CA1256397A - Method and apparatus for electron curing on a cooled drum - Google Patents
Method and apparatus for electron curing on a cooled drumInfo
- Publication number
- CA1256397A CA1256397A CA000443818A CA443818A CA1256397A CA 1256397 A CA1256397 A CA 1256397A CA 000443818 A CA000443818 A CA 000443818A CA 443818 A CA443818 A CA 443818A CA 1256397 A CA1256397 A CA 1256397A
- Authority
- CA
- Canada
- Prior art keywords
- drum
- electron
- region
- sheet
- curing
- 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.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
- B05D1/286—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers using a temporary backing to which the coating has been applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N7/00—After-treatment, e.g. reducing swelling or shrinkage, surfacing; Protecting the edges of boards against access of humidity
- B27N7/005—Coating boards, e.g. with a finishing or decorating layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/10—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation for articles of indefinite length
-
- 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
- B29C41/24—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 indefinite length
- B29C41/26—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 indefinite length by depositing flowable material on a rotating drum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B21/06—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
- B44C1/14—Metallic leaves or foils, e.g. gold leaf
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
- B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
- B44C5/0476—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper with abrasion resistant properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0007—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure
- D06N7/0023—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure obtained by physical means, e.g. differential heating or differential irradiation; masking certain areas during treating
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06Q—DECORATING TEXTILES
- D06Q1/00—Decorating textiles
- D06Q1/04—Decorating textiles by metallising
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/02—Metal coatings
- D21H19/04—Metal coatings applied as foil
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/02—Patterned paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
- D21H27/28—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures treated to obtain specific resistance properties, e.g. against wear or weather
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K5/00—Irradiation devices
- G21K5/10—Irradiation devices with provision for relative movement of beam source and object to be irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/22—Paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/02—Sheets of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/72—Cured, e.g. vulcanised, cross-linked
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0875—Treatment by energy or chemical effects by wave energy or particle radiation using particle radiation
- B32B2310/0887—Treatment by energy or chemical effects by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
Abstract
METHOD AND APPARATUS FOR ELECTRON CURING
ON A COOLED DRUM
ABSTRACT
This disclosure is concerned with a method of transfer-coating electron-beam-curable materials, by applying such materials to the surface of a cooled drum, either through a sheet or web carrying the same over the drum or from the drum surface itself, curing the material against the drum at a region of electron-beam radiation directed thereupon and releasing the cured material from the drum surface; and with the latter, where desired, reflecting radiation back into the material being cured.
ON A COOLED DRUM
ABSTRACT
This disclosure is concerned with a method of transfer-coating electron-beam-curable materials, by applying such materials to the surface of a cooled drum, either through a sheet or web carrying the same over the drum or from the drum surface itself, curing the material against the drum at a region of electron-beam radiation directed thereupon and releasing the cured material from the drum surface; and with the latter, where desired, reflecting radiation back into the material being cured.
Description
3 ~
J~ AND APPARATUS ~OR ELECTRON CURING
ON A ~,OOL]~ DRUM
l'he present invention relates to electron-beam curing techniques and apparatus, being more particu-larly conccrned with curing transfer coatings and other electron-beam-cUrable materials such as printing inks, film coatings, magnetic tape materials~ transfer metal-lization o~ paper and other substrates, and similar applications where release layers or surfaces and~or cooling by such surfaces is required or desirable.
In prior U.S. Patent 4,246,297 Or Energy Sciences Inc., the common assignee of the present invention, it was disclosed that the penetrating capabilities o~
energetic electronS enabled them to cure "buried" elec-tron-beam-curable coatings on products made of paper, fabric and similar thin substrates i.e. (thickness ~
400 g/m2). In these cases, electrons of modest energy (E ~300 keV) can readily penetrate the product and uni-formly irradiate the coating, which may be in contact with a release surface. Examples were shown, in the above referenced patent, Or such transrer coating art, using a release paper with irradiatlon ef~ected either through the product substrate itselr, or through the release paper. In accordance with discoveries under-lying the present invention, the necessity for such release papers or the like is eliminated by the use of a drum release surface which at the same time, unlike prior release layers, may~ be cooled ror necessary pro-cess control in the particular application--despite the at first blush contraindication Or directing electron beam energy at a metallic or slmilar drum.
Drums have been used for other purposes in elec-tron processors~ as shown in our prior U.S. Patent No~
4,252,413 wherein a web is presented continuously to an electron beam so that the environmental conditions (radiation levels, ozone concentration, oxygen concen-tration in the process zone, process temperature, etc.) can be precisely controlled for successrul practice Or the art on an industrial scale. Among the techniques discussed in this patent, particularly for high speed graphics applications, is the use Or a roller which serves to remove heat from the rilm or web while lt ~5~3~7 remains in contact wlth the roller surface9 and at the same tlme provides a compact shlelding geometry. This use Or roller or drum-like surfaces, however, while an assist in cooling, has nothing to do with coating transfer and related applications.
