|Publication number||USRE28688 E|
|Application number||US 05/385,050|
|Publication date||Jan 20, 1976|
|Filing date||Aug 2, 1973|
|Priority date||Oct 31, 1960|
|Publication number||05385050, 385050, US RE28688 E, US RE28688E, US-E-RE28688, USRE28688 E, USRE28688E|
|Inventors||Paul M. Cook|
|Original Assignee||Raychem Corporation|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (12), Non-Patent Citations (6), Referenced by (46), Classifications (78)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This invention relates to elastomeric materials and products and has particular reference to the production of elastomeric articles having heat-activated dimensional memory characteristics.
Elastomers or rubbers are important products being used in a very large number of applications for commercial uses and constituting a very large and important market. Elastomers are generally called rubbers. The word "rubber" is used in two different senses, originally being applied only to the natural product rubber. Recent use, however, has been the development of a very large number of synthetic rubbers having a wide variety of chemical constitutions, so that today the term rubber is commonly employed not to characterize the specific chemical substance obtained from the rubber tree, but to characterize a state of matter, i.e., any material comparable to natural rubber and possessing the physical property of elastic extensibility. Hence, an elastic material or rubber will stretch an amount directly proportional to the applied force and will recover upon the removal of the force.
The principal property of rubbers or elastomers which leads to their wide usage is the property of elastic deformation and the resulting flexibility and resilience of articles made of such materials. The most important commercial use of rubbers today is for the production of rubber tires for automobiles and other wheeled vehicles. The important factor in the use of rubber in this application is the property of elastic deformation, the ability to deform and recover quickly serving to cushion the blows from surface irregularities as the tire travels along the road. Although rubber materials in general have relatively poor toughness and abrasion resistance, the significant factor in terms of the long life of such materials in difficult physical environments is the fact that the application of wearing surfaces, such as sharp edges of stones or pebbles, will cause the rubber to deform and assume a new shape, wherein the applied stress is redistributed over a much wider area, thereby causing less wear and abrasion. Upon removal of the stress the rubber returns to its original vulcanized size and shape. On the other hand, a non-elastic thermoplastic material subjected to the same conditions would, because of a high unit pressure, deform by passing the yield point and thereby lead to a permanent deformation which is not recoverable.
A series of important commercial products have been developed over the past few years, based upon the property of plastic memory. Two different techniques are used for the production of such so-called dimensionally heat-unstable or perhaps more properly "heat-recoverable" thermoplastic materials, i.e., products which change their size and shape upon the application of heat without the necessity for the application of external forces. The first technique is that of imparting a considerable amount of built-in stresses during fabrication, followed by a cold temperature quench to hold the molecules in the stressed condition. Upon careful heating, this fabricated product will tend to reform or recover to the original configuration. However, upon slight over heating, or upon heating too long, such thermoplastic materials will melt and relax to a new size and shape. More recently, a series of cross-linked thermoplastic products have been fabricated wherein the memory characteristic of the plastic is obtained by a 3-dimensional network rather than built-in stresses in a 2-dimensional system. For example, a cross-linked polyethylene can be heated to above the crystalline melting temperature, at which point it behaves as an elastomer wherein the application of a force will lead to a deformation directly proportional to that force. If, while the cross-linked polyethylene is in the elastomeric state, a force is applied to cause deformation proportional to the force, and this is followed by a reduction in temperature, crystallization will take place which will maintain the cross-linked polyethylene in its deformed condition. Upon the subsequent application of heat sufficient to remelt the crystals (in the absence of a deforming force), the material will rapidly recover to the exact size and shape in which it has been cross-linked. However, such materials, being of crystalline thermoplastic nature, will exhibit normal thermoplastic properties while in the crystalline state, and will act as elastomers only at the elevated temperatures wherein the crystals are melted.
A very large variety of applications of commercial importance can be envisioned for elastomeric articles which are heat-recoverable, i.e., having the properties of changing shape and/or size upon the application of heat without the necessity of the application of external forces, but exhibiting essentially the elastomeric property of elastic deformation under stress. The commercial importance of such a series of products is believed to be clear to anyone familiar with rubber and rubber-like products.
Accordingly, it is a primary object of the present invention to provide novel elastomeric articles of manufacture capable of changing size and/or shape upon the application of heat.
A further object of the present invention is to provide novel elastomeric articles possessing dimensional memory characteristics and capable of returning to an original, predetermined, vulcanized or cross-linked configuration upon the application of heat.
Another object of this invention is to provide a novel process for the production of elastomeric articles.
Still another object of the present invention is to provide a novel process for the production of elastomeric articles having dimensional memory characteristics.
Other objects and advantages of this invention it is believed will be readily apparent from the following detailed description of preferred embodiment thereof.
Briefly, this invention comprehends within its scope the discovery that elastomer products can be made having the properties of elastic deformation substantially equal to true elastomers, and at the same time having the properties of changing shape and/or size merely upon the application of heat and recovering to the original, vulcanized or cross-linked shape and size. As used in the specification and claims herein, the term "elastomeric" and similar terms are intended to mean and include products or articles of any configuration having a Young's modulus in the range of from about 50 to 3,000 p.s.i. and exhibitng the characteristic rubber-like elastic deformability under the action of comparatively small stresses, .Iadd.and .Iaddend.returning substantially to the original size and shape upon the removal of the applied stress. The Young's modulus is measured at room temperature and determined in accordance with ASTM D638-58T. As will be more fully brought out below, an essential aspect of the present invention is that the elastomeric component of the articles of the present invention must be cross-linked. As used in the specification and claims herein, the term "cross-linked" and similar terms as applied to the articles of the present invention are intended to mean and comprehend a 3-dimensional molecular network having a modulus of elasticity of at least about 10 p.s.i., as measured at a temperature of 50° C. above the softening or flow temperature of the thermoplastic or resinous material component, as hereinafter defined. For the purpose of this definition, the modulus of elasticity is determined in accordance with the method of Black, R. M., The Electrical Manufacturer, October 1957, as is further described below. The softening or flow temperature is measured in accordance with ASTM D569-48.
