WO2000024967A1 - Barrier coatings - Google Patents

Barrier coatings Download PDF

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Publication number
WO2000024967A1
WO2000024967A1 PCT/GB1999/003555 GB9903555W WO0024967A1 WO 2000024967 A1 WO2000024967 A1 WO 2000024967A1 GB 9903555 W GB9903555 W GB 9903555W WO 0024967 A1 WO0024967 A1 WO 0024967A1
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WO
WIPO (PCT)
Prior art keywords
copolymers
styrene
acrylonitrile
coating
barrier
Prior art date
Application number
PCT/GB1999/003555
Other languages
French (fr)
Inventor
Anthony Charles Ward
Original Assignee
Proman Coatings Limited
Henry & Leigh Slater Limited
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 Proman Coatings Limited, Henry & Leigh Slater Limited filed Critical Proman Coatings Limited
Priority to AU63586/99A priority Critical patent/AU6358699A/en
Publication of WO2000024967A1 publication Critical patent/WO2000024967A1/en

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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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • D21H19/08—Metal coatings applied as vapour, e.g. in vacuum
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof

Definitions

  • the present invention relates to barrier coatings in particular in metallised substrates such as metallised papers, cards or boards
  • metallised substrates can be produced by a direct vacuum metallisation process
  • a substrate to be metallised is initially coated with a solvent-based coating to produce a smooth primed surface
  • This primed substrate is then introduced into a vacuum chamber and vaporised metal, usually aluminium, is deposited onto the primed surface
  • This metallised surface is then overcoated with an organic solvent-based lacquer coating to prevent oxidation and protect the metal surface
  • Metallised papers produced by such a process typically have a moisture vapour transmission rate (MVTR) down to around 10 grams per square metre per day measured at tropical conditions (38°C & 90% relative humidity (RH) using test method ISO 9932 1990)
  • MVTR moisture vapour transmission rate
  • the present invention seeks to provide the following advantages over the prior art 1 Provide a treated substrate with a significantly reduced MVTR This has the advantage of allowing the coated substrate to be used where high barriers to water vapour are necessary, for example in food packaging
  • a process for the preparation of a metallised substrate comprising the steps of applying a water-based barrier composition to the substrate, allowing the composition to dry to form a barrier coating, and then applying a metal coating thereto
  • the present invention provides the use of a water-based barrier composition as a primer for a substrate in a metallisation process
  • the metal coating is applied using a vacuum deposition process in a generally conventional manner
  • the metal is aluminium
  • the barrier coating has a surface energy of 40 dvnes/cm or more
  • the barrier coating contains no low molecular species that could interfere with the metallisation process by volatilising during the vacuum deposition step
  • the barrier coating has a MNTR of 100g/ m 2 /da ⁇ or less
  • the barner composition comprises a polymenc material selected from polyvinyl chlorides, polyacrylates and polymethacrylates copolymers of vinyl chloride with vinyl acetate and optionally an unsaturated carboxy c acid, copolymers of styrene with butadiene and optionally acrylonitrile copolymers of styrene with acrylonitrile, copolymers of acrylonitrile with butadiene, copolymers of styrene with an acrylate and/or methacrylate, polyvmy dene chloride, and copolymers of ethylene acrylic acid, or mixtures thereof
  • a polymenc material selected from polyvinyl chlorides, polyacrylates and polymethacrylates copolymers of vinyl chloride with vinyl acetate and optionally an unsaturated carboxy c acid, copolymers of styrene with butadiene and optionally acrylonitrile copolymers of styrene with acrylonitrile,
  • the metallised surface is further provided with a protective overcoat which may be the same polymeric based material as the barner coating or a different polymeric material Alternatively, the overcoat may be a conventional organic solvent-based lacquer
  • the protective overcoat may include one or more waxes selected from paraffin wax, polyethylene wax, camauba wax and PTFE
  • a pre-coating composition is applied before application of the barrier composition to form the barrier coating
  • such a pre-coat has a surface energy of 38 dynes/cm or more
