CA2102054C - Polyamide/polyolefin alloy-based laminates and objects obtained therefrom - Google Patents
Polyamide/polyolefin alloy-based laminates and objects obtained therefrom Download PDFInfo
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- CA2102054C CA2102054C CA002102054A CA2102054A CA2102054C CA 2102054 C CA2102054 C CA 2102054C CA 002102054 A CA002102054 A CA 002102054A CA 2102054 A CA2102054 A CA 2102054A CA 2102054 C CA2102054 C CA 2102054C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
- B29C63/0017—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor characterised by the choice of the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
- B29K2995/0017—Heat stable
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0055—Resistive to light
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0087—Wear resistance
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0094—Geometrical properties
- B29K2995/0096—Dimensional stability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
-
- 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
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A laminate, notably in film or sheet form, is provided for the reinforcement, protection and decoration of a substrate, said laminate comprising (i) at least one layer of a polyamide/polyolefin alloy containing an agent ensuring compatibility, and (ii) at least one layer of a co-extrusion binder, the layer of co-extrusion binder being in contact with said substrate.
Description
POLYAMIDE/POLYOLEFIN ALLOY-BASED LAMINATES
AND OBJECTS OBTAINED THEREFROM
BACKGROUND OF THE INVENTION
The present invention relates to laminates based on polyamide and polyolefin alloys and co-extrusion binders, and to objects obtained therefrom. The present invention par-ticularly relates to articles, sheets and films obtained from, or incorporating, such laminates, intended for sub-strate reinforcement, protection and decoration purposes.
The decoration of various substrates such as metal, wood, thermosetting polymers, plastic materials and others requires materials possessing specific properties. Thus, depending on the use to which the object will be put, the decoration needs to be protected from external factors such as dust, impact, scratching to mention but a few.
In parallel with the requirements for long-term sta-bility under extremely demanding environmental conditions, there has been an increased demand for decorations which are increasingly complex and sophisticated. New techniques for providing suitable decors have thus been developed. Such techniques are, in particular, the transfer of sublimable inks, and notably, the sublimation method. The latter is described in French Patent No. 2,387,793.
This decorative technique using sublimation provides considerable advantage over current technologies such as the application of varnishes including: depth of colour and pro-tection of the decor vis-a-vis scratching, tear-off and the like. Materials used in this technique act as a support for the decoys, and are also responsible for protecting the surfaces of the substrates whether they be metal, wood, plastics, thermo-setting polymers or otherwise.
Thus, there is a requirement for materials having a range of properties. Sheets of films are designed to protect and/or to decorate varying surfaces (metal, wood, polymer); the material needs to be chemically resistant, mechanically strong (both as regards heat and cold), and should have low moisture absorption. Apart from such intrinsic properties, the material should be capable of being shaped when hot, and bonding of the films or sheets onto the substrate should advantageously be possible in a single operation during thermoforming or in accordance with any technique such as insert molding thereof onto a film, injection molding of the constituents onto a structure, and the like; the material needs to be suited to the conditions employed during the sublimation process, and needs to lead to high quality decoys under readily-employable processing condition.
The present invention sets out to provide such a material designed to be used, in particular, in the technique of decoration by sublimation.
Acrylonitrile/butadiene/styrene or ABS polymers are known for this purpose. However, these polymers have poor performance regarding their ability to withstand temperature, resist scratching and solvent attack; they are relatively rigid and are hence not easy to shape.
Polyurethanes are also known, but the sublimation technique cannot be readily applied to them. Moreover, the practical use of polyurethanes is very different from that t 2a of thermoplastics as the polyurethanes do not possess the ease of shaping that the latter have.
French Patent 2,596,286 discloses the use of a support consisting of an outer layer in polyamide 11 and a sub-layer of sequenced polyamide-polyether (PEBA). But this type of support poses the problem of creep resistance when hot, when provided in flexible grades, as well as a problem concerning its adhesion onto substrates.
French Patent Application serial No. 900 74 20 corresponding to CA-A-2 044 527 discloses bonding films which introduce an improvement over French Patent Application published under No. 2,596,286 by replacing the sub-layer by a material in a composition based on polyamide and modified polyolefins. Nevertheless, these assemblies employ highly sophisticated materials which have disadvantages in economic terms. There are also problems with shaping these assemblies as a result of significant high-temperature creep and, moreover, it is difficult to thermoform them notably when the substrates acting as their support have pronounced angles, and the cycle time for the decoration phase by sublimation is relatively long (of the order of 5 minutes at 150°C).
In order to provide the outer layer, unmodified (PA6 or PA66) polyamides or ones that are slightly modified by the addition of fillers, impact resistance-improving agents, etc, also possess many advantages but moisture takeup, which is known in these products, brings about significant dimensional changes of the manufactured products, and significant reduc-tion in their mechanical properties. Polyamides PA 6 and PA
6,6 copolyamides PA 6/6,6 and, generally speaking, polyamides PA are also known, on the one hand, to be sensitive to polar solvents, and, on the other hand to be poorly resistant to hydrolysis phenomena (by mineral and organic acids).
Polypropylenes (PPs) can be used but their mechanical strength (particularly as regards cold impact and abrasion resistance) is low. Their heat resistance is also limited and these products are hardly suitable for providing decora-3o tion by sublimation or by the use of conventional painting techniques which require the paint film to adhere strongly to the substrate. Polypropylenes, or generally speaking, the pvlyolefins do in fact have a reputation of being difficult to paint.
AND OBJECTS OBTAINED THEREFROM
BACKGROUND OF THE INVENTION
The present invention relates to laminates based on polyamide and polyolefin alloys and co-extrusion binders, and to objects obtained therefrom. The present invention par-ticularly relates to articles, sheets and films obtained from, or incorporating, such laminates, intended for sub-strate reinforcement, protection and decoration purposes.
The decoration of various substrates such as metal, wood, thermosetting polymers, plastic materials and others requires materials possessing specific properties. Thus, depending on the use to which the object will be put, the decoration needs to be protected from external factors such as dust, impact, scratching to mention but a few.
In parallel with the requirements for long-term sta-bility under extremely demanding environmental conditions, there has been an increased demand for decorations which are increasingly complex and sophisticated. New techniques for providing suitable decors have thus been developed. Such techniques are, in particular, the transfer of sublimable inks, and notably, the sublimation method. The latter is described in French Patent No. 2,387,793.
This decorative technique using sublimation provides considerable advantage over current technologies such as the application of varnishes including: depth of colour and pro-tection of the decor vis-a-vis scratching, tear-off and the like. Materials used in this technique act as a support for the decoys, and are also responsible for protecting the surfaces of the substrates whether they be metal, wood, plastics, thermo-setting polymers or otherwise.
Thus, there is a requirement for materials having a range of properties. Sheets of films are designed to protect and/or to decorate varying surfaces (metal, wood, polymer); the material needs to be chemically resistant, mechanically strong (both as regards heat and cold), and should have low moisture absorption. Apart from such intrinsic properties, the material should be capable of being shaped when hot, and bonding of the films or sheets onto the substrate should advantageously be possible in a single operation during thermoforming or in accordance with any technique such as insert molding thereof onto a film, injection molding of the constituents onto a structure, and the like; the material needs to be suited to the conditions employed during the sublimation process, and needs to lead to high quality decoys under readily-employable processing condition.
The present invention sets out to provide such a material designed to be used, in particular, in the technique of decoration by sublimation.
Acrylonitrile/butadiene/styrene or ABS polymers are known for this purpose. However, these polymers have poor performance regarding their ability to withstand temperature, resist scratching and solvent attack; they are relatively rigid and are hence not easy to shape.
Polyurethanes are also known, but the sublimation technique cannot be readily applied to them. Moreover, the practical use of polyurethanes is very different from that t 2a of thermoplastics as the polyurethanes do not possess the ease of shaping that the latter have.
French Patent 2,596,286 discloses the use of a support consisting of an outer layer in polyamide 11 and a sub-layer of sequenced polyamide-polyether (PEBA). But this type of support poses the problem of creep resistance when hot, when provided in flexible grades, as well as a problem concerning its adhesion onto substrates.
French Patent Application serial No. 900 74 20 corresponding to CA-A-2 044 527 discloses bonding films which introduce an improvement over French Patent Application published under No. 2,596,286 by replacing the sub-layer by a material in a composition based on polyamide and modified polyolefins. Nevertheless, these assemblies employ highly sophisticated materials which have disadvantages in economic terms. There are also problems with shaping these assemblies as a result of significant high-temperature creep and, moreover, it is difficult to thermoform them notably when the substrates acting as their support have pronounced angles, and the cycle time for the decoration phase by sublimation is relatively long (of the order of 5 minutes at 150°C).
In order to provide the outer layer, unmodified (PA6 or PA66) polyamides or ones that are slightly modified by the addition of fillers, impact resistance-improving agents, etc, also possess many advantages but moisture takeup, which is known in these products, brings about significant dimensional changes of the manufactured products, and significant reduc-tion in their mechanical properties. Polyamides PA 6 and PA
6,6 copolyamides PA 6/6,6 and, generally speaking, polyamides PA are also known, on the one hand, to be sensitive to polar solvents, and, on the other hand to be poorly resistant to hydrolysis phenomena (by mineral and organic acids).
Polypropylenes (PPs) can be used but their mechanical strength (particularly as regards cold impact and abrasion resistance) is low. Their heat resistance is also limited and these products are hardly suitable for providing decora-3o tion by sublimation or by the use of conventional painting techniques which require the paint film to adhere strongly to the substrate. Polypropylenes, or generally speaking, the pvlyolefins do in fact have a reputation of being difficult to paint.
SUN~iARY OF THE INVENTION
Thus, there is a requirement for a material which overcomes the disadvantages of the prior art and fulfils the above-stated technical requirements.
The present invention provides a laminate for the reinforcement, protection and decoration of a substrate, comprising:
(i) at least one layer of a polyamide/polyolefin alloy containing an agent ensuring compatibility, (ii) at least one layer of a co-extrusion binder, the layer of coextrusion binder being in contact with said substrate.
PA6/polyolefin or PA66/polyolefin alloys, notably PA6/PP or PA66/PP absorb far less moisture than PA6 or PA66. No solvents are known for PA6/polyolefin alloys or PA66/polyolefin alloys and the resistance to hydrolysis of PA/polyolefin alloys is very significantly higher than that of the corresponding polyamide. The chemical resistance of a PA/polyolefin alloy is hence far superior to that of the polyamide present in its composition, and this applies regardless of the polyamide considered. Compared to the polyamides 11 and 12, the heat resistance of a PA6 or PA66 alloy, or yet again, of a copolyamide 6/66 alloy with polypropylene is appreciably higher. Because of this, PA/polyolefin alloys present a significant advantage, com-pared to existing technologies, as regards chemical inert-ness, heat resistance, as well as the unique combination of properties that these PA/polyolefin alloys provide when compared to the use of a polyamide alone, as well as through the high working temperatures that can be employed with these PA/polyolefin alloys.
Moreover, the PA/polyolefin alloys are painted using the techniques generally employed for painting the PA: brief exposure to heat from a flame or polyamide-type undercoating fo_= example, or tried and tested techniques for painting on polyolefins: exposure to the heat from a flame for example or plasma treatment.
The quality of decoration obtained by sublimation increases with the temperature at which this sublimation operation is carried out. The high melting point of PA6/polyolefin o r PA66/polyolefin alloys allows sublimation to be carried out at high temperatures. The decor obtained is hence of a higher quality compared to what is obtained starting from ABS or PA at low melting point temperatures, or yet again, w~.th polypropylene.
Nevertheless, the chemical inertness of the PA/polyolefin alloys mentioned above is such that bonding of these products is impossible using known assembly methods employing solvent-based adhesives.
Direci: bonding of PA/polyolefin alloys onto metals or wood substrate, or onto synthetic (thermosetting, for instance) surfaces by application of heat and pressure is more difficult, and in the majority of cases, impossible.
The present invention consequently provides a laminate or multi-layer sheet (with at least two layers) the surface layer of which comprises a polyamide/polyolefin polymer rendered compatible, and including an adhesive binder-based layer allowing said polymer alloy to be bonded onto various sL~.bstrates. The alloy consists of at least one polyamide and at least one polyolefin and includes an agent which establishes compatibility. These sheets or films can be easily shaped and sublimed and can be employed for reinforcing, protecting or decorating a range of substrates.
