CA2047421A1 - Plastic laminate comprising aromatic polyether imide and aromatic polyether sulfone - Google Patents
Plastic laminate comprising aromatic polyether imide and aromatic polyether sulfoneInfo
- Publication number
- CA2047421A1 CA2047421A1 CA002047421A CA2047421A CA2047421A1 CA 2047421 A1 CA2047421 A1 CA 2047421A1 CA 002047421 A CA002047421 A CA 002047421A CA 2047421 A CA2047421 A CA 2047421A CA 2047421 A1 CA2047421 A1 CA 2047421A1
- Authority
- CA
- Canada
- Prior art keywords
- aromatic polyether
- core layer
- aromatic
- laminate
- imide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/408—Matt, dull surface
-
- 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
- B32B2309/02—Temperature
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
Coextruded polymer laminates, comprising a core layer made of an aromatic polyether imide or its mixture with at most 40 wt.% of a compatible thermoplastic polymer material and cover layers that are made of an aromatic polyether sulfone and connected so as to adhere to both sides of the core layer, are characterized by flame resistant properties and surprisingly high elongation at break values. They can be provided with a surface structure and be formed in the thermally softened state without lose of this structure.
RLC\saf
Coextruded polymer laminates, comprising a core layer made of an aromatic polyether imide or its mixture with at most 40 wt.% of a compatible thermoplastic polymer material and cover layers that are made of an aromatic polyether sulfone and connected so as to adhere to both sides of the core layer, are characterized by flame resistant properties and surprisingly high elongation at break values. They can be provided with a surface structure and be formed in the thermally softened state without lose of this structure.
RLC\saf
Description
~7 ~
TITLE OF THE INVENTION
PLASTIC LAMINATE COMPRISING AROMATIC
POLYETHER IMIDE AND AROMATIC POLYETHER SULFONE
BACKGROUND OF THE INVENTION
Field o~ the Invention:
The present invention relates to a new polymer laminate with flame retardant properties comprising an aromatic polyether imide and an aromatic polyether sulfone. The aforementioned plastics belong to a group of aromatic polymers that are called structural plastics or "engine~ring plastics".
They are characterized'by thermoformability, high heat resistance, good impact strength and high strength values, but differ in their fire behavior, e.g., in their flame retardant properties.
Discussion of the Backqround:
A preferred field of application of structural plastics lies in the extrusion of flat plastic webs with a uniform thickness ranging from about 1 to 5 mm. They may be molded in the thermally softened state into three dimensional molded parts, which are used, for example, as the inner lining of motor vehicles, ships or airplanes. For these applications a dulled surface is desired. Therefore, the webs are directed immediately following extrusion through an embossing calender, where a granular dull structure is produced with a dulling roller. This structure is to remain preserved during forming.
Aromatic polyether sulfones fulfill this requirement.
They can be formed under conditions under which the dull structure of the surface is not lost. Unfortunately the elongation at break of the aromatic polyether sulfones leave much to be desired for many applications.
An important condition for the application of structural plastics in airplane construction is the fulfillment of the fire requirements according to the OSU test (Ohio State University). It demands, starting August 1990, that a heat un,~ 14,1991 release rate release velocity of 65 kW min/m2 and a heat h~ F Of 65 kW/m2 within the first 2 minutes of fire stress are not exceeded; these measurement values are called HR and HRR.
The aromatic polyether sulfones in the pure form do not satisfy the requirements of the OSU fire test. To meet this standard, they must be mixed with flame resistant additives Ju~ 14,1991 ~mechanical and physical~
Qthat, as a rule have a negative impact on the~f~notie~a~
properties.
Aromatic polyether imides are flame retardant, without specific additives, as defined by the OSU fire test, but they are too brittle for many applications. Therefore, they are sometimes mixe~ with tougher, compatible polymers and thereby exhibit an improved impact strength, However, such mixtures have an unsatis~actory elongation at break. The OSU test is also fulfilled by some mix~ures of this kind. It has been further demonstrated that when thermoforming webs made of these plastics, the embossed granular sur~ace structure does ~Q~7~21 not remain preserved, but rather the surface is smooth and glossy, a feature that in undesired. The mandatory dull structure must, therefore, be produced in a subsequent operation by applying matt-finish paint.