The heat-recoverable elastomeric materials or articles of the present invention are produced by forming or fabricating into the desired configuration a composition comprising either (1) an uncured elastomer in which is incorporated a normally solid, heat-flowable material capable of being formed by the application of heat and an external force, e.g., a thermoplastic or non-elastic resinous material, or (2) a plasticized thermoplastic material having elastomeric properties as herein defined, such as a plasticized polyvinyl chloride; then vulcanizing or cross-linking the formed composition or article; heating it to a temperature at which the thermoplastic or resinous material loses the major portion of its strength, e.g., a temperature above the thermoplastic melting or softening point or range; then applying an external force or forces to deform the article to the desired heat-recoverable configuration; and then quenching or cooling the article to a temperature at which the thermoplastic or resinous material regains its strength, e.g., to a temperature below the thermoplastic melting or softening point or range. After such cooling, the external force or forces are released and the article remains in the heat-recoverable configuration, not returning to its original vulcanized or cross-linked configuration, as would be the case with a true elastomer. The non-elastic thermoplastic or resinous material in some manner holds the article in the heat-recoverable form until the article has been heated to or above the softening temperature as hereinabove defined, whereupon the unrestrained and heated article will return to the original as-formed, vulcanized or cross-linked configuration. The essential feature of the present invention resides in the fact that the cooled or quenched heat-recoverable article has resiliency and exhibits the property of elastic deformation upon the application of force.
More specifically, the squence of steps utilized in carrying out the process of the present invention is as follows.
(1) Intimately mixing the thermoplastic or resinous material with the elastomer or rubber gum in the uncured state, or mixing the plasticizer and cross-linkable thermoplastic material. The usual fillers, extenders, curing agents, accelerators and the like are included at this stage if desired, depending upon the desired properties of the final article.
(2) The composition formed in step 1 is then fabricated or formed into an article of predetermined configuration and cross-linked or vulcanized. The cross-linking or vulcanization may be accomplished by a chemical cross-linking technique wherein a vulcanizing agent or cross-linking agent is added, the subsequent application of heat and/or pressure bringing about the desired cure. Alternatively, the cross-linking may be brought about by exposure of the article to high energy radiation such as from an accelerated electrons, X-rays, gamma rays, alpha particles, beta particles, neutrons, etc., without the necessity for the addition of cross-linking or vulcanizing agents. Further, the cross-linking or vulcanization can be accomplished by a combination of these two techniques. The degree of chemical cross-linking or the radiation dosage are sufficient to produce at least the minimum high temperature modulus of elasticity of 10 p.s.i. referred to hereinabove. Generally, the minimum radiation dosage is of the order of 2×106 rads.
(3) The cross-linked and cured article is then heated to a temperature sufficiently high to soften the thermoplastic component, i.e., above the melting or softening point or range, and while the material is maintained at that temperature an external force or forces are applied to change the size and/or shape of the article to a more convenient configuration for later application and use.
(4) The deformed article is cooled or quenched while still under the external deforming stresses, whereupon the article will retain the deformed shape upon the release of the external stresses. The article is now in the heat-recoverable state but may be left for an indefinite period of time at room temperature without danger of its recovering back to its original size and shape.
The use of articles produced in accordance with the above process is simple and straight-forward. The article is simply put into the position for use and heat is applied to it, whereupon the article will recover quickly to its original vulcanized or cross-linked configuration. A particularly useful example of an article within the scope of the present invention is heat-recoverable elastomeric tubing. In producing such articles, the starting material, such as a mixture of rubber and thermoplastic or resinous material, is properly compounded and extruded into tubing form. The extruded tubing is cured by radiation or by the proper application of heat with a cross-linking or vulcanizing agent, resulting in a cured, rubber-like tough, strong tubing. This tubing is then heated to a temperature above the thermoplastic melting or softening point or range, followed by the application of a deformation force while the tubing is at the elevated temperature, as by the application of pressure upon the inside of the tubing or a reduction of pressure on the outside of the tubing, resulting in an expansion of the tubing. Quenching or cooling of the thus formed tubing while it is in the expanded state locks the tubing in that state. The tubing has a diameter greater than the original diameter of the extruded and cured tubing and it will remain in this increased diameter condition indefinitely while at room temperature. The tubing is thus available for application at any time. For example, the expanded tubing is placed over articles which are desired to be encapsulated, adequate clearance between the tubing and the articles being provided to permit easy application. The brief application of heat to the deformed tubing will cause it to shrink and attempt to return to its original vulcanized or cross-linked dimensions. This recovery permits the tubing to tightly clad and cover the article which had been inserted therein prior to application of the heat. Such an article and process finds great utility in the covering of a group of wires cabled together such as in wire harness and the like, the resulting rubber jacket providing the desired toughness abrasion resistance and other properties of rubber or elastomeric materials. This method of encapsulating cable wires and the like is far superior from the standpoint of expense and ease of application to the acepted techniques of application of air pressure to temporarily expand tubing during the application of the tubing to the cabled wires, or the difficult, cumbersome and expensive method of application of uncured rubber jackets followed by heat or radiation cure in place.
It will be readily apparent that heat-expandable rather than heat-shrinkable elastomers can be made in accordance with the present invention. Thus, for example, a heat-expandable elastomeric tubing can be made by the process described above, except that rather than expanding the tubing in the heated condition, it is longitudinally stretched while heated, resulting in a contraction of the tubing diametrically as well as extension in length. Quenching and cooling of the thus formed tubing while it is in the elongated, contracted state locks the tubing in that state, the tubing then being available for use. For example, the tubing can be placed inside of a pipe or tube, the brief application of heat causing it to expand and to attempt to return to its original vulcanized or cross-linked condition, this recovery permitting the tubing to tightly engage the inside of the pipe forming a lining thereof.
