433658B2 (en) 2017-07-26 2022-09-06 3M Innovative Properties Company Method of making a physical object by additive manufacturing
US11786345B2 (en) 2017-11-21 2023-10-17 3M Innovative Properties Company Method of making a physical object
WO2021130293A1 (en) * 2019-12-23 2021-07-01 Essilor International Method for manufacturing an optical component with improved quality surface using additive manufacturing
EP3842221A1 (en) * 2019-12-23 2021-06-30 Essilor International Method for manufacturing an optical component with improved quality surface using additive manufacturing
CN114867597A (en) * 2019-12-23 2022-08-05 依视路国际公司 Method of manufacturing an optical component with an improved quality surface using additive manufacturing
CN114393751A (en) * 2022-03-22 2022-04-26 中车戚墅堰机车车辆工艺研究所有限公司 Mold preparation method, mold and rail vehicle connecting piece

Also Published As

Publication number Publication date
JP2000318048A (en) 2000-11-21

Similar Documents

Publication Publication Date Title
WO2000067981A1 (en) Method of post-treatment of photofabricated object and mold
JP2578459B2 (en) Information recording medium, method for manufacturing substrate for information recording medium, and mold for molding substrate for information recording medium
CN102947073B (en) Process for production of replica mold for imprinting use
US20060226578A1 (en) Processes for facilitating removel of fabricated objects from platens of programmed material consolidation equipment, and fabrication processes employing the object release elements
WO1994027787A1 (en) Grinding tape and method of manufacturing the same
EP1131197B1 (en) Method of processing a resin mold and the resin mold
EP0950502A2 (en) Three-dimensional object including an integral structural member, resin mold and manufacturing process
JP4778416B2 (en) Photocurable adhesive composition and its use in optical field
JP2011083912A (en) Hard coat layer transfer sheet
JP2001079855A (en) Mold for photo fabrication
JP2007291380A (en) Resin composition and decorative sheet using the same resin composition
JPS6017446A (en) Manufacture of support for photographic printing paper
JP4202544B2 (en) Partial matte surface protective layer transfer sheet
CN112976577A (en) Post-processing method for printing intermediate of photocuring 3D printed piece
JP3135319B2 (en) Cosmetic material having high-grade paint feeling and method for producing the same
JP2018126905A (en) Release sheet, transfer sheet, and method of manufacturing decorative molding
JP3351820B2 (en) Method for manufacturing uneven pattern formed body
JP6960467B2 (en) How to make a relief image from a liquid photopolymerizable resin
JP4149185B2 (en) Resin plate for concrete formwork
JP2001328175A (en) Stereo lithography capable of reducing warp and resin mold for molding
JPH03199047A (en) Manufacture of decorative sheet
JPH01176531A (en) Manufacture of molding having protective layer
JP2006224664A (en) Ink-jet recording head, manufacturing method of the head and composition for ink-jet recording head
JP4093334B2 (en) Synchronized embossed decorative sheet and method for producing the same
JP3964253B2 (en) Resin plate for concrete formwork

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase