JPH06505210A - Improved flexible flame-retardant multilayer structure containing poly(vinyl chloride) and polyamide layers and method for producing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Improved flexible flame retardant multilayer structure containing poly(vinyl chloride) and polyamide layers Background of the invention and its manufacturing method 1. Field of invention The present invention provides a first structure comprising poly(vinyl chloride) and a poly(vinyl chloride) that exhibits sufficient flame retardancy. The present invention relates to an improved structure including a second structure containing an amide and a method for producing the same.

The improved structure provides electrical insulation structures for current conductors, i.e. wires and cables. It is particularly useful as a structure.

2. Description of prior art technology Multilayer structures typically include at least two or more layers characterized by different physical properties. Contains further layers of material whose properties are optimized to meet the specific requirements at hand It is best to The purpose of shaping such structures is to providing a structure in which the individual layers of the structure are made of composite material. The material in each layer acts to form, and the material in each layer gives the functionality to design the structure. Contribute to Examples of such structures are well known in the art and include forming thin films. including composite materials used to form thin films, where each layer forming a thin film is certain properties, such as impermeability to gases or certain wavelengths of light or radiation It can be characterized as a barrier against sexual energy. A struct like this Another example is that used to form insulating structures for electrical conductors. where each layer forming an envelope around the conductor has an improved It is thought that the characteristics include wear resistance and improved voltage resistance. Structure like this Other uses for the body are well known and known in the art.

The use of such multilayer structures is widespread with electrical conductors. these The conductor is typically a wire conductor (often containing copper) surrounded by a multilayer structure. It is made of metal. Examples of such structures include U.S. Pat. ．． Specification No. 940; Specification No. 3.860.686; Specification No. 4. 079. 1 Specification No. 91; Specification No. 4.292.463; Specification No. 4,327.248 Specifications - Specification No. 4,419.538; Specification No. 4,472.597; Specification No. 4,510.348; No. 4,626.619; and No. 4,626.619; There is one shown in the specification of No. 4°691.082. In them, each layer Various structures can be made of reamers, metals, elastomeric materials, fiber materials etc. are disclosed in which each layer has specific advantages, namely voltage resistance, water impermeability. Gives hypersensitivity, etc.

A preferred material that can be used in the construction of electrical conductors is poly(vinyl chloride) (hereinafter interchangeably referred to as rPVcJ) and polyamide (hereinafter interchangeably referred to as rPVcJ) rPAJ). These materials are suitable for PVC, which is generally a sufficiently flexible insulator. PA is preferred because it forms the body and at the same time generally exhibits sufficient abrasion resistance. Poly( Electrical conductor with a multilayer structure of an inner layer of vinyl chloride (vinyl chloride) and an outer layer of polyamide Examples include Japanese Patent No. 59146105 and British Patent No. 1257810. This is shown in the specification and in Dutch Patent No. 6,917,475.

Multilayer structures containing layers of PvC and PA when used as electrical conductors are well suited for However, such structures exhibit certain undesirable properties. also brings. One such property is the flame retardancy of such multilayer structures.

Forming an electrically insulating layer applied to a current conductor, e.g. a wire or wires When using such materials for construction, the requirement of adequate flame retardancy is of paramount importance. knowledge Commercial, residential or other structures (i.e. office buildings) Electrical cables present in residential buildings, public buildings and installations) are contained within the jacket layer. Contains a large number of individual wires or other blenheims. Fire inside such a structure In the event of a disaster, such a fire hazard is caused by the fact that the insulation layer applied to the current conductor burns. or where the wire is exposed in contact with another current path by melting or melting. (will increase).Such a current path is or, in less desirable cases, structures or structures present with the human body. can be an element of a struct. Furthermore, the melting of the insulating layer of the current conductor can, in particular, Contact between wires if the insulation layer is located closest to another current conductor that has similarly collapsed posing a risk of ignition and the formation of short circuits; cause. Alternatively, if the surrounding material does not ignite, mold an insulating layer over the wire. There remains a risk of ignition, combustion or melting and consequential danger of materials used to There is. Such materials can often be lethal in sufficient concentrations. releases harmful emissions.

Various structures that provide sufficient flame retardancy are known in the art. for example, To increase the flame retardancy of polyamide compositions, various flame retardants have been added to them. known to contain; such materials include antimony oxide-related There are halogenated organic materials. Such additives provide sufficient flame retardancy for polyamides. These additives are often in relatively high concentrations and typically contain halogens. Up to 20% chemical organic material and up to 5% antimony oxide must be present. There is. Other materials known to provide sufficient flame retardant behavior to polyamides One additive is effective at concentrations as low as 20% by weight in the composition. It is known as red phosphorus. However, both of these additive systems have drawbacks. It is known to do. Both systems have a polyamide-containing composition that is their component It is known to reduce the bending and elongation properties of objects. Ultimate elongation is 100% Highly desirable are polyamide-containing compositions that are Where it is considered useful for forming parts of soft structures that are well suited for In this case, the use of additives of this type may further improve It is known to substantially reduce the ultimate elongation and other bending properties of objects. Change Red phosphorus is known to impart a dark color to polyamide compositions; is also often undesirable.