Another example of an article within the scope of the present invention is a molded covering for cable breakout legs, such article being Y-shaped or the like, adapted for application onto a cable breakout or transition and shrinking into place thereupon upon the application of heat.
Any elastomeric material may be used in carrying out the present invention, for example: nautral rubber; butadiene-styrene copolymers (GR-S); butadiene-acrylonitrile copolymers (Buna N); isoprene-isobutylene copolymers (Butyl); polyisoprene; polybutadiene; polysulfide (Thiokol); polychloroprene (neoprene); polysiloxane (silicone); fluorocarbon (viton A, etc.); chlorosulfonated polyethylene (Hypalon); plasticized polyvinyl chloride; polybutene.
For each elastomeric material, a wide range of thermoplastic or resinous materials, generally added in relatively small proportions, have been found which will produce the desired results in accordance with the present invention. Such thermoplastic or resinous materials include: acrylic plastics; polyethylene; polytetrafluoroethylene; polychlorotrifluoroethylene; polyvinyl formal; polyvinyl butyral; polyvinyl chloride; vinyl chloride-vinyl acetate copolymers; polyvinylidene chloride; polystyrene; polycarbonates; polyamides; cellulose acetate butyrate; cellulose acetate propionate; ethyl cellulose; polypropylene; ethylenepropylene copolymers; epoxy resins; polyester resins.
It has been found that from the standpoint of commercial practability, for each combination of each thermoplastic or resinous material and each elastomer, there is a narrow range of proportions of the thermoplastic or resinous materials which will accomplish the desired result. The addition of too small a quantity of the thermoplastic or resinous material will not produce the desired permanent deformation upon the subsequent cooling after deforming at elevated temperatures. The addition of too high an amount of the thermoplastic or resinous material will result in the article assuming properties more closely allied to the thermoplastic or resinous materials rather than retaining the properties of the elastomeric or rubber-like materials. Thus, it is evident that for each system under consideration, in order to obtain optimum properties a relatively narrow range of concentrations must be observed. However, it is possible to impart memory characteristics to elastomers within a range of concentrations of the thermoplastic or resinous material of from approximately 5 to 50% by weight, based upon the total weight of the thermoplastic or resinous material and elastomer. In general, the lower modulus elastomers require less thermoplastic or resinous material to accomplish the desired result, while the higher modulus elastomers require more thermoplastic or resinous material. Further, the nature of the memory additive itself is important and certain materials will impart greater memory characteristics than others. For example, high density, high molecular weight polyethylene is a better memory additive than is low density, low molecular polyethylene. A further restricted requirement in the practice of the present invention is the selection of suitable curing agents and/or the use of a composition susceptible to radiation vulcanization or cross-linking.
Those skilled in the art of rubber chemistry and the art of proper compounding of rubber-like materials, will understand that in the practice of this invention a very wide variety of properties are obtainable and that normal rubber compounding techniques will apply, modified only as required by the inclusion of the thermoplastic material.
As will be apparent from the above, the most important commercial applications for the articles of the present invention lie in applications or articles which permit the deformed configuration to be retained at room temperature and for it to be released upon the application of heat above room temperature. For convenience and practicality, it is important that the articles can be shipped in normal fashion without having to cool them to below room and weather temperature conditions. This permits standard, easy packaging and straight-forward commercial applications. In addition, a normal requirement is that the articles be able to withstand temperatures normally encountered in weather conditions around the world and still prevent premature recovery of the article to its predetermined size and shape. Thus, in the specific examples given below, materials have been compounded specifically to meet this requirement, and to not shrink or change in shape even upon the application of temperatures encountered in the tropics or in warehouses where temperatures as high as 140° F. are reached.
To simplify the practice of the present invention it is necessary to select thermoplastic or resinous materials for addition to each rubber which can be easily mixed and dispersed therewith. Although almost all thermoplastic materials can be used with each rubber, it is necessary for simplicity in commercially feasible practice, to pick material which can be mixed together and which are compatible, the quick and easy dispersion of the thermoplastic material in the rubber material being a necessary commercial consideration. Therefore, the selection of a thermoplastic or resinous material which is similar in chemical structure to the elastomer is preferred in carrying out the invention.
The specific examples set forth below are illustrative of the articles and processes of the present invention, but it is to be understood that the invention is not to be limited to the specific details thereof.
The following methods of sample preparation and test procedures were utilized in carrying out the specific examples:
The method of incorporating the resin into the elastomer is important. If the resin is not dispersed thoroughly and completely throughout the elastomer, the properties of the compound are impaired. The preferred method used in the examples is as follows: A quantity of the resin is placed on a 2-roll mixer operating at a temperature sufficient to soften or melt the resin. The resin is milled until completely softened and then an equal amount of elastomer is slowly added to the resin. Mixing is continued until an homogeneous composition is secured. This is removed from the rolls and cooled. The balance of the mixture is done by placing a requisite amount of mixture on a cold 2-roll mill and adding the additional elastomer along with antioxidants, accelerators, fillers, plasticizers, etc., as required.
Molded slabs were prepared using a 6" × 6" × .062" rubber mold as described in ASTM D-15. The time-temperature cycles were varied depending upon the particular rubber-memory plastic system.
Samples were irradiated using a General Electric resonant transformer operating effectively at 850 kv. and 5 milliamps. The samples were cross-fired to insure uniform irradiation through the sample, and the irradiation dose was predetermined by Faraday cage measurements. A well-grounded thermocouple in contact with the sample served to measure the temperature of the sample.
All tests were run at room temperature using the variable speed automatic recording Instron tester. All samples were tested at a crosshead speed of 20+1 inch per minute.
The tensile strength and elongation were determined in accordance with ASTM D-412. .[.Young's modulus was determined in accordance with ASTM D-638..].
The basic technique for determining these values has been described by Black, R. M., The Electrical Manufacturer, October 1957.
