GB2194951A - Production of urethane polymer films - Google Patents

Production of urethane polymer films Download PDF

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Publication number
GB2194951A
GB2194951A GB08721200A GB8721200A GB2194951A GB 2194951 A GB2194951 A GB 2194951A GB 08721200 A GB08721200 A GB 08721200A GB 8721200 A GB8721200 A GB 8721200A GB 2194951 A GB2194951 A GB 2194951A
Authority
GB
United Kingdom
Prior art keywords
process according
fluid material
viscous fluid
film
urethane
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.)
Granted
Application number
GB08721200A
Other versions
GB2194951B (en
GB8721200D0 (en
Inventor
Thomas Jonathon Swanston
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel UK PLC
Original Assignee
Courtaulds PLC
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 Courtaulds PLC filed Critical Courtaulds PLC
Publication of GB8721200D0 publication Critical patent/GB8721200D0/en
Publication of GB2194951A publication Critical patent/GB2194951A/en
Application granted granted Critical
Publication of GB2194951B publication Critical patent/GB2194951B/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29C41/28—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 an endless belt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • 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
    • 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
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08J2375/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Abstract

A continuously cast film of a urethane polymer is formed from a viscous fluid material comprising a urethane prepolymer having reactive end groups which are ester groups of an unsaturated carboxylic acid, for example an acrylate-functional urethane prepolymer, and a photo-initiator deposited on a moving band at a controlled thickness in the range of 10 to 500 microns. The viscous fluid material is carried by the band through a curing zone in which the viscous fluid material is cured to a solid self-supporting polymer film by irradiation with actinic radiation.

