CA2064365C - Polyamide-polyolefin release film and its use in producing a sheet molding compound - Google Patents
Polyamide-polyolefin release film and its use in producing a sheet molding compoundInfo
- Publication number
- CA2064365C CA2064365C CA002064365A CA2064365A CA2064365C CA 2064365 C CA2064365 C CA 2064365C CA 002064365 A CA002064365 A CA 002064365A CA 2064365 A CA2064365 A CA 2064365A CA 2064365 C CA2064365 C CA 2064365C
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- Prior art keywords
- polyamide
- film according
- alpha
- film
- grafted
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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
- 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
-
- 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
-
- 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)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (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)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A polyamide/polyolefin film useful in the preparation of molding compound products, more specifically a sheet molding compound, is provided, said film comprising (A) an alpha-olefin having a molecular weight of between 1000 and 1 000 000, (B) a malefic or acrylic grafted alpha-olefin of A, (C) a grafted copolymer of alpha mono-olefin consisting of a mono-amino oligoamide and an alpha-olefin grafted by a monomer able to react with the amine function of said oligoamide, and (D) an aliphatic polyamide.
Description
POLYAMIDE-POLYOLEFIN RELEASE FILM AND ITS USE IN
PRODUCING A SHEET MOLDING COMPOUND
BACKGROUND OF THE INVENTION
Field of the invention The present invention relates to a polyamide/polyolefin alloy film useful in the preparation of molding compound products, more specifically a sheet molding compound (SMC).
Such a sheet molding compound is employed for man-ufacturing fabricated parts in areas such as the automobile industry (fenders or bumpers, rear doors, etc), in boat-building (hulls of boats) as well as in the electronics indus-try (housings).
The SMC compound generally consists of a cross-linkable polymer resin, in particular an unsaturated polyester, togeth-er 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.
PRODUCING A SHEET MOLDING COMPOUND
BACKGROUND OF THE INVENTION
Field of the invention The present invention relates to a polyamide/polyolefin alloy film useful in the preparation of molding compound products, more specifically a sheet molding compound (SMC).
Such a sheet molding compound is employed for man-ufacturing fabricated parts in areas such as the automobile industry (fenders or bumpers, rear doors, etc), in boat-building (hulls of boats) as well as in the electronics indus-try (housings).
The SMC compound generally consists of a cross-linkable polymer resin, in particular an unsaturated polyester, togeth-er 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.
2~64~6 Following this, a further film of the same nature is layed 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 com-plete hardening. mhus, 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 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 2~~~~~5 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 resid-ual 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 to water, not to be changed during the SMC laminate manufacturing operations, during storage of the polyester or during trans-formation 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 ZO such rolls to be wrapped in aluminum foil.
Prior art 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 crystall-inity and consists of a mixture of 70 to 90~ by weight of a 2~64~6 polyamide (PA-6 and/or PA-6/6) having a crystallinity less than 35$, and of 10 to 30~ of a polyolefin compound or a copolymer thereof, the polyolefin having a crystallinity of less than 50~. The polyolefin is a high molecular weight S alpha-olefin or a copolymer thereof consisting of an alpha-olefin and a vinyl acetate monomer or alkyl acrylate monomer.
The film, which has a thickness comprised between 12.7 and 127 Vim, has a Graves tear strength of at least 400 g in the longitudinal direction, as determined by ASTM'D-1004-66 and a styrene permeability less than 200 x 10 9g-cm/cm2-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 devel-opment 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, lead-ing 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 man-ufactures and in SMC storage areas prior to final transforma-tion, thus leading to a not-insignificant increase in costs.
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 com-plete hardening. mhus, 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 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 2~~~~~5 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 resid-ual 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 to water, not to be changed during the SMC laminate manufacturing operations, during storage of the polyester or during trans-formation 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 ZO such rolls to be wrapped in aluminum foil.
Prior art 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 crystall-inity and consists of a mixture of 70 to 90~ by weight of a 2~64~6 polyamide (PA-6 and/or PA-6/6) having a crystallinity less than 35$, and of 10 to 30~ of a polyolefin compound or a copolymer thereof, the polyolefin having a crystallinity of less than 50~. The polyolefin is a high molecular weight S alpha-olefin or a copolymer thereof consisting of an alpha-olefin and a vinyl acetate monomer or alkyl acrylate monomer.
The film, which has a thickness comprised between 12.7 and 127 Vim, has a Graves tear strength of at least 400 g in the longitudinal direction, as determined by ASTM'D-1004-66 and a styrene permeability less than 200 x 10 9g-cm/cm2-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 devel-opment 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, lead-ing 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 man-ufactures and in SMC storage areas prior to final transforma-tion, thus leading to a not-insignificant increase in costs.
2~6~~~
SUMMARY OF THE INVENTION
The present invention provides a compatible polyamide/polyolefin film of thickness generally comprised between 10 and 130 ~,m, and preferably between 20 and 50 ~tm, 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 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) 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 below:
SUMMARY OF THE INVENTION
The present invention provides a compatible polyamide/polyolefin film of thickness generally comprised between 10 and 130 ~,m, and preferably between 20 and 50 ~tm, 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 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) 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 below:
206~~0~
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 copoJ_ymers 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 300 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, malefic, fumaric, itaconic, crotonic, 3-dicarboxylic-5-norbornene-2 acids, malefic, dimethylmaleic anhydrides, mono-sodium, di-sodium maleates, acrylamide, itaconic anhydrides, citraconic anhydrides, maleimide, N-phenylmaleimide, diethyl fumarate, vinyl pyridine, the vinyl silanes, 4-vinyl-pyridine, vinyl-thiethoxysilane, allylic alco-hol, and in particular malefic acid, malefic anhydride or 2~6~36~
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, vinyl-4-anisole, stilbene and indene or mixtures thereof. The other monomer can be selected from the group comprising:
malefic, itaconic, citraconic anhydrides, maleimide, and N-phenylmaleimide 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 particu-lar a 6- or 6/6-polyamide or a mixture of the two.
The percentages by weight of the various components are selected such that:
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 copoJ_ymers 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 300 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, malefic, fumaric, itaconic, crotonic, 3-dicarboxylic-5-norbornene-2 acids, malefic, dimethylmaleic anhydrides, mono-sodium, di-sodium maleates, acrylamide, itaconic anhydrides, citraconic anhydrides, maleimide, N-phenylmaleimide, diethyl fumarate, vinyl pyridine, the vinyl silanes, 4-vinyl-pyridine, vinyl-thiethoxysilane, allylic alco-hol, and in particular malefic acid, malefic anhydride or 2~6~36~
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, vinyl-4-anisole, stilbene and indene or mixtures thereof. The other monomer can be selected from the group comprising:
malefic, itaconic, citraconic anhydrides, maleimide, and N-phenylmaleimide 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 particu-lar a 6- or 6/6-polyamide or a mixture of the two.
The percentages by weight of the various components are selected such that:
30 < A + B + C < 60 0 < A < 60 and B + C > 1 where 0 < B < 60 and A + B + C + D = 100 where 0 < C < 60;
Preferred compositions of the films according to the invention are those in which:
30 < A + B + C < 45 and B + C > 5 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.
ILLUSTRATIVE EXAMPLES
The following examples illustrate the invention without however limiting it.
Example 1 (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 12$ by weight of ethylene, of melting point 158°C (copolymer main body), with a malefic grafting rate of 1.16$, grafted with a Mn 2700 monoamine PA-6 oligomer, prepared by the method described in European Patent 342 OG6, was continuously introduced into a Werner-type extruder. The material temperature was comprised between 255°C and 270°C along the extruder barrel. The screw rotation was 150 rpm and the material throughput 20 kg/li. The * trade mark granules obtained at the outlet from the extruder were trans-formed using an extrusion-blowing technique for tubular arti-cles in a Kaufman extruder with a three-groove rotating helical die of diameter 150 mm and a gap of 0.8 mm, in order to produce a 25 ~~m tubular film. The operating conditions were as follows:
cylinder temperature . 225-250°C
die temperature . 250-260°C
stretching speed . 28 m/min The PA employed was a polyamide-6 of melt index (MI) measured at 235°C under a load of 2.16 kg equal to 20 g/10 min and the polypropylene was a statistical copolymer of propylene and 3$ by weight of ethylene with a melt index of 2 g/10 min (sample 1.A).
In order to determine the film's suitability for peel-ing, 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 1.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) 40 or in Owens, D.K. and Wendt, R.C., J.Appl. Polymer Sci. 13 (1969) 1741. Typical examples of standard liquids are di-iodomethane, glycerol, and benzylic alcohol.
Test no. 1.A 1.B
Surface tension 32 46 (mN.m 1) 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 1L 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 2os4~s go from one limiting value to another was representative of the sample's permeability.
Temperature 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 To).
The styrene permeability of film 1.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 x 10 9 g-cm/cm2-h is con-sidered as good.
-' 2064365 Time Take-up weight (in $) 1.A 1.E
To 0 0 T = To + 4 h 2 3 T = To + 8 h 2 3 T = To + 24 h 2.1 3 T = To + 96 h 2.1 3.6 T = To + 120 h 2.1 3.6 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 malefic-grafted ethylene/propylene copolymer (EPRm) containing 70~ by weight of ethylene and 500 ppm of malefic 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 malefic grafted copolymer main body of example 1 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 ob-tained at the outlet from the extruder were transformed using a cast extrusion technique employing a Thoret extruder into trade marks 2~~~~~5 the form of a flat film or cast film of 25 um thickness (sam-ple 2.A). Operating conditions were as follows:
Temperature profile . 220-250°C
Cylinder temperature . 80°C
Screw speed . 28 rpm By way of comparison, a flat film of the same composi-tion and thickness as sample 1.B was employed (sample 2.B).
Surface tension measurements as defined for example 1 were carried out and are summarized in the table below:
______________________________________________ Test no. 2.A 2.B
Surface tension 32 46 (mN.m 1) ______________________________________________ Water vapor permeability measurements as well as humidi-ty take-up measurements were carried out and gave the follow-ing results:
Test no. Water vapor permeability (in g/m2/24 h) 2.A 50 2.B 380 ________________,_____________________________ 2~64~6~
Time Take-up weight (in $) 2.A 2.B
To 0 0 T = To + 4 h 1.5 3 T = To + 8 h 1.5 3 T = To + 24 h 1.7 3 T = To + 96 h 1.7 3.6 T = To + 120 h 1.7 3.6 The present invention also relates to a method of producing a sheet molding compound in which:
a) a layer of thermosetting resin suitable for thermal processing is poured, in fluid form, onto a polymer film according to the invention which is advancing continu-ously, b) a reinforcing material is introduced onto the advancing fluid layer, c) a polymer film according to the invention is placed in contact with the upper surface of the reinforced fluid layer thus forming a composite mass of sandwich-structure, d) the sandwich-structure composite mass is caused to advance through a series of kneading and compacting rollers, and e) the sandwich-structure composite mass is rolled into a roll for partial heat treatment.
The present invention also relates to a sandwich-structure comprising:
(i) a central layer of a reinforced unhardened thermosetting sheet molding product, (ii) two outer layers of polymer film according to the in-vention.
Preferred compositions of the films according to the invention are those in which:
30 < A + B + C < 45 and B + C > 5 and the viscosities of the various components are such that the polyamide phase constitutes a continuous phase, and can be characterized by the fact that a film about 20 microns thick keeps its shape when plunged into xylene at 130°C for 30 minutes.
ILLUSTRATIVE EXAMPLES
The following examples illustrate the invention without however limiting it.
Example 1 (sheath or tubular film) A mixture comprising, by weight, 33 parts of polypropylene, 57 parts of polyamide-6 and 10 parts of a sequenced copolymer of propylene and 12$ by weight of ethylene, of melting point 158°C (copolymer main body), with a malefic grafting rate of 1.16$, grafted with a Mn 2700 monoamine PA-6 oligomer, prepared by the method described in European Patent 342 OG6, was continuously introduced into a Werner-type extruder. The material temperature was comprised between 255°C and 270°C along the extruder barrel. The screw rotation was 150 rpm and the material throughput 20 kg/li. The * trade mark granules obtained at the outlet from the extruder were trans-formed using an extrusion-blowing technique for tubular arti-cles in a Kaufman extruder with a three-groove rotating helical die of diameter 150 mm and a gap of 0.8 mm, in order to produce a 25 ~~m tubular film. The operating conditions were as follows:
cylinder temperature . 225-250°C
die temperature . 250-260°C
stretching speed . 28 m/min The PA employed was a polyamide-6 of melt index (MI) measured at 235°C under a load of 2.16 kg equal to 20 g/10 min and the polypropylene was a statistical copolymer of propylene and 3$ by weight of ethylene with a melt index of 2 g/10 min (sample 1.A).
In order to determine the film's suitability for peel-ing, 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 1.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) 40 or in Owens, D.K. and Wendt, R.C., J.Appl. Polymer Sci. 13 (1969) 1741. Typical examples of standard liquids are di-iodomethane, glycerol, and benzylic alcohol.
Test no. 1.A 1.B
Surface tension 32 46 (mN.m 1) 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 1L 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 2os4~s go from one limiting value to another was representative of the sample's permeability.
Temperature 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 To).
The styrene permeability of film 1.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 x 10 9 g-cm/cm2-h is con-sidered as good.
-' 2064365 Time Take-up weight (in $) 1.A 1.E
To 0 0 T = To + 4 h 2 3 T = To + 8 h 2 3 T = To + 24 h 2.1 3 T = To + 96 h 2.1 3.6 T = To + 120 h 2.1 3.6 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 malefic-grafted ethylene/propylene copolymer (EPRm) containing 70~ by weight of ethylene and 500 ppm of malefic 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 malefic grafted copolymer main body of example 1 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 ob-tained at the outlet from the extruder were transformed using a cast extrusion technique employing a Thoret extruder into trade marks 2~~~~~5 the form of a flat film or cast film of 25 um thickness (sam-ple 2.A). Operating conditions were as follows:
Temperature profile . 220-250°C
Cylinder temperature . 80°C
Screw speed . 28 rpm By way of comparison, a flat film of the same composi-tion and thickness as sample 1.B was employed (sample 2.B).
Surface tension measurements as defined for example 1 were carried out and are summarized in the table below:
______________________________________________ Test no. 2.A 2.B
Surface tension 32 46 (mN.m 1) ______________________________________________ Water vapor permeability measurements as well as humidi-ty take-up measurements were carried out and gave the follow-ing results:
Test no. Water vapor permeability (in g/m2/24 h) 2.A 50 2.B 380 ________________,_____________________________ 2~64~6~
Time Take-up 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 thermosetting resin suitable for thermal processing is poured, in fluid form, onto a polymer film according to the invention which is advancing continu-ously, b) a reinforcing material is introduced onto the advancing fluid layer, c) a polymer film according to the invention is placed in contact with the upper surface of the reinforced fluid layer thus forming a composite mass of 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 relates to a sandwich-structure comprising:
(i) a central layer of a reinforced unhardened thermosetting sheet molding product, (ii) two outer layers of polymer film according to the in-vention.
Claims (16)
1. A polymer film formed of a polyamide/ polyolefin alloy for the production of a sheet molding compound, comprising components A, B, C and D in the following percentages by weight:
30 ~ A + B + C ~ 60 ~~0 ~ A ~ 60 and B + C ~ 1 ~~ 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;
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) a polyamide obtained from an amino-aliphatic acid or lactame having 6 to 24 carbon atoms.
30 ~ A + B + C ~ 60 ~~0 ~ A ~ 60 and B + C ~ 1 ~~ 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;
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) a polyamide obtained from an amino-aliphatic acid or lactame having 6 to 24 carbon atoms.
2. A film according to claim 1, wherein the polyolefin of component A is selected from the group comprising: polyethylene, polypropylene or polyisobutylene, copolymers of alpha-olefins with vinyl acetate monomers, and alkyl acrylate copolymers.
3. A film according to claim 2, wherein the copolymers of alpha-olefins with vinyl acetate monomers is ethylene/vinyl acetate copolymers.
4. A film according to claim 2, wherein the alkyl acrylate copolymers are selected from the group comprising: ethylene/methyl acrylate copolymers, ethylene/ethyl acrylate copolymers and copolymers of ethylene and an alpha olefin having 3 to 10 carbon atoms.
5. A film according to claim 1, wherein the molecular weight of the polyolefin of component A is comprised between 10 000 and 500 000.