These laminated or mufti-layer structures have the particular characteristic of being able to be bonded onto various substrates, of being easily decorated and exhibiting an extremely useful combination of heat resistance, chemical resistance and a low tendency towards moisture absorption phenomena.
The present invention covers such laminates or mufti-layer structures, their manufacture and their various uses, notably as decorative and surface-protection elements.
According to one embodiment, the polyamide forms the matrix of said alloy. The polyolefin is, in this embodiment, dispersed in the polyamide phase forming the matrix.
The polyolefin in the alloy is preferably a polyolefin having a molecular weight comprised between 1 000 and 106 and is advantageously polypropylene PP.
The polyamide in the alloy is preferably an aliphatic polya:mide, or a mixture of such a polyamide, such as PA6, PA6,6, PA11, PA12, PA12,12); advantageously, the polyamide is PA6 or PA6,6.
The polyamide preferably represents 25 to 75% by weight, advantageously 30 to 70% by weight of the total weight of the alloy, preferably 50 to 70% by weight.
6a The polyamide/polyolefin polymer alloys need, in order to have good mechanical properties, to include at least one agent ensuring compatibility.
This agent ensuring compatibility is generally comprised of a ~>olyolefin or a copolyolefin grafted with an acid group or a derivative thereof, for example malefic anhydride, or a copolymer comprising, for example, an ethylene monomer or an alpha-olefin monomer or, preferably, a diolefin monomer, with a co-monomer selected from vinylic esters of saturated carboxylic acid, unsaturated mono- and di-carboxylic acids, esters, salts, thereof and anhydrides of saturated or unsaturated dicarboxylic acids.
The expression "polymer grafted with a monomer", should be taken to mean a polymer onto which the graft, in monomer form, i;> grafted.
The expression polyolefin or copolyolefin should be taken to notably mean polyethylene, poly alpha-olefins, polydiolefins, ethylene and propylene copolymers, as well as block copolymers based on styrene and notably those consisting of polystyrene sequences and polybutadiene sequences (SBS), polystyrene sequences and sequences of polyisoprene (SIS), polystyrene sequences and poly (ethylene-butylene) sequences (SEBS), containing 0.2 to 0.8o by weight of malefic anhydride and from 30 to 55% of styrene in the case of the SBS, from 15 to 25% in the case of the SIS and from 13 to 32%
in the case of the SEBS.
The above-mentioned copolymers can be polymerized in a random or sequenced manner, and have a linear or branched structure.
In one embodiment, said alloy contains a compatibility-establishing agent comprising a polyolefin (or modified polyolefin) which is grafted preferably with malefic anhydride. This polyolefin or modified polyolefin, can be grafted furthermore with an oligoamide or a polyamide able to react with the malefic anhydride function, for instance.
For example, the following composition can be cited, described in French patent application serial No. 91 03870, corresponding to CA-A-2 064 365 as suitable for the PA/
polyolefin alloy:
A. an alpha-olefin of molecular weight comprised between 1,000 and 1,000,000;
B. a malefic-or acrylic-grafted alpha-olefin of A;
C. a copolymer of grafted alpha-olefin consisting of an oligoamide or a polyamide of molecular weight comprised be-tween 500 and 40,000, and monoaminated, and of alpha-olefin grafted with a monomer able to react with the amine function of the oligoamide or the polyamide;
D. an aliphatic polyamide or a mixture of aliphatic polyamide;
For the purposes of the present invention, components A, B, C and D are preferably present in proportions by weight whereby:
30 < A + H + C < 65; where 1 < A < 64;
and B +C > 1; where 0< B < 64;
and 35 < D < 70;
and A + B + C + D = 100; where 0 < C < 64.
It is also possible to mix elastomer compositions with the PA/polyolefin alloy composition described above, which perform a known role in any polymer matrix, their purpose 8 2~0~0~4 being to reduce the flexural modules and to increase impact resistance. These elastomers can be present in amounts of'up to 50~ by weight, preferably from 5 to 25~ by weight based on the weight of the final composition. The following can be cited as typical example of elastomers:
- ethylene and propylene rubbers, malefic-grafted (EPRm), which are particularly preferred by the applicant containing 0.1 to 2~ by weight of malefic anhydride;
- ethylene, propylene, diene monomer copolymers, malefic-grafted (EPDMm);
-copolymers of ethylene, alkyl (meth)acrylate (such as methyl, ethyl, ~1-butyl acrylate) and optionally malefic anhydride having 2 to 40~ by weight of alkyl (meth)acrylate and from 0.01 to 8~ by weight of anhydride, based on the total copolymer weight.
Various constituents can be incorporated into the above compositions, such as fillers, pigments or colouring agents and various additives.
As example of fillers, glass fibexs or spheres can be men-tinned, and.carbon or aramide fibers, -talc, silica, calcium carbonate, kaolin, ceramics, metallic salts and oxides such as aluminum, manganese, ground ferrite, and titanium oxide powders, and pigments in flake form providing a metalized finished appearance.
Generally up to 50~ by weight of these fillers based on the PA/polyolefin alloy composition rendered compatible, can be added. Preferably the fillers represent up to 40 $ of the total weight. Examples of additives include UV light pro-tection agents, optical brighteners, mold release agents, 3U ant~.statia agents, and agents protecting against deterior-ation due to heat .
The compositions can be prepared in one step notably by compounding. The constituents, which are most frequently in granular of average diameter less than 5 mm are mixed in their molten state generally in a kneader at a temperature comprised between 230 and 300°C. The compositions obtained are most frequently in granular form having an average diameter less than 5 mm. It is also possible to prepare the alloys in several steps notably by dilution or mixing a pre-alloy in PA or a polyolefin, this mixing or dilution step being moreover able to be implemented at the actual extrusion stage when the proportion of the constituents are adhered to.
Certain additives (coloring agents, mold release agents, lubricants, etc.) can be incorporated by mixing them with the mixture in the molten state, or with the granules obtained in the dry state.
Below, the term PA/PO alloy will be used to designate, for the sake of simplicity, the PA/polyolefin alloys described above. PA/PO alloys corresponding to the above definition are manufactured by Elf Atochem. They are marketed under the ORGALLOY trademark and corresponds to PA/PP, PA/PE, and PA/modified polyolefin alloys.
The co-extrusion binder is designed to ensure the alloy adheres t:o the substrate, and forms, at the final stage, a laminate with this alloy onto the substrate. This co-extrusion binder is sometimes also referred to as a thermoplastic binder, a hot melt binding agent, etc.
In one embodiment, said co-extrusion binder is a modified polyolefin, or a copolymer of polyolefin modified by means of an unsaturated carboxylic acid derivatives (copolymerisation, terpolymerisation or grafting). These (co) polyolefins can be employed alone or in mixture with other polyolefi:ns.
In o..der to obtain such compositions, United States Patent 4,452,942 teaches the following procedure:
1) the grafting of an unsaturated carboxylic acid derivative (for example malefic anhydride) onto a polyolefin (for example a linear polyethylene or a polypropylene);
2) mixing the resulting grafted (co)polymers with another polyolefin comprising:
- an ethylene homopolymer; or - an ethylene/alpha-olefin copolymer; or - a copolymer of ethylene and unsaturated esters 10 or derivatives thereof; or - a mixture of these polyolefins, all combina-tions being pos:;ible.
It is also possible, in order to obtain a co-extrusion binder, to carry out direct grafting of a mixture of polyolefins. Another possibility consists in employing a copolymer or terpolymer as binder which includes an unsaturated carboxylic acid derivative originating from radical copolymerisation.
By wa:~ of modified polyolefins employed for the binder, compositions can be cited by way of example obtained by polymerisation of:
A. an ethylene, alpha-olefin or optionally a di-olefin monomer, B. at least one co-monomer selected from saturated carboxylic acid vinylic esters, unsaturated mono- and di-carboxylic acids and esters and salts, thereof, and saturated or unsaturated di-carboxylic acids anhydrides.
The olefin, in other words the olefinic monomer, represents at least 50s and, preferably at least 60°s of the total weight of the copolymer. The copolymers can be randomly polymerised or sequenced and may have a linear or branched structure, regarding the copolyolefins of the invention.
Examples of such grafting processes, or of binder compositions arE: provided in the following patents, this list not being exclusive: EP-210,307, EP-33,220, EP-266,994, FR-2,7.32,780, EP-171,777, USP-4,758,477, USP-4,762,890, USP-4,966,810, USP-4,452,942, USP-3,658,948.
From among the coextrusion binders commonly employed in numerous associations, binders having the following chemical compositions are preferred here:
- copolymers of ethylene copolymerized with butene, hexene, octene, optionally mixed with ethylene-propylene copolymers grafted with malefic anhydride, said ethylene/olefin copolymers containing from 35 to 80% by weight of ethylene, the degree of grafted malefic anhydride being comprised between 0.01 and 1% by weight, preferably between 0.05 and 0.5% based on the total copolymer weight;
- copolymers of ethylene and vinyl acetate (EVA), with or without malefic anhydride (the malefic anhydride can be grafted or terpolymerised), particularly containing from 2 to 40% by weight of vinyl acetate from 0.01 to 0.5% by weight of grafted malefic anhydride or from 0 to ~10% by weight of terpolymerised malefic anhydride, based on the total copolymer weight;
- copolymers of ethylene, of alkyl (meth)acrylate (such as methyl, ethyl, t-butyl acrylate) and of malefic anhydride cont<~ining from 2 to 40% by weight of alkyl (meth)acrylate and from 0.01 to 8% by weight of anhydride based on the total copolymer weight.
Binders corresponding to the definition above are manufactured b~,~ Elf Atochem. One such binder is a mixture of polyolefins modified by a carboxylic acid group, through malefic anhydride grafting. This binder is available commer-cially in the form of granules bearing the OREVAC 18302 or OREVAC PP-C trademark.
Below, binder is used to designate the co-extrusion binder_ and should be considered as covering the modified polyolefin compositions described above.
It is possible to incorporate the same additives and/or fillers as those specified above for the alloys into the binders and generally speaking, in the same proportions.
By vi:ctue of their ease of use, their excellent mechanical properties (notably cold impact resistance, abrasion resistance, scratch or tear resistance) their excellent chemical inertness (no known solvent), and of their dimensional stability between -40 and +150°C, their excellent ageing behavior as well as their excellent suitability for bonding and decoration (heat resistance, creep resistance), the compositions according to the invention can be employed in a large variety of forms (molded or exti:uded parts, extruded films and sheets) for the protection, decoration or strengthening of composite objects notably the protection and/decoration of flat supports or complex shapes or molded parts. They can also be insert-molded over parts, bonded onto additional parts, thermo-formed over complex parts, and heat seal laminated with films or sheets.
The present invention also covers the provision of sheets or films and molded or extruded objects obtained from the alloy and binder comprising the final laminate according to the present invention. Thus, the present invention also covers the various methods for coating a substrate using the alloy and binder.
The films or sheets can be obtained using known extrusion techn_Lques, such as flat extrusion-calendering, heat seal laminating and extrusion, blow extrusion, etc.
The temperatures at which the PA/PO alloys are employed are generally from 20 to 60°C higher than the melting point of the PA used in the alloy. The temperatures the binders are used at are generally 20 to 60°C above the melting point of the binder employed for producing the laminate, when the laminate does indeed have a melting point.
In accordance with "Modern Plastics Encyclo-paedia", the expression "films" should be reserved for flat objects less than 250 um thick, and the expression "sheet"
should be reserved for thicker objects which can be up to several mm thick. In the present description, and for reasons of commodity and simplicity, both terms are used alternatively to designate either of the products.
Depending on the technology employed, films or sheets can be obtained haring thickness comprised between 10 um and 5 mm, or even higher.
Using coextrusion of a PA/PO alloy or of several layer of PA/PO alloy, or of several layers of material that are compatible with each other and in which the lower layer is compatible with the binder layer, and of a layer or several layers of binder, a laminate or double- or multiple-layer structure is obtained directly.
This laminate, in film or sheet form can be directly bonded onto the various substrates envisaged in the framework of the present invention.
In one embodiment of the invention, the method for coating a substrate in order to reinforce, protect and decorate it is characterized in that the PA/polyolefin alloy and the binder are co-extruded in order to prepare a film which is applied onto the substrate onto which it is caused to adhere.
It is also possible to manufacture the laminate by extruding the components in advance in film form and then assembling these films by heat seal laminating them: a sheet of binder manufactured in advance, notably by flat extrusion or blow extrusion is deposited on a previously-manufactured sheet of PA/PO alloy, the two sheets being pressed together under application of heat. Heat seal lamination of a film of binder immediately following manufacture by extrusion of a PA/PO alloy film gives good results, if hot calendering is carried out at the exit from the extruder.
According to one embodiment of the invention, the process for coating the substrate in order to reinforce, protect, and decorate it is characterized in that two films are prepared, one of PA/polyolefin alloy and the other of binder, these films then being heat seal laminated and the product thus obtained is applied onto the substrate, onto which adhesion :is caused to occur.
The films of binder and the single- or multi-layer film of the PA/PO alloy or alloys can also be placed one onto the other followed by application of pressure and heat (170°C for 2 to 3 min) at the time of use, in order to obtain the bonding between the different layers.
In one embodiment, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that two films are prepared, one of PA/polyolefin alloy and the other of binder, and these two films are applied to the substrate and adhesion thereto is brought about.
In one embodiment, the adhesion is brought about by hot pressing, heat seal laminating, or insert molding.
The temperature should be sufficient to achieve this and is advantageously higher than 130°C.
The films thus obtained can be bonded onto rigid 10 elements, notably metallic parts (such as cables, sheet, etc.), onto items in wood, onto bound aggregates, or onto items in synthetic materials, such as polyesters, epoxy resins, ABS copolymers, polystyrene and others, (with a phenolic binder, for example). These films are bonded onto the various substrates mentioned in this specification using the various preferred techniques indicated above, or using techniques known per se.
The present invention also envisages other embodiments of articles. Molded or extruded parts, which are in a shape other than that of the film or sheet, for example in the form of pre-shaped items can be obtained using preferred techniques and, failing this, using conventional techniques. Such items are referred to herein by the term "shaped parts".
The molded or extruded parts can be obtained by common injection molding or co-extrusion (using simul-taneous injection of alloy and binder) in order to obtain a composite item in a single operation, the binder layer being on that side on which the bonding onto the particular substrate is required to occur.
In accordance with one embodiment of the invention, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that a PA/polyolefin alloy and binder film is shaped and this shaped film is applied onto the substrate and adhesion thereto is caused to occur.
It is also possible to operate in two steps, by injection molding the alloy and then molding the binder thereover, or vice versa.
In one embodiment of the invention, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that a PA/polyolefin alloy film is shaped and the binder layer is insert-molded there-over, or vice versa, and the shaped part thus obtained is applied onto the substrate and adhesion thereto is caused to occur.
A PA/F?0 alloy part can also be obtained by mono-injection molding or mono-extrusion, a sheet or film of binder being inserted between the alloy and the substrate constituting its support. The hot bonding operation required to ensure the binder adheres to the substrate then enables simultaneous bonding of the binder onto the substrate and the PA/PO alloy sheet to be obtained. The part described above can also be a mufti-material composite part obtained by associating, using co-injection molding or co-extrusion, PA/PO alloys with PAs, PEs or, yet again modified polyo.lefins, and in general any thermoplastic polymer known for its adhesion properties onto polyolefin or polyamides.
In accordance with one embodiment of the present invention, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that a PA/polyolefin alloy film is shaped, and a film of binder is prepared, and the said film of binder is inserted between the thus shaped alloy part and the substrate, and adhesion is caused to occur.
The single- or multi-material injection-molded or extruded part can also be placed on a substrate consti-tuting its support which has been previously covered with a layer of binder, followed by a heat seal laminating, co-injection molding or insert-molding operation, in order to cause adhesion.
In one embodiment of the invention, the process for coating a substrate in order to reinforce, protect and decorate it is ~~haracterized in that a PA/polyolefin alloy film is shaped, the substrate is coated with a layer of binder, and the thus-shaped alloy part is applied onto the substrate coated with the layer of binder, and adhesion thereto is caused to occur.
In another embodiment, adhesion is caused to occur by a combination of heat and pressure, by heat seal lamination, or by insert molding. An adequate temperature should be emp_Loyed~ advantageously the temperature is higher than 130"C.
It is also possible to form the laminate using any suitable process, and to then insert it into a,mold and to injection-mo:Ld a filler which constitutes the substrate.
Generally speaking, the laminates are fixed onto the substrate by insert-molding or thermo-forming with simultaneous adhesion, or using thermo-forming followed by adhesion.
The materials of the present invention can be decorated using sublimable ink transfer printing techniques, and notably the methods described in French Patent 2,387,793. Decoration of these materials can also be implemented using other techniques such as screen printing, painting or varnishing, hot transfer, padding, ink jet printing, laser engraving, it being understood that all these decoration. techniques can be applied to all the films covered by the present invention, and all the articles in all their shapes or forms that derive therefrom.
In order even further improve the quality of decoration and protection thereof, it is also possible to provide a dual layer on the outside, consisting of a transparent or translucid layer of a PA/PO alloy (exempt of, or only containing a small amount of, coloring additive) in association with an opaque layer consisting of a PA/PO alloy or another alloy containing the constituents in different proportions, or another compatibility-establishing alloy, or even a PA that is identical to, or of the same chemical nature as, the one employed for producing the PA/PO alloy. The opaque layer will be preferably of a white color. The brilliance and colour depth of the decoration thus provided by sublimation will now be reinforced. Such multi-layer films or sheets are readily co-extruded, and do not require the use of a co-extrusion binder in order to ensure adhesion between the outer alloy layer and the inner, colored, alloy layer.
Care should be taken that the layer that is in contact with the binder is reactive vis-a-vis the latter.
In a further embodiment of the invention the laminate is characterized in that the alloy layer consists of at least two layers at least one of which is formed from the above stated alloy, and is in contact with the binder and contains a coloured additive. The coloured additive can also be an opacifier. Multi-layer structures are thus obtained, one o~ the layers being a PA/PO alloy, and the other layers) being either alloys, or other compatible materials in the sense that they adhere together without the use of a binder. It is also possible to employ non compatible materials and to bond them together using a layer of binder.
In accordance with the embodiment described above, the translucid layer has a thickness comprised between about 0.1 and about 1 mm, the thickness of the opaque layer being comprised between about 0.3 and about 2 mm. This layer can be decorated by sublimation through the translucid layer. The decoration is protected by the thickness of the transparent layer and is enhanced by the opaque layer. The latter may moreover have a masking effect as regards the substrate forming the support. The sublimation operation can be implemented at any time onto the laminate, the film or the shaped part.
Thus, in one embodiment of the invention, the layers of alloy, which can be the same or different, have thicknesses comprised between 0.1 and 1 mm, preferably between 0.15 and 0.8 mm. In this embodiment, the thickness of the binder layer is comprised between 0.1 and 1 mm, preferably between 0.15 and 0.5 mm.
Alternatively, and still with the aim of improving the quality of the decorative effect and the protection thereof, it is advantageous to provide a laminate in which the layer of binder is an opaque layer or is a coloured layer. This opaque or colored layer is preferably white in color; this color is obtained using conventional pigments, such as titanium dioxide. The brilliance and depth of color of the decorative effect thus obtained by sublimation will be reinforced, the decorative effect provided the thickness of the polyamide layer being enhanced by the opaque layer. In this embodiment there is a single layer of' alloy. Such laminates are obtained in a conventional manner, and do not pose any supplementary 10 problems.
Thus according to a further embodiment of the invention, the laminate is characterized in that the layer of binder contains a coloring additive. The expression "coloring additive" also covers opacifiers.
In this embodiment, the thickness of the alloy layer is comprised between 0.1 and 1 mm, preferably between 0.15 and 0.8 mm; the thickness of the binder layer is comprised between 0.1 and 1 mm, preferably between 0.15 and 0.5 mm.
20 According to one alternative embodiment, the laminate according to the invention has a final thickness comprised between 0.2 and 2 mm, preferably comprised between 0.4 and 1.3 mm.
Moreover, it is possible to associate reinforcing layers, such as layers or webs based on metal, resin, and notably epoxy resin or polyester with the products of the invention. Depending on the technique employed, cross-linking of the resin can be caused to occur when adhesion is provoked. This is particularly advantageous when textile mats impregnated with non-cross-linked resin are employed and where cross-linking is caused to occur during molding.
The present invention applies to all products in which there is an association of a PA/PO alloy and a polar or non-polar substrate. Apart from the substrates already mentioned above, the provision of mufti-layer films or shaped parts as:>ociating PA/PO alloys with polyolefins such as the polyethyl.enes and polypropylenes can be mentioned.
From among the many fields of application of the mufti-layer films obtained, the following can be specially mentioned:
- the automobile field with, for example, the provision of internal vehicle fittings such as all or part of the dashboard, arm rests, door trims, etc., and the provision of external bodywork parts for vehicles including, for example wings, doors, wheel trims, bumpers or overriders, etc.;
- the domestic appliance field such as the tops of washing machines, scales for weighing persons, etc.;
- the sanitary field through the provision of toilet covers, ~~ispensers, shelves and towel racks, - the electrical and electronic fields, typical examples being the provision of front panels for control boxes, manual controls, display panels, etc.~
- the: furnishing field, examples being doors of cupboards, windows, kitchen fittings, wall coverings, advertising panels;
- the sports field in which the product can particularly be used for decoration or protection of funboards, the decks of boats, water skis or windsurfing equipment.
The shaped parts can be used in many fields of application of which the following can be mentioned:
- the footwear field for the manufacture of reinforcing parts or parts added over the basic shoe or sole, etc.;
- the automobile field for the manufacture of items of varying sizes, such as for example model nameplates, control buttons, parts of bumpers, etc.;
- the domestic appliance field for the manu-facture of control buttons, decorative or superstructural elements, etc.;
- the furnishing field, for example, for decorative or handling elements, etc.
The present invention also relates to films obtained using the laminate as described above, as well as substrates coated with such a laminate. In particular, the present invention envisages the use of such a laminate for decoration, using the sublimation technique.
In accordance with the sublimation decoration technique, the decoration phase may, depending on the case, be carried out before the laminate is fixed onto the substrate or after it is fixed thereon; in the latter case, the substrate generally has a simple shape.
The present invention will be now described in more detail in -the following examples.
EXAMPLE I
In a flat co-extrusion machine provided with two extruder A and B, a Kaufman-type extension box, with a "clothes-peg"-type extrusion die (width 1 m) with a throttle bar and adjustable lips, a dual-layer sheet of a PA/PP alloy (Grgalloy 86000) and a binder layer (Orevac 18302) was manufactured. The Orgalloy 86000 marketed by Elf Atochem had the :Following typical characteristics:
~ Melt Flow Index (235°C, 2.16 kg) ...............6 to 12 .1.03-1.04 ~ density.....................................
~ Charpy notch impact test (ISO Standard 179)....................15-27 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50o HR (:CSO Standard 178) ...........1400-1700 MPa ~ equilibrium moisture content 50s RH, 23°C..........................................1.2-1.50 ~ melting point (ISO 81218)........................220°C
OREVAC 18302 marketed by Elf Atochem is a malefic anhydride-grafted low density polyethylene-type co-extrusion binder having the following typical characteristics:
~ density (ISO 1183)...............................Ø91 ~ Melt Flow Index (ASTM D1238)........Ø89 g/10 minutes ~ melting point: (ISO 81218)........................117°C
~ Shore A hardness (ISO 8868).........................48 ~ tensile modu7_us (ISO 8527)......................44 MPa Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter........................90 mm ~ length/diameter ratio.....................28/1 extrusion temperature..........230/240/250/255 - extruder B - malefic anhydride grafted polyethylene-based binder (OREVAC 18302) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........210/220/230/250 The die gap was set to 3 mm, calender roller spacing was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller..............................20°C
~ middle roller.............................60°C
~ lower roller..............................40°C
A dual-layer sheet, 1 mm thick, comprising 0.8 mm of ORGALLOY 86000 and 0.2 mm of OREVAC 18302 was obtained, (with a draw speed of 1 m/minute). Using hot pressing between temperatures of 130°C and 150°C for 3 to 5 minutes, an assembly ozrer a glass fiber reinforced epoxy or polyester structure was obtained. It was checked that adhesion between layers was good using a T peeling test carried out on :>amples 50 mm wide and 250 mm long. A cutter blade was used to commence peeling. A value of 11.7 N/mm, being the average value for five tests, was obtained.