For this investigation, a similar apparatus was used, consisting of a vertical glass tube with a glass jacket (similar to a Liebig condenser). The jacketed space was filled with boiling cyclohexanone and this kept the interior tube at a temperature of 150° C.
Strips of the cross-linked compound were prepared (.062" × .125" × 6"). Bench marks 1" apart were stamped in the middle portion of the sample. This strip was placed in the center tube and fastened securely at the top. Stress was applied to the sample by hanging weights on the bottom of the sample. Strain was measured by noting the increase in distance between the bench marks, the measurement being made at equilibrium after each addition of weight. The weights were increased until the sample broke.
From the stress-strain data obtained, a modulus chart was prepared. The slope of the line was determined as the M100 figure, or stress necessary to effect a strain of 100%. The breaking force was recorded as the Ultimate Strength or U.S.
For memory devices the modified elastomer must have certain physical properties. The importance of tensile strength, elongation, cold bend, etc., for proper functions are well known to those skilled in the art and need not be expounded here.
However, for heat shrinkable devices, the M100-U.S. ratio is a vital one. For the best use of such devices, either tubing or molded items, they must be capable of a significant amount of stretching or expansion without splitting at elevated temperatures. The M100 figure expresses the stress necessary to effect a stretch of 100% at a temperature above the resin softening point. The Ultimate Strength (U.S.) is the stress at the breaking point. The elongation at the breaking point expressed in percent is ##EQU1## Thus the larger the ratio, the more a compound can be stretched without danger of breaking.
Strips of cross-linked compound, 1/8" × .062" × 6" were marked in the middle with 2 parallel ink impressions 1" apart. The strip was heated 1 minute in a 150° C. glycerine bath, stretched until the 1" lines were 3 inches apart (200% stretch) where possible, removed from the hot bath and plunged into cold water. Five minutes after the cooling, the distance between the marks was measured as the extended length. This distance was expressed a percent increase in length over the original 1" and recorded as the "Memory." Twenty-four hours later the extended strip was placed in the 150° C. glycerine bath for 1 minute and allowed to freely retract or shrink. It was then cooled and the distance measured between the marks as the retracted distance. The "Retraction," calculated as a percentage as follows, was recorded: ##EQU2##
Following is a glossary of trademarks identifying the various materials used in carrying out the specifc examples:
A branched chain polyethylene
Density 0.93 g./ml.
Melt Index 3
A synthetic wax
Melting point 82° C.
Agerite Resin D:
Polymerized trimethyl dihydroquinoline
2,2' benzothiazyl disulfide
a butadiene-styrene copolymer
A polyester resin, a reaction product of bisphenol with fumaric or maleic anhydride
A butadiene-acrylonitrile copolymer
A coumarine-indene resin
Melting Point 90° C.
Epon 1031: An epoxy resin
Geon 101 EP: A general purpose polyvinyl chloride resin
Halowax 2141: A
A chlorinated naphthalene-approximately 50% chlorine
Melting point 131° C.
A linear polyethylene
Density 0.947 g./ml.
Melt Index 0.3
Hypalon 40: A chlorosulfonated polyethylene Methyl Tuads:
A french process zinc oxide
Particle size 0.11 micron
0.01% acidity as SO3. Used as a free radical promoter in sulfur cross-linking reactions
Tetrabasic lead fumarate
Stabilizer or acid-acceptor for polyvinyl chloride
Light calcined magnesium oxide
Particle size .09 micron. Used as an acid-acceptor in Neoprene Cures
Zinc di methyl dithiocarbamate
A butadiene-styrene copolymer
A stabilized polychloroprene
Contains no sulfur
Derivative of p-chloro meta xylanol
Resin R-4281: A low molecular weight siloxane polymer
Resin Z-6018; A low molecular weight siloxane resin
A general purpose silicone rubber of approximately 80 Shore A durometer hardness
An extremely low temperature silicon rubber stock of approximately 50 Shore A durometer hardness
Smoked sheet: Natural rubber-Commercial No. IX grade
Sterling S.O. Filler. Semi-reinforcing oil-type furnace black. Particle size 41 millimicrons.
Circo light process oil
A general purpose naphthenic-type softener and process aid
Single pressed, fish oil base stearic acid
Free radical promoter
A semi reinforcing oil-type furnace black
Particle size 51 millimicrons
Styron 666: A general purpose polystyrene thermoplastic
A branched chain polyethylene
Density 0.915 g./ml.
Melt Index 200
A furnace type carbon black, nonreinforcing
Particle size 320-472 millimicrons
Thiate A: Thio hydropyrimidene, accelerator
Tube brand sulfur:
Commercial rubber makers grade
Conditioned with MgCO3 for long flowing
A mixture of zinc dimethyl dithiocarbamate and zinc 2-mercaptobenzothiazole
Varox: A peroxide cross-linking agent containing 2.5 bis
(tert-butyl peroxy), 2,5-dimethyl hexane coated onto
an inert mineral carrier
Zinc salt of 2-mercaptobenzothiazole 6001 or DMD-6001 Polyethylene:
High density polyethylene
Density 0.95 g./ml. Melt Index 2.0
In the examples, the relative amounts set forth opposite the ingredients of the compositions are parts by weight, unless specifically indicated otherwise.