Two different structural plastics are known from EP-A 195 229 and US-A 4 576 842, said plastics differ in their allowable working temperatures to process into three layered laminates by coextrusion. From these laminates heat resistant kitchen dishes are produced by thermoforming. In many cases it is preferred that the inner layer of the laminate has a higher allowable working temperature than the outer layer in other cases the reverse. The suitable structural plastics also include polyether sulfones and polyether imides that are used alternatively as the core layer material. Laminates that have in common both of these two plastics are not known.
The invention is based on the problem of providing an extruded plastic web made of structural plastic with flame resistant properties and good mechanical properties. Above all, a structural plastic with a high elongation at break and toughness, that is provided with a surface structure, and can be deformed in the softened state without loss of this structure is provided for.
SUMMARY OF THE INVENTION
Accordingly, one object of this invention is provided by a polymer laminate, characterized by a core layer made of an 2 ~ L '~ .~
aromatic po~yether imide or a mixture thereof with at most 40 wt.% of a compatible polymer material and cover layers that are connected so as to adhere to both sides of the core layer and which are made of an aromatic polyether sulfone.
The new laminates can be formed in the thermally softened state while maintaining their surface structure.
Surprisingly, high elongation at break values, whlch can exceed those of the individual plastics themselves are obtained. Pure commercial polyether imide (Ultem 1000, trademark of General Electric Co.) has in the form of extruded webs, a tensile strength ranging from llO to 117 MPa and an elongation at break ranging from 29 to 46%. When mixed with a poly-~imide-siloxane) block copolymer (Ultem 1668, trademark of General Electric Co.), the tensile strength drops to 92 to 102 MPa and the elongation at break to 19 to 39%. A tensile strength of 97 MPa and an elongation at break of 67% were measured on a coextruded laminate of the present invention that bears on both sides 0.2 mm thick cover layers made of aromatic polyether sulfone on a core layer made of the aforementioned mixture. When pure polyether imide is used as the core material, such layers have an even greater effect on the properties of the plastic web. Through coextrusion with 0.2 mm thick cover layers made of polyether sulfone the elongation at break ranging from 30 to 45 for the core material alone increases to the astonishingly high value of 90 to 105% for the coextrudate. Similarly, the Gardner impact strength of 1 J rises to over 18 joules.
The new laminates largely fulfill the OSU fire test. An HR value of 19 and an HRR value of 73 were found for PEI/PES
laminates of the invention. When polyether imide is mixed with a poly-(imide/siloxane) block copolymer, the HR/HRR
values are reduced to g - 19/29 - 37.
~ DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
June .1~19,9~ '~ s ~ /~ de, An essential component of the core layer i~ an aromatic June 14, l99l f~ ~ olyether imide. Aromatic polyether ~mides that are suitable ~for the invention are known from the U.S. patents 3,847,867, 3,838,097 and 4,107,147. They are synthesized from repeating units of the general formula I
~CO~ o ~CO' The degrees of polymerization n lies preferably in the range of 10 to 10,000 or optionally above. R denotes a bifunctional aromatic group, which is bonded via ether oxygen atoms in the met~ or para position to the phthalimide units. R can also comprise several aromatic cores bonded preferably in the p, p' position by a single bond or by heteroatoms such an -0-, -S-, or by -S02- groups or alkylene groups such as methylene or ~. , ~7~2~
2,2-propylene. The imide nitrogen atoms are linked by identical aromatic groups R' that can, however, be different ~rom R. The preparation of aromatic polyether imides is generally known. Especially preferred is a polymer comprising repeating units of formula II.
L-Nf ~O~CCH3 ~0~ CO~, -1 To improve the impact strength and other properties, the polyether imides can be mixed with other polymer material that can be coextruded with said polyether imides and have a higher strength. Such mixtures are manufactured by introducing the two plastics into an extruder and mixing intimately in the melt. The proportion of the mixing component is kept as small as possible, in order to retain the flame resistant properties of the polyether imide, but must be large enough to obtain the required improvement of the toughness properties. An impact strength ranging from 12 to 18 joules in the Gardner test (in accordance with ASTM D 3029 - 28n) is adequate. As a rule, additional quantities rangin~ from about 10 to 50 wt.%, based on the weight of the mixture, are used.