The invention disclosed herein utilizes, to the contrary, the transrer coating art of U.S. Patent No.
4,246,297 (which employs film, foil or release paper surface control as a release liner) in conjunction with an under-beam chilled roll concept to attain simultan-eous coating release and cooling functions in a totally novel and unexpected manner and eliminates release papers or similar films.
An ob~ect of the invention, accordingly, is to provide a new and improved method of and apparatus for electron curing, particularly adapted for release-coat-ing applications as well as other uses, that obviates the necessity for release papers~ films, foils and the like and also enables facile process cooling simulta-neously with release functions.
Broadly speaking, the present invention overcomes the problems of the prior art by providing a method of transfer-coating electron-beam-curable material, that comprises, applying such material to the surface of a drum;
rotating the drum past a region where electron-beam radiation is directed towards the drum, to cure the material against the drum; cooling the drum; and releasing the cured material from the drum surface.
The above method may be carried out by an apparatus for electron-beam curing having, in combination, an electron-beam processor having window means for the emergence of electron-beam radiation and means for shielding the region of such emergence; drum means mounted below the region with means for rotating the same past the lower part of the region; means for shielding the drum means as it passes through the region; means for applying electron-beam-curable material to the surface of the drum means to permit curing of the same in the region; means for cooling the drum; and means for releasing the cured material from the drum surface.
The invention will now be described with reference to the accompanying drawings, Fig. 1 of which is a schematic transverse cross-section illustrating the LCM:mls i~ 2~63~7 invention applied to electron-beam curing against a drum;
Fig. 2 is a simliar view showing the technlque applied to curlng against a shielded, cooled drum;
Flg. 3 is a similar view of a modiried electron-beam transrer coatlng and drum curing system using the principles Or the invention; and Figs. 4, 5 and 6 respectively illustrate, in simi-lar fashlon, varlous electron-beam film casting arrangements utilizing the drum curing Or the inven-tio~.
Referring to Fig~ 1, an electron-beam processor as Or the types described ln said patents and marketed by .the asslgnee of the present inventlon~ Energy Sciences Inc., under the trademarks "Electrocurtain" and "Selr-shield", ls shown at 1, directing its beam downwardly (vertical arrows) through an electron-i ~ window W upon a region R within a shlelded enclosure H as of C~ e ~l the type described in said Patent 4,252,413. s~heet material 2 is shown passed by rollers 3 through lnlet and outlet slots Sl and S2 within the enclosure H over an internally water-chilled or otherwise cool~d drum D, having a metal suxface, later described, receiving electron b~kam radiation at the top region R, at which a web 21, passed thrcugh inclined inlet and outlet slots sll and S21, contacts the sheet 2, the sheet~ having thereon the coating or other material to be electron-be~m cured.
As shcwn in Fig. 1, the polished water~cooled drum D is positioned below the beam and, because of its inertia, is driven mechanically so that its surface velocity is synchronize~ with that of the pro~uc~ on which the coating is to be cured. The chilled drum D
need not contain any additional shielding since it is housed inside the nclosure H which preve~ts the escape of radiation accumulated by the stopping of th~ beam in the product or in the drum. Since certain applications may require visual access to the drum surface, the drum may also include a shielding liner, as later described in connection with embodlment o~ Fig. 2, such as leadl tantalum, etc. which, in conjunction with the outer shield provides a suitable dose rate reduction, in accordance wi-th the design criteria taught in said LoM:mls 6 ~S~i3~
Patent 4,252,413, so that the radiation levels a-t the infeed and outfeed slots S1, S2, etc. readily comply with the regulations for processor use.
In the embodiment of Fig. 2, the cooled drum D' is shown as provided with a shielded surface S', the details of which are shown expanded to the right, with coated sheet material 2 passed over the drum for electron-beam curing at region R
within an upper housing portion ~', as described in said Patent 4,252,413. The surface S' may be constructed of successive layers of lead, tantalum and stainless steel. Such a system is particularly useful for curing complex functional coatings ayainst the cooled drum D', such as those used in magnetic or optical recording tapes, providing Eor the reduction or elimination of the need for calendering of the cured film due to the surface quality provided through the technique of the invention. Particle orientation in the coatings can take place directly on the drum D' between slurry application and cure at R; either over the contact angle while the coated sheet or film
J~ AND APPARATUS ~OR ELECTRON CURING
ON A ~,OOL]~ DRUM
l'he present invention relates to electron-beam curing techniques and apparatus, being more particu-larly conccrned with curing transfer coatings and other electron-beam-cUrable materials such as printing inks, film coatings, magnetic tape materials~ transfer metal-lization o~ paper and other substrates, and similar applications where release layers or surfaces and~or cooling by such surfaces is required or desirable.