  • the pre-coating composition comprises a polymeric material selected from the same group of materials as the barrier coating composition, optionally further including one or more inorganic fillers Suitable fillers include clay, Kaolin, talcum, silica, calcium carbonate, diatomaceous earth, barium sulphate, titanium dioxide or mixtures thereof
  • the filler in the pre-coating serves to give additional roughness and enlarged contact surface
  • Figure 1 is a schematic cross-section through a metallised substrate produced in accordance with the broadest aspect of the present invention
  • Figure 2 is a schematic cross-section through a metallised substrate produced in accordance with the modification of the present invention
  • Foamex 7447 an antifoaming agent obtainable from TEGO
  • the first sample was conventionally prepared using solvent coating that has been metallised (Al) and subsequently ⁇ wercoated with 3g/m 2 dry weight of the water base barrier coating described above (Formulation A)
  • the second sample was prepared by utilising the same water based coating applied at a dry weight of 6g/m 2 dry weight of water based barrier composition, subsequent metallisation and overcoating with a 3g/m 2 dry weight of the same water based barrier composition
  • the MVTRs were measured using test method ISO 9932 1990 at the more stringent conditions of 90%RH, 38°C and the results are presented in Table 1 below
  • Neocryl BT67 (a 50% aqueous self crosslinking styrene acrylic from Zeneca)
  • Lucidene 606LS (a 50% aqueous styrene acrylic from Morton Chemicals) 0.2 parts Foamex 7447
  • the MVTR measured at 38°C and 90% RH was found to be 8.51 g/m 2 /day. This result shows that styrene acrylics can be also be formulated to produce low MVTR materials.
  • Example 5 In this example coated material was produced using industrial scale coating equipment.
  • the substrate was 84 g/m 2 HiFi gloss made by Sappi and the coatings consisted of:
  • Vacuum metallisation (aluminium) and Over-coat of 2.3 g/m 2 of Formulation A.
  • the next of stage of the testing was to look at the MVTR at tropical conditions of the final conversion (based on Sample D) under both creased and uncreased conditions. This is important as most packaging papers in use will be folded and creased when formed into a pack surrounding the packaged article It is normal after creasing for the MVTR to increase due to the stress applied to the barrier material, however in some instances the barrier will be destroyed and this would be undesirable
  • Sample D resists creasing with only a slight increase in the MVTR hence it would be suitable for use in creased and folded packaging
  • Sample D prepared as detailed in the above example was laminated to Kopparwhite 317 g/m 2 paperboard, using conventional commercial board laminating techniques, and the MVTR was then measured at 38°C and 90% RH using the test method ISO 9932 1990 The resulting MVTR was 0 62 g/m 2 /day compared to 0 77 g/m 2 /day for the unlaminated sample This result is within experimental reproducibility and demonstrates that there is no loss of performance for the laminated sample
  • metallised papers produced in accordance with the present invention may be laminated to paperboard (chip or folding boxboard) to produce packaging materials
  • the materials can be laminated with conventional lamination adhesives or preferentially with adhesives possessing barrier properties of their own

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)

Abstract

The present invention relates to barrier coatings in particular in metallised substrates such as metallised papers, cards or boards. There is described a process for the preparation of a metallised substrate, the process comprising the steps of applying a water-based barrier composition to the substrate, allowing the composition to dry to form a barrier coating, and then applying a metal coating thereto. There is also described the use of a water-based barrier composition as a primer for a substrate in a metallisation process. Preferably, the barrier composition comprises a polymeric material selected from polyvinyl chlorides, polyacrylates and polymethacrylates; copolymers of vinyl chloride with vinyl acetate and optionally an unsaturated carboxylic acid; copolymers of styrene with butadiene and optionally acrylonitrile; copolymers of styrene with acrylonitrile; copolymers of acrylonitrile with butadiene; copolymers of styrene with an acrylate and/or methacrylate; polyvinylidene chloride; and copolymers of ethylene acrylic acid; or mixtures thereof.