Suitable compatible thermoplastic polymer materials with higher strength are, e.g., aromatic polycarbonates and aromatic poly-(imide-siloxane) block copolymers. Among the ~7~
aromatic polycarbonates, the derivatives of the ~isphenol A
are especially preferred. Other polycarbonate plastics can be derived from other dihydroxyphenols, e.g., from bis-(4-hydroxyphenyl)-methane, 2,2-bis-(4~hydroxy-3-methylphenyl-)-propane, 4,4-bis-(4-hydroxyphenyl)-heptane.
Other polycarbonate plastics are known from US-A 2,999,835, 3,028,365 and 3,334,154.
Aromatic poly-(imide-siloxane) block copolymers are known from EP-A 273 150. They can be described by the formula III, [ ~CO~o-R-o~co~N R3-o'~R~;-o~);,;~ :11[
wherein n and m denots the degree of polymerization o* the participating polyether imide and polysiloxane blocks; they can have values ranging from 1 to 50. The variable a denotes the number of the two blocks and can have values ranging from 1 to 10,000. R and R' are biEunctional aromatic groups, which can have the same structure as in formula I. R" are aliphatic or aromatic groups such an methyl, phenyl, cyanoethyl or trifluoromethyl ethyl.
To form the cover layers, aromatic polyether sulfones having a melt viscosity suitable for extrusion are used. The MFI value (melt flow index) of the aromatic polyether sulfone is at 360C, e.g., at about 30 cm /lO min.
The aromatic polyether sulfones are synthesized from repeating units of the general structural formula - (Ar - SO2 - Ar ~ ) n ~
where Ar donates a bifunctional, mono sr polynuclear aromatic Ju 1 ~roup. ~referably the Ar groups comprise p-phenylene groups, ~ ~ w ~ch can bear optional substituents, like ~ewe~ line~r or June 14 ,1991 ~branched C1 l2 alkyl groups or cyclo C~ alkyl ~roups Polynuclear Ar groups contain, for example, two such phenylene groups, which can be coupled by a single bond or by an oxygen or sulfur atom or by S02-, methylene or isopropylidene groups.
The aromatic polyether sulfones can be optionally modified with flame resistant additives or similar auxiliary agents.
The new laminates are producad in a well-known manner through coextrusion of the core and cover layer naterial. The materials are melted in separated extruders and fed into a coextrusion adapter, whereby they are uni~ed into a three layered strand. Said strand is extruded at temperatures ranging from about 300 to 380C from a flat die in the shape o~ a flat web of uniform thickness. It can be, e.g., 500 to 2,500 mm wid~. The total thickness o~ the web can range from 1 to 5, preferably from 1 to 3 mm. 0.05 - O.5 mm, pre~erably O.2 to 0.5 mm o~ said thickness are allocated to the cover .
layers, respectively. If said cover layers are relatively thin, e.g., less than 0.2 mm thick, the improved strength values are not always obtained. With cover layers of greater thicknes~ there is the danger that the OSU fire test will not .
be fulfilled. Thus, the core material comprises about 60 to 80 wt.% of the new laminates; and the cover layer material comprises 20 to 40 wt.%. It must be mentioned that in many ca es with this construction a cost saving is achieved with respect to the web having uniform thickness and made of pure core material, since the polyether sulfones are as a rule less expensive than the modified polyether imides.
If a surface structure is desired, the extru~ion-hot multilayer web can be directed immediately following coextrusion through an embossing calendar, where the surface structure of the embossing roller is molded on the surface of the web and is stabilized ~elow the softening temperature through cooling. Preferably, a granular dull structure is produced with a dulling roller. As a rule it suffices if one of the cover layers is structured in this manner.
Molded par~s having three dimensional shapes such as elements for the inner lining of airplanes can be produced from the lamina~es of the invention in vacuum forming machines with positive tools. In so doing, the back side of the laminate abuts preferably the tool surface, whereas the structured front side is free. Forming at negative tools with structured surfaces is possible but less usable.