Values better than 24 N/mm were obtained if the ORGALLOY
86000 in this example was replaced by ORGALLOY RS60ES
marketed by Elf Atochem, the characteristics, provided by way of indication, of which are as follows:
~ Melt Flow Index (235°C, 2.16 kg) .......from 1.0 to 2.0 ~ density......................................1.03-1.04 ~ Charpy notch impact test (ISO Standard 179)....................20-30 kJoules/m2 ~ equilibrium :Flexural modulus at 23°C-50% HR I:ISO Standard 178) ...........1400-1700 MPa ~ equilibrium moisture content 50% RH, 23°C..........................................1.2-1.5%
~ melting point (ISO 81218)........................220°C
EXAMPLE II
Using the machine described in example I, a three-layer structure consisting of a layer of PA/PP alloy (ORGALLOY RS6000) , a layer of polyamide 6 colored white by incorporation of titanium oxide (RESNO TL white) and a layer of OREVAC 18302 binder.
10 RESNO TL, a polyamide 6-based resin, marketed by Elf Atochem has the following typical characteristics:
~ density (ISO 81183}..........:...............1.13-1.14 ~ Charpy notch impact test (ISO Standard 179)......................6-9 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50o HR (ISO Standard 178) ...........1100-1300 MPa ~ equilibrium moisture content 50o RH, 23°C..........................................2.3-2.80 In this example, a white product was obtained by 20 mixing 98 parts of PA6 and 2 parts by weight of a polystyrene master batch containing titanium oxide in a kneader.
Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter........................90 mm ~ length/diameter ratio.....................28/1 ~ extrusion temperature..........230/240/250/255 - extruder B - white colored heat and light stabilized polyamide 6(RESNO TL white) ~ extruder diameter ........................45 mm ~ length/diameter ratio .....................24/1 ~ extru~;ion temperature ..........230/240/250/255 - extruder C - malefic anhydride grafted polyethylene-based binder (OREVAC 18302) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........210/220/230/250 The die gap was set to 3 mm, calender roller spacing was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller ..............................20°C
~ middle roller .............................60°C
~ lower roller ..............................40°C
A dual-layer sheet, 1.2 mm thick, comprising 0.3 mm of ORGAhLOY RS6000, 0.7 mm of RESNO TL white and 0.2 mm of OREVAC 18302 was obtained, (with a draw speed of 1 m/minute). Using hot pressing between temperatures of 130°C and 150°C for 3 to 5 minutes, an assembly over a glass fiber reinforced epoxy or polyester structure was obtained.
It was checked that adhesion between layer was good using a T peeling test carried out on samples 50 mm wide and 250 mm long. A cutter blade was used to commence peeling. A value of 10 N/mm was obtained, this being the mean value for five tests.
EXAMPLE III
Using the machine described in Example 1, a three-layer structure was extruded, composed of:
- a 7_ayer of a PA/PP alloy (ORGALLOY RS6000), - a layer of binder type OREVAC 9314 (marketed by Elf Atochem, the said binder being a maleic-grafted copolymer of ethylene and vinyl acetate), and - a layer of polyethylene (1020 FN 24).
ORGALLOY RS6000 marketed by Elf Atochem has the following typical characteristics:
~ Melt Flow Index (235°C, 2.16 kg) ................4 to 9 ~ density......................................1.04-1.05 ~ Charpy notch impact test (ISO Standard. 179)....................15-27 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50~ HR (ISO Standard 178) ...........1300-1600 MPa ~ equilibrium moisture content 50~ RH, 23°C..........................................1.2-1.5~
~ melting point: (ISO 81218)........................220°C
The low density polyethylene known as LACQTENE
1020 FN 24 marketed by Elf Atochem has the following typical propert-es:
~ Melt Flow Index (190°C, 2.16 kg) ..............1.5 to 4 ~ density..................................Ø91 to 0.93 ~ elongation to rupture (ISO Standard 8527).............................> 400%
~ tensile modu:Lus (ISO Standard 8527......................200 to 400 MPa ~ Vicat point (ISO 8306).....................90 to 100°C
Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter........................90 mm 27a ~ length/diameter ratio.....................28/1 ~ extrusion temperature..........230/240/250/255 - extruder B - malefic anhydride grafted polyethylene-based binder (OREVAC 9314) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........200/210/220/240 - extruder C - polyethylene (1020 FN 24) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........165/170/190/190 The die gap was set to 3 mm, and the spacing of the calendering rollers was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller..............................20°C
~ middle roller.............................60°C
~ lower roller..............................40°C
A three-layer sheet 1.2 mm thick, comprising 0.3 mm of ORGAL7~OY RS6000, 0.2 mm of OREVAC 9314 and 0.7 mm of polyethylene 1020 FN 24 was obtained using a draw rate of 1/minute. A peeling test (see example II) was used to check adhesion between the layers was good, and was better than 12 N/mm.
EXAMPLE IV
Using the machine described in Example I, a three-layer structure was extruded, composed of:
- a layer of a PA/PP alloy (ORGALLOY RS6000), 27b - a layer of this same alloy modified by incorporating therein 10% by weight of an ethylene and propylene malefic-modified copoly-mer (EPRm). The composition obtained was colored white by addition of titanium oxide (ORGALLOY R60E10, white) and, - a layer of OREVAC 18302 binder.
ORGALLOY RS60E10 marketed by Elf Atochem has the following typical characteristics:
~ density (ISO 81183)..........................1.00-1.05 ~ Charpy notch impact test (ISO Standard 179)....................25-35 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50% HR (ISO Standard 178) ...........1200-1300 MPa ~ equilibrium moisture content 50% RH, 23°C.........................................1 to 1.4%
In this example, a white product was obtained by mixing 98 parts of ORGALLOY R60E10 and 2 parts by weight of a polystyrene master batch containing titanium oxide in a kneader.
Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter ........................90 mm ~ length/diameter ratio .....................28/1 ~ extrusion temperature ......... 230/240/250/255 - extruder B - PA/PP alloy colored white (ORGALLOY
R60E10 white) extruder diameter ........................45 mm ~ lengt.h/diameter ratio .....................24/1 ~ extrusion temperature ..........230/240/250/255 27c - extrude:r C - malefic anhydride grafted polyethylene-based binder (OREVAC 18302) ~ extructer diameter ........................45 mm ~ length/diameter ratio ...............-.....24/1 ~ extrusion temperature ..........210/220/230/250 The die gap wa~~ set to 3 mm, and the calendering roller spacing was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller ................ .............20°C
~ middle roller .......................... ..60°C
~ lower roller ..............................40°C
A three-layer sheet 1.2 mm thick, comprising 0.3 mm of ORGALLOY RS6000, 0.7 mm of ORGALLOY R60E10 and 0.2 mm of OREVA.C 18302 was obtained (using a draw rate of 1/minute). Using hot pressing between temperatures of 130°C
and 150°C for 3 to 5 minutes, an assembly over a glass fiber reinforced epoxy or polyester structure was obtained.
It was checked that adhesion between layers was good using a T peeling test carried out on samples 50 mm wide and 250 mm long. A cutter blade was used to commence peeling.
A value of 11 N/mm was obtained, this being the average for five tests.
EXAMPLE V
On the machine described in Example I, a two-layer structure was extruded, comprising:
- a layer_ of a PA/PE alloy (ORGALLOY LE6000), and - a layer of OREVAC 18302 binder.
27d ORGALLOY LE6000 marketed by Atochem has, by way of indication, the following characteristics:
~ density (ISO P,1183) ..........................1.00-1.05 ~ Charpy notch impact test (ISO Standard 179)....................50-60 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50% HR (:LSO Standard 178) ...........1000-1100 MPa ~ equilibrium moisture content 50% RH, 23°C..........................................1.2-1.5%
Extrusion conditions were as follows:
- extruder_ A - PA/PE alloy (ORGALLOY LE6000) ~ extruder diameter ........................90. mm ~ length/diameter ratio .....................28/1 ~ extrusion temperature ..........230/240/250/255 - extrude_r B - malefic anhydride grafted. polyethylene-based binder (OREVAC 18302) ~ extruder diameter ........................45 mm ~ length/diameter ratio .....................24/1 ~ extrusion temperature ..........210/220/230/250 The die gap was set to 3 mm, and the calendering roller spacing was 2.5 mm.
Calendering rol_~er temperatures were as follows:
~ upper roller ..............................20°C
~ middle roller .............................60°C
~ lower roller ..............................40°C
A dual-layer sheet 1.1 mm thick comprising 0.8 mm of ORGALLOY LE;6000, 0.3 mm OREVAC 18302 was obtained, (using the draw rate of 1 m/minute). An assembly over a glass fiber reinforced epoxy or polyester structure was 27e obtained using hot pressing between temperatures of 130°C
to 150°C for 3 t:o 5 minutes . It was checked that adhesion between the layers was good using a T peeling test carried out on samples 50 mm wide and 250 mm long. Cutting was initiated with a cutter blade. A value better than 11 N/mm (average for five tests) was obtained.
According to standard NF-T-76-112 (so called "climbing drum" method) it was checked that adhesion was better than 10 N/mm for the preceding examples.
Thus, there is a requirement for a material which overcomes the disadvantages of the prior art and fulfils the above-stated technical requirements.
The present invention provides a laminate for the reinforcement, protection and decoration of a substrate, comprising:
(i) at least one layer of a polyamide/polyolefin alloy containing an agent ensuring compatibility, (ii) at least one layer of a co-extrusion binder, the layer of coextrusion binder being in contact with said substrate.
PA6/polyolefin or PA66/polyolefin alloys, notably PA6/PP or PA66/PP absorb far less moisture than PA6 or PA66. No solvents are known for PA6/polyolefin alloys or PA66/polyolefin alloys and the resistance to hydrolysis of PA/polyolefin alloys is very significantly higher than that of the corresponding polyamide. The chemical resistance of a PA/polyolefin alloy is hence far superior to that of the polyamide present in its composition, and this applies regardless of the polyamide considered. Compared to the polyamides 11 and 12, the heat resistance of a PA6 or PA66 alloy, or yet again, of a copolyamide 6/66 alloy with polypropylene is appreciably higher. Because of this, PA/polyolefin alloys present a significant advantage, com-pared to existing technologies, as regards chemical inert-ness, heat resistance, as well as the unique combination of properties that these PA/polyolefin alloys provide when compared to the use of a polyamide alone, as well as through the high working temperatures that can be employed with these PA/polyolefin alloys.
Moreover, the PA/polyolefin alloys are painted using the techniques generally employed for painting the PA: brief exposure to heat from a flame or polyamide-type undercoating fo_= example, or tried and tested techniques for painting on polyolefins: exposure to the heat from a flame for example or plasma treatment.
The quality of decoration obtained by sublimation increases with the temperature at which this sublimation operation is carried out. The high melting point of PA6/polyolefin o r PA66/polyolefin alloys allows sublimation to be carried out at high temperatures. The decor obtained is hence of a higher quality compared to what is obtained starting from ABS or PA at low melting point temperatures, or yet again, w~.th polypropylene.
Nevertheless, the chemical inertness of the PA/polyolefin alloys mentioned above is such that bonding of these products is impossible using known assembly methods employing solvent-based adhesives.
Direci: bonding of PA/polyolefin alloys onto metals or wood substrate, or onto synthetic (thermosetting, for instance) surfaces by application of heat and pressure is more difficult, and in the majority of cases, impossible.