In the technical field, multilayer structures characterized by sufficient bending properties and sufficient flame retardancy are known. It is clear that there continues to be a need for structures and methods of manufacturing them. It should be easy. Such multilayer structures are particularly suitable for insulating structures for current conductors. It would be useful for molding.

subject The present invention shows sufficient flame retardant behavior, sufficient bending properties and multilayer structures for current conductors. The present invention provides multilayer structures that are particularly useful as bodies and in optical waveguides.

The present invention further provides for the production of multilayer structures exhibiting sufficient flame retardant behavior and sufficient bending properties. We provide an improved method for building

The multilayer structure of the invention comprises plasticized PvC and optionally additional additives. a first layer molded from a composition that can be made of polyamide and up to 20% by weight containing phosphonic esters with optionally additional ingredients as additives. "A part molded from a composition."

The present invention further provides an improved method for forming flexible flame retardant structures having two layers. .

In another embodiment of the invention, a flexible Provides an improved method for manufacturing insulating structures, which flexible insulating structures feature sufficient flame retardant properties. be a sign.

In yet another embodiment of the invention, an insulated current conductor is provided, wherein The insulating structure of the conductor comprises plasticized PvC, optionally with additional additives. a first layer molded from a composition that can include polyamide and up to 0 wt. % of phosphonic acid esters and optionally additional ingredients as additives. It becomes clear.

Brief description of the drawing FIG. 1 is an end perspective view of one embodiment of the invention in which the PvC and PA layers are generally A multilayer structure in planar form is shown.

FIG. 2 is an end perspective view of another embodiment of the invention, showing a multilayer structure according to the invention. A perspective view is shown.

FIG. 3 shows another embodiment of the present invention, which shows an electrical connection using the multilayer structure of the present invention. FIG. 3 illustrates an exploded perspective view of a conductor.

Figure 4 shows the industrial process for producing the multilayer structure of the invention by coextrusion technology. This is a schematic diagram of the

FIG. 5 shows an industrial process for manufacturing the multilayer structure of the present invention by tandem extrusion technology. This is another schematic diagram of the process.

According to the present invention, a multilayer film exhibiting sufficient flame retardant behavior and sufficient bending properties and for electrical applications can be obtained. A multilayer structure is provided that is particularly useful as a structure. The multilayer structure is made of plasticized PV C, and may optionally contain additional additives. with one layer of polyamide and up to 0% by weight of phosphonic ester; and a second layer formed from a composition containing additional ingredients as additives. Contains a layer of thermoplastic material.

As mentioned above, the first layer includes a composition comprising PVC, a plasticizer for PVC, and from additional conventional ingredients that may be desirable to include in the composition. Become.

The PvC that is formulated is moldable into the structures shown in this invention and the PvC is It was hoped that the PvC standard would allow for considerable flexibility in the PvC standard. It may be a brand name. PvC represents some desirable physical property, e.g. Amounts or weight ranges, temperature usage ratings, colorants can be indicated and technical field The amount of additives commonly used in Contain in amounts known not to be harmful to human health.

The additive blended into the PvC-containing composition forming the first layer is a plasticizer. concerned As known in the art, plasticizers reduce the viscosity of PVC during the manufacturing process. and thereby improve its processability. Plasticity that can be used The amount of agent is any amount that provides the desired processability for forming the structures of the present invention.

As a non-limiting example, in the manufacture of insulated wire, from about 10% by weight of plasticizer to 50% by weight is used in PVC, but higher and lower amounts are used. It's okay to stay. Examples of useful plasticizers include phthalate plasticizers, which are preferred. For example, di-2-ethylhexyl phthalate (DOP), diisodecyl phthalate ( DIDP), diundecyl phthalate (DUP) and ditridecyl phthalate (D One or more types from the group consisting of TDP). Similarly preferred is Limellitic acid ester plasticizers, especially trioctyl trimellitate (T.

TM) and triisooctyl trimellitate (TIOTM). these Preferred trimellitate and phthalate plasticizers are commercially available. available.

Optional additives to the PvC-containing composition forming said first layer of the multilayer structure. For one thing, the face can be mixed or otherwise incorporated into the PvC layer. or other coloring agents; such coloring agents may be Useful in separate and/or marking systems. Other additives are also included in the composition can be included inside. One of these types of additives is a multilayer structure such as It is an adhesion promoter to enhance the adhesion between body layers. Further ingredients, e.g. Lead stabilizers, tin stabilizers, inorganic fillers such as clay, calcium carbonate, talc , wollastonite or silica as well as those known and recognized in the art. Various commonly used lubricants and waxes may also be added to the composition according to the invention. It can be introduced as an agent. Further additives are useful for flame retardancy. There are things that are generally called "synergists." One disadvantage of such synergists is A limiting example is antimony oxide, but other compositions containing zinc borate and iron oxide as well and other compositions that behave as synergists are also included in the composition according to the subject matter of the present invention. be able to.

PVC, plasticizer, and what is used to create the composition of the first layer of the multilayer structure. Additional optional ingredients such as may allow the materials to be completely distributed among each other. They can be mixed in any way that can be used. recognized as suitable for use Methods of mixing include physical mixing, e.g. using a tampling container and There is physical mixing achieved by melt extrusion. Preferably, the components are melt extruded where measured amounts of PVC, plasticizer and any additional ingredients are physically added. After thorough mixing, use a -screw extruder, twin screw extruder or plastic into a ficator and heated to a temperature higher than the softening point of at least one component. and then continue extruding the ingredients through a die to form a strand, which is then pelletize. The PVC, plasticizer and other materials ultimately used to form the first layer The resulting pellets, including and any optional ingredients, are subjected to further extrusion operations according to the invention It can be used as feedstock for industry.