In prior U.S. Patent 4,246,297 Or Energy Sciences Inc., the common assignee of the present invention, it was disclosed that the penetrating capabilities o~
energetic electronS enabled them to cure "buried" elec-tron-beam-curable coatings on products made of paper, fabric and similar thin substrates i.e. (thickness ~
400 g/m2). In these cases, electrons of modest energy (E ~300 keV) can readily penetrate the product and uni-formly irradiate the coating, which may be in contact with a release surface. Examples were shown, in the above referenced patent, Or such transrer coating art, using a release paper with irradiatlon ef~ected either through the product substrate itselr, or through the release paper. In accordance with discoveries under-lying the present invention, the necessity for such release papers or the like is eliminated by the use of a drum release surface which at the same time, unlike prior release layers, may~ be cooled ror necessary pro-cess control in the particular application--despite the at first blush contraindication Or directing electron beam energy at a metallic or slmilar drum.
Drums have been used for other purposes in elec-tron processors~ as shown in our prior U.S. Patent No~
4,252,413 wherein a web is presented continuously to an electron beam so that the environmental conditions (radiation levels, ozone concentration, oxygen concen-tration in the process zone, process temperature, etc.) can be precisely controlled for successrul practice Or the art on an industrial scale. Among the techniques discussed in this patent, particularly for high speed graphics applications, is the use Or a roller which serves to remove heat from the rilm or web while lt ~5~3~7 remains in contact wlth the roller surface9 and at the same tlme provides a compact shlelding geometry. This use Or roller or drum-like surfaces, however, while an assist in cooling, has nothing to do with coating transfer and related applications.
The invention disclosed herein utilizes, to the contrary, the transrer coating art of U.S. Patent No.
4,246,297 (which employs film, foil or release paper surface control as a release liner) in conjunction with an under-beam chilled roll concept to attain simultan-eous coating release and cooling functions in a totally novel and unexpected manner and eliminates release papers or similar films.
An ob~ect of the invention, accordingly, is to provide a new and improved method of and apparatus for electron curing, particularly adapted for release-coat-ing applications as well as other uses, that obviates the necessity for release papers~ films, foils and the like and also enables facile process cooling simulta-neously with release functions.
Broadly speaking, the present invention overcomes the problems of the prior art by providing a method of transfer-coating electron-beam-curable material, that comprises, applying such material to the surface of a drum;
rotating the drum past a region where electron-beam radiation is directed towards the drum, to cure the material against the drum; cooling the drum; and releasing the cured material from the drum surface.
The above method may be carried out by an apparatus for electron-beam curing having, in combination, an electron-beam processor having window means for the emergence of electron-beam radiation and means for shielding the region of such emergence; drum means mounted below the region with means for rotating the same past the lower part of the region; means for shielding the drum means as it passes through the region; means for applying electron-beam-curable material to the surface of the drum means to permit curing of the same in the region; means for cooling the drum; and means for releasing the cured material from the drum surface.
The invention will now be described with reference to the accompanying drawings, Fig. 1 of which is a schematic transverse cross-section illustrating the LCM:mls i~ 2~63~7 invention applied to electron-beam curing against a drum;
Fig. 2 is a simliar view showing the technlque applied to curlng against a shielded, cooled drum;
Flg. 3 is a similar view of a modiried electron-beam transrer coatlng and drum curing system using the principles Or the invention; and Figs. 4, 5 and 6 respectively illustrate, in simi-lar fashlon, varlous electron-beam film casting arrangements utilizing the drum curing Or the inven-tio~.
Referring to Fig~ 1, an electron-beam processor as Or the types described ln said patents and marketed by .the asslgnee of the present inventlon~ Energy Sciences Inc., under the trademarks "Electrocurtain" and "Selr-shield", ls shown at 1, directing its beam downwardly (vertical arrows) through an electron-i ~ window W upon a region R within a shlelded enclosure H as of C~ e ~l the type described in said Patent 4,252,413. s~heet material 2 is shown passed by rollers 3 through lnlet and outlet slots Sl and S2 within the enclosure H over an internally water-chilled or otherwise cool~d drum D, having a metal suxface, later described, receiving electron b~kam radiation at the top region R, at which a web 21, passed thrcugh inclined inlet and outlet slots sll and S21, contacts the sheet 2, the sheet~ having thereon the coating or other material to be electron-be~m cured.