In carrying out this example several specimens comprising polychloroprene elastomer and polyvinyl chloride were made and tested. As indicated by the data set forth below, as little as 10% of polyvinyl chloride, based on the total of the polyvinyl chloride and elastomer, imparts memory properties to the article in accordance with the invention. By increasing the amount of polyvinyl chloride the memory properties are progressively improved, excellent properties being obtained with as much as 40% polyvinyl chloride without sacrifice in tensile strength and with substantial retention of the elastomeric properties of the elastomer. The followinge compositions or mixes were press cured for 10 minutes at 350° F.:
______________________________________Mixes 1 2 3 4______________________________________Geon 101 EP 10 20 30 40Neoprene W 90 80 70 60JZF 2 2 2 2Stearic acid 1 1 1 1Vancide 51Z 1 1 1 1Maglite D 4 4 4 4Sterling V 15 15 15 15Flexol TOF 9.2 8.4 7.6 6.8ZnO 5 5 5 5______________________________________
______________________________________TENSILE AND ELONGATION______________________________________ Average P.s.i. Percent .[.Young's elongation modulus (p.s.i.)______________________________________Specimen:1 1,151 533 1132 1,146 457 1783 1,094 407 3604 917 193 656.].______________________________________
______________________________________ELASTIC MODULUS AND ULTIMATESTRENGTH AT 150° C. M100 (p.s.i.) U.S. (p.s.i.)______________________________________Specimen:1 79 1942 70 1873 68 2184 63 133______________________________________
______________________________________MEMORY CHARACTERISTICS 1 2 3 4______________________________________Memory, percent 40 80 130 200Retraction, percent 100 100 100 100______________________________________
This example illustrates that a wide variety of thermoplastics, resins and waxes can be incorporated in polychloroprene compositions to produce articles within the scope of this invention. The basic formulation was as follows:
Compounds were prepared as described in mixing procedure.
______________________________________BASIC FORMULA______________________________________ PartsMemory ingredient 35Neoprene W 65Stearic acid 1MgO 4Sterling V 15Vancide 51Z 1Flexol TOF 5ZnO 5JZF 2______________________________________
Test specimen slabs made up using the memory ingredient indicated were press cured for 20 minutes at 340° F. and tested with the following results:
__________________________________________________________________________ Specimen No. 1 2 3 4 5 6 7 8 9 10 11 12 13__________________________________________________________________________ Memory ingredient Sili- Cu- Hal- Acro- Ala- 6001 Mar- cone mar Atlac Epon owax wax Styron Geon Tenite thon poly- bon Hi-Fax R 4281 S 382 1031 2141 B 666 101 EP 812 34 ethylene 8000 1400__________________________________________________________________________Tensile strength (p.s.i.) 926 959 1,062 736 1,157 384 1,071 1,479 770 826 985 1,206 1,144Elongation (percent) 480 510 410 180 460 400 420 317 200 230 252 518 338M100 (p.s.i.) 58 76 73 123 36 35 56 109 32 45 70 38 60U.S. (p.s.i.) 288 121 251 222 218 56 182 390 100 120 200 130 190Memory (percent) 180 190 200 150 70 190 200 200 125 100 100 100 150Retraction (percent) 100 94 100 93 100 100 95 100 86 100 100 82 100__________________________________________________________________________
This example illustrates that the conventional polychloroprene rubber accelerators function as such in the compositions of the present invention. In carrying out this example the following compositions were press cured for 10 minutes at 350° F.:
______________________________________Specimen No 1 2 3 4 5 6______________________________________Geon 101 EP 40 40 40 40 40 40Neoprene W 60 60 60 60 60 60JZF 1 1 1 1 1 1Maglite D 4 4 4 4 4 4Stearic acid 1 1 1 1 1 1Flexol TOF 5 5 5 5 5 5Sterling V 15 15 15 15 15 15ZnO 5 5 5 5 5 5Ottacide P 1 1 1 1Methyl zimate 1 0.5Zetax 1 0.5Thiate A 1Vancide 51Z 1______________________________________
Test results for the articles thus formed were as follows:
__________________________________________________________________________Specimen No 1 2 3 4 5 6__________________________________________________________________________Tensile strength (p.s.i.) 1,220 1,911 1,806 1,448 2,410 1,709Elongation (percent) 253 230 273 297 203 320M100 (p.s.i.) 18 26 62 60 142 58U.S. (p.s.i.) 157 220 295 302 272 246Memory (percent) 200 200 200 200 200 200Retraction (percent) 100 100 100 100 100 100__________________________________________________________________________
To illustrate that by the inclusion of a suitable low-temperature plasticizer, heat-recoverable polychloroprene articles can be produced having low temperature flexibilities equivalent to those of conventional polychloroprene articles, and in fact having adequate flexibility at -55° C., the following compositions were prepared and press cured for 10 minutes at 350° F.:
______________________________________Specimen No 1 2 3______________________________________Geon 101 EP 35 35 35Neoprene W 65 65 64JZF 1 1 1Stearic acid 1 1 1MgO 4 4 4ZnO 5 5 5Sterling V 15 15 15Vancide 51Z 1 1 1Flexol TOF 2.5 5 10______________________________________
Cold Bend tests were performed in accordance with MIL-R-6855, as follows:
The test specimens were strips 51/2" × 1/4" × .062". The bending devices consisted of 2 parallel jaws 21/2" apart.
The ends of the strips were inserted into the jaws for a distance of 3/4" and fastened firmly with the middle portion of the strip forming a loop between the jaws. This assembly was conditioned in dry air at the indicated temperature for five hours. While still at this low temperature, the jaws were moved rapidly from the 21/2" to a 1" separation. Failure was denoted by cracking of the sample. The results were as follows:
______________________________________Specimen No 1 2 3______________________________________-40° C OK OK OK-45° C .sup.(1) OK OK-50° C OK OK-55° C .sup.(1) OKTensile strength (p.s.i.) 1,421 1,409 1,521Elongation (percent) 230 250 260M100 (p.s.i.) 71 75 77U.S. (p.s.i.) 276 308 299Memory (percent) 200 190 170Retraction (percent) 100 97 94______________________________________ .sup.(1) Broke.