Description

SPECIFICATION Production of urethane polymer films This invention relates to a process for the continuous production of cast films of a urethane polymer. Polyurethane films can be formed by extrusion, but extruded films generally have an oriented structure and a relatively low surface energy. The oriented structure leads to reduced dimensional stability, and the low surface energy may make it difficult to apply adhesives to the film where it is required that the film should be bonded to a substrate. One particular use for polyurethane film is as a protective film on the underbody and/or the inner side of the door skin of cars. For this use the film requires the tough properties associated with polyurethane films and also a very high dimensional stability.
Films of many polymers are made by casting from a volatile solvent. When making polyurethane films this process has the disadvantage that the solvents or solvent mixtures required to dissolve polyurethane are toxic, expensive and unpleasant to handle and the cost of plant for solvent recovery is high.
A process according to the invention for continuously forming a cast film of a urethane polymer is characterised in that a viscous fluid material comprising a urethane prepolymer having reactive end groups which are ester groups of an unsaturated carboxylic acid and a photoinitiator deposited on a moving band at a controlled thickness in the range of 10 to 500 microns is carried by the band through a curing zone in which the viscous fluid material is cured to a solid self-supporting polymer film by irradiation with actinic radiation.
The urethane prepolymer generally has a molecular weight in the range 500 to 10,000, preferably 600 to 2,000. The urethane prepolymer is preferably an acrylate-functional prepolymer and is generally produced by reacting a hydroxy-functional prepolymer with a polyisocyanate in which one of the isocyanate groups has been reacted with a hydroxy-functional acrylate or methacrylate such as hydroxyethyl acrylate. The hydroxy-functional prepolymer can be a polyether or polyester diol or may be a prepolymer containing urethane linkages. The polyisocyanate can be aromatic or aliphatic and is preferably a diisocyanate. Aliphatic diisocyanates are more expensive but may be preferred to aromatic diisocyanates when the film is required to have excellent resistance to discolouration by sunlight.Acrylate-functional urethane prepolymers are available commercially and examples of suitable prepolymers include those sold under the trade marks Actocryl 300, 305 and 310, Crestomer NV 1170 and Synacure 3134.
Alternatively all or part of the urethane prepolymer may be a prepolymer having cinnamate ester end groups rather than acrylate groups. Cinnamate groups do not readily undergo conventional addition polymerisation but dimerise under the influence of actinic radiation to form a ring structure. This reaction gives chain extension of the urethane without crosslinking, which may be advantageous in forming films of increased extensibility.
The viscous fluid material generally contains 10 to 99 per cent by weight of the urethane prepolymer. An acrylate-functional urethane prepolymer is preferably mixed with an addition polymerisable diluent whch can be present at up to 90 per cent by weight. The polyermisable diluent is a liquid monomer which reduces the viscosity of the fluid material and is capable of being copolymerised with the acrylate-functional urethane prepolymer. The mixture of urethane prepolymer and polymerisable diluent preferably comprises 40 to 95 per cent by weight, most preferably 55 to 85 per cent by weight, of acrylate-functional urethane prepolymer and 5 to 60 per cent by weight, most preferably 14 to 45 per cent, of addition polymerisable diluent.
The addition polymerisable diluent comprises at least one ethylenically unsaturated monomer and preferably comprises a monomer containing acrylate functional groups. The addition polymerisable diluent can be a difunctional acrylate. Difunctional acrylates containing ether linkages such as tripropylene glycol diacrylate, tetrapropylene glycol diacrylate or tetraethylene glycol diacrylate are particularly preferred; hexanediol diacrylate is an alternative. Such diacrylates give both chain extension and cross-linking of the urethane polymer film on curing. More highly functional acrylates such as trimethylol propane triacrylate or glyceryl propoxy triacrylate can be used, although they are not preferred. Mono-ethylenicaly unsaturated addition polymerisable monomers, for example styrene, which give chain extension of the polymer without cross linking, can also be included.
Examples of photoinitiators are aromatic carbonyl compounds such as benzophenone, thioxanthone, 2-chlorothioxanthone, Michler's ketone, 2,2-diethoxyacetophenone, a benzoin ether or 1hydroxycylohexyl phenyl ketone of the formula:
which is sold commercially under the trade mark 'Irgacure 184' or ethyl 4-(dimethylamino)benzoate which is sold commercially under the trade mark 'Quantacure EPD'. Mixtures of photoinitiators can be used, for example benzophenone with Irgacure 184 or a benzoin ether. The amount of photoinitiator used is generally in the range 0.1 to 10 per cent by weight of the viscous fluid material, preferably 1.5 to 8 per cent.
The viscous fluid material can include an amine catalyst for the photoinitiator, for example a secondary or tertiary amine such as methyl ethanolamine or dimethyl ethanolamine.
The viscous fluid material is preferably free from non-polymerisable solvents and diluents so that no solvents or diluents are emitted from the film and there is no need for solvent recovery.
The process of the invention is particularly suitable for the production of clear cast films.
Alternatively, one or more pigments or fillers can be included in the viscous fluid material if their presence in the cast film is desired.
The moving band is preferably a stainless steel band; alternatively the moving band may be a release sheet, for example a release paper, which is supported on a conveyor such as a steel band. In either case the steel band is preferably a continuous band. When the viscous fluid material is deposited on a moving band the thickness of the cast film is controlled by controlling the rate of feed of the viscous fluid material onto the band, generally moving in a substantially horizontal direction, and the speed of the band. The viscous fluid material is preferably fed to the band through a slot die; this gives a film of very uniform thickness across its width. The viscosity of the fluid material is preferably 200 to 3,000 poise which allows it to flow sufficiently to produce a film with a smooth surface.The viscous fluid material can alternatively be fed to the band at a controlled rate and spread across the band by passing under a doctor blade.
The film is preferably cured by ultraviolet irradiation of wavelength 200 nm to 500 nm, for example by passing the film under one or more high-pressure mercury lamps. The intensity of radiation is preferably that provided by a mercury lamp of 50 to 500 watts per centimetre width of film. The ultraviolet lamp or lamps are preferably surrounded by a reflector. Irradiation of the film is preferably carried out under a blanket of nitrogen or other inert gas. The time of passage through the ultraviolet curing system is generally 0.05 to 120 seconds, preferably 0.1 to 30 seconds.
After the film has been cured it is preferably stripped from the band, if it has been cast directly on a stainless steel band, and taken up on a reel. if the film has been cast on a release sheet the release sheet is separated from the band supporting it and the cast film on its release sheet is taken up on a reel. The release sheet can be removed when the urethane polymer film is subsequently processed. Whether or not a release sheet is used the film after radiation curing should be non-tacky and capable of being stripped as a self-supporting film.
Film produced according to the invention generally has a surface energy of at least 70 dynes per square cm. Both water-based and solvent-based adhesives can readily be spread on the film surface. Examples of uses of the film are as a protective film for the underbody and/or the door skin of cars or as a protective outer covering for mattresses. For such uses the thickness of the cast film is preferably 100 to 500 microns, for example about 300 microns for use on cars.
Examples of viscous fluid materials which can be cast and cured by ultraviolet radiation to form a urethane polymer film according to the invention are the following (percentages are by weight).
Example 1 Actocryl 305 aliphatic urethane acrylate prepolymer 66.6% Hexanediol diacrylate 28.6% Benzophenone 2.4% Irgacure 184 2.4% Example 2 Crestomer NV 1170 urethane acrylate prepolymer 66.6% Tripropylene glycol diacrylate 28.6% Benzophenone 2.4% Irgacure 184 2.4% Each of the above formulations could be cast on a release paper carried on a horizontal moving band at a thickness of 300 microns and cured by a 80 watts per cm high-pressure mercury lamp with a residence time of 2.5 seconds to form a cured tack-free dimensionally stable urethane polymer film having a smooth surface and surface energy of above 70 dynes per square cm.

