IE75708B1 - Polyamide/polyolefin blend release film for the production of a sheet moulding compound and the sheet moulding compound produced with such film - Google Patents

Polyamide/polyolefin blend release film for the production of a sheet moulding compound and the sheet moulding compound produced with such film

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Publication number
IE75708B1
IE75708B1 IE920998A IE920998A IE75708B1 IE 75708 B1 IE75708 B1 IE 75708B1 IE 920998 A IE920998 A IE 920998A IE 920998 A IE920998 A IE 920998A IE 75708 B1 IE75708 B1 IE 75708B1
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IE
Ireland
Prior art keywords
polyamide
film
film according
grafted
alpha
Prior art date
Application number
IE920998A
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IE920998A1 (en
Inventor
Alain Bouilloux
Jacques Girard
Michel Glotin
Original Assignee
Atochem Elf Sa
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Publication date
Application filed by Atochem Elf Sa filed Critical Atochem Elf Sa
Publication of IE920998A1 publication Critical patent/IE920998A1/en
Publication of IE75708B1 publication Critical patent/IE75708B1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/68—Release sheets
    • 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
    • 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
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • 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
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Moulding By Coating Moulds (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyamides (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Polymer film made from a polyamide/polyolefin alloy for the manufacture of a sheet compounding product, characterised in that it comprises the components A, B, C and D according to the following percentages by weight: 30 /= 1 where 0