Description

BARRIER COATINGS
The present invention relates to barrier coatings in particular in metallised substrates such as metallised papers, cards or boards
Conventionally metallised substrates can be produced by a direct vacuum metallisation process In this procedure a substrate to be metallised is initially coated with a solvent-based coating to produce a smooth primed surface This primed substrate is then introduced into a vacuum chamber and vaporised metal, usually aluminium, is deposited onto the primed surface This metallised surface is then overcoated with an organic solvent-based lacquer coating to prevent oxidation and protect the metal surface
Metallised papers produced by such a process typically have a moisture vapour transmission rate (MVTR) down to around 10 grams per square metre per day measured at tropical conditions (38°C & 90% relative humidity (RH) using test method ISO 9932 1990)
The present invention seeks to provide the following advantages over the prior art 1 Provide a treated substrate with a significantly reduced MVTR This has the advantage of allowing the coated substrate to be used where high barriers to water vapour are necessary, for example in food packaging
2 Allow high barriers to be achieved with paper-based substrates, thereby potentially providing a recyclable and biodegradable final product compared with other barrier packaging
3 Reduce or replace conventional solvent base lacquers and coatings to reduce solvent emissions in the converting process
According to the present invention, there is provided a process for the preparation of a metallised substrate, the process comprising the steps of applying a water-based barrier composition to the substrate, allowing the composition to dry to form a barrier coating, and then applying a metal coating thereto
In a further aspect, the present invention provides the use of a water-based barrier composition as a primer for a substrate in a metallisation process
Typically, the metal coating is applied using a vacuum deposition process in a generally conventional manner Typically, the metal is aluminium
Preferably, the barrier coating has a surface energy of 40 dvnes/cm or more
Preferably, the barrier coating contains no low molecular species that could interfere with the metallisation process by volatilising during the vacuum deposition step
Preferably, the barrier coating has a MNTR of 100g/ m2/da\ or less
Preferably, the barner composition comprises a polymenc material selected from polyvinyl chlorides, polyacrylates and polymethacrylates copolymers of vinyl chloride with vinyl acetate and optionally an unsaturated carboxy c acid, copolymers of styrene with butadiene and optionally acrylonitrile copolymers of styrene with acrylonitrile, copolymers of acrylonitrile with butadiene, copolymers of styrene with an acrylate and/or methacrylate, polyvmy dene chloride, and copolymers of ethylene acrylic acid, or mixtures thereof
Preferably, the metallised surface is further provided with a protective overcoat which may be the same polymeric based material as the barner coating or a different polymeric material Alternatively, the overcoat may be a conventional organic solvent-based lacquer The protective overcoat may include one or more waxes selected from paraffin wax, polyethylene wax, camauba wax and PTFE In a modification of the process of the present invention, applicable to porous substrates, a pre-coating composition is applied before application of the barrier composition to form the barrier coating Preferably, such a pre-coat has a surface energy of 38 dynes/cm or more Preferably, the pre-coating composition comprises a polymeric material selected from the same group of materials as the barrier coating composition, optionally further including one or more inorganic fillers Suitable fillers include clay, Kaolin, talcum, silica, calcium carbonate, diatomaceous earth, barium sulphate, titanium dioxide or mixtures thereof The filler in the pre-coating serves to give additional roughness and enlarged contact surface to provide adequate adhesion of the subsequently applied barrier coating
The above and other aspects of the present invention will now be described in further detail with reference to the following examples and the accompanying figures, in which
Figure 1 is a schematic cross-section through a metallised substrate produced in accordance with the broadest aspect of the present invention and Figure 2 is a schematic cross-section through a metallised substrate produced in accordance with the modification of the present invention
Example 1
An 84g/m2 base paper (type HI Fi Gloss made by Sappi) was coated at a dry weight of 6g m" with a water-based barrier composition with the following formulation
Formulation A
0 1 parts Foamex 7447 (an antifoaming agent obtainable from TEGO)
99 9 parts RB 958 (an aqueous ethylene acr\hc acid dispersion (25% water) obtainable from Proman Chemicals Ltd)
This was then vacuum metallised (aluminium) and the metallised surface over-coated using conventional solvent based lacquers at typical production weight The samples were then tested for MVTR using test method ISO 9932 1990 at 75% relative humidity (RH), at 20°C The results for this sample gave an average MVTR of 0 21 g/ m2/ day This compared to conventionally produced material having an MVTR of 8 3 g/m2/ day Thus showing the advantage of the present invention over conventional production techniques in achieving a lower MVTR