6. A film according to claim 1, wherein the functionalized monomer of component B is selected from the group comprising: acrylic, methacrylic, malefic, fumaric, itaconic, crotonic, 3-dicarboxylic-5-norbornene-2 acids, malefic, dimethylmaleic anhydrides, mono-sodium, di-sodium maleates, acrylamide, itaconic anhydrides, citraconic anhydrides, maleimide, N-phenylmaleimide, diethyl fumarate, vinylpyridine, the vinylsilanes, 4-vinylpyridine, vinylthiethoxysilane, allylic alcohol, and a mixture thereof.
7. A film according to claim 1, wherein said functionalized monomer is selected from the group comprising malefic acid, malefic anhydride and fumaric acid.
8. A film according to claim 1, wherein the functionalized monomers of component B are selected one from the group comprising styrene, 2-methylstyrene, 4-methylstyrene, alpha-methylstyrene, beta-methylstyrene, vinyl-4-anisole, stilbene and indene and mixture thereof, and the other is selected from the group comprising:
malefic, itaconic, citraconic anhydrides, maleimide , and N-phenylmaleimide or mixtures thereof.
malefic, itaconic, citraconic anhydrides, maleimide , and N-phenylmaleimide or mixtures thereof.
9. A film according to claim 1, wherein the grafting rate of compound B is less than 2% by weight.
10. A film according to claim 1, wherein compound D consists of a 6 polyamide, 6/6 polyamide or a mixture thereof.
11. A film according to claim 1, wherein the following holds: 30 ~ A + B + C ~ 45 and B + C ~ 5.
12. A film according to claim 1, comprising the following components A, B, C and D:
- A is polypropylene;
- B, if present, is a copolymer of ethylene and malefic-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.
- A is polypropylene;
- B, if present, is a copolymer of ethylene and malefic-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.
13. A film according to claim 1, wherein the thickness of said film is comprised in the range of from 10 to 130 µm.
14. A film according to claim 1, wherein the thickness of said film is comprised in the range of from 20 to 50 µm.
15. A sandwich-structure comprising:
(i) a central layer of a reinforced unhardened thermosetting sheet molding product, (ii) two outer layers of polymer film according to Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.
(i) a central layer of a reinforced unhardened thermosetting sheet molding product, (ii) two outer layers of polymer film according to Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.
16. A method for producing a sheet molding compound in which:
a) a layer of thermosetting resin suitable for thermal processing is poured, in fluid form, onto a polymer film as defined in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, advancing continuously, b) a reinforcing material is introduced onto the advancing fluid layer, c) a polymer film as defined in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 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.
a) a layer of thermosetting resin suitable for thermal processing is poured, in fluid form, onto a polymer film as defined in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, advancing continuously, b) a reinforcing material is introduced onto the advancing fluid layer, c) a polymer film as defined in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9103870 | 1991-03-29 | ||
| FR9103870 | 1991-03-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2064365A1 CA2064365A1 (en) | 1992-09-30 |
| CA2064365C true CA2064365C (en) | 1999-11-16 |
Family
ID=9411291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002064365A Expired - Fee Related CA2064365C (en) | 1991-03-29 | 1992-03-27 | Polyamide-polyolefin release film and its use in producing a sheet molding compound |
Country Status (13)
| Country | Link |
|---|---|
| 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) | FI921362A (en) |