Description

The present invention relates to a polyamide/polyolefin alloy film useful in the preparation of molding compounds, more specifically a sheet molding compound (SMC).
Such a sheet molding compound is employed for manufacturing fabricated parts in areas such as the automobile industry (fenders or bumpers, rear doors, etc), in boatbuilding (hulls of boats) as well as in the electronics industry (housings).
The SMC compound generally consists of a crosslinkable polymer resin, in particular an unsaturated polyester, together with reinforcing fillers such as glass fibers, along with various other additives present in smaller amounts.
The SMC compound is normally prepared by laying the fibers on a layer of unsaturated polyester resin, which itself is supported by a removable film generally composed of polyethylene or polyamide.
Following this, a further film of the same nature is laid on top of the resin/filler system in order to form a composite laminate or sandwich structure between the two films. The laminate structure is then passed through a series of kneading and compacting rollers and is generally rolled into large diameter rolls.
After this, it is stored prior to its use in final manufacturing. During the storage period, partially cross-linking of the polyester resin takes place leading to an increase of the SMC compound's viscosity until it reaches a consistency suitable for molding.
Users of the SMC compound who generally are molders, cut off a piece of suitable size from the roll, peel off the support film and insert the SMC compound into a heated mold in order for it to undergo simultaneous transformation and complete hardening. Thus, composite masses in SMC laminate lend themselves readily to use in compression molding operations.
Three properties of the resulting laminate structure film are of capital importance to manufacturers and users of the SMC laminate.
The first of these relates to the styrene 5 permeability of the peelable film. It is essential for the peelable film to have very low styrene permeability in order to avoid loss of styrene monomer, this latter performing the function of cross-linking agent in the SMC laminate. Such loss of styrene monomer is also harmful to the health of operatives during manufacture of the SMC and storage thereof .
The second property concerns the ease of peeling of this film once on the polyester structure, in order to avoid residual film staying stuck to the structure and to avoid the danger of tearing the film during the SMC manufacturing and transformation operations.
Finally, such peelable films need to have very low humidity take-up and water permeability in order for the quality of the polyester resin, which is highly sensitive 0 to water, not to be changed during the SMC laminate manufacturing operations, during storage of the polyester or during transformation of the SMC.
As has been said above, polyethylene is employed for the peelable film in SMC laminates. Although the characteristics of polyethylene are suitable for the performance of automatic peeling operations, and it exhibits satisfactory inertness towards water for this application, it does however suffer from high permeability to styrene, thus generally requiring such rolls to be wrapped in aluminium foil.
GB-A-2,225,583 discloses and claims polyamide and grafted copolyolefin films, in which the polyamide represents 70% and more by weight. This film is used in the SMC field. The examples state weight proportions, for the polyamide constituent, of 87%, 86%, 85%, 84%, 83% and 80%.
European Patent 27,191 in the name of Allied Chemical Corporation, describes a polyamide release film for use in the manufacture of SMC compounds where the film has low crystalline and consists of a mixture of 70 to 90% by weight of a polyamide (PA-6 and/or PA-6/6) having a crystalline less than 35%, and of 10 to 30% of a polyolefin compound or a copolymer thereof, the polyolefin having a crystalline of less than 50%. The polyolefin is a high molecular weight alpha-olefin or a copolymer thereof consisting of an alphaolefin and a vinyl acetate monomer or alkyl acrylate monomer. The film, which has a thickness comprised between 12.7 and 127 μχη, has a Graves tear strength of at least 400 g in the longitudinal direction, as determined by ASTM D-100466 and a styrene permeability less than 200 x lO9gcm/cm^-h.
Commercially available PA films, although they have good characteristics as regards styrene permeability, only have sufficient peelability properties provided that the film is stripped off manually, these properties becoming insufficient when automatic film stripping processes currently under development are applied.
Moreover, with the progressive replacement of PE films by PA films, there is the additional problem of the high sensitivity of polyamides to humidity. Water effectively leads to deterioration of the polyester or epoxy resin, leading to major defects in the parts, produced in SMC. In order to overcome this, suppliers of such films have to protect the rolls by applying aluminum films before supply to SMC manufacturers and in SMC storage areas prior to final transformation, thus leading to a not-insignificant increase in costs.
