WO1997002313A1 - Lamination by photografting - Google Patents
Lamination by photografting Download PDFInfo
- Publication number
- WO1997002313A1 WO1997002313A1 PCT/SE1996/000883 SE9600883W WO9702313A1 WO 1997002313 A1 WO1997002313 A1 WO 1997002313A1 SE 9600883 W SE9600883 W SE 9600883W WO 9702313 A1 WO9702313 A1 WO 9702313A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photo
- films
- grafted
- layer
- ldpe
- Prior art date
Links
Classifications
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- 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
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- 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
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
- B32B2333/04—Polymers of esters
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
Definitions
- Present invention relates to a photografting method, in which one or multi layer(s) of films or sheets, with intermediate layer(s) of a photo ⁇ polymerizable composition, the intermediate layer(s) is/are grafted onto adjacent polymer surfaces.
- the present invention also relates to a process for preparing laminate or composite material and laminates or composite materials made by the proces ⁇ .
- the present invention relates to a use of the laminates or the composite materials .
- This invention is based on our previous invention of " surface photografting" of polymer sheets, films, filaments and yarns ( B. R&nby, Z. M. Gao, A. Huh and P. Y. Zhang, Polvmer Preprints. ACS, 27:2, 38-39 (1986)).
- the invention has been developed as a batch process, where initiator and monomer in vapor phase are transferred and initiated by UV i ⁇ adiation to react at the substrate surface, and a continuous p rocess, where initiator and monomer in liquid phase are transferred to the substrate surface by presoal ⁇ ng immediately before the irradiation with UV light ( B. Rinby, Z. M Gao. A Huh and P. Y.
- the continuous surface photografting is a rapid and efficient process for sheet, film, filament and yarn.
- the process modifies the substrate surface with a very thin layer of grafted polymer (2 to 8 nm).
- hydrophilic monomers like acrylic acid, acrylamide or 4- vinyl pyridine
- the modified surface of an inert substrate polymer shows increased wetting with water ( lower contact angle), increased adso ⁇ tion of dyes (by a factor of 5 to 15) and increased adhesion to epoxy resins (by a factor of 3 to 6) Fu ⁇ her results are presented in a printed thesis by Zhang Pei Yao, Surface Modification tn Continuous Graft Copolymerization. Royal Institute of . Sweden, October 14, 1988.
- the substrates studied are commercially available samples like polyethylene tape film, polypropylene film strips, polyethylene fibers and polypropylene fibers, which are surface photografted using the continuous process with acrylic acid and acrylamide as monomers, benzophenone as initiator and an aliphati ketone, e.g. acetone, as solvent.
- Zhang * s disse ⁇ ation contains four papers which ar printed in J. Applied Polymer Science 4Q, 1647 (1990), 41, 1459 and 1469(1990) an 43, 621(1991).
- the batch process for surface photografting is slow wuh UV lrradiauon times ot a few minutes, because the transfer of initiator and monomer in vapor phase is inefficient
- the con ⁇ nuous process is much faster with UV irradianon umes of 5 to 10 seconds because the transfer of ln ator and monomer in liquid phase is efficient and fast
- initiator and monomer form a liquid composition between two substrate films of which the top film is transparent to the ln ating UV irradiation
- the two top films should be transparent to the lnitiaung UV irradiation
- Ethylenic hydrogens are not abstracted by die excited benzophenone due to the high bond strength (104 kcal/mole).
- the photografung lamination is initiated at die polymer surfaces in contact with the liquid composiuon.
- the grafted chains grow until they are terminated by combinauon of two chain end radicals or by combmauon of a chain end radical widi a ketyl radical (from benzophenone)
- the reacting composition is a photoinitiator dissolved in reactive monomer
- the two substrate surfaces are grafted and die polyme ⁇ zed composition forms an mtermediate layer which fills the space between the two films It forms a strong. adhesive bond between the two films and can also be a bar ⁇ er for a penetrant
- the grafted polyacrylic acid is an efficient oxygen bar ⁇ er (Examplel)
- the intermediate layer of die grafted polymer in this case consists of two layers, grafted onto each substrate surface. Therefore, the two substrate films are separated if the grafted laminate is immersed in a solvent for the grafted polymer, e g , hot water for grafted acrylic acid.
- a photopolymerizable composition A was prepared by dissolving 5 g benzophenone and 2 g cellulose acetate (40%) in 100 g acrylic acid.