| IE (1) | IE75708B1 (en) |
| NO (1) | NO304076B1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2697465A1 (en) * | 1992-10-30 | 1994-05-06 | Atochem Elf Sa | Laminates based on polyamide / polyolefin alloys and coextrusion binders, objects obtained therefrom, coating methods therewith. |
| FR2731702B1 (en) * | 1995-03-17 | 1997-04-30 | Atochem Elf Sa | PROCESS FOR HYDROGENOLYSIS OF CHLOROFLUOROCARBONS AND HYDROCHLOROFLUOROCARBONS |
| FR2743746B1 (en) | 1996-01-23 | 1998-04-03 | Atochem Elf Sa | NEW RELEASE FILM FOR SHEET MOLDING COMPOUNDING PRODUCT |
| US6045919A (en) * | 1997-01-06 | 2000-04-04 | Elf Atochem S.A. | Antistatic film for packaging materials diffusing volatile products |
| JPH11140250A (en) * | 1997-11-04 | 1999-05-25 | Kanegafuchi Chem Ind Co Ltd | Isobutylene-based rubber particle, graft copolymer particle and resin composition containing the same particle |
| FR2783747B1 (en) * | 1998-09-30 | 2000-12-08 | Atochem Elf Sa | FILM COMPRISING A CENTRAL POLYOLEFIN LAYER AND TWO EXTERNAL POLYAMIDE / POLYOLEFIN ALLOY LAYERS |
| EP1156080A1 (en) * | 2000-05-15 | 2001-11-21 | Atofina | Coextruded film comprising two outer polyamide or polyamide/polyolefin alloy layers and a central polyolefin or polyamide or polyamide/polyolefin alloy layer |
| KR100508907B1 (en) | 2001-12-27 | 2005-08-17 | 주식회사 엘지화학 | Nanocomposite blend composition having super barrier property |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3067169D1 (en) * | 1979-10-10 | 1984-04-26 | Allied Corp | Polyamide release film for sheet molding compound, sheet compound prepared therewith and process of making |
| FR2629090B1 (en) * | 1988-03-24 | 1990-11-23 | Atochem | GRAFT COPOLYMER BASED ON ALPHA-MONO-OLEFIN, ITS MANUFACTURING PROCESS, ITS APPLICATION TO THE MANUFACTURE OF THERMOPLASTIC ALLOYS, THERMOPLASTIC ALLOYS OBTAINED |
| GB2225583A (en) * | 1988-12-05 | 1990-06-06 | Du Pont Canada | Films of polyamide and grafted olefin copolymer |
| GB2225582A (en) * | 1988-12-05 | 1990-06-06 | Du Pont Canada | Film of polyamide and grafted polyolefin |
-
1992
- 1992-03-17 DK DK92400707.3T patent/DK0506515T3/en active
- 1992-03-17 ES ES92400707T patent/ES2090538T3/en not_active Expired - Lifetime
- 1992-03-17 DE DE69212681T patent/DE69212681T2/en not_active Expired - Lifetime
- 1992-03-17 AT AT92400707T patent/ATE141205T1/en not_active IP Right Cessation
- 1992-03-17 EP EP92400707A patent/EP0506515B1/en not_active Expired - Lifetime
- 1992-03-26 NO NO921180A patent/NO304076B1/en unknown
- 1992-03-27 FI FI921362A patent/FI921362A/en unknown
- 1992-03-27 AU AU13817/92A patent/AU645188B2/en not_active Ceased
- 1992-03-27 IE IE920998A patent/IE75708B1/en not_active IP Right Cessation
- 1992-03-27 CA CA002064365A patent/CA2064365C/en not_active Expired - Fee Related
- 1992-03-28 CN CN92102939A patent/CN1041315C/en not_active Expired - Lifetime
- 1992-03-28 KR KR1019920005194A patent/KR960002980B1/en not_active IP Right Cessation
- 1992-03-30 JP JP4103669A patent/JPH0662793B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0662793B2 (en) | 1994-08-17 |
| AU645188B2 (en) | 1994-01-06 |
| NO921180L (en) | 1992-09-30 |
| NO921180D0 (en) | 1992-03-26 |
| CN1041315C (en) | 1998-12-23 |
| DE69212681T2 (en) | 1997-01-02 |
| NO304076B1 (en) | 1998-10-19 |
| KR960002980B1 (en) | 1996-03-02 |
| DE69212681D1 (en) | 1996-09-19 |
| JPH05156045A (en) | 1993-06-22 |
| AU1381792A (en) | 1992-10-01 |
| CA2064365A1 (en) | 1992-09-30 |
| EP0506515A1 (en) | 1992-09-30 |
| FI921362A0 (en) | 1992-03-27 |
| IE75708B1 (en) | 1997-09-10 |
| ES2090538T3 (en) | 1996-10-16 |
| FI921362A (en) | 1992-09-30 |
| EP0506515B1 (en) | 1996-08-14 |
| IE920998A1 (en) | 1992-10-07 |
| CN1066278A (en) | 1992-11-18 |
| DK0506515T3 (en) | 1996-09-09 |
| KR920018129A (en) | 1992-10-21 |
| ATE141205T1 (en) | 1996-08-15 |
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