Example 2
In this example three samples were compared The first sample was conventionally prepared using solvent coating that has been metallised (Al) and subsequently ςwercoated with 3g/m2 dry weight of the water base barrier coating described above (Formulation A) The second sample was prepared by utilising the same water based coating applied at a dry weight of 6g/m2 dry weight of water based barrier composition, subsequent metallisation and overcoating with a 3g/m2 dry weight of the same water based barrier composition The MVTRs were measured using test method ISO 9932 1990 at the more stringent conditions of 90%RH, 38°C and the results are presented in Table 1 below
TABLE 1
Figure imgf000006_0001
These results show that the use of water-based barrier coating prior to metallisation gives a much lower MNTR result than either conventional solvent even if the overcoat remains the same The addition of water based barrier coatings as over-coats also offers advantages over organic solvent-based over-coats in terms of lowering MNTR but not as dramatically as the barrier coating Example 3
In this example an alternative formulation for the water based barrier composition was utilised for both the barrier coating and over-coating the metal layer. The composition of the composition is given below.
Formulation B
73.5 parts Neocryl BT67 (a 50% aqueous self crosslinking styrene acrylic from Zeneca)
26.3 parts Lucidene 606LS (a 50% aqueous styrene acrylic from Morton Chemicals) 0.2 parts Foamex 7447
When applied at 6g/m2 dry coating weight as the barrier coating, metallised and applied at 6g/m2 dry coating weight as the over-coat, the MVTR measured at 38°C and 90% RH was found to be 8.51 g/m2/day. This result shows that styrene acrylics can be also be formulated to produce low MVTR materials.
Example 4
In this example low coating weights were used using a pre-coating layer (Figure 2) to increase hold out. The pre-coating, barrier coating and over-coat in this instance are of the same composition, Formulation A.
Again using an 84 g/m2 base paper (type HI Fi Gloss made by Sappi) 1.5 g/m2 dry weight of a pre-coating composition was applied to the paper and subsequently treated with a further 1.5 g/m2 as a barrier coating. It was then metallised and overcoated in an amount of 3g/m2. The MVTR measured at 38°C and 90% RH was found to be
1.55 g/m2/day.
This result shows that low MVTR can be achieved even using low coating weights of the water based barrier coating.
Example 5 In this example coated material was produced using industrial scale coating equipment. The substrate was 84 g/m2 HiFi gloss made by Sappi and the coatings consisted of:
Pre-coating of 2.6 g/m2 dry weight of Formulation A, Barrier coating of 2.3 g/m2 dry weight of Formulation A,
Vacuum metallisation (aluminium) and Over-coat of 2.3 g/m2 of Formulation A.
The MVTR measured at 25°C and 75% RH of the substrate was recorded as each layer was applied and for comparison with and without the metallisation layer. These results are tabulated in Table 2 below.
TABLE 2
Figure imgf000008_0001
These results show the application of vacuum deposited metal to a water based barrier coating shows a considerable lowering of MNTR and low coating weights can be utilised in the current invention to achieve reduced MVTR compared to conventionally produced metallised materials The application of barrier compositions as an over-coat over the metal layer lowers further the MVTR.
The next of stage of the testing was to look at the MVTR at tropical conditions of the final conversion (based on Sample D) under both creased and uncreased conditions. This is important as most packaging papers in use will be folded and creased when formed into a pack surrounding the packaged article It is normal after creasing for the MVTR to increase due to the stress applied to the barrier material, however in some instances the barrier will be destroyed and this would be undesirable
The results of these materials carried out using the creasing procedure is ISO 2528 1974, Annex C and then tested for MVTR using ISO 9932 1990 at 30°C and 90% RH are tabulated below
Figure imgf000009_0001
It can be seen that Sample D resists creasing with only a slight increase in the MVTR hence it would be suitable for use in creased and folded packaging
Example 8
In this example Sample D prepared as detailed in the above example was laminated to Kopparwhite 317 g/m2 paperboard, using conventional commercial board laminating techniques, and the MVTR was then measured at 38°C and 90% RH using the test method ISO 9932 1990 The resulting MVTR was 0 62 g/m2/day compared to 0 77 g/m2/day for the unlaminated sample This result is within experimental reproducibility and demonstrates that there is no loss of performance for the laminated sample
Subsequently, metallised papers produced in accordance with the present invention, may be laminated to paperboard (chip or folding boxboard) to produce packaging materials The materials can be laminated with conventional lamination adhesives or preferentially with adhesives possessing barrier properties of their own