Claims (14)

1. A process for continuously forming a cast film of a urethane polymer, characterised in that a viscous fluid material comprising a urethane prepolymer having reactive end groups which are ester groups of an unsaturated carboxylic acid and a photoinitiator deposited on a moving band at a controlled thickness in the range of 10 to 500 microns is carried by the band through a curing zone in which the viscous fluid material is cured to a solid self-supporting polymer film by irradiation with actinic radiation.
2. A process according to claim 1, in which the viscosity of the viscous fluid material is 200 to 3,00 poise.
3. A process according to claim 1 or claim 2, in which the viscous fluid material is fed to a horizontal moving band through a slot die.
4. A process according to any of claims 1 to 3, in which the moving band is a stainless steel band.
5. A process according to any of claims 1 to 3, in which the moving band is a release sheet supported on a conveyor.
6. A process according to any of claims 1 to 5, in which the photoinitiator comprises 1.5-8% by weight of the viscous fluid material and the film is cured by ultra violet irradiation of wave length 200 nm to 500 nm.
7. A process according to any of claims 1 to 6, in which the urethane prepolymer has a molecular weight in the range of 600 to 2,000.
8. A process according to any of claims 1 to 7, in which the urethane prepolymer is an acrylate-functional prepolymer.
9. A process according to claim 8, in which the viscous fluid material comprises 40 to 95% by weight of the acrylate-functional urethane prepolymer and 5 to 60% by weight of an addition polymerisable liquid monomer.
10. A process according to claim 8, in which the viscous fluid material comprises 55 to 85% by weight of the acrylate-functional urethane prepolymer and 14 to 45% by weight of an addition polymerisable liquid monomer.
11. A process according to claim 9 or claim 10, in which the addition polymerisable liquid monomer is a difunctional acrylate containing ether linkages.
12. A process according to any of claims 1 to 7, in which the urethane prepolymer is a cinnamate-functional prepolymer.
13. A process for continuously forming a cast film of a urethane polymer carried out substantially as described in either of the Examples.
14. A reeled-up cast film of a urethane polymer having a thickness of 100 to 500 microns and a surface energy of at least 70 dynes/cm2 when formed by a process as clqimed in any of claims 1 to 13.
GB8721200A 1986-09-10 1987-09-09 Production of urethane polymer films Expired - Lifetime GB2194951B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB868621835A GB8621835D0 (en) 1986-09-10 1986-09-10 Urethane polymer films