To form, the laminate is heated to 270 to 300C. To this end, a heating station comprising an upper and bottom heating J~ 14,1991 ~ t is suitable. The thermoplastically softened web,is-~dYe~
June~14~ 199 ~ ~ ~ cd in a clamping frame, grasping the edge, _ (/ is directed to a position above the forming tool, ~~; ~
J~
un~ 14 1991 its and placed against this surface by means of a vacuum. To ~c. ~ guarantee accurate detail forming, it can be expedient to heat the tool. Following cooling below the softening temperature, venting occurs and the molded part is removed.
Other features of the invention will become apparent in the course of the following description of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
Embodiment Undyed commercial polyether imide extrusion molding compound (trade name ~Ultem 1000", trademark of General Electric Co.) and pigmented polyether sulfone extrusion molding compound (trade name ~Ultrason E 3000, trademark of BASF AG) are melted in separate extruders and united into a three layer strand in a coextrusion adapter. Said strand is introduced into an extrusion flat die and extruded at 350C in the shape of a 2~5 mm thic~ web, which contains the polyether imide as core layer and a 0.3 mm thick cover layer made of polyether sulfones on each side of the core layer. The extruded web is taken over by an embossing calender, where it une~4,1991 smoothed is pe~ibd~ or dulled on one surface and is cooled below the softening temperature. The web is divided with a separating device into sheets of desired size.
~7~21 For comparison purposes a uniformly thick web made of polyether imide was extruded alone. The following mechanical properties were determined on the extrudates.
_ single layer laminate of comparison the invention material tensile strength (MPa) 110 110 modulus of elasticity (MPa) 3300 3300 elongation at break (%)29 - 46 90 - 105 Gardner impact strength (J) approx. 1 > 18 OSU fire test values HR ~kW min/m2) 9 - 22 12 - 19 HRR (kW/m2) 72 - 76 73 - 77 The laminate of the present example displays a significantly improved Gardner implact strength as compared with the single layer material.
Embodiment 2 A three layer laminate and a single layer comparison material are manufactured as in embodiment 1, but in place of polyether imide its mixture with a poly-(imide-siloxane)-block copolymer is added. This mixture is commercially available under the name "Ultem 1668" (trademark of General Electric Co . ) .
The following mechanical properties were determined on the extrudates.
~ ~1 L1 7 i~
_ _ _ single layer laminate of comparison the invention material tensile strength (MPa)90 - 100 97 modulus of elasticity (MPa) 3300 3300 elongation at break (%)19 - 39 67 Gardner impact strength ~J) > 18 > 18 OSU fire test values HR (kW min/m2) 0 - 30 9 - 19 HRR (kW/m2) 17 - 55 29 - 37 The lamina-te of the present example displays a significantly improved elongation at break strength.
Obviously, numerous modifications and variations of the present invention are possible in light of the abave teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
TITLE OF THE INVENTION
PLASTIC LAMINATE COMPRISING AROMATIC
POLYETHER IMIDE AND AROMATIC POLYETHER SULFONE
BACKGROUND OF THE INVENTION
Field o~ the Invention:
The present invention relates to a new polymer laminate with flame retardant properties comprising an aromatic polyether imide and an aromatic polyether sulfone. The aforementioned plastics belong to a group of aromatic polymers that are called structural plastics or "engine~ring plastics".
They are characterized'by thermoformability, high heat resistance, good impact strength and high strength values, but differ in their fire behavior, e.g., in their flame retardant properties.
Discussion of the Backqround:
A preferred field of application of structural plastics lies in the extrusion of flat plastic webs with a uniform thickness ranging from about 1 to 5 mm. They may be molded in the thermally softened state into three dimensional molded parts, which are used, for example, as the inner lining of motor vehicles, ships or airplanes. For these applications a dulled surface is desired. Therefore, the webs are directed immediately following extrusion through an embossing calender, where a granular dull structure is produced with a dulling roller. This structure is to remain preserved during forming.
Aromatic polyether sulfones fulfill this requirement.