Polyamides suitable for use in connection with the present invention include those having repeating amide groups. The well-known polyester is a long chain polymeric structure having as part of the polymer backbone. There is an amide. Preferably, the polyamide is 9.2% by weight in 90% formic acid. It has a relative viscosity of about 40 to about 250, measured at a concentration of .

Non-limiting examples of such polyamides include: (a) Polymerization of a lactam, preferably epsilon-caprolactam (nylon 6 ) Manufactured by; (b) condensation with dibasic acids such as diamines, preferably hexamethylene diamines; Condensation with dipic acid (nylon 6, 6); hexamethylene diamine and sebacin Condensation with acid (nylon 6, 10); tetramethylenediamine and adipic acid condensation (nylon 4.6) and condensation of hexamethylene diamine with azelaic acid. (C) self-condensation of amino acids, preferred Preferably, self-condensation of 11-aminoundecanoic acid (nylon 11) and 12- produced by self-condensation of aminododecanoic acid (nylon 12); and (d) Polymerized vegetable oil or two or more of these polyamides or random, block or graft copolymers consisting of polyamide blends. It is used as a base.

Preferred polyamides include polyepsilon caprolactam (nylon 6), polyhexane xamethylene adipamide (nylon 6.6) and polyepsilon caprolacta is a copolymer (nylon 6.6/6) of aluminum and polyhexamethylene adipamide. . The most preferred polyamide is polyepsilon caprolactam.

Amorphous polyamides, such as di- and meta- or para-xylene diamines ,4. 4'-methylene dianiline, 1,3- or 1,4-phenylene dianiline manufactured using amine or 2,4- or 2,6-diamittoluene is also useful.

The aforementioned polyamides with various terminal functional groups are also suitable for use in the present invention. ing. These include (a) a carbon bonded to one end of the polymer chain; a boxyl group and an acetamide group bonded to the other end, (b) polymer chain (C) an amino group bonded to both ends of the polymer chain; (C) a carboxyl group bonded to one end of the polymer chain; the xyl group and the amino group bonded to the other end and (d) both of the polymer chain. Contains polycaprolactam (nylon 6) with terminally attached carboxyl groups Preferred are polyamides. The most preferable among these are the above (c) and It is classified as a carboxyl group attached to one end of the polymer chain. and polycaprolactam which has an amino group attached to the other end.

According to the content of the invention, the second layer further comprises a phosphonic acid ester, where: The phosphonate ester is a polyamide-containing composition used to form the second layer. Contains up to 20% by weight of porcelain. A suitable phosphonate ester has a chemical structure. Construction (wherein the value of "X" may be 0 or 1) It is possible. Such materials are characterized by excellent thermal stability, low volatility and It can be easily processed. Preferably, the phosphonic ester according to the invention is As shown, the overwhelming majority of phosphonic esters have a value of "X" of 0, and the substituted A phosphonic acid ester having a small amount of phosphonic acid ester with a group rxJ value of "1" It is a formulation of Stell. These phosphonic acid esters are viscous, straw-colored liquids. Commercially available as a body, generally Alfright to Richmond, v. & Wilson Incorporated, Copyright 1998. . These phosphonic acid esters are manufactured by Mobil φ Oil Corporation (Mo U.S. Patent No. 3.789.091, assigned to Bi'l Oi I Corp. No. 3,849.368 and the description thereof. is incorporated herein by reference.

According to the content of the invention, the phosphonic ester is used to provide flame retardant properties to the polyamide-containing layer of the structure. used to form the second layer with the sole condition that improved properties are achieved. It can be present in any amount up to about 20% by weight of the composition. present invention In the use of compositions for forming structures characterized by the advantages of the content of The exact amount of phosphonate to be added is best determined by experimental methods and It should be clear to those skilled in the art that the number of optimizations can be optimized. Preferably, PA-containing The weight percentage of phosphonate ester in the composition comprises about 0.001% to 20%. within the range, more preferably within the range of about 0.01% to 20%, and Most preferably within the range of about 0.01% to 8.8%.

The polyamide layer may optionally be of the type commonly used in the art. Various amounts of additives may be included. Examples of such additives include pigments, dyes, additives, heat stabilizers, lubricants, plasticizers including caprolactam, UV absorbers and stabilizers. There is a drug.

Typical UV absorbers and light stabilizers include various substituted resorcinols. These include alcohol, salicylate, benzotriazole, and benzophenone.

Typical suitable lubricants and mold release agents include stearic acid and stearyl alcohol. stearamide, sodium stearate and zinc stearate.

Suitable colorants, including dyes and pigments, include, by way of example, cadmium sulfide, Cadmium renide, titanium dioxide, phthalocyanine, ultramarine blue, carbon black, etc. There is.

Typical oxidation and thermal stabilizers include metal halides from group I of the periodic table of elements. , for example, sodium halides, potassium halides, lithium halides; and cupric halides; and also chlorides, bromides, iodides. Change , hindered phenols, hydroquinones, aromatic amines and substitutions of the aforementioned groups. Members and their combinations.