The present invention- provides a compatible polyamide/polyolefin film of thickness generally comprised between 10 and 130 μπι, and preferably between 20 and 50 μπι, comprising products A, B, C, D, where: A consists of at least one polyolefin comprising a totally or partially linear alpha-olefin the molecular weight of which is comprised between 1000 and 1 000 000; B represents the alpha-olefin specified under A on which one or two functionalized monomers have been grafted, the grafting rate of the ' functionalized monomer or monomers being comprised between 500 ppm and 6% by weight; C is a grafted polymer consisting of at least one polyamide mono-amino oligomer and a polymer or copolymer of alpha mono-olefin grafted with a monomer able to react with the amine function of said mono-amino oligomer; D is constituted by at least one aliphatic (co)polyamide consisting: (i) of a polyamide obtained from aliphatic dicarboxylic acid and an aliphatic diamine, each of which has between 6 and 24 carbon atoms, and/or (ii) of a polyamide obtained from an amino-aliphatic acid or lactame having 6 to 24 carbon atoms.
Components A, B, C and D are described in detail 20 below: A consists of at least one polyolefin consisting of a totally or partially linear alpha-olefin of high molecular weight, for example polyethylene, polypropylene or polyisobutylene, copolymers of alpha-olefins with vinyl acetate monomers, such as ethylene/vinyl acetate copolymers, or alkyl acrylate copolymers, such as ethylene/methyl acrylate copolymers or ethylene/ethyl acrylate copolymers or copolymers of ethylene and an alpha-olefin having 3 to 10 carbon atoms. The molecular weight of component A is generally comprised between 1000 and 1,000,000 and * preferably between 10,000 and 500,000, which corresponds to a melt index MI comprised between 0.1 and 3 00 g/min measured at 230°C under 2.16 kg.
B represents the alpha-olefin described under A on which a functionalized monomer has been grafted, said functionalized monomer being selected from the group comprising: acrylic, methacrylic, maleic, fumaric, itaconic, crotonic, 3dicarboxylic-5-norbornene-2 acids, maleic, dimethylmaleic anhydrides, mono-sodium, di-sodium maleates, acrylamide, itaconic anhydrides, citraconic anhydrides, maleimide, Nphenylmaleimide, diethyl fumarate, vinyl pyridine, the vinyl silanes, 4-vinyl-pyridine, vinyl-thiethoxysilane, allylic alcohol, and in particular maleic acid, maleic anhydride or fumaric acid. Two monomers for grafting can be used simultaneously and can be selected from styrene, 2-methyl-styrene, 4-methyl-styrene, alpha-methyl-styrene, beta-methyl-styrene, vinyl4-anisole, stilbene and indene or mixtures thereof. The other monomer can be selected from the group comprising: maleic, itaconic, citraconic anhydrides, maleimide, and Nphenylmaleimide or mixtures thereof. Generally, the grafting rate of the functionalized monomer or monomers is comprised between 500 ppm and 6% by weight, and is preferably less than 2%.
C is a grafted polymer consisting of at least one polyamide mono-amino, oligomer and a polymer or copolymer of alpha mono-olefin grafted with a monomer able to react with the amine function of the mono-amino oligomer described in European Patent 342,066.
D is at least one aliphatic (co)polyamide consisting: (i) of a polyamide obtained from aliphatic dicarboxylic acid and an aliphatic diamine, each of which has between 6 and 24 carbon atoms, and/or (ii) a polyamide obtained from an amino-aliphatic acid or lactame having 6 to 24 carbon atoms, in particular a 6- or 6/6-polyamide or a mixture of the two.
The percentages by weight of the various components are selected such that: I where 0 < B < 60 and A + B + C + D = 100 where 0 < C <_ 60; and the viscosities of the various components are such that the polyamide phase constitutes a continuous phase, and can be characterized by the fact that a film about 20 microns thick keeps its shape when plunged into xylene at 130°C for 30 minutes.
Preferred compositions of the films according to the invention are those in which: 5.
The following examples illustrate the invention without however limiting it.
Example I (sheath or tubular film) A mixture comprising, by weight, 33 parts of polypropylene, 57 parts of polyamide-6 and 10 parts of a sequenced copolymer of propylene and 120 by weight of ethylene, of melting point 158°C (copolymer main body), with a maleic grafting rate of 1.16%, grafted with a Mn 2700 monoamine PA-6 oligomer, prepared by the method described in European Patent 342 066, was continuously introduced into a Werner-type extruder. The material temperature was comprised between 255°C and 270°C along the extruder barrel. The screw rotation was 150 rpm and the material throughput 20 kg/h. The granules obtained at the outlet from the extruder were transformed using an extrusion-blowing technique for tubular articles in a Kaufman extruder with a three-groove rotating helical die of diameter 150 mm and a gap of 0.8 mm, in order to produce a 25 μτη tubular film. The operating conditions were as follows : cylinder temperature : 225-250°C die temperature : 250-260°C stretching speed : 28 m/min The PA employed was a polyamide-6 of melt index (MI) measured at 235°C under a load of 2.16 kg equal to 20 g/10 min and the polypropylene was a random copolymer of propylene and 3% by weight of ethylene with a melt index of 2 g/10 min (sample l.A).