- a low density polye ⁇ ylene (LDPE) film 188 ⁇ m ick and a polyethylene terephthalate (PET) film 256 ⁇ m thick were cut to pieces of 60 X 60 mm square.
- LDPE low density polye ⁇ ylene
- PET polyethylene terephthalate
- PCA 10 ⁇ l was applied by a microsyringe on the surface of the PET film and die LDPE film was deposited on top.
- a clear quartz plate 8 mm thick covering the laminate and a brass weight of 1,588 kg was placed on top of the laminate. After a few seconds the brass weight was removed.
- the laminate widi the quartz plate on top was irradiated for 25 sec. at 55°C with a 2 kW high pressure mercury lamp HPM 15 (from Philips) at a distance of 15 cm from lamp to laminate.
- HPM 15 from Philips
- the lamination by photografting is performed as shown in Fig. 1 for LDPE film on top of PET film.
- the adhesion of the two films was measured as a 90° peel test in an Instron instrument at an extension rate of 20 mm / min..
- the grafted laminate failed by breaking of the LDPE film and not by separation in the PCA adhesive layer.
- PCB photopolymerizable composition B
- a film of LDPE 32 ⁇ m thick was cut to pieces 60 X 60 mm square Of the photopolymenzable composition PCA 25 ⁇ l was applied as an intermediate layer between two LDPE film samples using the same procedure as in Example 1.
- the assembly was ⁇ radiated with UV light for 30 sec. under the same conditions as in Example 1.
- the oxygen permeability was measured in an OX-TRAN 2/20 MH instrument from MOCON, Minneapolis, .Minn., USA.
- the permeability value 12,0 cc Q- ⁇ J day m 2 was obtained for the photografted laminate and the value 948 cc O / day m2 for a blank sample, e.g two LDPE films without grafted layer.
- the photografted layer of poly(acrylic acid) is a most efficient C ⁇ barrier.
- a photopolymerizable composition C was prepared by dissolving 5 g benzophenone and 2 g poly(vinyl acetate) PVAc widi Mn 500,000 in 100 g of a monomer mixture of 20 vol. % acrylic acid and 80 vol. % butyl acrylate.
- An LDPE film 63 ⁇ m thick was cut to samples 95 X 95 mm square, an assembly of two film samples with 25 ⁇ l of PCC as intermediate layer was prepared by die same procedure as in Example 1. The assembly was irradiated for 60 sec. at 55°C under a 2 kW HPM lamp at a distance of 15 cm.
- oxygen permeability P was measured by Terra Pak Materials R & D Inc., Lincolnshire, IL, USA, using a proprietary method.
- the grafted intermediate layer is a rubber-like polymer with rather poor barrier properties.
- a se ⁇ es of laminates were prepared
- the photopolymerizable composition PCA was used, descnbed in Example 1. with a thickness of 7 ⁇ m.
- the laminates were prepared as descnbed in Example 1 and irradiated for 30 sec. at 55°C with a HPM 15 UV lamp from Philips at a distance of 15 cm.
- the oxygen permeability of the photografted laminates and the blank samples of two LDPE films without PCA layer was measured in a MOCON transmission analysis instrument OX-TRAN 2/20 with air (21% O 2 ) and pure oxygen (100% 0 2 ) and given as cc/day m 2 .
- Table 1 Permeability measurements
- Blank 686 3267 3 Laminate 13.0 62.0 4 Blank 705 3357 5 Laminate 1 1 .0 52 4 6 Blank 715 3405
- the oxygen permeabdity for blank samples vanes by about ⁇ 2% which is less than the vananon in thickness of the film ⁇ 7%.
- the oxygen permeability for the laminates vanes by about ⁇ 25% which indicates a large va ⁇ ation in tiiickness of the photografted layer
- the photografted layer is an efficient 0 2 bar ⁇ er. It decreases tiie permeability of the laminates for oxygen tacto- 40 to 60
- PET polyvinylidene chloride
- PVDC polyvinylidene chloride
- PVA polyvinyl alcohol
- P* Values in the last column are P x Thickness ( ⁇ m) and represent a specific permeation rate for oxygen (die accuracy is about 3 figures).
- a PVA film is laminated between an LDPE film (top) on a PET film (bottom).
- the permeability of the resulting photografted laminates was measured by Tetra Pak Materials R & D, Inc., using a proprietary method and given as cc 0 2 / day m 2 .