In a manner similar to that discussed above in connection with PvC-containing compositions, the multilayer structure The PA, phosphonate ester and and additional optional ingredients to allow the materials to be completely distributed among each other. Mixing can be done in either method. Persons deemed suitable for use Methods include physical mixing, e.g. by use of tampling vessels and melting. There is physical mixing achieved by extrusion. Preferably, the components are melt extruded; Therein, a measured amount of PA, phosphonic ester and any additional ingredients. After physically mixing the at a temperature higher than the softening point of at least one component. and subsequently extrude the ingredients through a die to form a strand, then to pellet it. Consists of the composition that is ultimately used to form the The resulting pellets can be used as feedstock for further extrusion operations according to the invention. I can be there.

Both layers, i.e. the first layer containing plasticized PvC and the PA and phosphonate The second layer containing the stellates is in the form of a thin film or sheet obtained by a separate extrusion process. or can be coextruded. Similarly, PvC-containing layer and PA-containing layers have different morphologies, the morphologies can be divided separately or sequentially. or coextrusion. Depending on the specific intended use, typically PV The thickness of the C-containing layer is about 0.25 to about 2.30 mm (about 0.010 to about 0.090 mm) inch) and typically the thickness of the PA-containing layer is about 0.05 to about 0.40 mm (inch). from about 0.002 inches to about 0.016 inches). These thicknesses are for illustrative purposes only. It is understood that this should not be considered as limiting the applicability of the subject matter of the present invention. should be understood.

The multilayer structure according to the invention can be used in any application where a multilayer structure is required. Can be used. In general, multilayer structures are useful as insulation and protective envelopes. be. More specifically, the multilayer structure in tubular form can be used, in particular, as a current conductor, e.g. i.e. attached to metal or metal wire consisting of a single strand or multiple strands. It can be used to attach to optical fibers and/or to attach to optical fibers. In this specification, The term "attach" used in (in the case of electric wires) or the outer surface (in the case of electric wires that do not have a roughly circular cross section), or What should be construed as wrapping, coating or wrapping an optical waveguide You should understand. Assembly for forming the PA-containing layer of the multilayer structure presented herein The flame retardancy of plastic materials is determined by the Underwriters Association on Flammability of Plastic Materials. Latries (Underwriter’s Laboratories) UL -94 test protocols, the complete contents of which are herein incorporated by reference. Copyright 1973, 1988 and March 1990. Publication “Safety Standards - Combustion of Plastic Materials for Parts of Equipment and Appliances” revised on the 19th. Baking test (Standard for 5afty-Tests forFla mmability of plastic materials for pa rts in Devices and Appliances) J 7-10 "Materials 94-V-0, 94-V-1, 94-■-2" fully described on page Vertical Burning Test for classification or Classifying Materials 94-V-0,94-V -1,94-V-2) JT: Shitakatte evaluation. Summarize Ruto, UL- The 94 Vertical Burn Test is used to evaluate the performance of bar specimens when in contact with flame.

The sample bar of each specimen is first conditioned in a circulating air oven and then the sample bar to be evaluated is Place one end of each of the five bars of each sample so that they extend perpendicularly from the support. To support. After placing a layer of dry absorbent cotton 12 inches below the bar, direct the flame to the center of the bar. for ten (10) seconds. Remove the flame and continue to hold the bar for 30 (30) seconds. Visually observe and record the time of flaming combustion and/or flameless combustion.

If it is difficult to distinguish between flaming and flameless combustion, place the cotton in contact with the bar, and If the bar ignites, the state of the bar is considered to be flammable combustion. Test on each sample bar Repeat with the same sample bar to determine its flammability again. observe and record The desired conditions are (a) the flaming combustion time after the first flame application, (b) the second flammable combustion time after flame application; (c) flammable combustion and flameless combustion after second flame application; time, (d) whether the specimen is burnt out and up to the holding clamp, and (e ) The specimen may or may not shed flame particles that ignite the cotton swatch.

Specimens evaluated according to the UL-94 protocol above are assigned to one of the three classes. I'll fit it in.

Class r94-V-QJ means that after the first or second application of the test flame (10) does not burn with flaming combustion for more than 2 seconds, and each set of 5 specimens 10 (10) The total flaming combustion time for flame application does not exceed 50 seconds; The retaining mount does not burn up to the fixture and was placed 12 inches below the sample being tested. has no analytes to drop the flame particles that would ignite the dry surgical cotton, and Specimens with flameless combustion that persists for more than thirty (30) seconds after the second flame removal This shows a sample that does not have any.

Class r94-V-IJ means that after either application of the test flame, 30 (thirty seconds) 10 for each set of 5 specimens. (10) The total flaming combustion time regarding flame application does not exceed 250 seconds, and The attachment will not burn out until the tool is placed 12 inches below the sample being tested. We do not have any specimens that drop the flame particles that ignite the cotton, and the second Do not have any specimens with flameless combustion that persists for more than sixty (60) seconds after removal of the flame. Indicates a sample that has not been tested.

Class r94-V-2J means that after the first or second application of the test flame It does not burn with flaming combustion for more than (30) seconds and each set of five specimens 10 (10) The total flaming combustion time for flame application does not exceed 250 seconds. The retaining mount does not burn up to the fixture and is placed 12 inches below the specimen being tested. containing one or more specimens that drop flaming particles that ignite dry surgical cotton. for more than sixty (60) seconds after the second flame removal. A sample with no analytes with sustained flameless combustion is shown.