As shcwn in Fig. 1, the polished water~cooled drum D is positioned below the beam and, because of its inertia, is driven mechanically so that its surface velocity is synchronize~ with that of the pro~uc~ on which the coating is to be cured. The chilled drum D
need not contain any additional shielding since it is housed inside the nclosure H which preve~ts the escape of radiation accumulated by the stopping of th~ beam in the product or in the drum. Since certain applications may require visual access to the drum surface, the drum may also include a shielding liner, as later described in connection with embodlment o~ Fig. 2, such as leadl tantalum, etc. which, in conjunction with the outer shield provides a suitable dose rate reduction, in accordance wi-th the design criteria taught in said LoM:mls 6 ~S~i3~
Patent 4,252,413, so that the radiation levels a-t the infeed and outfeed slots S1, S2, etc. readily comply with the regulations for processor use.
In the embodiment of Fig. 2, the cooled drum D' is shown as provided with a shielded surface S', the details of which are shown expanded to the right, with coated sheet material 2 passed over the drum for electron-beam curing at region R
within an upper housing portion ~', as described in said Patent 4,252,413. The surface S' may be constructed of successive layers of lead, tantalum and stainless steel. Such a system is particularly useful for curing complex functional coatings ayainst the cooled drum D', such as those used in magnetic or optical recording tapes, providing Eor the reduction or elimination of the need for calendering of the cured film due to the surface quality provided through the technique of the invention. Particle orientation in the coatings can take place directly on the drum D' between slurry application and cure at R; either over the contact angle while the coated sheet or film
2 is in con-tact with the top of the drum D', or while the same is in contact with a coating prov.ided -to the lower portion of the drum and carried upward as in the embodiment of Fig. 3.
LCM:
LCM:
3~7 Turning to Fig. 3, the coating A' i9 shown appli-cable to the bottom region of the drum D' by roller appli-cators 5 contacting a coating reservoir R'. The sheet or web 2 contacts the drum-carried coating A' near region R and the curing is effected against the drum D'. The sheet having the cured coating thereon is then released or transferred rrom the drum D'. The upper shielding at H' may be as in Fig. 2.
Other advantages of the design of Fig. 3 reside in the fact that the shielded drum is incorporated into a separable shield assembly which provides visual access to the rotating drum surface in the closed condition and full access to the drum-electron processor window assembly in the opened condition. Because of the very slender access chan-nel required for the treatment of film, paper, textiles, etc., the substrates of prime interest for the processes made possible with this geometry, a very efficient shielding geometry is possible for the absorption of x-rays. Shields ~h~
such as ~t- shown in Fig. 3 have been constructed which show no measurable radiation a-t the access slots with the electron processor at full power (say 1-2 kilowatts of beam mls/lb ! ~
G~
3~ ~' _g_ power per inch Or process zone width). Visual access to the coating statlon is a prime advantage ofrered by this arrangement.
While a cooled drum D' can clearly reMove heat rrom a thin web 2 in contact with lt, unexpected pro-cess advantages o~ such a geometry have been round that are unl~ue to electron-inltiated additlon polymeriza tlon reactions, such as are used in the application Or these processors to trans~er coating of paper~ ~ilm and roil, ror example. As explained in said Patent 4,246,~
297, the penetrating ability of electrons may be used to reach the coatings applied to the reverse side of a substrate-to-be-coated; the coatings themselves being in contact with a release liner or sheet against which they are cured. Various schemes ~or transrer coating and film coatlng are therein described; but none is adapted to employ simultaneous cooling, or to eliminate the need for separate release surraces or sheets, or to enable electron reflection or scatter back into the coating-to-be-cured. It ls these advantages which the present invention rOr the rirst time affords through utilizing the surface of the cooled drum as the release "liner" itsel~ on a continous basis, and with no need ror a replaceable liner or release sheet, as heretofore practiced ror textile and paper transrer coating uslng conyentional technologies normally employing condensation polymerizatlon.
Some Or the unexpected advantages Or the synchro-nized drum technlque Or the invention ~or the curing of coatlngs on paper, rllm, roil, textiles, etc. have become evident in curing studies conducted on such "Electrocurtain" assemblies using in-line coating tech-niques unique to thse studies. Among these are the fact that temperature control of the web can be pre~
cise~ in that ror th-ln webs the substrate will be reduced to the drum temperature even at very high speeds. Such a system has been used for detailed study Or these errects in magnetic tape, rOr example, with the drum outslde the shield housing to permit precise measurements Or the dynamic temperature behavior Or the tape or fllm as a ~unction Or various process para-meters. For example, ror some electron-init:Lated reac-tions, it may be desirable to maintain the system tem-perature well above amblent, but at levels well below the distortion temperature Or the tape or film or other sheets. This can now be accomplished by precise moni-toring and control Or the drum surface temperature with ~ZSi~3~
the geometries o~ the structures Or the inventionO
Inerting Or the coating surrace is eliminated since the coating is now in the protected, "closed"
zone between the substrate and the drum surface. In addition9 any homopolymer formed rrom the monomer in the coating during the curing process~ or any other light coating fractions which would volatilize under normal "coating up" curing, are now held against the substrate-coating surrace and will be reacted into the coating with a higher probability. These ef~ects of monomer trapping, etc. lead to a much cleaner curing environment from both operational processor as well as ecological, points Or view.