In order to determine the film's suitability for peeling, surface tension measurements were carried out on the film and, by way of comparison, on a peelable film consisting of a mixture of, by weight, 89% polyamide-6 and 10% of an ethylene/vinyl acetate copolymer containing 9% of vinyl acetate and 1% of titanium dioxide (sample l.B). The surface tension of the two samples was determined by measuring, using a goniometer, the forward contact angle, at equilibrium, of standard drops of liquid on the substrate in conformity with the method described in Fowkes, F.M., Ind. Eng.Chem. , 56 (1964) 4 0 or in Owens, D.K. and Wendt, R.C., J.Appl. Polymer Sci. 13 (1969) 1741. Typical examples of standard liquids are diiodomethane, glycerol, and benzylic alcohol.
Test no. l.A l.B Surface tension 32 46 (mN.ra 4) The low surface tension enabled automatic peeling of the film to be carried out on the SMC composite without causing tearing of the film to start, this necessitating shutting down of the production line when manufacturing SMC products.
Water vapor permeability measurements were also carried out under the following conditions: Apparatus: Lyssy vapor permeation tester IL 80 - 40000 Temperature: 38 °C Relative humidity: 90% Resistive humidity detector Measurement principle : The membrane to be tested was placed in a saturated atmosphere and in a space provisionally brought to a dry atmosphere. A resistive humidity detector placed in the dry space recorded continuous relative humidity variations as a function of time. The time measurement needed for humidity to go from one limiting value to another was representative of the sample's permeability.
Time measurement was converted into permeability values by comparison with values measured previously using a known permeability standard test.
The results are expressed in g/m2/24h and are summarized in the table below: Test no. Water vapor permeability 1 .A 56 1 .B 380 Humidity take-up measurements were also carried out using a weighing method (measurement of take-up in weight at 100% relative humidity at 23°C starting from a time T) .
Time Take-up weight (in %) 1 .A l.B To 0 0 T = To + 4h 2 3 T = To + 8h 2 3 T = To + 24h 2.1 3 T = To + 96h 2.1 3.6 T = To +120h 2.1 3.6 The styrene permeability of film l,A was also measured using the method described in American Institute of Chemical Engineers, 53rd National Meeting, Preprint no, 32d, 1964, by Bixler and Michaels. According to this method, the sample had a styrene permeability of about 8 x 10-9g-cm/cm2-h, A styrene permeability that is less than 200 χ 10-9 g-cm/cm2-h is considered as good.
Example 2 (flat film) A mixture comprising, by weight, 29.7 parts of polypropylene homopolymer of MI (230°C/2.16 kg) equal to 5.10 parts of maleic-grafted ethylene/propylene copolymer (EPRm) containing 70% by weight of ethylene and 500 ppm of maleic anhydride of melt index 9 g/10 min (230°C/10 kg), 51.3 parts of polyamide-6 of MI 20 g/lOmin (235°C/2.16 kg), 9 parts of the grafted and maleic grafted copolymer main body of example I was continuously introduced into a Werner extruder. Along the extruder shaft, the material temperature was comprised between 250°C and 270°C, the screw rotation speed was 150 rpm and the material throughput was 20 kg/h. The granules obtained at the outlet from the extruder were transformed using a cast extrusion technique employing a Thoret extruder into the form of a flat film or cast film of 25 μπι thickness (sample 2.A); Operating conditions were as follows : temperature profile : 220-250°C cylinder temperature : 8 0°C screw speed : 28 rpm By way of comparison, a flat film of the same composition and thickness as sample l.B was employed (sample 2.B) .
Surface tension measurements as defined in example 1 were carried out and are summarised in the table below: Test No. 2 .A 2.B Surface tension 32 46 (mN.m-1) Water vapor permeability measurements as well as humidity take-up measurements were carried out and gave the following results: Test no. Water vapor permeability (in g/m2/24h) 4 2 .A 50 2 .B 380 Time Take-UD weight (in 2 .A 2 .B To 0 0 T = To + 4 h 1.5 3 T = To + 8 h 1.5 3 T = To + 24 h 1.7 3 T = To + 96 h 1.7 3.6 T = To + 120 h 1.7 3.6 The present invention also relates to a method of producing a sheet molding compound in which: a) a layer of thermo-setting resin suitable for thermal processing is poured, in fluid form, onto a polymer film as defined in any one of claims I to 11, advancing continuously, b) a reinforcing material is introduced onto the advancing fluid layer, c) a polymer film as defined in any one of claims I to 11 is placed in contact with the upper surface of the reinforced fluid layer thus forming a composite mass of a sandwich-structure, d) the sandwich-structure composite mass is caused to advance through a series of kneading and compacting rollers, and e) the sandwich-structure composite mass is rolled into a roll for partial heat treatment.
The present invention also covers a sandwich-St ructure comprising : (i) a central layer of a reinforced unhardened thermo-setting sheet molding product, (ii) two outer layers of polymer film according to the invention.