The present invention consequently provides a laminate or multi-layer sheet (with at least two layers) the surface layer of which comprises a polyamide/polyolefin polymer rendered compatible, and including an adhesive binder-based layer allowing said polymer alloy to be bonded onto various sL~.bstrates. The alloy consists of at least one polyamide and at least one polyolefin and includes an agent which establishes compatibility. These sheets or films can be easily shaped and sublimed and can be employed for reinforcing, protecting or decorating a range of substrates.
These laminated or mufti-layer structures have the particular characteristic of being able to be bonded onto various substrates, of being easily decorated and exhibiting an extremely useful combination of heat resistance, chemical resistance and a low tendency towards moisture absorption phenomena.
The present invention covers such laminates or mufti-layer structures, their manufacture and their various uses, notably as decorative and surface-protection elements.
According to one embodiment, the polyamide forms the matrix of said alloy. The polyolefin is, in this embodiment, dispersed in the polyamide phase forming the matrix.
The polyolefin in the alloy is preferably a polyolefin having a molecular weight comprised between 1 000 and 106 and is advantageously polypropylene PP.
The polyamide in the alloy is preferably an aliphatic polya:mide, or a mixture of such a polyamide, such as PA6, PA6,6, PA11, PA12, PA12,12); advantageously, the polyamide is PA6 or PA6,6.
The polyamide preferably represents 25 to 75% by weight, advantageously 30 to 70% by weight of the total weight of the alloy, preferably 50 to 70% by weight.
6a The polyamide/polyolefin polymer alloys need, in order to have good mechanical properties, to include at least one agent ensuring compatibility.
This agent ensuring compatibility is generally comprised of a ~>olyolefin or a copolyolefin grafted with an acid group or a derivative thereof, for example malefic anhydride, or a copolymer comprising, for example, an ethylene monomer or an alpha-olefin monomer or, preferably, a diolefin monomer, with a co-monomer selected from vinylic esters of saturated carboxylic acid, unsaturated mono- and di-carboxylic acids, esters, salts, thereof and anhydrides of saturated or unsaturated dicarboxylic acids.
The expression "polymer grafted with a monomer", should be taken to mean a polymer onto which the graft, in monomer form, i;> grafted.
The expression polyolefin or copolyolefin should be taken to notably mean polyethylene, poly alpha-olefins, polydiolefins, ethylene and propylene copolymers, as well as block copolymers based on styrene and notably those consisting of polystyrene sequences and polybutadiene sequences (SBS), polystyrene sequences and sequences of polyisoprene (SIS), polystyrene sequences and poly (ethylene-butylene) sequences (SEBS), containing 0.2 to 0.8o by weight of malefic anhydride and from 30 to 55% of styrene in the case of the SBS, from 15 to 25% in the case of the SIS and from 13 to 32%
in the case of the SEBS.
The above-mentioned copolymers can be polymerized in a random or sequenced manner, and have a linear or branched structure.
In one embodiment, said alloy contains a compatibility-establishing agent comprising a polyolefin (or modified polyolefin) which is grafted preferably with malefic anhydride. This polyolefin or modified polyolefin, can be grafted furthermore with an oligoamide or a polyamide able to react with the malefic anhydride function, for instance.
For example, the following composition can be cited, described in French patent application serial No. 91 03870, corresponding to CA-A-2 064 365 as suitable for the PA/
polyolefin alloy:
A. an alpha-olefin of molecular weight comprised between 1,000 and 1,000,000;
B. a malefic-or acrylic-grafted alpha-olefin of A;
C. a copolymer of grafted alpha-olefin consisting of an oligoamide or a polyamide of molecular weight comprised be-tween 500 and 40,000, and monoaminated, and of alpha-olefin grafted with a monomer able to react with the amine function of the oligoamide or the polyamide;
D. an aliphatic polyamide or a mixture of aliphatic polyamide;
For the purposes of the present invention, components A, B, C and D are preferably present in proportions by weight whereby:
30 < A + H + C < 65; where 1 < A < 64;
and B +C > 1; where 0< B < 64;
and 35 < D < 70;
and A + B + C + D = 100; where 0 < C < 64.
It is also possible to mix elastomer compositions with the PA/polyolefin alloy composition described above, which perform a known role in any polymer matrix, their purpose 8 2~0~0~4 being to reduce the flexural modules and to increase impact resistance. These elastomers can be present in amounts of'up to 50~ by weight, preferably from 5 to 25~ by weight based on the weight of the final composition. The following can be cited as typical example of elastomers:
- ethylene and propylene rubbers, malefic-grafted (EPRm), which are particularly preferred by the applicant containing 0.1 to 2~ by weight of malefic anhydride;
- ethylene, propylene, diene monomer copolymers, malefic-grafted (EPDMm);
-copolymers of ethylene, alkyl (meth)acrylate (such as methyl, ethyl, ~1-butyl acrylate) and optionally malefic anhydride having 2 to 40~ by weight of alkyl (meth)acrylate and from 0.01 to 8~ by weight of anhydride, based on the total copolymer weight.
Various constituents can be incorporated into the above compositions, such as fillers, pigments or colouring agents and various additives.
As example of fillers, glass fibexs or spheres can be men-tinned, and.carbon or aramide fibers, -talc, silica, calcium carbonate, kaolin, ceramics, metallic salts and oxides such as aluminum, manganese, ground ferrite, and titanium oxide powders, and pigments in flake form providing a metalized finished appearance.
Generally up to 50~ by weight of these fillers based on the PA/polyolefin alloy composition rendered compatible, can be added. Preferably the fillers represent up to 40 $ of the total weight. Examples of additives include UV light pro-tection agents, optical brighteners, mold release agents, 3U ant~.statia agents, and agents protecting against deterior-ation due to heat .
The compositions can be prepared in one step notably by compounding. The constituents, which are most frequently in granular of average diameter less than 5 mm are mixed in their molten state generally in a kneader at a temperature comprised between 230 and 300°C. The compositions obtained are most frequently in granular form having an average diameter less than 5 mm. It is also possible to prepare the alloys in several steps notably by dilution or mixing a pre-alloy in PA or a polyolefin, this mixing or dilution step being moreover able to be implemented at the actual extrusion stage when the proportion of the constituents are adhered to.
Certain additives (coloring agents, mold release agents, lubricants, etc.) can be incorporated by mixing them with the mixture in the molten state, or with the granules obtained in the dry state.
Below, the term PA/PO alloy will be used to designate, for the sake of simplicity, the PA/polyolefin alloys described above. PA/PO alloys corresponding to the above definition are manufactured by Elf Atochem. They are marketed under the ORGALLOY trademark and corresponds to PA/PP, PA/PE, and PA/modified polyolefin alloys.
The co-extrusion binder is designed to ensure the alloy adheres t:o the substrate, and forms, at the final stage, a laminate with this alloy onto the substrate. This co-extrusion binder is sometimes also referred to as a thermoplastic binder, a hot melt binding agent, etc.
In one embodiment, said co-extrusion binder is a modified polyolefin, or a copolymer of polyolefin modified by means of an unsaturated carboxylic acid derivatives (copolymerisation, terpolymerisation or grafting). These (co) polyolefins can be employed alone or in mixture with other polyolefi:ns.
In o..der to obtain such compositions, United States Patent 4,452,942 teaches the following procedure:
1) the grafting of an unsaturated carboxylic acid derivative (for example malefic anhydride) onto a polyolefin (for example a linear polyethylene or a polypropylene);
2) mixing the resulting grafted (co)polymers with another polyolefin comprising:
- an ethylene homopolymer; or - an ethylene/alpha-olefin copolymer; or - a copolymer of ethylene and unsaturated esters 10 or derivatives thereof; or - a mixture of these polyolefins, all combina-tions being pos:;ible.
It is also possible, in order to obtain a co-extrusion binder, to carry out direct grafting of a mixture of polyolefins. Another possibility consists in employing a copolymer or terpolymer as binder which includes an unsaturated carboxylic acid derivative originating from radical copolymerisation.
By wa:~ of modified polyolefins employed for the binder, compositions can be cited by way of example obtained by polymerisation of:
A. an ethylene, alpha-olefin or optionally a di-olefin monomer, B. at least one co-monomer selected from saturated carboxylic acid vinylic esters, unsaturated mono- and di-carboxylic acids and esters and salts, thereof, and saturated or unsaturated di-carboxylic acids anhydrides.
The olefin, in other words the olefinic monomer, represents at least 50s and, preferably at least 60°s of the total weight of the copolymer. The copolymers can be randomly polymerised or sequenced and may have a linear or branched structure, regarding the copolyolefins of the invention.
Examples of such grafting processes, or of binder compositions arE: provided in the following patents, this list not being exclusive: EP-210,307, EP-33,220, EP-266,994, FR-2,7.32,780, EP-171,777, USP-4,758,477, USP-4,762,890, USP-4,966,810, USP-4,452,942, USP-3,658,948.
From among the coextrusion binders commonly employed in numerous associations, binders having the following chemical compositions are preferred here:
- copolymers of ethylene copolymerized with butene, hexene, octene, optionally mixed with ethylene-propylene copolymers grafted with malefic anhydride, said ethylene/olefin copolymers containing from 35 to 80% by weight of ethylene, the degree of grafted malefic anhydride being comprised between 0.01 and 1% by weight, preferably between 0.05 and 0.5% based on the total copolymer weight;
- copolymers of ethylene and vinyl acetate (EVA), with or without malefic anhydride (the malefic anhydride can be grafted or terpolymerised), particularly containing from 2 to 40% by weight of vinyl acetate from 0.01 to 0.5% by weight of grafted malefic anhydride or from 0 to ~10% by weight of terpolymerised malefic anhydride, based on the total copolymer weight;
- copolymers of ethylene, of alkyl (meth)acrylate (such as methyl, ethyl, t-butyl acrylate) and of malefic anhydride cont<~ining from 2 to 40% by weight of alkyl (meth)acrylate and from 0.01 to 8% by weight of anhydride based on the total copolymer weight.
Binders corresponding to the definition above are manufactured b~,~ Elf Atochem. One such binder is a mixture of polyolefins modified by a carboxylic acid group, through malefic anhydride grafting. This binder is available commer-cially in the form of granules bearing the OREVAC 18302 or OREVAC PP-C trademark.
Below, binder is used to designate the co-extrusion binder_ and should be considered as covering the modified polyolefin compositions described above.
It is possible to incorporate the same additives and/or fillers as those specified above for the alloys into the binders and generally speaking, in the same proportions.
By vi:ctue of their ease of use, their excellent mechanical properties (notably cold impact resistance, abrasion resistance, scratch or tear resistance) their excellent chemical inertness (no known solvent), and of their dimensional stability between -40 and +150°C, their excellent ageing behavior as well as their excellent suitability for bonding and decoration (heat resistance, creep resistance), the compositions according to the invention can be employed in a large variety of forms (molded or exti:uded parts, extruded films and sheets) for the protection, decoration or strengthening of composite objects notably the protection and/decoration of flat supports or complex shapes or molded parts. They can also be insert-molded over parts, bonded onto additional parts, thermo-formed over complex parts, and heat seal laminated with films or sheets.
The present invention also covers the provision of sheets or films and molded or extruded objects obtained from the alloy and binder comprising the final laminate according to the present invention. Thus, the present invention also covers the various methods for coating a substrate using the alloy and binder.
The films or sheets can be obtained using known extrusion techn_Lques, such as flat extrusion-calendering, heat seal laminating and extrusion, blow extrusion, etc.
The temperatures at which the PA/PO alloys are employed are generally from 20 to 60°C higher than the melting point of the PA used in the alloy. The temperatures the binders are used at are generally 20 to 60°C above the melting point of the binder employed for producing the laminate, when the laminate does indeed have a melting point.
In accordance with "Modern Plastics Encyclo-paedia", the expression "films" should be reserved for flat objects less than 250 um thick, and the expression "sheet"
should be reserved for thicker objects which can be up to several mm thick. In the present description, and for reasons of commodity and simplicity, both terms are used alternatively to designate either of the products.
Depending on the technology employed, films or sheets can be obtained haring thickness comprised between 10 um and 5 mm, or even higher.
Using coextrusion of a PA/PO alloy or of several layer of PA/PO alloy, or of several layers of material that are compatible with each other and in which the lower layer is compatible with the binder layer, and of a layer or several layers of binder, a laminate or double- or multiple-layer structure is obtained directly.