Additionally, if only one of the five sample specimens of the composition does not comply with the requirements, A second set of five specimens of one composition should be tested. From this second set All specimens were classified as 94-V-1, 94-V-2 or 94-V-3. Follow most of the appropriate requirements for proper classification.

Since it is not part of the UL Laboratories protocol, the inventor L　For materials that showed flammability in samples exceeding 94-V-2 or 94-V-3 grade. Apply the grade of rHBJ.

Another test that is useful in determining the flammability of installed wires is the August 1983 “Reference for Electrical Wires, Cables and Soft Cords” dated 15th 5 standard for Electrical Wires, Cables and Flexible Cords) J, (c) Underwriters LA Underwriters, fully described in Volatries, pages 100-102. Laboratories UL1581r Thermoplastic and Rubber Insulated Wire and Cable Horizontal-8pecimen Flame test Te5t for Thermo-plastjc-and Rubber-I nsulated Wjresand Cables) J. summarize The test shall be performed on a completed single conductor thermoplastic insulated wire or cable. Support the specimen length in a horizontal position and place a drop of water on dry surgical cotton 9 inches below the specimen. You need to lay down a flat layer of flat. Next, place the gas flame at the midpoint of the insulated wire for 30 minutes. After contact for seconds, remove the flame. The flammable combustion time of the insulation layer, and the Record the progress of flaming or other decomposition of the edging material. In addition, any particles or droplets Note whether or not it is expelled and whether this ignites the cotton.

Another test was further conducted to determine the flammability of the structure. Ultimate oxygen index (Lo l) the minimum concentration of oxygen required to sustain candle-like combustion of the sample structure; It was determined. In this test, the test specimen is placed vertically into a glass cylinder. Ignite and direct a gas stream of a mixture of oxygen and nitrogen through a vertically oriented wire sample. Aim upwards through the glass cylinder to pass over. initial oxygen concentration , ignite the specimen from the top, and record the length and time of combustion. Continued to increase or decrease the oxygen concentration in the stream, reignite the same sample, or A new specimen is placed in a glass cylinder and ignited in a similar manner. this exam , the minimum concentration of oxygen required to support constant candle-like combustion of the analyte is maintained. Repeat until done. The determined values are based on the oxygen/nitrogen gas flow used during the test. It is a number equal to the percentage of oxygen gas; a higher percentage of oxygen increases the flame resistance of the sample. and, conversely, a lower oxygen percentage indicates easier flammability of the test sample.

Evaluation of the physical properties of the composition forming any sample is performed using the following protocol: That is, ASTM D-256 test for notched and unnotched Izot impact. , ASTM D-790 Test for Flexural Properties, ASTM D-790 Test for Tensile Strength and Properties 638 on molded test bars. Prototypes for these properties Cols are well known to those skilled in the art.

In addition to these aforementioned tests, in multilayer structures as shown by the inventors The elongation of the PA-containing layer was evaluated as follows. That is, two layers extruded onto the wire The PA-containing layer containing the phosphonate ester was separated from the PVC-containing layer from the structure. . Next, the PA-containing layer was cut into 8-inch wide strips using a 178-inch die cutter. After cutting into strips, the initial elongation was measured according to ASTM 1581 test protocol. Testing was performed to determine the initial elongation of the layer.

Referring now to the drawings, FIG. 1 illustrates that the PvC and PA layers are generally flat. FIG. 2 is an end perspective view of the multilayer structure shown in planar form. Such a large number A layered structure is a rigid and structurally self-supporting black and/or plastic structure. It also shows small products such as sheets, as well as larger products such as thin films or sheets. It is the meaning. Furthermore, such a multilayer structure as shown may be Representing thin film or coating structures suitable for use with the structure It should be understood that this is possible. As illustrated, the structure 10 has two layers. The first layer 12 comprises plasticized PVC and the second layer 14 of PA comprises phosphonic acid. Compositions that include an ester and additional optional ingredients. Such a struct is Accordingly, an adhesive material can be included intermediate the first layer 12 and the second layer 14.

FIG. 2 is an end perspective view of another structure 20 according to the invention; Figure 2 shows a perspective view of the multilayer structure. Structure 20, in contrast to structure 10 according to FIG. a first core-type layer 2 which is generally non-planar in morphology but is found to be cylindrical; Contains 2. Structure 20 further includes a PA layer and in alignment with first layer 22. 24, which is overlaid. Although not shown in detail, the first and second layers to provide sufficient adhesion between the composition comprising the layers and for the first layer 22 and the second layer 24. and another intermediate structure or material.

FIG. 3 illustrates another embodiment of the invention and uses the multilayer structure of the invention. 3 illustrates an exploded perspective view of an electrical conductor 30. FIG. The electrical conductor 30 is made of copper, aluminum, copper Molded from any suitable metal including coated tin, silver-plated copper and stainless steel It includes a wire conductor 32 that can be used. The wire conductor 32 may have a thickness of, but not limited to, 1,000 0, OOOCM (r circular mil") ~ approx. 22AWG (r American wire gauge") ), but other dimensions not within this particularly preferred range. It is anticipated that electrical wire conductors may also have the benefits of the present invention. Furthermore, the electric wire conductor 3 2 is a single solid metal conductor, such as a metal strand, which may be a twisted metal conductor. It may be a body or multiple metal conductors.