- The advantageous efrects o~ electron backscatter, generically described in U.S. Patent 4,246,297, are op~
timized in the constructions of the present invention, High atomic number coatings as at 5' in Fig. 2, can be utiliæed on the drum surrace to enhance recovery Or this albedo energy, which ls now absorbed with high efriciency in the coating or blnder layer.
I~e invention also enables ready electron-beam rllm casting with its drum technique, as shown in Fig.
Other advantages of the design of Fig. 3 reside in the fact that the shielded drum is incorporated into a separable shield assembly which provides visual access to the rotating drum surface in the closed condition and full access to the drum-electron processor window assembly in the opened condition. Because of the very slender access chan-nel required for the treatment of film, paper, textiles, etc., the substrates of prime interest for the processes made possible with this geometry, a very efficient shielding geometry is possible for the absorption of x-rays. Shields ~h~
such as ~t- shown in Fig. 3 have been constructed which show no measurable radiation a-t the access slots with the electron processor at full power (say 1-2 kilowatts of beam mls/lb ! ~
G~
3~ ~' _g_ power per inch Or process zone width). Visual access to the coating statlon is a prime advantage ofrered by this arrangement.
While a cooled drum D' can clearly reMove heat rrom a thin web 2 in contact with lt, unexpected pro-cess advantages o~ such a geometry have been round that are unl~ue to electron-inltiated additlon polymeriza tlon reactions, such as are used in the application Or these processors to trans~er coating of paper~ ~ilm and roil, ror example. As explained in said Patent 4,246,~
297, the penetrating ability of electrons may be used to reach the coatings applied to the reverse side of a substrate-to-be-coated; the coatings themselves being in contact with a release liner or sheet against which they are cured. Various schemes ~or transrer coating and film coatlng are therein described; but none is adapted to employ simultaneous cooling, or to eliminate the need for separate release surraces or sheets, or to enable electron reflection or scatter back into the coating-to-be-cured. It ls these advantages which the present invention rOr the rirst time affords through utilizing the surface of the cooled drum as the release "liner" itsel~ on a continous basis, and with no need ror a replaceable liner or release sheet, as heretofore practiced ror textile and paper transrer coating uslng conyentional technologies normally employing condensation polymerizatlon.
Some Or the unexpected advantages Or the synchro-nized drum technlque Or the invention ~or the curing of coatlngs on paper, rllm, roil, textiles, etc. have become evident in curing studies conducted on such "Electrocurtain" assemblies using in-line coating tech-niques unique to thse studies. Among these are the fact that temperature control of the web can be pre~
cise~ in that ror th-ln webs the substrate will be reduced to the drum temperature even at very high speeds. Such a system has been used for detailed study Or these errects in magnetic tape, rOr example, with the drum outslde the shield housing to permit precise measurements Or the dynamic temperature behavior Or the tape or fllm as a ~unction Or various process para-meters. For example, ror some electron-init:Lated reac-tions, it may be desirable to maintain the system tem-perature well above amblent, but at levels well below the distortion temperature Or the tape or film or other sheets. This can now be accomplished by precise moni-toring and control Or the drum surface temperature with ~ZSi~3~
the geometries o~ the structures Or the inventionO
Inerting Or the coating surrace is eliminated since the coating is now in the protected, "closed"
zone between the substrate and the drum surface. In addition9 any homopolymer formed rrom the monomer in the coating during the curing process~ or any other light coating fractions which would volatilize under normal "coating up" curing, are now held against the substrate-coating surrace and will be reacted into the coating with a higher probability. These ef~ects of monomer trapping, etc. lead to a much cleaner curing environment from both operational processor as well as ecological, points Or view.
- The advantageous efrects o~ electron backscatter, generically described in U.S. Patent 4,246,297, are op~
timized in the constructions of the present invention, High atomic number coatings as at 5' in Fig. 2, can be utiliæed on the drum surrace to enhance recovery Or this albedo energy, which ls now absorbed with high efriciency in the coating or blnder layer.
I~e invention also enables ready electron-beam rllm casting with its drum technique, as shown in Fig.