They can be formed under conditions under which the dull structure of the surface is not lost. Unfortunately the elongation at break of the aromatic polyether sulfones leave much to be desired for many applications.
An important condition for the application of structural plastics in airplane construction is the fulfillment of the fire requirements according to the OSU test (Ohio State University). It demands, starting August 1990, that a heat un,~ 14,1991 release rate release velocity of 65 kW min/m2 and a heat h~ F Of 65 kW/m2 within the first 2 minutes of fire stress are not exceeded; these measurement values are called HR and HRR.
The aromatic polyether sulfones in the pure form do not satisfy the requirements of the OSU fire test. To meet this standard, they must be mixed with flame resistant additives Ju~ 14,1991 ~mechanical and physical~
Qthat, as a rule have a negative impact on the~f~notie~a~
properties.
Aromatic polyether imides are flame retardant, without specific additives, as defined by the OSU fire test, but they are too brittle for many applications. Therefore, they are sometimes mixe~ with tougher, compatible polymers and thereby exhibit an improved impact strength, However, such mixtures have an unsatis~actory elongation at break. The OSU test is also fulfilled by some mix~ures of this kind. It has been further demonstrated that when thermoforming webs made of these plastics, the embossed granular sur~ace structure does ~Q~7~21 not remain preserved, but rather the surface is smooth and glossy, a feature that in undesired. The mandatory dull structure must, therefore, be produced in a subsequent operation by applying matt-finish paint.
Two different structural plastics are known from EP-A 195 229 and US-A 4 576 842, said plastics differ in their allowable working temperatures to process into three layered laminates by coextrusion. From these laminates heat resistant kitchen dishes are produced by thermoforming. In many cases it is preferred that the inner layer of the laminate has a higher allowable working temperature than the outer layer in other cases the reverse. The suitable structural plastics also include polyether sulfones and polyether imides that are used alternatively as the core layer material. Laminates that have in common both of these two plastics are not known.
The invention is based on the problem of providing an extruded plastic web made of structural plastic with flame resistant properties and good mechanical properties. Above all, a structural plastic with a high elongation at break and toughness, that is provided with a surface structure, and can be deformed in the softened state without loss of this structure is provided for.
SUMMARY OF THE INVENTION
Accordingly, one object of this invention is provided by a polymer laminate, characterized by a core layer made of an 2 ~ L '~ .~
aromatic po~yether imide or a mixture thereof with at most 40 wt.% of a compatible polymer material and cover layers that are connected so as to adhere to both sides of the core layer and which are made of an aromatic polyether sulfone.
The new laminates can be formed in the thermally softened state while maintaining their surface structure.
Surprisingly, high elongation at break values, whlch can exceed those of the individual plastics themselves are obtained. Pure commercial polyether imide (Ultem 1000, trademark of General Electric Co.) has in the form of extruded webs, a tensile strength ranging from llO to 117 MPa and an elongation at break ranging from 29 to 46%. When mixed with a poly-~imide-siloxane) block copolymer (Ultem 1668, trademark of General Electric Co.), the tensile strength drops to 92 to 102 MPa and the elongation at break to 19 to 39%. A tensile strength of 97 MPa and an elongation at break of 67% were measured on a coextruded laminate of the present invention that bears on both sides 0.2 mm thick cover layers made of aromatic polyether sulfone on a core layer made of the aforementioned mixture. When pure polyether imide is used as the core material, such layers have an even greater effect on the properties of the plastic web. Through coextrusion with 0.2 mm thick cover layers made of polyether sulfone the elongation at break ranging from 30 to 45 for the core material alone increases to the astonishingly high value of 90 to 105% for the coextrudate. Similarly, the Gardner impact strength of 1 J rises to over 18 joules.
The new laminates largely fulfill the OSU fire test. An HR value of 19 and an HRR value of 73 were found for PEI/PES
laminates of the invention. When polyether imide is mixed with a poly-(imide/siloxane) block copolymer, the HR/HRR
values are reduced to g - 19/29 - 37.
~ DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
June .1~19,9~ '~ s ~ /~ de, An essential component of the core layer i~ an aromatic June 14, l99l f~ ~ olyether imide. Aromatic polyether ~mides that are suitable ~for the invention are known from the U.S. patents 3,847,867, 3,838,097 and 4,107,147. They are synthesized from repeating units of the general formula I
~CO~ o ~CO' The degrees of polymerization n lies preferably in the range of 10 to 10,000 or optionally above. R denotes a bifunctional aromatic group, which is bonded via ether oxygen atoms in the met~ or para position to the phthalimide units. R can also comprise several aromatic cores bonded preferably in the p, p' position by a single bond or by heteroatoms such an -0-, -S-, or by -S02- groups or alkylene groups such as methylene or ~. , ~7~2~
2,2-propylene. The imide nitrogen atoms are linked by identical aromatic groups R' that can, however, be different ~rom R. The preparation of aromatic polyether imides is generally known. Especially preferred is a polymer comprising repeating units of formula II.
L-Nf ~O~CCH3 ~0~ CO~, -1 To improve the impact strength and other properties, the polyether imides can be mixed with other polymer material that can be coextruded with said polyether imides and have a higher strength. Such mixtures are manufactured by introducing the two plastics into an extruder and mixing intimately in the melt. The proportion of the mixing component is kept as small as possible, in order to retain the flame resistant properties of the polyether imide, but must be large enough to obtain the required improvement of the toughness properties. An impact strength ranging from 12 to 18 joules in the Gardner test (in accordance with ASTM D 3029 - 28n) is adequate. As a rule, additional quantities rangin~ from about 10 to 50 wt.%, based on the weight of the mixture, are used.
Suitable compatible thermoplastic polymer materials with higher strength are, e.g., aromatic polycarbonates and aromatic poly-(imide-siloxane) block copolymers. Among the ~7~
aromatic polycarbonates, the derivatives of the ~isphenol A
are especially preferred. Other polycarbonate plastics can be derived from other dihydroxyphenols, e.g., from bis-(4-hydroxyphenyl)-methane, 2,2-bis-(4~hydroxy-3-methylphenyl-)-propane, 4,4-bis-(4-hydroxyphenyl)-heptane.
Other polycarbonate plastics are known from US-A 2,999,835, 3,028,365 and 3,334,154.
Aromatic poly-(imide-siloxane) block copolymers are known from EP-A 273 150. They can be described by the formula III, [ ~CO~o-R-o~co~N R3-o'~R~;-o~);,;~ :11[
wherein n and m denots the degree of polymerization o* the participating polyether imide and polysiloxane blocks; they can have values ranging from 1 to 50. The variable a denotes the number of the two blocks and can have values ranging from 1 to 10,000. R and R' are biEunctional aromatic groups, which can have the same structure as in formula I. R" are aliphatic or aromatic groups such an methyl, phenyl, cyanoethyl or trifluoromethyl ethyl.
To form the cover layers, aromatic polyether sulfones having a melt viscosity suitable for extrusion are used. The MFI value (melt flow index) of the aromatic polyether sulfone is at 360C, e.g., at about 30 cm /lO min.
The aromatic polyether sulfones are synthesized from repeating units of the general structural formula - (Ar - SO2 - Ar ~ ) n ~
where Ar donates a bifunctional, mono sr polynuclear aromatic Ju 1 ~roup. ~referably the Ar groups comprise p-phenylene groups, ~ ~ w ~ch can bear optional substituents, like ~ewe~ line~r or June 14 ,1991 ~branched C1 l2 alkyl groups or cyclo C~ alkyl ~roups Polynuclear Ar groups contain, for example, two such phenylene groups, which can be coupled by a single bond or by an oxygen or sulfur atom or by S02-, methylene or isopropylidene groups.
The aromatic polyether sulfones can be optionally modified with flame resistant additives or similar auxiliary agents.