The first layer 34 (i.e., the "inner layer") in contact with the electrical conductor 20 is a Contains plasticized PvC and other additives by volume. This first layer can be It can be shaped around the electrical conductor 20 by. Extrusion method would be preferable cormorant. The thickness of the first layer 34 may be any desired thickness and may be any thickness necessary to the practice of the present invention. Not the point. However, it is preferred to use commonly used thicknesses.

No. 36 (i.e., the "outer layer") comprises PA and phosphonate and optional additives and can be molded around the first layer 32 by any suitable means. Extrusion method is preferred. Similarly, the thickness of second layer 36 is not necessary to enjoy the present invention. Although not natural, commonly used thicknesses can be used.

Referring now to FIG. 4, the multilayer structure of the present invention is manufactured by coextrusion techniques. A schematic diagram of the industrial process for

The wire coating line 40 is formed by forming a structure on the wire 41 according to the present invention. PvC-containing compositions and PA-containing compositions containing optional ingredients can be extruded Extruder 50 with two barrels 50A and 50B with coextrusion die 52 including. In some cases, the wire sheathing line 40 includes a wire winding for supplying the wire 41. Output reel 42A1 A wire take-up reel for collecting the wire 41 after it has been coated. A series of capstors that serve to guide and/or transport wires 41 In front of the pinch rollers 44A, 44B, 44C, 44D and the extruder 50 Wire pre-processing machine 46, wire post-processing machine 47 and marking station 4 located Includes additional equipment including 8.

The manufacturing process required to have the advantages of the present invention provides multi-layer insulated wire and cables. It is a process commonly used for molding. Logic related to FIGS. 4 and 5. The process characteristics described above should be considered illustrative as is and not limiting. stomach. Generally, the bare wire 41 is fed from a wire unwinding reel 42A where it is passes through rollers 44A and to wire preconditioner 46. Wire pre-treatment The processing machine 46 is an arbitrary processing device, and inside it, the bare wire 41 is passed through the extruder 50. It can be conditioned before coating with. For this kind of conditioning, , preheating, chemical/physical cleaning operations and/or other operations. . The wire 41 is then divided into two parts according to the structure and composition logic disclosed above. It includes a die 52 capable of extruding the layers, i.e., the first layer and the second layer, onto the wire. into a crosshead provided by two extruders 50. 2 extruders 5 0 and coextrusion die 52 may be of any type or materials currently known in the art. Still in development useful when extruding multiple layers of material onto wire or other structures It may be any of the following. One currently known in the technical field Examples include each having at least one storage hopper and having a PvC-containing composition. and two extruders supplying the PA-containing composition and the PA-containing composition. minutes to the heat barrel of each extruder, which softens and softens each composition. After passing through a suitably shaped die 52, the material is extruded onto a wire or other structure. vinegar. Such extruders typically include a rotating screw within each thermal barrel (see Figure (shown as 50A and 50B in Section 4), each of its components was efficiently mixed. and press it into die 52. Single-stage extrusion method allows for rapid throughput and total production Offering benefits including speed.

Following the co-extrusion, the discharged electric wire 41 is optionally supplied to a wire post-processing machine 47. The electrical wire 41 may be conditioner or conditioning process. The post-processing machine 47 is used for any condition adjustment process. cooling operations, expulsion of all organic materials and/or is an additional heating step that results in curing of one or both layers extruded onto wire 41 , may include quench operations such as water baths or other beneficial conditioning treatments. next, Wire 41 passes through another capstan/pinch roller 44B and then The outer surface of the edge line 41 is characterized by all information in a manner well known in the art. It can pass to a stamping station 48 where it is applied. Next, the electric wire 41 is further Another capstan/pin passes through rollers 44C, 44D and the wire winding reel 42B. Thereby, the insulated wire 41 is connected to the wire sheathing line 40. It can be taken out and used.

Figure 5 shows the process for producing the multilayer structure of the invention by the "tandem" extrusion method. This is another sketch of Seth. This wire extrusion line 54 is as shown in FIG. Only the replacement of a single crosshead die 52 differs substantially from that illustrated in FIG. , has two extruders 60.64 and their own dies 62.66; as a result, FIG. 4 and 5 are considered interchangeable, and Notes on tasks such as those discussed in Section 4 are considered equivalent and may be used as a reference in this book. Incorporated herein. In this embodiment of the invention as shown in FIG. The wire 41 entering the corresponding die 62 is fed by the extruder 60 and as previously discussed. coated with a first layer such as The wire 41 thus provided by the first layer is Subsequently, the polyamide is produced in a second die 66 fed by an extruder 64. coated with a layer to form a superstructure according to the invention.

In accordance with the foregoing logic of FIGS. 4 and 5, in C, the use of the multilayer structure of the present invention can or has been theorized and described regarding the forming of insulating structures for electric wire cables. . However, the utility of the invention in other potentially beneficial applications is negligible. The use of other strand-type materials including fibers, optical fibers, etc. It is clearly expected. Furthermore, the relative terms "internal" and "external" refer to PvC used to describe the relative position of PA-containing and PA-containing layers; Examples are included for convenience and not necessity. The PA layer forms the “inner” layer and A structure is envisaged in which the PvC-containing layer forms the "outer" layer.

In the following embodiments of the invention, in any description of the composition, the composition is All percentages refer to the ingredients used to produce the It should be understood as "% by weight" of a particular ingredient relative to the composition. This custom Exceptions to the examples are detailed. .