4. Liquid rilm A" rrom a reservoir R" is applied by q~
app~icator rolls 5 to the drum D' at its lowermost reglon and ls subJected to electron-beam curing at top region R within the shielded upper housing H', passing then over a casting blade 6 to release or transfer rrom the drum D' a cast fllm F that may then be wound at statlon 7. For such film casting (or transrer coating as in other embodirnents) the drum D' may be contin-uously cleaned at 8 as lt returns from the film trans-fer point (where the substrate or film leaves the drum surface) to the point where the liquid coating is being continuously applied to the drum surface from reservoir R".
In these and other applications, the invention eliminates the need ror consumable release liner or sheet which has an important impact on the eccnomics of transfer coatlng Or rlexible or semiflexible webs such as paper, paperboard~ non-wovens, rilm, foil, textiles, etc. Surrace texturizing Or the web, moreover, is rea-dlly accornplished by the etching or engraving of the drum surrace. Difrerential drum~web speeds rnay also be used to provide special texturing erfects in the coat-ing, in much the same way as dirferential web-transrer roll speeds are used in ofrset gravure coating.
3~
Unusual hold-out advantages are possible with the geometries of Figs. 1 and 2 in ~hat very short dwell times of the coating on the substrate prior to cure are possible, assisting in high gloss surfaces as taught in U.S. Patent No. 4,537,811 issued August 27, 1985; and the geometries described herein greatly minimize these effects under pre-cisely controllable conditions.
Other uses of the techniques of the invention for transfer casting of films are shown in Figs. 5 and 6. These techniques also permit the optimization of processes for the generation of unique, fault-free films for dielectric appli-cations (capacitor film) and the like. In the embodiment of Figs. 5 and 6, electron-beam-curable coatings are applie~
to carrier films before and during passage over the drum D', respectively, with the carrier being separated by casting blades 6 from the electron-beam cast film F to the right of the curing region R.
Further modifications will occur to those skilled in this art and such are considered to fall within the spirit and scope of the invention as defined in the appended claims.
vtd/ Cl~
app~icator rolls 5 to the drum D' at its lowermost reglon and ls subJected to electron-beam curing at top region R within the shielded upper housing H', passing then over a casting blade 6 to release or transfer rrom the drum D' a cast fllm F that may then be wound at statlon 7. For such film casting (or transrer coating as in other embodirnents) the drum D' may be contin-uously cleaned at 8 as lt returns from the film trans-fer point (where the substrate or film leaves the drum surface) to the point where the liquid coating is being continuously applied to the drum surface from reservoir R".
In these and other applications, the invention eliminates the need ror consumable release liner or sheet which has an important impact on the eccnomics of transfer coatlng Or rlexible or semiflexible webs such as paper, paperboard~ non-wovens, rilm, foil, textiles, etc. Surrace texturizing Or the web, moreover, is rea-dlly accornplished by the etching or engraving of the drum surrace. Difrerential drum~web speeds rnay also be used to provide special texturing erfects in the coat-ing, in much the same way as dirferential web-transrer roll speeds are used in ofrset gravure coating.
3~
Unusual hold-out advantages are possible with the geometries of Figs. 1 and 2 in ~hat very short dwell times of the coating on the substrate prior to cure are possible, assisting in high gloss surfaces as taught in U.S. Patent No. 4,537,811 issued August 27, 1985; and the geometries described herein greatly minimize these effects under pre-cisely controllable conditions.
Other uses of the techniques of the invention for transfer casting of films are shown in Figs. 5 and 6. These techniques also permit the optimization of processes for the generation of unique, fault-free films for dielectric appli-cations (capacitor film) and the like. In the embodiment of Figs. 5 and 6, electron-beam-curable coatings are applie~
to carrier films before and during passage over the drum D', respectively, with the carrier being separated by casting blades 6 from the electron-beam cast film F to the right of the curing region R.
Further modifications will occur to those skilled in this art and such are considered to fall within the spirit and scope of the invention as defined in the appended claims.
vtd/ Cl~
Claims (16)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of transfer-coating electron-beam-curable material, that comprises, applying such material to the surface of a drum;
rotating the drum past a region where electron-beam radiation is directed towards the drum, to cure the material against the drum;
cooling the drum; and releasing the cured material from the drum surface.
rotating the drum past a region where electron-beam radiation is directed towards the drum, to cure the material against the drum;
cooling the drum; and releasing the cured material from the drum surface.
2. A method as claimed in claim 1 and in which said material is carried by a continuous sheet, film or web drawn over the drum.
3. A method as claimed in claim 1 and in which said material is applied to the drum at one location and is carried by the drum to another location at the said region of electron-beam radiation.
4. A method as claimed in claim 3 and in which a sheet or web is drawn over the material on the drum.
5. A method as claimed in claim 3 and in which said releasing is effected by lifting the cured material as a cast film from the drum surface.
6. A method as in claim 4 and in which said sheet is a carrier film passed over the drum at said region so that the cured material will adhere to it, and the cured material is subsequently released from said carrier film as a cast film.