Claims

Claims.
1 A process for the preparation of a metallised substrate, the process comprising the steps of applying a water-based barrier composition to the substrate, allowing the composition to dry to form a barrier coating, and then applying a metal coating thereto.
2. A process as claimed in claim 1 wherein the barrier coating has a surface energy of 40 dynes/cm or more
3 A process as claimed in claim 1 or claim 2 wherein the barrier coating has a
MVTR of 100g/m /day or less
4 A process as claimed in any one of claims 1 to 3 wherein the barrier composition comprises a polymeric material selected from polyvinyl chlorides, polyacrylates and polymethacrylates; copolymers of vinyl chloride with vinyl acetate and optionally an unsaturated carboxylic acid, copolymers of styrene with butadiene and optionally acrylonitrile, copolymers of styrene with acrylonitrile, copolymers of acrylonitrile with butadiene, copolymers of styrene with an acrylate and/or methacrylate; polyvinylidene chloride; and copolymers of ethylene acrylic acid; or mixtures thereof.
5 A process as claimed in any one of Claims 1 to 4 further comprising the step of applying a protective overcoat to the metal layer.
6 A process as claimed in Claim 5 wherein the protective overcoat is formed of the same polymeric material as the barrier coating or a combination thereof with one or more waxes. 7 A process as claimed in Claim 6 wherein the was is selected from paraffin wax, polyethylene wax, carnauba wax, and PTFE
8 A process as claimed in any preceding claim wherein the substrate has a pre- coating applied thereto prior to application of the barrier composition
9 A process as claimed in Claim 8 wherein the pre-coating composition comprises a polymeric material selected from polyvinyl chlorides, polyacrylates and polymethacrylates, copolymers of vinyl chloride with vinyl acetate and optionally an unsaturated carboxylic acid, copolymers of styrene with butadiene and optionally acrylonitrile, copolymers of styrene with acrylonitrile, copolymers of acrylonitrile with butadiene, copolymers of styrene with an acrylate and/or methacrylate, polyvinylidene chloride; and copolymers of ethylene acrylic acid, or mixtures thereof
10 A process as claimed in Claim 9 wherein the pre-coating composition further comprises an inorganic filler
1 1 A process as claimed in Claim 10 wherein the filler is selected from clay, Kaolin, talcum, silica, calcium carbonate, diatomaceous earth, barium sulphate, titanium dioxide or mixtures thereof
12 The use of a water-based barrier composition as a primer for a substrate in a metallisation process.
13 The use as claimed in Claim 12 wherein the composition comprises a polymeric material selected from polyvinyl chlorides, polyacrylates and polymethacrylates, copolymers of vinyl chloride with vinyl acetate and optionally an unsaturated carboxylic acid; copolymers of styrene with butadiene and optionally acrylonitrile; copolymers of styrene with acrylonitrile, copolymers of acrylonitrile with butadiene, copolymers of styrene with an acrylate and/or methacrylate, polyvinylidene chloride; and copolymers of ethylene acrylic acid, or mixtures thereof
PCT/GB1999/003555 1998-10-27 1999-10-27 Barrier coatings WO2000024967A1 (en)

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