- the reactive PCC contains 5 g benzophenone and 2 g poly(vinylacetate) dissolved in a monomer mixture of 80 g butylacrylate and 20g acrylic acid .
- the UV i ⁇ adiation was made with a 2 kW HPM 15 lamp for 60 sec.
- Laminate Film samples ,Thickness in ⁇ m P (cc O-i/m 2 day)
- Films of LDPE, OPP, PVDC and PVA but not films of PET are sufficiently transparent to UV irradiation of wavelength 250—400 nm for photografting as measured in separate experiments. Therefore, the laminates cannot be photografted with UV inadiation through a PET film which has been observed in the photografting of the laminates in Table 3.
- laminanon photografting involves UV-irradiated grafting of two or more polyme ⁇ c films or of fiber reinforcement between two or more polymer films with intermediate layers of a photopolymenzable composition (PC) in liquid state
- the lamination photografung process is based on our previous invenoon of "surface photografting" for surface modification of polymer sheet, film, filament and yarn
- the PC is deposited or injected to fo ⁇ n a thin layer (usually 5 to 15 ⁇ m thick) between the two films to be photografted with or without fiber reinforcement enclosed.
- the assembly is irradiated widi UV light of wavelengths 250 to 400 nm (near UV) from one or both sides.
- polyethylene, polypropylene, polyvinylidene chloride and polyvinyl alcohol but not poly(ethylene terephthalate) are transparent enough to the near UV irradiation used (250 to 400 nm).
- photografting occurs on both film surfaces, forming a layer which swells with a solvent and allows separation of die two grafted films of which both after separation are covered with a swollen layer of grafted polymer.
- the monomer/initiator solution contains a small amount of multifunctional vinyl or allyl monomer as crosslinker
- die grafted layer forms a crosslinked gel which may swell but does not dissolve.
- Crosslinking gives, therefore, a more permanent laminate than grafting without crosslinker added.
- the viscosity of the PC solution increases which makes it more easy to apply and retain as an intermediate layer during photografting.
- crosslinker and soluble polymers gives grafted layers of higher strength but has only a minor effect on the permeability for small molecules like oxygen.
- Lamination by photografting of proper monomers can give efficient barrier properties to a laminate, e.g.a 7 ⁇ m layer of photografted poly(acrylic acid) between two 30 to 35 ⁇ m thick films of LDPE decreases the permeability for oxygen by a factor 40 to 60.
- Lamination by photografting is an efficient method to laminate films of very low permeability, e.g. PET, PVDC and PVA films, onto or between carrier films of high permeability, e.g. polyethylene and polypropylene. Laminates of high mechanical strength and very low permeability have been prepared in this way. Many combinations of films and photografting compositions are possible to obtain specific properties. Films of PVA and ed ylene-vinyl alcohol copolymers (EVOH) have barrier properties which are much affected by d e water content, i.e. the humidity of the penetrant.
- EVOH ed ylene-vinyl alcohol copolymers
- EVOH films e.g. by photografting lamination with HDPE or PP films on both sides.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96922358A EP0835280A1 (en) | 1995-06-30 | 1996-07-01 | Lamination by photografting |
JP9505073A JPH11508632A (en) | 1995-06-30 | 1996-07-01 | Laminating by photography |
AU63256/96A AU6325696A (en) | 1995-06-30 | 1996-07-01 | Lamination by photografting |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9502406-3 | 1995-06-30 | ||
SE9502406A SE506869C2 (en) | 1995-06-30 | 1995-06-30 | Method of lamination by photo-grafting, laminates made according to the method and its use |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997002313A1 true WO1997002313A1 (en) | 1997-01-23 |
Family
ID=20398828
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE1996/000883 WO1997002313A1 (en) | 1995-06-30 | 1996-07-01 | Lamination by photografting |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0835280A1 (en) |