7. A method as claimed in claim 1 and in which said drum surface reflects electron beam radiation back into said material.
8. A method as claimed in claim 1 and in which the further step is performed of shielding the drum as it rotates past the said region.
9. A method as claimed in claim 8 and in which a shield is disposed to serve as the drum surface.
10. Apparatus for electron-beam curing having, in combination, an electron-beam processor having window means for the emergence of electron-beam radiation and means for shielding the region of such emergence; drum means mounted below said region with means for rotating the same past the lower part of said region; means for shielding the drum means as it passes through said region; means for applying electron-beam-curable material to the surface of the drum means to permit curing of the same in said region; means for cooling said drum; and means for releasing the cured material from the drum surface.
11. Apparatus as claimed in claim 10 and in which said material is applied to the drum at a location outside said region.
12. Apparatus as claimed in claim 10 and in which said material is applied to the drum by a sheet or web passing over the drum at said region.
13. Apparatus as claimed in claim 11 and in which means is provided for separating said material after its cure from the drum, as a cast film.
14. Apparatus as claimed in claim 10 and in which said drum is provided with an electron-beam-reflecting surface.
15. Apparatus as claimed in claim 14 and in which said surface comprises layers of lead, tantalum and stainless steel.
16. Apparatus as claimed in claim 10 and in which said drum is inertia-rotated by means for passing sheet material over the drum.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US41553482A | 1982-09-07 | 1982-09-07 | |
US06/432,569 US4490409A (en) | 1982-09-07 | 1982-10-04 | Process and apparatus for decorating the surfaces of electron irradiation cured coatings on radiation-sensitive substrates |
US06/487,461 US4521445A (en) | 1982-09-07 | 1983-04-22 | Method and apparatus for electron curing on a cooled drum |
US487,461 | 1983-04-22 | ||
US84711786A | 1986-04-03 | 1986-04-03 | |
US07/175,615 US4844764A (en) | 1982-09-07 | 1988-03-29 | Process of in-line coating and decorative-layer lamination with panel board material employing electron beam irradiation |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1256397A true CA1256397A (en) | 1989-06-27 |
Family
ID=39590542
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000426810A Expired CA1230847A (en) | 1982-09-07 | 1983-04-27 | Transferring decorative coating from release layer to electron beam cured adhesive coating |
CA000443818A Expired CA1256397A (en) | 1982-09-07 | 1983-12-20 | Method and apparatus for electron curing on a cooled drum |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000426810A Expired CA1230847A (en) | 1982-09-07 | 1983-04-27 | Transferring decorative coating from release layer to electron beam cured adhesive coating |
Country Status (8)
Country | Link |
---|---|
US (3) | US4490409A (en) |
EP (3) | EP0105573B1 (en) |
JP (2) | JPS5968240A (en) |
AU (1) | AU588812B2 (en) |
CA (2) | CA1230847A (en) |
DE (1) | DE3380579D1 (en) |
FR (2) | FR2533840B1 (en) |
HK (1) | HK51390A (en) |
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JP6717191B2 (en) * | 2014-04-18 | 2020-07-01 | 株式会社ニコン | Film forming apparatus, substrate processing apparatus, and device manufacturing method |
WO2016106301A1 (en) | 2014-12-22 | 2016-06-30 | Graphic Packaging International, Inc. | Systems and methods for forming laminates |
BR112018003774A2 (en) * | 2015-08-26 | 2018-09-25 | Energy Sciences Inc | electron beam apparatus with adjustable air space |
ES2734748T3 (en) * | 2016-09-02 | 2019-12-11 | SWISS KRONO Tec AG | Procedure for the manufacture of an oriented chip board provided with a structured surface |
PT3936338T (en) * | 2020-07-07 | 2024-03-04 | Barberan Latorre Jesus Francisco | Method and system for adhesive bonding of substrates |
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US3644161A (en) * | 1967-11-13 | 1972-02-22 | Scm Corp | Process for curing air-inhibited resins by radiation |