This laminate, in film or sheet form can be directly bonded onto the various substrates envisaged in the framework of the present invention.
In one embodiment of the invention, the method for coating a substrate in order to reinforce, protect and decorate it is characterized in that the PA/polyolefin alloy and the binder are co-extruded in order to prepare a film which is applied onto the substrate onto which it is caused to adhere.
It is also possible to manufacture the laminate by extruding the components in advance in film form and then assembling these films by heat seal laminating them: a sheet of binder manufactured in advance, notably by flat extrusion or blow extrusion is deposited on a previously-manufactured sheet of PA/PO alloy, the two sheets being pressed together under application of heat. Heat seal lamination of a film of binder immediately following manufacture by extrusion of a PA/PO alloy film gives good results, if hot calendering is carried out at the exit from the extruder.
According to one embodiment of the invention, the process for coating the substrate in order to reinforce, protect, and decorate it is characterized in that two films are prepared, one of PA/polyolefin alloy and the other of binder, these films then being heat seal laminated and the product thus obtained is applied onto the substrate, onto which adhesion :is caused to occur.
The films of binder and the single- or multi-layer film of the PA/PO alloy or alloys can also be placed one onto the other followed by application of pressure and heat (170°C for 2 to 3 min) at the time of use, in order to obtain the bonding between the different layers.
In one embodiment, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that two films are prepared, one of PA/polyolefin alloy and the other of binder, and these two films are applied to the substrate and adhesion thereto is brought about.
In one embodiment, the adhesion is brought about by hot pressing, heat seal laminating, or insert molding.
The temperature should be sufficient to achieve this and is advantageously higher than 130°C.
The films thus obtained can be bonded onto rigid 10 elements, notably metallic parts (such as cables, sheet, etc.), onto items in wood, onto bound aggregates, or onto items in synthetic materials, such as polyesters, epoxy resins, ABS copolymers, polystyrene and others, (with a phenolic binder, for example). These films are bonded onto the various substrates mentioned in this specification using the various preferred techniques indicated above, or using techniques known per se.
The present invention also envisages other embodiments of articles. Molded or extruded parts, which are in a shape other than that of the film or sheet, for example in the form of pre-shaped items can be obtained using preferred techniques and, failing this, using conventional techniques. Such items are referred to herein by the term "shaped parts".
The molded or extruded parts can be obtained by common injection molding or co-extrusion (using simul-taneous injection of alloy and binder) in order to obtain a composite item in a single operation, the binder layer being on that side on which the bonding onto the particular substrate is required to occur.
In accordance with one embodiment of the invention, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that a PA/polyolefin alloy and binder film is shaped and this shaped film is applied onto the substrate and adhesion thereto is caused to occur.
It is also possible to operate in two steps, by injection molding the alloy and then molding the binder thereover, or vice versa.
In one embodiment of the invention, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that a PA/polyolefin alloy film is shaped and the binder layer is insert-molded there-over, or vice versa, and the shaped part thus obtained is applied onto the substrate and adhesion thereto is caused to occur.
A PA/F?0 alloy part can also be obtained by mono-injection molding or mono-extrusion, a sheet or film of binder being inserted between the alloy and the substrate constituting its support. The hot bonding operation required to ensure the binder adheres to the substrate then enables simultaneous bonding of the binder onto the substrate and the PA/PO alloy sheet to be obtained. The part described above can also be a mufti-material composite part obtained by associating, using co-injection molding or co-extrusion, PA/PO alloys with PAs, PEs or, yet again modified polyo.lefins, and in general any thermoplastic polymer known for its adhesion properties onto polyolefin or polyamides.
In accordance with one embodiment of the present invention, the process for coating a substrate in order to reinforce, protect and decorate it is characterized in that a PA/polyolefin alloy film is shaped, and a film of binder is prepared, and the said film of binder is inserted between the thus shaped alloy part and the substrate, and adhesion is caused to occur.
The single- or multi-material injection-molded or extruded part can also be placed on a substrate consti-tuting its support which has been previously covered with a layer of binder, followed by a heat seal laminating, co-injection molding or insert-molding operation, in order to cause adhesion.
In one embodiment of the invention, the process for coating a substrate in order to reinforce, protect and decorate it is ~~haracterized in that a PA/polyolefin alloy film is shaped, the substrate is coated with a layer of binder, and the thus-shaped alloy part is applied onto the substrate coated with the layer of binder, and adhesion thereto is caused to occur.
In another embodiment, adhesion is caused to occur by a combination of heat and pressure, by heat seal lamination, or by insert molding. An adequate temperature should be emp_Loyed~ advantageously the temperature is higher than 130"C.
It is also possible to form the laminate using any suitable process, and to then insert it into a,mold and to injection-mo:Ld a filler which constitutes the substrate.
Generally speaking, the laminates are fixed onto the substrate by insert-molding or thermo-forming with simultaneous adhesion, or using thermo-forming followed by adhesion.
The materials of the present invention can be decorated using sublimable ink transfer printing techniques, and notably the methods described in French Patent 2,387,793. Decoration of these materials can also be implemented using other techniques such as screen printing, painting or varnishing, hot transfer, padding, ink jet printing, laser engraving, it being understood that all these decoration. techniques can be applied to all the films covered by the present invention, and all the articles in all their shapes or forms that derive therefrom.
In order even further improve the quality of decoration and protection thereof, it is also possible to provide a dual layer on the outside, consisting of a transparent or translucid layer of a PA/PO alloy (exempt of, or only containing a small amount of, coloring additive) in association with an opaque layer consisting of a PA/PO alloy or another alloy containing the constituents in different proportions, or another compatibility-establishing alloy, or even a PA that is identical to, or of the same chemical nature as, the one employed for producing the PA/PO alloy. The opaque layer will be preferably of a white color. The brilliance and colour depth of the decoration thus provided by sublimation will now be reinforced. Such multi-layer films or sheets are readily co-extruded, and do not require the use of a co-extrusion binder in order to ensure adhesion between the outer alloy layer and the inner, colored, alloy layer.
Care should be taken that the layer that is in contact with the binder is reactive vis-a-vis the latter.
In a further embodiment of the invention the laminate is characterized in that the alloy layer consists of at least two layers at least one of which is formed from the above stated alloy, and is in contact with the binder and contains a coloured additive. The coloured additive can also be an opacifier. Multi-layer structures are thus obtained, one o~ the layers being a PA/PO alloy, and the other layers) being either alloys, or other compatible materials in the sense that they adhere together without the use of a binder. It is also possible to employ non compatible materials and to bond them together using a layer of binder.
In accordance with the embodiment described above, the translucid layer has a thickness comprised between about 0.1 and about 1 mm, the thickness of the opaque layer being comprised between about 0.3 and about 2 mm. This layer can be decorated by sublimation through the translucid layer. The decoration is protected by the thickness of the transparent layer and is enhanced by the opaque layer. The latter may moreover have a masking effect as regards the substrate forming the support. The sublimation operation can be implemented at any time onto the laminate, the film or the shaped part.
Thus, in one embodiment of the invention, the layers of alloy, which can be the same or different, have thicknesses comprised between 0.1 and 1 mm, preferably between 0.15 and 0.8 mm. In this embodiment, the thickness of the binder layer is comprised between 0.1 and 1 mm, preferably between 0.15 and 0.5 mm.
Alternatively, and still with the aim of improving the quality of the decorative effect and the protection thereof, it is advantageous to provide a laminate in which the layer of binder is an opaque layer or is a coloured layer. This opaque or colored layer is preferably white in color; this color is obtained using conventional pigments, such as titanium dioxide. The brilliance and depth of color of the decorative effect thus obtained by sublimation will be reinforced, the decorative effect provided the thickness of the polyamide layer being enhanced by the opaque layer. In this embodiment there is a single layer of' alloy. Such laminates are obtained in a conventional manner, and do not pose any supplementary 10 problems.
Thus according to a further embodiment of the invention, the laminate is characterized in that the layer of binder contains a coloring additive. The expression "coloring additive" also covers opacifiers.
In this embodiment, the thickness of the alloy layer is comprised between 0.1 and 1 mm, preferably between 0.15 and 0.8 mm; the thickness of the binder layer is comprised between 0.1 and 1 mm, preferably between 0.15 and 0.5 mm.
20 According to one alternative embodiment, the laminate according to the invention has a final thickness comprised between 0.2 and 2 mm, preferably comprised between 0.4 and 1.3 mm.
Moreover, it is possible to associate reinforcing layers, such as layers or webs based on metal, resin, and notably epoxy resin or polyester with the products of the invention. Depending on the technique employed, cross-linking of the resin can be caused to occur when adhesion is provoked. This is particularly advantageous when textile mats impregnated with non-cross-linked resin are employed and where cross-linking is caused to occur during molding.
The present invention applies to all products in which there is an association of a PA/PO alloy and a polar or non-polar substrate. Apart from the substrates already mentioned above, the provision of mufti-layer films or shaped parts as:>ociating PA/PO alloys with polyolefins such as the polyethyl.enes and polypropylenes can be mentioned.
From among the many fields of application of the mufti-layer films obtained, the following can be specially mentioned:
- the automobile field with, for example, the provision of internal vehicle fittings such as all or part of the dashboard, arm rests, door trims, etc., and the provision of external bodywork parts for vehicles including, for example wings, doors, wheel trims, bumpers or overriders, etc.;
- the domestic appliance field such as the tops of washing machines, scales for weighing persons, etc.;
- the sanitary field through the provision of toilet covers, ~~ispensers, shelves and towel racks, - the electrical and electronic fields, typical examples being the provision of front panels for control boxes, manual controls, display panels, etc.~
- the: furnishing field, examples being doors of cupboards, windows, kitchen fittings, wall coverings, advertising panels;
- the sports field in which the product can particularly be used for decoration or protection of funboards, the decks of boats, water skis or windsurfing equipment.
The shaped parts can be used in many fields of application of which the following can be mentioned:
- the footwear field for the manufacture of reinforcing parts or parts added over the basic shoe or sole, etc.;
- the automobile field for the manufacture of items of varying sizes, such as for example model nameplates, control buttons, parts of bumpers, etc.;
- the domestic appliance field for the manu-facture of control buttons, decorative or superstructural elements, etc.;
- the furnishing field, for example, for decorative or handling elements, etc.
The present invention also relates to films obtained using the laminate as described above, as well as substrates coated with such a laminate. In particular, the present invention envisages the use of such a laminate for decoration, using the sublimation technique.
In accordance with the sublimation decoration technique, the decoration phase may, depending on the case, be carried out before the laminate is fixed onto the substrate or after it is fixed thereon; in the latter case, the substrate generally has a simple shape.
The present invention will be now described in more detail in -the following examples.
EXAMPLE I
In a flat co-extrusion machine provided with two extruder A and B, a Kaufman-type extension box, with a "clothes-peg"-type extrusion die (width 1 m) with a throttle bar and adjustable lips, a dual-layer sheet of a PA/PP alloy (Grgalloy 86000) and a binder layer (Orevac 18302) was manufactured. The Orgalloy 86000 marketed by Elf Atochem had the :Following typical characteristics:
~ Melt Flow Index (235°C, 2.16 kg) ...............6 to 12 .1.03-1.04 ~ density.....................................
~ Charpy notch impact test (ISO Standard 179)....................15-27 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50o HR (:CSO Standard 178) ...........1400-1700 MPa ~ equilibrium moisture content 50s RH, 23°C..........................................1.2-1.50 ~ melting point (ISO 81218)........................220°C
OREVAC 18302 marketed by Elf Atochem is a malefic anhydride-grafted low density polyethylene-type co-extrusion binder having the following typical characteristics:
~ density (ISO 1183)...............................Ø91 ~ Melt Flow Index (ASTM D1238)........Ø89 g/10 minutes ~ melting point: (ISO 81218)........................117°C
~ Shore A hardness (ISO 8868).........................48 ~ tensile modu7_us (ISO 8527)......................44 MPa Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter........................90 mm ~ length/diameter ratio.....................28/1 extrusion temperature..........230/240/250/255 - extruder B - malefic anhydride grafted polyethylene-based binder (OREVAC 18302) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........210/220/230/250 The die gap was set to 3 mm, calender roller spacing was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller..............................20°C
~ middle roller.............................60°C
~ lower roller..............................40°C
A dual-layer sheet, 1 mm thick, comprising 0.8 mm of ORGALLOY 86000 and 0.2 mm of OREVAC 18302 was obtained, (with a draw speed of 1 m/minute). Using hot pressing between temperatures of 130°C and 150°C for 3 to 5 minutes, an assembly ozrer a glass fiber reinforced epoxy or polyester structure was obtained. It was checked that adhesion between layers was good using a T peeling test carried out on :>amples 50 mm wide and 250 mm long. A cutter blade was used to commence peeling. A value of 11.7 N/mm, being the average value for five tests, was obtained.