Example Examples 1-4 Specific gravity according to ASTM D-792 is 1.13 and melting point is approximately 420 degrees F. and the following physical properties, namely, ultimate elongation in the form of a pellet. bending strength: approx. 15.4001) 8i% flexural modulus: approx. 377.000 Mainly psi1 notched izot impact strength approximately 1,0ft-1bs/inch THHNSTHWN1 Marine cables, architectural wires and non-metallic armored casings Functionally characterized as a mid-year heat-stabilized extrusion grade resin suitable for extrusion of plastics. Materials Albright & Wilson (Albright and conditions , that is, temperature profile; zone 1 set temperature 266 degrees 01 zone 2 set temperature 2 61 degrees 01 area 3 setting temperature 255 degrees 01 area 4 setting temperature 250 degrees 01 area 5 setting Temperature 240 degrees 01 zone 6 set temperature 240 degrees 01 zone 7 under set temperature 240 degrees C Provided for supply of operating single screw extruder. operate the screw Rotate at 1100RP and adjust the pressure at the breaker plate to 700ps. I set it. The extrudates were formed into strands and then pelletized. continue that beret It was used for the formulation and production of mushroom test samples.

Contains additional Capron 8224H8 resin according to the percentages shown in Table 1 below. Various experimental compositions were formulated with various proportions of the masterbatch composition including 6 inches x 1/2 inch x 1/32 in an Arburg injection molding machine Table 1 - Experimental compositions Capron (R) 8224H8-1002587,5 Table 2 - Physical properties bending strength, psi (1000's) near, 19 15.46 8.35 11.7 6 bending modulus, psi (1000's): 166 377 200 296 tensile yield strength, psi (1000's): 5.12 12.09 7.79 9.55 Yield stretch, %: 4 5 5 5 ultimate tensile strength, psi (1000's): 4.49 7. 46 5. 78 6. 7 8 ultimate elongation %: 49 198 151 185 Izotsu with notch, ft-1b/inch +0.65 0.7 0.79 Izot without notch, ft-1b/inch: 4.8 11.6 18 Table 3 shows each of the experimental compositions. We report findings from UL-94 flame testing on five standard test bars.

Table 4 reports findings from tests to determine the ultimate oxygen index, in which samples were Tested according to the protocol outlined above.

Table 4 As can be seen by inspection, the composition of Example 2 is a control sample and is not treated according to the invention. does not contain phosphonate esters as shown, but is provided for comparison purposes. .

Example 1.3 in comparison with the case of Example 2 with respect to the properties reported in Table 2 The ultimate tensile strength, especially the ultimate elongation, of the samples with respect to the flexural properties of Example 3 and that the ultimate elongation of Example 4 can be compared particularly conveniently. It can be easily observed that the respective values of 151% and 185% are reported Compares favorably with the ultimate elongation of Comparative Example 2, whose value is 198%. Here Table 3 With reference to the results reported in Table 4 and Table 4, the improvement is even more pronounced. Example The composition of No. 2 is not shown in Table 3, fails the UL-94 test protocol and However, the results of Examples 1.3 and 4 are applicable to the rHBJ grade described in Well, the UL-94 test, which was briefly explained above, is based on the protocol. I'[4-V-OJ, r94-V-2J and r94-V- Applicable to grade 2. Therefore, the percentage shown to be suitable Polyamide-containing compositions containing sulfonate esters are characterized by adequate to excellent flame retardancy. It is understood that the vines are shown to be strong and at the same time retain their elongation properties well.

Examples 5-7 Field of the art useful for extrusion onto current conductors (i.e., wires and cables) A typical plasticized poly(vinyl chloride) composition masterbath of composition known as GeorgiaGulf, Inc. Approximately 55% virgin PVC resin designated as R1095J sold by Inc. ~65%, Ansin Incorporated of Philadelphia, PA on Inc,) from “Dys tha 1-Env” Lead stabilizer 3-6%, both commercially available under the trade name Trioctyl trimellitate (T OTM) 20-30%, diundecyl phthalate, a phthalate ester plasticizer (DUP) 4-8%, electrical insulation grade clay 3-6%, antimony oxide 1-2%. Inclusive. Another component in the PvC-containing composition is a vinyl chloride-containing copolymer, For more information, please visit Union Carbide Corp. in Danbury, CT. Union Carbide Corp) and rV Vinyl chloride with 2% excess hydroxyl content, called AGHJ terpolymer/ The vinyl acetate/vinyl alcohol terpolymer was 3.5%. This VAGH The terpolymer contains 90% by weight of vinyl chloride units, 4% by weight of vinyl acetate units and 6% by weight of alcohol units and about 2.3% by weight of hydroxyl functionality. and a hydroxyl value of 76. These materials further include A It is stated that the specific gravity according to STM D792 is 1.39. For more details , VAGH resin has a glass transition temperature of 79 degrees C and a number average molecular weight of 27.000. It is stated that. The use of such terpolymers allows for superimposed PvC Theorizing the usefulness of such materials to increase the adhesion of the containing layer and the PA containing layer. Co-pending and commonly assigned U.S. patent filed September 10, 1990 No. 580,232. This vinyl chloride - vinyl acetate - The vinyl alcohol terpolymer is greater than 0% by weight of the PvC-containing layer according to the invention. and can be present in an amount consisting of less than 10% by weight.