Claims (17)

1. - A polymer film formed of a polyamide/polyolefin alloy for the production of a sheet molding compound, characterized in that it comprises components A, B, C and D in the following percentages by weight: 30 < A + B + C < 60 0 < A < 60 and B + C > I where 0 < B < 60 and A + B + C + D = 100 where 0 < C < 60; said components A, B, C and D having the following compositions : A consists of at least one polyolefin comprising a totally or partially linear alpha-olefin the molecular weight of which is comprised between 1000 and 1 000 000; B represents the alpha-olefin specified under A on which one or two functionalized monomers have been grafted, the grafting rate of the functionalized monomer or monomers being comprised between 500 ppm and 6% by weight; C is a grafted polymer consisting of at least one polyamide mono-amino oligomer and a polymer or copolymer of alpha mono-olefin grafted with a monomer able to react with the amine function of said mono-amino oligomer; is constituted by at least (co)polyamide consisting: one aliphatic (i) of a polyamide obtained from aliphatic dicarboxylic acid and an aliphatic diamine, each of which has atoms, and/or between 6 and 24 carbon (ii) of a polyamide obtained from an amino- aliphatic acid or lactame having 6 to 24 carbon atoms .
2. - Film according to claim 1, characterized in that the polyolefin of component A is selected from the group comprising: polyethylene, polypropylene or polyisobutylene, copolymers of alpha-olefins with vinyl acetate monomers, notably ethylene/-vinyl acetate copolymers, alkyl acrylate copolymers, notably ethylene/methyl acrylate copolymers or ethylene/ethyl acrylate copolymers or copolymers of ethylene and an alpha-olefin having 3 to 10 carbon atoms.
3. - Film according to claim 1 or 2, characterized in that the molecular weight of the polyolefin of component A is comprised between 10 000 and 500 000.
4. - Film according to any one of claims 1 to 3, characterized in that the functionalized monomer of component B is selected from the group comprising: acrylic, methacrylic, maleic, fumaric, itaconic, crotonic, 3-dicarboxylic-5-norbornene-2 acids, maleic, dimethylmaleic anhydrides, mono-sodium, di-sodium maleates, acrylamide, itaconic anhydrides, citraconic anhydrides, maleimide, N-phenylmaleimide, diethyl fumarate, vinylpyridine, the vinylsilanes, 4vinylpyridine, vinylthiethoxysilane, allylic alcohol, or a mixture thereof .
5. - Film according to claim 4, characterized in that said functionalized monomer is selected from the group comprising: maleic acid, maleic anhydride or fumaric acid.
6. - Film according to any one of claims 1 to 5, characterized in that the functionalized monomers of component B are selected one from the group comprising styrene, 2-methylstyrene, 4-methylstyrene, alphamethylstyrene, beta-methylstyrene, vinyl-4-anisole, stilbene and indene or mixtures thereof, and the other is selected from the group comprising: maleic, itaconic, citraconic anhydrides, maleimide, and N-phenylmaleimide or a mixture thereof.
7. - Film according io any one of claims 1 to 5, characterized in that the grafting rate of compound B is less than 2% by weight.
8. - Film according to any one of claims 1 to 5, characterized in that compound D consists of a 6 polyamide, 6/6 polyamide or a mixture thereof.
9. - Film according to claim 1, characterized in that the following holds: 30 < A + B + C <. 45 and B + C > 5
10. - Film according to any one of claims 1 to 9, comprising the following components A, B, C and D: - A is polypropylene; B, if present, is a copolymer of ethylene and maleic-grafted propylene; - C is a grafted copolymer consisting of at least one mono-amino oligoamide and a (co)polymer of alpha-olefin grafted by a monomer able to react with the amine function of said oligoamide; - D is 6-polyamide and/or 6/6-polyamide.
11. - Film according to any one of claims 1 to 10, characterized in that the thickness of said film is comprised in the range of from 10 to 130 μιη, and preferably from 20 to 50 μιη.
12. - A sandwich-structure comprising: (i) a central layer of a reinforced unhardened thermo-setting sheet molding product, (ii) two outer layers of polymer film according to any one of claims I to 11.
13. - A method for producing a sheet molding compound in which: a) a layer of thermo-setting resin suitable for thermal processing is poured, in fluid form, onto a polymer film as defined in any one of claims 1 to 11, advancing continuously, b) a reinforcing material is introduced onto the advancing fluid layer, c) a polymer film as defined in any one of claims 1 to 11 is placed in contact with the upper surface of the reinforced fluid layer thus forming a composite mass of a sandwich-structure, d) the sandwich-structure composite mass is caused to advance through a series of kneading and compacting rollers, and e) the sandwich-structure composite mass is rolled into a roll for partial heat treatment.
14. - A polymer film substantially as hereinbefore described and exemplified.
15. - A sandwich-structure substantially as hereinbefore described and exemplified.
16. - A method for producing a sheet molding compound, substantially as hereinbefore described and exemplified.
17. - A sheet molding compound, whenever produced by a method claimed in a preceding claim.
IE920998A 1991-03-29 1992-03-27 Polyamide/polyolefin blend release film for the production of a sheet moulding compound and the sheet moulding compound produced with such film IE75708B1 (en)