Values better than 24 N/mm were obtained if the ORGALLOY
86000 in this example was replaced by ORGALLOY RS60ES
marketed by Elf Atochem, the characteristics, provided by way of indication, of which are as follows:
~ Melt Flow Index (235°C, 2.16 kg) .......from 1.0 to 2.0 ~ density......................................1.03-1.04 ~ Charpy notch impact test (ISO Standard 179)....................20-30 kJoules/m2 ~ equilibrium :Flexural modulus at 23°C-50% HR I:ISO Standard 178) ...........1400-1700 MPa ~ equilibrium moisture content 50% RH, 23°C..........................................1.2-1.5%
~ melting point (ISO 81218)........................220°C
EXAMPLE II
Using the machine described in example I, a three-layer structure consisting of a layer of PA/PP alloy (ORGALLOY RS6000) , a layer of polyamide 6 colored white by incorporation of titanium oxide (RESNO TL white) and a layer of OREVAC 18302 binder.
10 RESNO TL, a polyamide 6-based resin, marketed by Elf Atochem has the following typical characteristics:
~ density (ISO 81183}..........:...............1.13-1.14 ~ Charpy notch impact test (ISO Standard 179)......................6-9 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50o HR (ISO Standard 178) ...........1100-1300 MPa ~ equilibrium moisture content 50o RH, 23°C..........................................2.3-2.80 In this example, a white product was obtained by 20 mixing 98 parts of PA6 and 2 parts by weight of a polystyrene master batch containing titanium oxide in a kneader.
Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter........................90 mm ~ length/diameter ratio.....................28/1 ~ extrusion temperature..........230/240/250/255 - extruder B - white colored heat and light stabilized polyamide 6(RESNO TL white) ~ extruder diameter ........................45 mm ~ length/diameter ratio .....................24/1 ~ extru~;ion temperature ..........230/240/250/255 - extruder C - malefic anhydride grafted polyethylene-based binder (OREVAC 18302) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........210/220/230/250 The die gap was set to 3 mm, calender roller spacing was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller ..............................20°C
~ middle roller .............................60°C
~ lower roller ..............................40°C
A dual-layer sheet, 1.2 mm thick, comprising 0.3 mm of ORGAhLOY RS6000, 0.7 mm of RESNO TL white and 0.2 mm of OREVAC 18302 was obtained, (with a draw speed of 1 m/minute). Using hot pressing between temperatures of 130°C and 150°C for 3 to 5 minutes, an assembly over a glass fiber reinforced epoxy or polyester structure was obtained.
It was checked that adhesion between layer was good using a T peeling test carried out on samples 50 mm wide and 250 mm long. A cutter blade was used to commence peeling. A value of 10 N/mm was obtained, this being the mean value for five tests.
EXAMPLE III
Using the machine described in Example 1, a three-layer structure was extruded, composed of:
- a 7_ayer of a PA/PP alloy (ORGALLOY RS6000), - a layer of binder type OREVAC 9314 (marketed by Elf Atochem, the said binder being a maleic-grafted copolymer of ethylene and vinyl acetate), and - a layer of polyethylene (1020 FN 24).
ORGALLOY RS6000 marketed by Elf Atochem has the following typical characteristics:
~ Melt Flow Index (235°C, 2.16 kg) ................4 to 9 ~ density......................................1.04-1.05 ~ Charpy notch impact test (ISO Standard. 179)....................15-27 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50~ HR (ISO Standard 178) ...........1300-1600 MPa ~ equilibrium moisture content 50~ RH, 23°C..........................................1.2-1.5~
~ melting point: (ISO 81218)........................220°C
The low density polyethylene known as LACQTENE
1020 FN 24 marketed by Elf Atochem has the following typical propert-es:
~ Melt Flow Index (190°C, 2.16 kg) ..............1.5 to 4 ~ density..................................Ø91 to 0.93 ~ elongation to rupture (ISO Standard 8527).............................> 400%
~ tensile modu:Lus (ISO Standard 8527......................200 to 400 MPa ~ Vicat point (ISO 8306).....................90 to 100°C
Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter........................90 mm 27a ~ length/diameter ratio.....................28/1 ~ extrusion temperature..........230/240/250/255 - extruder B - malefic anhydride grafted polyethylene-based binder (OREVAC 9314) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........200/210/220/240 - extruder C - polyethylene (1020 FN 24) ~ extruder diameter........................45 mm ~ length/diameter ratio.....................24/1 ~ extrusion temperature..........165/170/190/190 The die gap was set to 3 mm, and the spacing of the calendering rollers was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller..............................20°C
~ middle roller.............................60°C
~ lower roller..............................40°C
A three-layer sheet 1.2 mm thick, comprising 0.3 mm of ORGAL7~OY RS6000, 0.2 mm of OREVAC 9314 and 0.7 mm of polyethylene 1020 FN 24 was obtained using a draw rate of 1/minute. A peeling test (see example II) was used to check adhesion between the layers was good, and was better than 12 N/mm.
EXAMPLE IV
Using the machine described in Example I, a three-layer structure was extruded, composed of:
- a layer of a PA/PP alloy (ORGALLOY RS6000), 27b - a layer of this same alloy modified by incorporating therein 10% by weight of an ethylene and propylene malefic-modified copoly-mer (EPRm). The composition obtained was colored white by addition of titanium oxide (ORGALLOY R60E10, white) and, - a layer of OREVAC 18302 binder.
ORGALLOY RS60E10 marketed by Elf Atochem has the following typical characteristics:
~ density (ISO 81183)..........................1.00-1.05 ~ Charpy notch impact test (ISO Standard 179)....................25-35 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50% HR (ISO Standard 178) ...........1200-1300 MPa ~ equilibrium moisture content 50% RH, 23°C.........................................1 to 1.4%
In this example, a white product was obtained by mixing 98 parts of ORGALLOY R60E10 and 2 parts by weight of a polystyrene master batch containing titanium oxide in a kneader.
Extrusion conditions were as follows:
- extruder A - PA/PP alloy (ORGALLOY 86000) ~ extruder diameter ........................90 mm ~ length/diameter ratio .....................28/1 ~ extrusion temperature ......... 230/240/250/255 - extruder B - PA/PP alloy colored white (ORGALLOY
R60E10 white) extruder diameter ........................45 mm ~ lengt.h/diameter ratio .....................24/1 ~ extrusion temperature ..........230/240/250/255 27c - extrude:r C - malefic anhydride grafted polyethylene-based binder (OREVAC 18302) ~ extructer diameter ........................45 mm ~ length/diameter ratio ...............-.....24/1 ~ extrusion temperature ..........210/220/230/250 The die gap wa~~ set to 3 mm, and the calendering roller spacing was 2.5 mm.
Calendering roller temperatures were as follows:
~ upper roller ................ .............20°C
~ middle roller .......................... ..60°C
~ lower roller ..............................40°C
A three-layer sheet 1.2 mm thick, comprising 0.3 mm of ORGALLOY RS6000, 0.7 mm of ORGALLOY R60E10 and 0.2 mm of OREVA.C 18302 was obtained (using a draw rate of 1/minute). Using hot pressing between temperatures of 130°C
and 150°C for 3 to 5 minutes, an assembly over a glass fiber reinforced epoxy or polyester structure was obtained.
It was checked that adhesion between layers was good using a T peeling test carried out on samples 50 mm wide and 250 mm long. A cutter blade was used to commence peeling.
A value of 11 N/mm was obtained, this being the average for five tests.
EXAMPLE V
On the machine described in Example I, a two-layer structure was extruded, comprising:
- a layer_ of a PA/PE alloy (ORGALLOY LE6000), and - a layer of OREVAC 18302 binder.
27d ORGALLOY LE6000 marketed by Atochem has, by way of indication, the following characteristics:
~ density (ISO P,1183) ..........................1.00-1.05 ~ Charpy notch impact test (ISO Standard 179)....................50-60 kJoules/m2 ~ equilibrium flexural modulus at 23°C-50% HR (:LSO Standard 178) ...........1000-1100 MPa ~ equilibrium moisture content 50% RH, 23°C..........................................1.2-1.5%
Extrusion conditions were as follows:
- extruder_ A - PA/PE alloy (ORGALLOY LE6000) ~ extruder diameter ........................90. mm ~ length/diameter ratio .....................28/1 ~ extrusion temperature ..........230/240/250/255 - extrude_r B - malefic anhydride grafted. polyethylene-based binder (OREVAC 18302) ~ extruder diameter ........................45 mm ~ length/diameter ratio .....................24/1 ~ extrusion temperature ..........210/220/230/250 The die gap was set to 3 mm, and the calendering roller spacing was 2.5 mm.
Calendering rol_~er temperatures were as follows:
~ upper roller ..............................20°C
~ middle roller .............................60°C
~ lower roller ..............................40°C
A dual-layer sheet 1.1 mm thick comprising 0.8 mm of ORGALLOY LE;6000, 0.3 mm OREVAC 18302 was obtained, (using the draw rate of 1 m/minute). An assembly over a glass fiber reinforced epoxy or polyester structure was 27e obtained using hot pressing between temperatures of 130°C
to 150°C for 3 t:o 5 minutes . It was checked that adhesion between the layers was good using a T peeling test carried out on samples 50 mm wide and 250 mm long. Cutting was initiated with a cutter blade. A value better than 11 N/mm (average for five tests) was obtained.
According to standard NF-T-76-112 (so called "climbing drum" method) it was checked that adhesion was better than 10 N/mm for the preceding examples.
Claims (16)
1.- A laminate for the reinforcement, protection and decoration of a substrate, comprising:
(i) at least one layer of a polyamide/polyolefin alloy containing an agent ensuring compatibility, (ii) at least one layer of a co-extrusion binder, the layer of coextrusion binder being in contact with said substrate.
(i) at least one layer of a polyamide/polyolefin alloy containing an agent ensuring compatibility, (ii) at least one layer of a co-extrusion binder, the layer of coextrusion binder being in contact with said substrate.
2.- The laminate according to claim 1, wherein the polyamide constitutes the matrix of said alloy.
3.- The laminate according to claim 1 or 2, wherein said polyolefin in said alloy is polypropylene PP.
4.- The laminate according to one of claims 1 to 3, wherein said polyamide in said alloy is PA6 or PA6,6.
5.- The laminate according to any one of claim 1 to 4, wherein said polyamide represents from 30 to 70% by weight of said alloy.
6.- The laminate according to any one of claim 1 to 5, wherein said agent ensuring compatibility comprises a (co)polyolefin on which a carboxylic acid function or a derivative of said function is grafted.
7.- The laminate according to any one of claims 1 to 6, wherein said alloy contains the following composition:
A. an alpha-olefin of molecular weight comprised between 1,000 and 1,000,000;
B. a maleic-or acrylic-grafted alpha-olefin of A;
C. a grafted copolymer of alpha-olefin consisting of a oligoamide or a polyamide of molecular weight comprised between 500 and 40,000 and monoaminated, and of alpha-olefin grafted with a monomer able to react with the amine function of the oligoamide or the polyamide;
D. an aliphatic polyamide or a mixture of aliphatic polyamide;
components A, B, C and D being present in proportions by weight whereby:
30 < A + B + C < 65; 1 < A < 64; B + C > 1; 0< B < 64;
35 < D < 70; 0 < C < 64.