The new laminates are producad in a well-known manner through coextrusion of the core and cover layer naterial. The materials are melted in separated extruders and fed into a coextrusion adapter, whereby they are uni~ed into a three layered strand. Said strand is extruded at temperatures ranging from about 300 to 380C from a flat die in the shape o~ a flat web of uniform thickness. It can be, e.g., 500 to 2,500 mm wid~. The total thickness o~ the web can range from 1 to 5, preferably from 1 to 3 mm. 0.05 - O.5 mm, pre~erably O.2 to 0.5 mm o~ said thickness are allocated to the cover .
layers, respectively. If said cover layers are relatively thin, e.g., less than 0.2 mm thick, the improved strength values are not always obtained. With cover layers of greater thicknes~ there is the danger that the OSU fire test will not .
be fulfilled. Thus, the core material comprises about 60 to 80 wt.% of the new laminates; and the cover layer material comprises 20 to 40 wt.%. It must be mentioned that in many ca es with this construction a cost saving is achieved with respect to the web having uniform thickness and made of pure core material, since the polyether sulfones are as a rule less expensive than the modified polyether imides.
If a surface structure is desired, the extru~ion-hot multilayer web can be directed immediately following coextrusion through an embossing calendar, where the surface structure of the embossing roller is molded on the surface of the web and is stabilized ~elow the softening temperature through cooling. Preferably, a granular dull structure is produced with a dulling roller. As a rule it suffices if one of the cover layers is structured in this manner.
Molded par~s having three dimensional shapes such as elements for the inner lining of airplanes can be produced from the lamina~es of the invention in vacuum forming machines with positive tools. In so doing, the back side of the laminate abuts preferably the tool surface, whereas the structured front side is free. Forming at negative tools with structured surfaces is possible but less usable.
To form, the laminate is heated to 270 to 300C. To this end, a heating station comprising an upper and bottom heating J~ 14,1991 ~ t is suitable. The thermoplastically softened web,is-~dYe~
June~14~ 199 ~ ~ ~ cd in a clamping frame, grasping the edge, _ (/ is directed to a position above the forming tool, ~~; ~
J~
un~ 14 1991 its and placed against this surface by means of a vacuum. To ~c. ~ guarantee accurate detail forming, it can be expedient to heat the tool. Following cooling below the softening temperature, venting occurs and the molded part is removed.
Other features of the invention will become apparent in the course of the following description of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
Embodiment Undyed commercial polyether imide extrusion molding compound (trade name ~Ultem 1000", trademark of General Electric Co.) and pigmented polyether sulfone extrusion molding compound (trade name ~Ultrason E 3000, trademark of BASF AG) are melted in separate extruders and united into a three layer strand in a coextrusion adapter. Said strand is introduced into an extrusion flat die and extruded at 350C in the shape of a 2~5 mm thic~ web, which contains the polyether imide as core layer and a 0.3 mm thick cover layer made of polyether sulfones on each side of the core layer. The extruded web is taken over by an embossing calender, where it une~4,1991 smoothed is pe~ibd~ or dulled on one surface and is cooled below the softening temperature. The web is divided with a separating device into sheets of desired size.
~7~21 For comparison purposes a uniformly thick web made of polyether imide was extruded alone. The following mechanical properties were determined on the extrudates.
_ single layer laminate of comparison the invention material tensile strength (MPa) 110 110 modulus of elasticity (MPa) 3300 3300 elongation at break (%)29 - 46 90 - 105 Gardner impact strength (J) approx. 1 > 18 OSU fire test values HR ~kW min/m2) 9 - 22 12 - 19 HRR (kW/m2) 72 - 76 73 - 77 The laminate of the present example displays a significantly improved Gardner implact strength as compared with the single layer material.
Embodiment 2 A three layer laminate and a single layer comparison material are manufactured as in embodiment 1, but in place of polyether imide its mixture with a poly-(imide-siloxane)-block copolymer is added. This mixture is commercially available under the name "Ultem 1668" (trademark of General Electric Co . ) .
The following mechanical properties were determined on the extrudates.
~ ~1 L1 7 i~
_ _ _ single layer laminate of comparison the invention material tensile strength (MPa)90 - 100 97 modulus of elasticity (MPa) 3300 3300 elongation at break (%)19 - 39 67 Gardner impact strength ~J) > 18 > 18 OSU fire test values HR (kW min/m2) 0 - 30 9 - 19 HRR (kW/m2) 17 - 55 29 - 37 The lamina-te of the present example displays a significantly improved elongation at break strength.