A number of heat-recoverable polychloroprene articles were prepared by press-curing the following compositions for 20 minutes at 340° F. to illustrate that the properties of the articles can be changed by varying the amounts and type of compounding ingredients:
______________________________________Mix No 1 2 3 4 5 6______________________________________Geon 101 EP 50 50 50 50 50 50Neoprene W 50 50 50 50 50 50Stearic acid 1 1 1 1 1 1JZF 2 2 2 2 2 2Vancide 51Z 1 1 1 1 1 1Flexol TOF 3 3 3 3 3 3MgO 4 4 4 4 4 4ZnO 5 5 21/2 21/2 5 21/2DOTG .5Sulfur .25Sterling V 15 15 15Thermax 5 5______________________________________
Following are the results of the physical tests:
__________________________________________________________________________Specimen No 1 2 3 4 5 6__________________________________________________________________________Tensile strength (p.s.i.) 827 1,088 978 1,282 846 810Elongation (percent) 133 103 113 80 133 140M100 (p.s.i.) 26 66 58 140 31 31U.S. (p.s.i.) 101 173 162 224 123 111Memory (percent) 120 160 140 200 170 140Retraction (percent) 96 100 100 100 97 92__________________________________________________________________________
A heat-shrinkable elastomeric tubing was produced by extruding the composition set forth below in a 11/2" Davis Standard extruder with a conventional thermoplastic screw. The tubing had a 0.250 I.D. and a 0.031" wall thickness. The tubing was vulcanized in a cylindrical steam vulcanizer at a pressure of 70 p.s.i. for 2 hours (Sample No. 1) and 3 hours (Sample No. 2).
Percent______________________________________Geon 101 EP vinyl resin 29.0Neoprene W 43.0JZF 1.5Flexol TOF 7.5Maglite D 3.0Stearic acid 1.0Vancide 51Z 1.0Sterling S.O. 10.0Zinc oxide 4.0______________________________________
To produce the heat-shrinkable tubing, the samples were expanded using a hot glycerine bath and a heated mandrel to 100% and 200%. The tubing was then cooled while over the mandrel in cold water and removed. The tubing showed an initial shrinkage of 10%-15% and thereupon remained expanded until it was heated above the softening range of the polyvinyl chloride whereupon it shrank to its original dimension.
Test results were as follows:
ELASTIC MODULUS AND ULTIMATESTRENGTH AT 150° C. M100 U.S. (p.s.i.) (p.s.i.)______________________________________Sample No.:1 29 1922 38 181______________________________________
TENSILE STRENGTH AND ELONGATION Average Percent p.s.i. elongation______________________________________Sample No.:1 1.077 2502 1.007 260______________________________________
Another form of heat-shrinkable article was made utilizing the following milled composition:
Geon 101 EP 40 Neoprene W 60 JZF 1 Stearic acid 1 MgO 4 Vancide 51Z 1 Sterling V 15 Flexol TOF 10 ZnO 5
The milled material was molded in a compression type mold to form a hollow 3-finger splice cover for use in cable harnesses. The configuration was roughly T-shaped.
The parts were cured 15 minutes at 360° F. As molded, one of the hollow fingers had a .375" orifice. The parts were immersed in 150° C. glycerine for 1 minute and the specified finger orifice was mechanically expanded to 1.250", and the expanded part cooled in water.
The expanded hole was remeasured immediately after expansion and again after two weeks at room temperature. The parts were then placed in 150° C. glycerine for 1 minute, cooled and remeasured. Results on six samples were:Inches Immediately Original Expanded after Re-Sample OD to expansion 2 weeks covered______________________________________1 .375 1.250 .940 .905 .3902 .375 1.250 1.000 .940 .3853 .375 1.250 1.062 1.600 .3854 .375 1.250 .980 .900 .3905 .375 1.250 1.002 1.000 .3856 .375 1.250 1.062 1.010 .380______________________________________
In another test, a similar molding was made and expanded. However, it was held two weeks at 55° C. (131° F.) and then remeasured. Data obtained was:
Inches Expanded Immediately After Re-Original OD to- after expansion 2 weeks covered______________________________________.375 1.250 1.170 .955 .385______________________________________
This example illustrates the production of heat-recoverable silicone elastomeric articles in accordance with the present invention. Test specimens having the compositions set forth below were made as described above and irradiated at a dose level of 10 megarads with the following results:
(1) PercentSilastic 82U 906001 polyethylene 10Memory 62Retraction 94(2) PercentSilastic 82U 90Styron 666 10Memory 87Retraction 100
This example illustrates the production of heat-recoverable silicone elastomeric articles wherein the memory ingredient is a silicone resin. As is apparent from the test results, as little as 10% silicone resin is effective, excellent results being obtained with 30% of the silicone resin. The test specimens were prepared from the following compositions press cured for 10 minutes at 350° F.:
1 2 3______________________________________Silastic 82U 90 85 70Resin Z 6018 10 15 30Varox 2 2 2______________________________________ 1 2 3______________________________________Tensile strength (p.s.i.) 742 616 515Elongation (percent) 397 283 250M100 (p.s.i.) 61 55 67U.S.(p.s.i.) 210 215 200Memory (percent) 120 150 200Retraction (percent) 100 100 100______________________________________
In carrying out this example a shrinkable silicone rubber tubing having a 100-mil wall thickness was prepared as described in Example 6 utilizing the following extrusion compound:
Tenite 812A 16Marbon 8000A 4Agerite Resin D 1Silastic 916U 64Silastic 82U 16Varox 2
These samples were prepared by vulcanizing the extruded tubing at 70 p.s.i. steam pressure in a cylindrical rubber vulcanizer for 60 minutes (Sample No. 1), 45 minutes (Sample No. 2) and 30 minutes (Sample No. 3).
The tubing was expanded 100% utilizing the process and apparatus described in Cook et al., U.S. patent application, Ser. No. 43,230, on Process and Apparatus for Producing Materials Having Plastic-Memory, now Pat. No. 3,086,242. The samples showed very little initial recovery (5% to 10%) and remained expanded until heated above the softening range of the polyethylene additive whereupon they shrunk to their original dimensions. Physical test results were as follows:
TENSILE STRENGTH AND ELONGATION Average Percent p.s.i. elongation______________________________________1 887 3832 856 3933 836 390______________________________________
ELASTIC MODULUS AND ULTIMATESTRENGTH AT 150° C. M100 (p.s.i.) U.S. (p.s.i.)______________________________________1 93 1282 83 1023 84 150______________________________________
This example illustrates the production of heat-recoverable articles of cross-linked plasticized polyvinyl chloride. Sheets were molded from the several milled compositions set forth below in a 6" × 6" × 0.062" flask-type mold and samples were irradiation cross-linked at 5 and 10 megarads.