A. an alpha-olefin of molecular weight comprised between 1,000 and 1,000,000;
B. a maleic-or acrylic-grafted alpha-olefin of A;
C. a grafted copolymer of alpha-olefin consisting of a oligoamide or a polyamide of molecular weight comprised between 500 and 40,000 and monoaminated, and of alpha-olefin grafted with a monomer able to react with the amine function of the oligoamide or the polyamide;
D. an aliphatic polyamide or a mixture of aliphatic polyamide;
components A, B, C and D being present in proportions by weight whereby:
30 < A + B + C < 65; 1 < A < 64; B + C > 1; 0< B < 64;
35 < D < 70; 0 < C < 64.
8.- The laminate according to any one of claims 1 to 7, wherein said coextrusion binder is a polyolefin modified by means of an unsaturated carboxylic acid derivative.
9.- The laminate according to any one of claims 1 to 8, wherein said coextrusion binder have the following composition obtained by polymerisation of:
A. an ethylene, alpha-olefin or di-olefin monomer, B. at least one co-monomer selected from saturated carboxylic acid vinylic esters, unsaturated mono- and di-carboxylic acids and esters, salts, thereof, and saturated or unsaturated di-carboxylic acids anhydrides.
A. an ethylene, alpha-olefin or di-olefin monomer, B. at least one co-monomer selected from saturated carboxylic acid vinylic esters, unsaturated mono- and di-carboxylic acids and esters, salts, thereof, and saturated or unsaturated di-carboxylic acids anhydrides.
10.- The laminate according to either one of claims 8 or 9, wherein, in said co-extrusion binder, the olefin-based monomer makes up at least 50% by weight of the total weight of binder.
11.- The laminate according to any one of claims 1 to 10, wherein the layer of binder contains a coloured additive.
12.- The laminate according to any one of claims 1 to 11, wherein the final thickness of said laminate is comprised between 0.2 and 2 mm.
13. The laminate according to claim 12, wherein the final thickness of said laminate is comprised between 0.4 and 1.3 mm.
14. A substrate coated with a laminate according to any one of claims 1 to 13.
15. The use of a laminate according to any one of claims 1 to 13, for decorative purposes using the sublimation technique.
16. A process for reinforcing, protecting and decorating a laminate according to claim 1 on a substrate, comprising insert-molding the laminate over the substrate, or thermoforming the laminate with simultaneous adhesion, or thermoforming the laminate followed by adhesion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9213040 | 1992-10-30 | ||
| FR9213040A FR2697465A1 (en) | 1992-10-30 | 1992-10-30 | Laminates based on polyamide / polyolefin alloys and coextrusion binders, objects obtained therefrom, coating methods therewith. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2102054A1 CA2102054A1 (en) | 1994-05-01 |
| CA2102054C true CA2102054C (en) | 2000-02-08 |
Family
ID=9435042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002102054A Expired - Fee Related CA2102054C (en) | 1992-10-30 | 1993-10-29 | Polyamide/polyolefin alloy-based laminates and objects obtained therefrom |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0595706B1 (en) |
| JP (1) | JP2604345B2 (en) |
| KR (1) | KR960005304B1 (en) |
| CN (1) | CN1057488C (en) |
| AT (1) | ATE157044T1 (en) |
| CA (1) | CA2102054C (en) |
| DE (1) | DE69313241T2 (en) |
| DK (1) | DK0595706T3 (en) |
| ES (1) | ES2106989T3 (en) |
| FI (1) | FI934817A (en) |
| FR (1) | FR2697465A1 (en) |
| NO (1) | NO933902L (en) |
| TW (1) | TW304179B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190218708A1 (en) * | 2016-09-28 | 2019-07-18 | Dow Global Technologies Llc | Coated Polyester Fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0766913B1 (en) * | 1995-10-05 | 2001-01-03 | Atofina | Method for treating soils by fumigation |
| FR2740385B1 (en) * | 1995-10-27 | 1998-01-16 | Indec | LAMINATE, IN PARTICULAR FOR DECORATING A SUBSTRATE, AND ARTICLE OBTAINED FROM A SUBSTRATE INCLUDING THE SAME, THEIR MANUFACTURING METHODS AND THE DECORATING METHOD USING THE SAME |
| AU7309096A (en) * | 1995-10-27 | 1997-05-15 | Elf Atochem S.A. | Mixture of polyolefin and polyamide alloy, and fabrication process |
| FR2740381A1 (en) * | 1995-10-27 | 1997-04-30 | Atochem Elf Sa | Polymer mixtures with polyolefin matrix and a dispersed phase of polyamide alloy |
| FR2740384B1 (en) * | 1995-10-27 | 1998-01-16 | Indec | SUBSTRATE DECORATING LAMINATES AND DECORATING METHOD USING THE SAME |
| FR2743746B1 (en) * | 1996-01-23 | 1998-04-03 | Atochem Elf Sa | NEW RELEASE FILM FOR SHEET MOLDING COMPOUNDING PRODUCT |
| EP0907508B1 (en) * | 1997-01-06 | 2004-08-25 | Atofina | Antistatic film for packaging materials diffusing volatile products |
| AU3438400A (en) * | 1999-03-31 | 2000-10-16 | Atofina | Polyamide and polypropylene mixtures and injected parts produced with said mixtures |
| GB9920010D0 (en) * | 1999-08-25 | 1999-10-27 | British Polythene Ltd | Improved films |
| FR2801532B1 (en) * | 1999-11-29 | 2002-07-26 | Nobel Plastiques | DECORATIVE PLASTIC SHEET AND MANUFACTURING METHOD THEREOF |
| FR2801530A1 (en) * | 1999-11-29 | 2001-06-01 | Nobel Plastiques | Decorative sheet material, used for e.g. for motor vehicle trim has decorative layer, comprises decorative layer, polymer connecting layer and transparent polymer protective layer |
| DE10124535B4 (en) * | 1999-12-01 | 2004-06-09 | Nordenia Deutschland Gronau Gmbh | Coextruded, flat medium that can be written on using the inkjet printing process |
| DE19957935B4 (en) * | 1999-12-01 | 2004-05-13 | Nordenia Deutschland Gronau Gmbh | Flat medium that can be written on using the inkjet printing process |
| FR2806348B1 (en) * | 2000-03-17 | 2002-11-15 | Rhodia Engineering Plastics Sa | ARTICLES COMPRISING A POLYOLEFIN-BASED ELEMENT ASSEMBLED TO A POLYAMIDE-BASED ELEMENT, AND METHOD FOR OBTAINING SAME |
| CN1250391C (en) * | 2000-08-25 | 2006-04-12 | 国际纸业公司 | Multilayer paperboard packaging structure including polyolefin/polyamide blend layer |
| JP5323294B2 (en) * | 2001-05-17 | 2013-10-23 | ホリスター・インコーポレイテッド | Stomatological pouch formed from chlorine-free multilayer thin film with a barrier layer of polyamide blend |
| US7335276B2 (en) * | 2002-10-01 | 2008-02-26 | E.I. Du Pont De Nemours And Company | Formation of aramid paper laminate |
| FI20022095A (en) * | 2002-11-25 | 2004-05-26 | Schauman Wood Oy | Coated wood-based board, process for its preparation and its use |
| JP2007069103A (en) * | 2005-09-06 | 2007-03-22 | Nagoya Oil Chem Co Ltd | Masking material |
| EP2162293B1 (en) * | 2007-06-29 | 2010-10-20 | Merck Patent GmbH | Microsphere comprising a polymer core, a shell and an absorber |
| WO2015046984A1 (en) * | 2013-09-30 | 2015-04-02 | 코오롱인더스트리 주식회사 | Film for laminating metal plate |
| CN103980699B (en) * | 2014-06-03 | 2016-01-20 | 山东瀚氏汽车零部件有限公司 | Automotive upholstery anti-aging high temperature resistant PA6/PP alloy and preparation method |
| SG11201907705VA (en) | 2017-03-16 | 2019-09-27 | Toyota Boshoku Kk | Thermoplastic resin sheet, laminated sheet, and molded object |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA988831A (en) * | 1971-10-11 | 1976-05-11 | Kenichi Hattori | Adhesive resins |
| US4395263A (en) * | 1977-04-21 | 1983-07-26 | Davis R Elbert | Unitary laminate with permanent indicia pattern: transfer printings onto plastic-coated rigid panels |
| US4397916A (en) * | 1980-02-29 | 1983-08-09 | Mitsui Petrochemical Industries, Ltd. | Laminated multilayer structure |
| JPS5787363A (en) * | 1980-11-19 | 1982-05-31 | Hida Seisakusho Kk | Decorative board |
| AU1415083A (en) * | 1982-05-21 | 1983-11-24 | Dow Chemical Company, The | Multilayer polyamide film |
| JPS60110740A (en) * | 1983-11-21 | 1985-06-17 | Mitsui Petrochem Ind Ltd | Propylene polymer composition |
| DE3634885A1 (en) * | 1986-10-14 | 1988-04-21 | Hoechst Ag | Composite element |
| JPS6462354A (en) * | 1987-09-01 | 1989-03-08 | Nissan Motor | Plastic molding material |
| GB8724240D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
| 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 |
| JPH0366735A (en) * | 1989-08-04 | 1991-03-22 | Tonen Chem Corp | Thermoplastic resin composition for laminated formed products |
| JPH03200867A (en) * | 1989-12-28 | 1991-09-02 | Showa Denko Kk | Polyamide-polyolefin resin composition |
| FR2664531A1 (en) * | 1990-07-11 | 1992-01-17 | Brun Pierre | Multi-material part and method for obtaining it |
| ES2090538T3 (en) * | 1991-03-29 | 1996-10-16 | Atochem Elf Sa | POLYAMIDE / POLYOLEFIN ALLOY REMOVAL FILM FOR THE MANUFACTURE OF A PRODUCT COMPOSED OF LEAF MOLDING, PRODUCT COMPOSED OF LEAF MOLDING PREPARED WITH THIS FILM. |
-
1992
- 1992-10-30 FR FR9213040A patent/FR2697465A1/en active Pending
-
1993
- 1993-10-26 AT AT93402619T patent/ATE157044T1/en not_active IP Right Cessation
- 1993-10-26 DK DK93402619.6T patent/DK0595706T3/en active
- 1993-10-26 EP EP93402619A patent/EP0595706B1/en not_active Expired - Lifetime
- 1993-10-26 DE DE69313241T patent/DE69313241T2/en not_active Expired - Fee Related
- 1993-10-26 ES ES93402619T patent/ES2106989T3/en not_active Expired - Lifetime
- 1993-10-28 NO NO933902A patent/NO933902L/en unknown
- 1993-10-29 FI FI934817A patent/FI934817A/en unknown
- 1993-10-29 CA CA002102054A patent/CA2102054C/en not_active Expired - Fee Related
- 1993-10-30 KR KR1019930022879A patent/KR960005304B1/en not_active IP Right Cessation
- 1993-10-30 CN CN93121071A patent/CN1057488C/en not_active Expired - Fee Related
- 1993-11-01 JP JP5296123A patent/JP2604345B2/en not_active Expired - Lifetime
- 1993-12-27 TW TW082111033A patent/TW304179B/zh active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190218708A1 (en) * | 2016-09-28 | 2019-07-18 | Dow Global Technologies Llc | Coated Polyester Fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2102054A1 (en) | 1994-05-01 |
| EP0595706B1 (en) | 1997-08-20 |
| DK0595706T3 (en) | 1997-12-01 |
| FI934817A0 (en) | 1993-10-29 |
| ATE157044T1 (en) | 1997-09-15 |
| DE69313241D1 (en) | 1997-09-25 |
| ES2106989T3 (en) | 1997-11-16 |
| KR960005304B1 (en) | 1996-04-23 |
| NO933902D0 (en) | 1993-10-28 |
| NO933902L (en) | 1994-05-02 |
| TW304179B (en) | 1997-05-01 |
| EP0595706A1 (en) | 1994-05-04 |
| KR940008878A (en) | 1994-05-16 |
| CN1088153A (en) | 1994-06-22 |
| CN1057488C (en) | 2000-10-18 |
| FR2697465A1 (en) | 1994-05-06 |
| DE69313241T2 (en) | 1998-02-05 |
| FI934817A (en) | 1994-05-01 |
| JP2604345B2 (en) | 1997-04-30 |
| JPH06278255A (en) | 1994-10-04 |
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