In a Hensche 1 mixer with bowl and mixing vanes pvc, Dieteruenve, TOTMSDUP and antimony oxide at room temperature. After addition, the mixture was thoroughly mixed for approximately 10-15 minutes while increasing the temperature. Next, the ingredients Electrical insulation grade clay and VAGH terpolymer at a temperature of 190 degrees F. and blend the mixture once the batch reaches 200-210 degrees F. removed from the bowl. Then feed the mixture into a short barrel screw extruder feed into the hopper and heat to plasticize it and then form the strands After that, it was pelletized.

The produced pelletized composition is then passed through a heated barrel and die head section. Barrier Madox was engineered to have a temperature of approximately 370 degrees Fahrenheit. A first extruder was fed with an ier Maddox screw.

Operate the screw to rotate at about 35 RPM, and the motor produces about 115 amps. A current was generated and the pressure was maintained at approximately 2000 psi. The amount of wire extrusion is 20 Under working conditions, i.e. the temperature profile through the thermal barrel and gui head is approx. It was held at 500 degrees F. Operate the screw to rotate the motor at approximately 46 RPM. produced a current of about 45 amperes and the pressure was held at about 1100 psi. .

I pushed it out. The structure formed on the wire included the structure of Example 5, which Manufactured as a comparative example without phosphonic acid ester as indicated by the invention. It was.

Similarly, another structure according to the invention was manufactured under the same conditions except that: did. The structure of Example 6 used the same PvC-containing composition forming the first layer. However, the second layer, which is a PA-containing layer further comprising a phosphonate ester, is according to Example 3. The composition was used to extrude onto the first layer. Similarly, another example shown as Example 7 One structure used a plasticized PvC-containing composition to form the first layer, and the example 4 was used to produce the extruded wire of Example 5 above. Extruded onto AWG 14 gauge solid wire under substantially the same conditions as used in Ta.

Underwriters Laboratories Co., Ltd. For classifying UL-94r materials 94-V-0, 94-V-1, 94-V-2 The results of this test are reported in Table 5.

Table 5 - Flammability [UL-94 test protocol] Electric wire sample Sample number 1st combustion (seconds) 2nd combustion (seconds) Example 5 1 30 1 Example 6 1 4 2 Example 7 1 12 4 Examples 8-9 Examples 5-7 on two wire samples containing 500, OOOCM twisted strand copper. A 0.064 inch thick layer of the PvC composition of the masterbatch was first extruded; Samples of coated wire were collected from the Underwriters Laboratory briefly described above. Horizontal inspection of UL 1581r thermoplastic and rubber insulated wires and cables Tested using body flame test JUL 1581. The results are summarized in Table 6 below.

Table 6 Underwriter Zoo Laboratories UL 1581 Commentary on various test results and In particular, the present invention provides superior resistance as demonstrated in the UL1581 horizontal flame test. improved fuel behavior while retaining sufficient flexibility and other physical properties. Provides a constructed structure.

The specification and examples herein are by way of illustration and not by way of limitation. without departing from the spirit and scope of the invention. Modifications and changes may be made and the limitations are limited only by the scope of the claims. It is understood that it is bound.

Submission of translation of written amendment

Claims (10)

[Claims] 1. A first layer containing a plasticizer, poly(vinyl chloride) and a second layer containing polyamide. A multilayer structure comprising a structure, the second layer having a structure ▲ a mathematical formula, a chemical formula, a table, etc. Masu▼ (In the formula, "x" is 0 or 1) The multilayer structure described above further comprises a phosphonic acid ester having the following. 2. Polyamides include polyepsilon caprolactam (nylon 6) and polyhexane. methylene adipamide (nylon 6,6) and polyepsilon caprolactam Group consisting of copolymers of polyhexamethylene adipamide (nylon 6,6/6) The structure according to claim 1, which is selected from: 3. Polyamide is hydroxyl, carboxyl, carboxyl compound, amide , acetamide, and amine. Or the structure described in Section 2. 4. Plasticizers include di-2-ethylhexyl phthalate (DOP) and diisode phthalate. sil (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate ( DTDP); phthalate ester plasticizer containing trioctyl trimellitate (T OTM) and trisooctyl trimellitate (TIOTM) 2. The structure according to claim 1, wherein the structure is selected from the group of acid ester-based softeners. 5. The first layer is a vinyl chloride-vinyl acetate-vinyl alcohol terpolymer. Claim 1 further comprising an amount greater than 0% and less than 10% by weight relative to the layer. The structure described in section. 6. The phosphonate ester comprises more than 0.001% by weight of the composition of the second layer of the structure. and contains less than 20% by weight of the structure according to any one of claims 1 to 5. Structure. 7. The second layer is the structure ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ contains two phosphonate esters having a value of "x" equal to 0. , represents one phosphonate ester, and if the value of "x" is equal to 1, then another A structure according to claim 1 representing a phosphonate ester of. 8. The amount of phosphonate ester represented by the structure where the value of "x" is equal to 0 is , the amount of phosphonate represented by the structure with the value of "x" equal to 1. The structure according to claim 7, which rotates. 9. Manufacturing the multilayer structure according to any one of claims 1 to 8 above. How to do it. 10. Used to form plates, membranes or electrical cable insulation structures The structure according to any one of claims 1 to 8.