Publications (3)

Publication Number Publication Date
GB8721200D0 GB8721200D0 (en) 1987-10-14
GB2194951A true GB2194951A (en) 1988-03-23
GB2194951B GB2194951B (en) 1990-01-10

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Family Applications (2)

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GB868621835A Pending GB8621835D0 (en) 1986-09-10 1986-09-10 Urethane polymer films
GB8721200A Expired - Lifetime GB2194951B (en) 1986-09-10 1987-09-09 Production of urethane polymer films

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB868621835A Pending GB8621835D0 (en) 1986-09-10 1986-09-10 Urethane polymer films

Country Status (1)

Country Link
GB (2) GB8621835D0 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0798355A2 (en) * 1996-03-15 1997-10-01 LINTEC Corporation Base material for adhesive tape
WO2004028772A1 (en) * 2002-09-25 2004-04-08 Porvair Plc Polymer film production
EP2371881A1 (en) * 2010-03-31 2011-10-05 Entrotech, Inc. Methods for polymerizing films in-situ using a radiation source
US9790318B2 (en) 2008-09-26 2017-10-17 entrotech, inc Methods for polymerizing films in-situ
US11420427B2 (en) 2007-09-25 2022-08-23 Entrotech, Inc. Paint replacement film, composites therefrom, and related methods
US11577501B2 (en) 2008-01-19 2023-02-14 Entrotech, Inc. Protected graphics and related methods
US11827823B2 (en) 2016-09-20 2023-11-28 Ppg Advanced Surface Technologies, Llc Paint film appliques with reduced defects, articles, and methods

Citations (18)

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Publication number Priority date Publication date Assignee Title
GB1453429A (en) * 1974-08-08 1976-10-20 Kansai Paint Co Ltd Photocurable compositions
US4131602A (en) * 1977-09-29 1978-12-26 Union Carbide Corporation Radiation curable acrylated polyurethane
GB2002009A (en) * 1977-07-12 1979-02-14 Union Carbide Corp >Radiation curable coating composition
GB2010880A (en) * 1977-12-23 1979-07-04 Armstrong Cork Co Curable coating compositions and coatings obtained therefrom
GB2012290A (en) * 1978-01-03 1979-07-25 Lord Corp Actinic radiation curable formulations
GB2018263A (en) * 1978-03-30 1979-10-17 Union Carbide Corp Acrylyl capped urethane obligomers
GB2022599A (en) * 1978-05-18 1979-12-19 Lord Corp Coating composition
US4192762A (en) * 1978-04-20 1980-03-11 Union Carbide Corporation Radiation curable urethane compositions
GB1564541A (en) * 1976-08-07 1980-04-10 Dennison Mfg Co Radiation curable coatings
GB2040297A (en) * 1979-01-09 1980-08-28 Lord Corp Actinic radiation-curable formulations
EP0015593A1 (en) * 1979-02-12 1980-09-17 Hüls Aktiengesellschaft Process for preparing stably storable urethane acryls
GB1575898A (en) * 1977-03-21 1980-10-01 Witco Chemical Corp Crosslinkable polyurethane resins
GB1590412A (en) * 1976-08-02 1981-06-03 Lord Corp Radiation curable compositions
GB1590413A (en) * 1976-07-23 1981-06-03 Lord Corp Radiation curable coating composition
GB2095271A (en) * 1981-03-23 1982-09-29 Lord Corp Thermosensitive polymer compositions and films
GB2163172A (en) * 1984-06-30 1986-02-19 Yokohama Rubber Co Ltd Ultraviolet-curing resin composition
GB2163443A (en) * 1984-07-10 1986-02-26 Yokohama Rubber Co Ltd Photocurable resin composition
GB2170497A (en) * 1985-02-04 1986-08-06 Sanyo Kokusaku Pulp Co Photo-curable urethane oligomer composition