______________________________________Sample No 1 2 3 4 5 6______________________________________Molding compositions: Geon 101 EP 90 80 60 70 100 100 Lectro 78 2 2 2 2 1 1 Triallyl cyanurate 10 20 10 10 20 40 Flexol TOF 30 20 60 40______________________________________
__________________________________________________________________________Sample No 1 2 3 4 5 6__________________________________________________________________________Irradiation dose (megarads) 5 10 5 10 5 10 5 10 5 10 5 10Tensile strength (p.s.i.) Too brittle to test 1,668 2,037 2,579 2,791 2,071 2,400 2,041 2,582Elongation (percent) 220 200 170 120 320 250 330 200M100 (p.s.i.) 22 61 44 87 33 85 20 123U.S. (p.s.i.) 37 52 65 95 100 146 84 109Memory (percent) 185 1 Broke 100 100 190 100 180 175Retraction (percent) 100 -- 100 100 90 100 100 100__________________________________________________________________________ 1 Sample ruptured in attempting to expand it 100%. A sample was then expanded 75% with 100% retraction.
This example illustrates the production of heat-recoverable articles utilizing polyvinyl chloride or polyethylene in various elastomers, cured by chemical cross-linking or by high energy radiation. In making the specimens, masterbatches were prepared by milling equal amounts of elastomer and resin on a hot mill. These were then incorporated into finished stock on a cold mill. Two types of masterbatches were made as follows:
GramsGeon 101 EP polyvinyl chloride 100Elastomer 100Flexol TOF 5JZF 2
6001 polyethylene 100Elastomer 100JZF 2
The cross-linking was carried out as follows:
1 Cured 20 minutes at 307°F.1A Irradiated 20 megarads3 Cured 20 minutes at 287°F.3A Irradiated 20 megarads
2 Cured 10 minutes at 307°F.2A Irradiated 20 megarads4 Cured 20 minutes at 307°F.4A Irradiated 20 megarads5 Cured 15 minutes at 287°F.5A Irradiated 15 megarads6 Cured 20 minutes at 287°F.6A Irradiated 20 megarads
The following are the specific mixes which were prepared:
Geon 101 EP 30Hypalon 40 70Litharge 25Sterling V 15Process oil 5Tetrone A 2Altax 0.5
Geon 101 EP 30Hypalon 40 70Litharge 25Sterling V 15Process oil 5
6001 polyethylene 30Chemigum N3 70Stearic acid 1ZnO 5Flexol TOF 5Sterling V 15Altax 1.5Methyl Tuads 0.1Sulfur 1
6001 polyethylene 30Chemigum N3 70Stearic acid 1ZnO 5Flexol TOF 5Sterling V 15
Geon 101 EP 30ASRC 3105 70Stearic acid 1ZnO 5Sterling V 15Process oil 5Altax 1Cumate 0.1Sulfur 1.5
Geon 101 EP 30ASRC 3105 70Stearic acid 1ZnO 5Sterling V 15Process oil 5
6001 polyethylene 30Hypalon 40 70Litharge 25Sterling V 15Process oil 5Tetrone A 2Altax 0.5
6001 polyethylene 30Hypalon 40 70Litharge 25Sterling V 15Process oil 5
6001 polyethylene 30Smoked sheet 70Stearic acid 1ZnO 5Process oil 5Sterling V 15Altax 1Methyl Tuads 0.1Sulfur 1
6001 polyethylene 30Smoked sheet 70Stearic acid 1ZnO 5Process oil 5Sterling V 15
6001 polyethylene 30ASRC 3105 70Stearic acid 1ZnO 5Sterling V 15Process oil 5Altax 1Cumate 0.1Sulfur 1.5
6001 polyethylene 30ASRC 3105 70Stearic acid 1ZnO 5Sterling V 15Process oil 5
Test results were as follows:
MODULUS OF ELASTICITY AND ULTIMATESTRENGTH AT 150° C.______________________________________ M100 (p.s.i.) U.S. (p.s.i.)______________________________________Specimen:1 228 3222 170 943 150 914 132 1175 81 2566 73 178 1A 139 156 2A 246 147 3A 65 75 4A 124 165 5A 18 251 6A 66 126.58______________________________________
PLASTIC MEMORY______________________________________ Memory, Retraction, percent percent______________________________________Specimen:1 70 1002 80 1003 30 1004 95 1005 100 1006 100 100______________________________________ Memory, Retraction, percent percent______________________________________Specimen:1A 80 1002A 40 1003A 50 1004A 100 1005A 90 1006A 100 100______________________________________
TENSILE AND ELONGATION______________________________________ Average P.s.i. Percent .[.Young's elongation modulus (p.s.i.)______________________________________Specimen:1 2,596 200 4872 575 253 3323 553 407 2414 1,762 147 1,6445 2,470 483 5766 872 527 503 1A 1,771 250 841 2A 766 93 761 3A 368 340 167 4A 1,507 130 1,368 5A 1,168 350 423 6A 981 480 533.].______________________________________
Having fully described my invention, it is to be understood that I do not wish to be limited to the details set forth, but my invention is of the full scope of the appended claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2194579 *||Oct 13, 1934||Mar 26, 1940||B B Chem Co||Plastic composition and method of molding the same|
|US2342977 *||Aug 2, 1940||Feb 29, 1944||Wingfoot Corp||Packaging|
|US2458152 *||Apr 3, 1945||Jan 4, 1949||Us Rubber Co||Plastic rivet and method of making same|
|US2549122 *||Apr 3, 1948||Apr 17, 1951||Wingfoot Corp||Packaging in stretched film|
|US2603838 *||Aug 1, 1949||Jul 22, 1952||Dow Chemical Co||Method for preshrinking crystalline vinylidene chloride copolymer film|