DE1924110A1 (en) * | 1969-05-12 | 1971-05-13 | Licentia Gmbh | Laminate of resin impregnated layers |
US3702412A (en) * | 1971-06-16 | 1972-11-07 | Energy Sciences Inc | Apparatus for and method of producing an energetic electron curtain |
US3769600A (en) * | 1972-03-24 | 1973-10-30 | Energy Sciences Inc | Method of and apparatus for producing energetic charged particle extended dimension beam curtains and pulse producing structures therefor |
US3745396A (en) * | 1972-05-25 | 1973-07-10 | Energy Sciences Inc | Elongated electron-emission cathode assembly and method |
DE2705273A1 (en) * | 1977-02-09 | 1978-08-10 | Herberts & Co Gmbh Dr Kurt | METHOD AND DEVICE FOR COATING FILM OR FOIL WEBS |
US4215170A (en) * | 1978-02-28 | 1980-07-29 | Eurographics Holding, N. V. | Metallization process |
DE2966367D1 (en) * | 1978-09-01 | 1983-12-08 | Mobil Oil Corp | Method for applying coatings to substrates |
US4246297A (en) * | 1978-09-06 | 1981-01-20 | Energy Sciences Inc. | Process and apparatus for the curing of coatings on sensitive substrates by electron irradiation |
US4252413A (en) * | 1978-10-05 | 1981-02-24 | Energy Sciences Inc. | Method of and apparatus for shielding inert-zone electron irradiation of moving web materials |
US4294782A (en) * | 1979-04-10 | 1981-10-13 | Jerome Bauer | Method for substantially instantaneous liquid molding of an article |
JPS55163294A (en) * | 1979-05-31 | 1980-12-19 | Dainippon Printing Co Ltd | Vapor deposited paper |
US4322450A (en) * | 1979-09-24 | 1982-03-30 | Scott Paper Company | Surface replication on a coated substrate |
NL8000967A (en) * | 1980-02-15 | 1981-09-16 | Leer Koninklijke Emballage | METALLIC COATED COMPOSITION STRUCTURE AND METHOD FOR MANUFACTURING IT. |
DE3010060A1 (en) * | 1980-03-15 | 1981-10-01 | Letron GmbH, 8750 Aschaffenburg | MULTI-LAYERED PLATE HAVING A VARNISH SURFACE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
JPS56164853A (en) * | 1980-05-23 | 1981-12-18 | Toppan Printing Co Ltd | Metal evaporated transcribing foil |
DE3022709A1 (en) * | 1980-06-18 | 1982-01-07 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | WATERPROOF PHOTOGRAPHIC PAPER AND METHOD FOR THE PRODUCTION THEREOF |
JPS5763257A (en) * | 1980-10-04 | 1982-04-16 | Dainippon Printing Co Ltd | Manufacture of decorative wood with tuned embossed pattern |
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-
1982
- 1982-10-04 US US06/432,569 patent/US4490409A/en not_active Expired - Lifetime
-
1983
- 1983-04-22 US US06/487,461 patent/US4521445A/en not_active Expired - Lifetime
- 1983-04-27 CA CA000426810A patent/CA1230847A/en not_active Expired
- 1983-06-01 JP JP58097770A patent/JPS5968240A/en active Granted
- 1983-06-06 EP EP83303250A patent/EP0105573B1/en not_active Expired
- 1983-06-07 FR FR8309392A patent/FR2533840B1/en not_active Expired
- 1983-12-05 DE DE8383307373T patent/DE3380579D1/en not_active Expired
- 1983-12-05 EP EP83307373A patent/EP0122998B1/en not_active Expired
- 1983-12-20 CA CA000443818A patent/CA1256397A/en not_active Expired
-
1984
- 1984-01-04 EP EP84300035A patent/EP0147906A1/en not_active Ceased
- 1984-04-20 JP JP59080032A patent/JPS59206043A/en active Granted
- 1984-04-24 FR FR8406420A patent/FR2544633A1/en not_active Withdrawn
-
1985
- 1985-06-19 AU AU43821/85A patent/AU588812B2/en not_active Ceased
-
1988
- 1988-03-29 US US07/175,615 patent/US4844764A/en not_active Expired - Fee Related
-
1990
- 1990-07-12 HK HK513/90A patent/HK51390A/en unknown
Also Published As
Publication number | Publication date |
---|---|
FR2544633A1 (en) | 1984-10-26 |
US4521445A (en) | 1985-06-04 |
EP0122998A2 (en) | 1984-10-31 |
AU4382185A (en) | 1986-12-24 |
EP0105573A3 (en) | 1984-11-28 |
EP0147906A1 (en) | 1985-07-10 |
US4844764A (en) | 1989-07-04 |
DE3380579D1 (en) | 1989-10-19 |
FR2533840A1 (en) | 1984-04-06 |
JPH0536212B2 (en) | 1993-05-28 |
AU588812B2 (en) | 1989-09-28 |
FR2533840B1 (en) | 1988-05-27 |
EP0122998A3 (en) | 1985-08-28 |
US4490409A (en) | 1984-12-25 |
EP0122998B1 (en) | 1989-09-13 |
CA1230847A (en) | 1987-12-29 |
HK51390A (en) | 1990-07-20 |
JPS59206043A (en) | 1984-11-21 |
EP0105573B1 (en) | 1988-02-24 |
EP0105573A2 (en) | 1984-04-18 |
JPS5968240A (en) | 1984-04-18 |
JPS6356829B2 (en) | 1988-11-09 |
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