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453429A (en) * 1974-08-08 1976-10-20 Kansai Paint Co Ltd Photocurable compositions
GB1590413A (en) * 1976-07-23 1981-06-03 Lord Corp Radiation curable coating composition
GB1590412A (en) * 1976-08-02 1981-06-03 Lord Corp Radiation curable compositions
GB1564541A (en) * 1976-08-07 1980-04-10 Dennison Mfg Co Radiation curable coatings
GB1575898A (en) * 1977-03-21 1980-10-01 Witco Chemical Corp Crosslinkable polyurethane resins
GB2002009A (en) * 1977-07-12 1979-02-14 Union Carbide Corp >Radiation curable coating composition
US4131602A (en) * 1977-09-29 1978-12-26 Union Carbide Corporation Radiation curable acrylated polyurethane
GB2006241A (en) * 1977-09-29 1979-05-02 Union Carbide Corp Radiation curable acrylated polyurethane
GB2010880A (en) * 1977-12-23 1979-07-04 Armstrong Cork Co Curable coating compositions and coatings obtained therefrom
GB2012290A (en) * 1978-01-03 1979-07-25 Lord Corp Actinic radiation curable formulations
GB2018263A (en) * 1978-03-30 1979-10-17 Union Carbide Corp Acrylyl capped urethane obligomers
US4192762A (en) * 1978-04-20 1980-03-11 Union Carbide Corporation Radiation curable urethane compositions
GB2022599A (en) * 1978-05-18 1979-12-19 Lord Corp Coating composition
GB2040297A (en) * 1979-01-09 1980-08-28 Lord Corp Actinic radiation-curable formulations
EP0015593A1 (en) * 1979-02-12 1980-09-17 Hüls Aktiengesellschaft Process for preparing stably storable urethane acryls
GB2095271A (en) * 1981-03-23 1982-09-29 Lord Corp Thermosensitive polymer compositions and films
GB2163172A (en) * 1984-06-30 1986-02-19 Yokohama Rubber Co Ltd Ultraviolet-curing resin composition
GB2163443A (en) * 1984-07-10 1986-02-26 Yokohama Rubber Co Ltd Photocurable resin composition
GB2170497A (en) * 1985-02-04 1986-08-06 Sanyo Kokusaku Pulp Co Photo-curable urethane oligomer composition

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0798355A2 (en) * 1996-03-15 1997-10-01 LINTEC Corporation Base material for adhesive tape
EP0798355A3 (en) * 1996-03-15 1998-09-09 LINTEC Corporation Base material for adhesive tape
US6139953A (en) * 1996-03-15 2000-10-31 Lintec Corporation Adhesive tape, base material for adhesive tape and their manufacturing methods
WO2004028772A1 (en) * 2002-09-25 2004-04-08 Porvair Plc Polymer film production
US11420427B2 (en) 2007-09-25 2022-08-23 Entrotech, Inc. Paint replacement film, composites therefrom, and related methods
US11577501B2 (en) 2008-01-19 2023-02-14 Entrotech, Inc. Protected graphics and related methods
US9790318B2 (en) 2008-09-26 2017-10-17 entrotech, inc Methods for polymerizing films in-situ
EP2371881A1 (en) * 2010-03-31 2011-10-05 Entrotech, Inc. Methods for polymerizing films in-situ using a radiation source
US8828303B2 (en) 2010-03-31 2014-09-09 Entrotech, Inc. Methods for polymerizing films in-situ using a radiation source
US11827823B2 (en) 2016-09-20 2023-11-28 Ppg Advanced Surface Technologies, Llc Paint film appliques with reduced defects, articles, and methods
US11884849B2 (en) 2016-09-20 2024-01-30 Ppg Advanced Surface Technologies, Llc Paint film appliques with reduced defects, articles, and methods

Also Published As

Publication number Publication date
GB8621835D0 (en) 1986-10-15
GB2194951B (en) 1990-01-10
GB8721200D0 (en) 1987-10-14

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19920909