Obviously, numerous modifications and variations of the present invention are possible in light of the abave teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
Claims (9)
1. A polymer laminate, wherein a core layer made of an aromatic polyether imide or its mixture with at most 40 wt.%
of a compatible thermoplastic polymer material and cover layers that are made of an aromatic polyether sulfone and connected so as to adhere to both sides of the core layer.
of a compatible thermoplastic polymer material and cover layers that are made of an aromatic polyether sulfone and connected so as to adhere to both sides of the core layer.
2. The polymer laminate of claim 1, wherein as a compatible, thermoplastic polymer material the core layer contains an aromatic polycarbonate or an aromatic poly-(imide-siloxane) block copolymer.
3. The polymer laminate of claim 1 or 2, wherein said core layer has a uniform thickness ranging from 1 to 3 mm and said cover layers have uniform thicknesses ranging from 0.05 to 0.5 mm, preferably from 0.2 to 0.5 mm.
4. The polymer laminate of claim 1 or 2, wherein the surface at least one of the cover layers has a dulled structure.
5. The polymer laminate of claim 4, wherein said laminate has a three dimensional shape.
6. The polymer laminate of claim 1, wherein said core layer is made of an aromatic polyether and 10-40 wt.% of a compatible thermoplastic polymer material.
7. A process of manufacturing a polymer laminate, as claimed in claim 1, comprising:
a) melting a material for said core layer and a material for said cover layers; and b) uniting said core layer and said cover layer into a three layered strand c) coextruding said strand to form a laminate.
a) melting a material for said core layer and a material for said cover layers; and b) uniting said core layer and said cover layer into a three layered strand c) coextruding said strand to form a laminate.
8. The process of claim 7, further comprising, directing said three layered strand through an embossing calender.
9. The process of claim 7 or 8, further comprising forming said three layered strand into a three dimensional shape at a temperature ranging from 270 to 300°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE9010873U DE9010873U1 (en) | 1990-07-21 | 1990-07-21 | |
| DEG9010873.6 | 1990-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2047421A1 true CA2047421A1 (en) | 1992-01-22 |
Family
ID=6855824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002047421A Abandoned CA2047421A1 (en) | 1990-07-21 | 1991-07-19 | Plastic laminate comprising aromatic polyether imide and aromatic polyether sulfone |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0468276A1 (en) |
| JP (1) | JPH04226753A (en) |
| KR (1) | KR920002327A (en) |
| BR (1) | BR9102683A (en) |
| CA (1) | CA2047421A1 (en) |
| DE (1) | DE9010873U1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439208A (en) * | 2016-08-02 | 2019-03-08 | 南通凯英薄膜技术有限公司 | A kind of high toughness polyimide material and its application |
| KR102194517B1 (en) * | 2019-05-17 | 2020-12-24 | (주)진양이피에스 | Multi-layer film comprising polycarbonate and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3843478A (en) * | 1972-04-28 | 1974-10-22 | Crown Zellerbach Corp | Matte finish film |
| EP0232441A3 (en) * | 1986-02-07 | 1987-12-02 | Amoco Corporation | Cookware formed from a laminate |
| US4609592A (en) * | 1985-04-12 | 1986-09-02 | General Electric Company | Multilayered structure |
-
1990
- 1990-07-21 DE DE9010873U patent/DE9010873U1/de not_active Expired - Lifetime
-
1991
- 1991-06-26 BR BR919102683A patent/BR9102683A/en not_active Application Discontinuation
- 1991-07-10 EP EP91111465A patent/EP0468276A1/en not_active Ceased
- 1991-07-17 JP JP3176481A patent/JPH04226753A/en active Pending
- 1991-07-19 KR KR1019910012297A patent/KR920002327A/en not_active Application Discontinuation
- 1991-07-19 CA CA002047421A patent/CA2047421A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| BR9102683A (en) | 1992-02-11 |
| JPH04226753A (en) | 1992-08-17 |
| DE9010873U1 (en) | 1991-11-21 |
| KR920002327A (en) | 1992-02-28 |
| EP0468276A1 (en) | 1992-01-29 |
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