Applications Claiming Priority (1)

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FR9103870 1991-03-29

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IE75708B1 true IE75708B1 (en) 1997-09-10

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EP (1) EP0506515B1 (en)
JP (1) JPH0662793B2 (en)
KR (1) KR960002980B1 (en)
CN (1) CN1041315C (en)
AT (1) ATE141205T1 (en)
AU (1) AU645188B2 (en)
CA (1) CA2064365C (en)
DE (1) DE69212681T2 (en)
DK (1) DK0506515T3 (en)
ES (1) ES2090538T3 (en)
FI (1) FI921362L (en)
IE (1) IE75708B1 (en)
NO (1) NO304076B1 (en)

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FR2743746B1 (en) 1996-01-23 1998-04-03 Atochem Elf Sa NEW RELEASE FILM FOR SHEET MOLDING COMPOUNDING PRODUCT
JP2001505856A (en) * 1997-01-06 2001-05-08 エルフ アトケム ソシエテ アノニム Antistatic film for packaging materials that emit volatile compounds
JPH11140250A (en) * 1997-11-04 1999-05-25 Kanegafuchi Chem Ind Co Ltd Isobutylene rubber particles, graft copolymer particles, and resin composition containing the particles
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US7029735B2 (en) 2003-03-17 2006-04-18 Arkema Polyamide and polyolefin blends with a polyamide matrix and containing nanofillers
CN100523086C (en) * 2003-03-17 2009-08-05 阿托菲纳公司 Polyamide and polyolefine blend containing nanometer filler and with polyamide as matrix
CN103044909A (en) * 2012-11-25 2013-04-17 安徽六方重联机械股份有限公司 Packaging plastic substrate thin film containing nylon PA6
WO2015046984A1 (en) * 2013-09-30 2015-04-02 코오롱인더스트리 주식회사 Film for laminating metal plate
CN104118643B (en) * 2014-06-26 2016-08-24 江西春光药品包装材料股份有限公司 A kind of preparation method of the packaging material of antistripping

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GB2225582A (en) * 1988-12-05 1990-06-06 Du Pont Canada Film of polyamide and grafted polyolefin
GB2225583A (en) * 1988-12-05 1990-06-06 Du Pont Canada Films of polyamide and grafted olefin copolymer

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CA2064365A1 (en) 1992-09-30
NO921180D0 (en) 1992-03-26
CN1066278A (en) 1992-11-18
ES2090538T3 (en) 1996-10-16
DE69212681D1 (en) 1996-09-19
FI921362A7 (en) 1992-09-30
DK0506515T3 (en) 1996-09-09
JPH05156045A (en) 1993-06-22
IE920998A1 (en) 1992-10-07
KR920018129A (en) 1992-10-21
NO921180L (en) 1992-09-30
FI921362A0 (en) 1992-03-27
ATE141205T1 (en) 1996-08-15
AU645188B2 (en) 1994-01-06
AU1381792A (en) 1992-10-01
CN1041315C (en) 1998-12-23
DE69212681T2 (en) 1997-01-02
JPH0662793B2 (en) 1994-08-17
EP0506515B1 (en) 1996-08-14
KR960002980B1 (en) 1996-03-02
EP0506515A1 (en) 1992-09-30
FI921362L (en) 1992-09-30
NO304076B1 (en) 1998-10-19
CA2064365C (en) 1999-11-16

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