JP (1) | JPH11508632A (en) |
AU (1) | AU6325696A (en) |
SE (1) | SE506869C2 (en) |
WO (1) | WO1997002313A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0872512A2 (en) * | 1997-04-14 | 1998-10-21 | Hüls Aktiengesellschaft | Process for modifying the surface of polymeric substrates by graft polymerisation |
US9434829B2 (en) | 2012-09-27 | 2016-09-06 | 3M Innovative Properties Company | Ligand grafted substrates |
US9616394B2 (en) | 2012-06-05 | 2017-04-11 | 3M Innovative Properties Company | Graft copolymer functionalized article |
US10493101B2 (en) | 2005-12-14 | 2019-12-03 | Convatec Technologies Inc. | Antimicrobial composition |
IT201900011958A1 (en) | 2019-07-17 | 2021-01-17 | Milano Politecnico | Metallization of plastic substrates |
US11135315B2 (en) | 2010-11-30 | 2021-10-05 | Convatec Technologies Inc. | Composition for detecting biofilms on viable tissues |
US11286601B2 (en) | 2012-12-20 | 2022-03-29 | Convatec Technologies, Inc. | Processing of chemically modified cellulosic fibres |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5190825A (en) * | 1987-06-16 | 1993-03-02 | Saint-Gobain Vitrage | Adhesive layer used in the manufacture of laminated glazings, method of manufacturing and laminated glazings comprising such layer |
-
1995
- 1995-06-30 SE SE9502406A patent/SE506869C2/en not_active IP Right Cessation
-
1996
- 1996-07-01 JP JP9505073A patent/JPH11508632A/en active Pending
- 1996-07-01 WO PCT/SE1996/000883 patent/WO1997002313A1/en not_active Application Discontinuation
- 1996-07-01 EP EP96922358A patent/EP0835280A1/en not_active Withdrawn
- 1996-07-01 AU AU63256/96A patent/AU6325696A/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5190825A (en) * | 1987-06-16 | 1993-03-02 | Saint-Gobain Vitrage | Adhesive layer used in the manufacture of laminated glazings, method of manufacturing and laminated glazings comprising such layer |
Non-Patent Citations (3)
Title |
---|
JOURNAL OF ADHESION SCIENCE AND TECHNOLOGY, Volume 9, No. 5, May 1995, BENGT RANBY, "Surface Photografting onto Polymers - a New Method for Adhesion Control", pages 599-613. * |
MAKROMOL. CHEM., MACROMOL. SYMP., Volume 63, 1992, BENGT RANBY, "Surface Modification of Polymers by Photoinitiated Graft Polymerization", pages 55-67. * |
POLYMERS FOR ADVANCED TECHNOLOGIES, Volume 5, 1994, BENGT RANBY, ""Surface-Photografting": New Applications to Synthetic Fibers", pages 829-836. * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0872512A2 (en) * | 1997-04-14 | 1998-10-21 | Hüls Aktiengesellschaft | Process for modifying the surface of polymeric substrates by graft polymerisation |
EP0872512A3 (en) * | 1997-04-14 | 1999-12-08 | Degussa-Hüls Aktiengesellschaft | Process for modifying the surface of polymeric substrates by graft polymerisation |
US10493101B2 (en) | 2005-12-14 | 2019-12-03 | Convatec Technologies Inc. | Antimicrobial composition |
US11135315B2 (en) | 2010-11-30 | 2021-10-05 | Convatec Technologies Inc. | Composition for detecting biofilms on viable tissues |
US9616394B2 (en) | 2012-06-05 | 2017-04-11 | 3M Innovative Properties Company | Graft copolymer functionalized article |
US10471398B2 (en) | 2012-06-05 | 2019-11-12 | 3M Innovative Properties Company | Graft copolymer functionalized article |
US9434829B2 (en) | 2012-09-27 | 2016-09-06 | 3M Innovative Properties Company | Ligand grafted substrates |
US9981244B2 (en) | 2012-09-27 | 2018-05-29 | 3M Innovative Properties Company | Ligand grafted substrates |
US11286601B2 (en) | 2012-12-20 | 2022-03-29 | Convatec Technologies, Inc. | Processing of chemically modified cellulosic fibres |
IT201900011958A1 (en) | 2019-07-17 | 2021-01-17 | Milano Politecnico | Metallization of plastic substrates |
WO2021009282A1 (en) | 2019-07-17 | 2021-01-21 | Politecnico Di Milano | Metallization of plastic substrates |
Also Published As
Publication number | Publication date |
---|---|
AU6325696A (en) | 1997-02-05 |
SE506869C2 (en) | 1998-02-23 |
EP0835280A1 (en) | 1998-04-15 |
JPH11508632A (en) | 1999-07-27 |
SE9502406D0 (en) | 1995-06-30 |
SE9502406L (en) | 1996-12-31 |
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