|US2769789 *||Jan 7, 1953||Nov 6, 1956||Dunlop Tire & Rubber Corp||Rubber reinforcing agents and compositions containing such agents|
|US2821155 *||Dec 11, 1953||Jan 28, 1958||Richard A Fisch||Process of applying protective coatings|
|US2989515 *||Aug 13, 1956||Jun 20, 1961||Du Pont||Process of copolymerizing aromatic dienes and monoolefins with catalyst of metal halide and organometal compound|
|US3042652 *||Jul 31, 1959||Jul 3, 1962||Du Pont||Elastomeric compositon comprising a benzene-soluble chloroprene polymer and a benzene-insoluble radiation cross-linked chloroprene polymer|
|US3056171 *||May 17, 1960||Oct 2, 1962||Mimx Corp||Inhibitor and thermal insulation liner for propellant grains|
|US3086242 *||Jul 15, 1960||Apr 23, 1963||Raychem Corp||Process and apparatus for producing materials having plastic memory|
|US3139468 *||Jun 20, 1960||Jun 30, 1964||Phillips Petroleum Co||Altering dimension of vulcanized transpolybutadiene and heating to cause same to appoach original shape|
|1||*||Einfuhrung in de Chemie & Technologie dor Runststoffe, Berlin, 1952, p. 48, F. Runge.|
|2||*||Kunststoffe, 50, (1960), p. 480.|
|3||*||Merrett & Wood, Proceedings of the Institution of the Rubber Industry, Vol. 3, (1956), pp. 36-37.|
|4||*||Plastics, Vol. 21, (October 1956), p. 273.|
|5||*||Plastuarlden, Vol. 4, (1954), p. 125.|
|6||*||Schmidt et al., Principles of High Polymer Theory & Practice; N.Y., 1948, pp. 302, 303 & 308.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4659871||Jun 24, 1986||Apr 21, 1987||Raychem Limited||Cable with flame retarded cladding|
|US4910085 *||Oct 11, 1988||Mar 20, 1990||American National Can Company||Multiple layer packaging films and packages formed thereof|
|US4966795 *||May 5, 1988||Oct 30, 1990||American National Can Company||Multiple layer sheet structures and package|
|US5011719 *||Jul 27, 1987||Apr 30, 1991||American National Can Company||Polymeric compositions and films|
|US5043383 *||Nov 17, 1989||Aug 27, 1991||Minnestoa Mining And Manufacturing Company||Heat-shrinkable film having high shrinkage upon brief exposure to low activation temperatures|
|US5071686 *||Nov 29, 1985||Dec 10, 1991||Genske Roger P||Films of polypropylene blends and polyethylene blends and articles made therewith|
|US5073599 *||Jun 13, 1988||Dec 17, 1991||American National Can Company||Films using blends of polypropylene and polyisobutylene|
|US5120138 *||Feb 15, 1991||Jun 9, 1992||Minnesota Mining And Manufacturing Company||Flexible bag closure system|
|US5501679 *||Mar 30, 1990||Mar 26, 1996||Minnesota Mining And Manufacturing Company||Elastomeric laminates with microtextured skin layers|
|US5567757 *||Jul 18, 1995||Oct 22, 1996||Rjf International Corporation||Low specific gravity binder for magnets|
|US5691034 *||May 16, 1995||Nov 25, 1997||Krueger; Dennis L.||Elastomeric laminates with microtextured skin layers|
|US5843068 *||Sep 12, 1997||Dec 1, 1998||J&M Laboratories, Inc.||Disposable diaper having elastic side panels|
|US6419798||Dec 15, 2000||Jul 16, 2002||Kimberly-Clark Worldwide, Inc.||Methods of making disposable products having materials having shape-memory|
|US6436529||Jul 18, 1997||Aug 20, 2002||3M Innovative Properties Company||Elatomeric laminates and composites|
|US6533987||Dec 15, 2000||Mar 18, 2003||Kimberly-Clark Worldwide, Inc.||Methods of making materials having shape-memory|
|US6550481 *||Sep 22, 2000||Apr 22, 2003||Thämert Orthopädische Hilfsmittel GmbH & Co. KG||Method for producing an orthopedic cushion having a soft elastic region|
|US6627673||Jul 24, 2001||Sep 30, 2003||Kimberly-Clark Worldwide, Inc.||Methods of making humidity activated materials having shape-memory|
|US6664436||Jul 24, 2001||Dec 16, 2003||Kimberly-Clark Worldwide, Inc.||Disposable products having humidity activated materials with shape-memory|
|US6933421||Jul 24, 2001||Aug 23, 2005||Kimberly-Clark Worldwide Inc.||Methods of making disposable products having humidity activated materials with shape-memory|
|US6994469||Nov 13, 2002||Feb 7, 2006||The Glad Products Company||Shirred elastic sheet material|
|US7074484||Dec 15, 2000||Jul 11, 2006||Kimberly-Clark Worldwide, Inc.||Materials having shape-memory|
|US7300395||Sep 9, 2005||Nov 27, 2007||The Glad Products Company||Method for manufacturing a bag|
|US7459191||Sep 9, 2005||Dec 2, 2008||The Glad Products Company||Shirred elastic sheet material|
|US7582178||Nov 22, 2006||Sep 1, 2009||Kimberly-Clark Worldwide, Inc.||Nonwoven-film composite with latent elasticity|
|US7585382||Oct 31, 2006||Sep 8, 2009||Kimberly-Clark Worldwide, Inc.||Latent elastic nonwoven composite|
|US7717893||Jun 3, 2005||May 18, 2010||The Procter & Gamble Company||Absorbent articles comprising a slow recovery elastomer|
|US7905872||Jun 3, 2005||Mar 15, 2011||The Procter & Gamble Company||Absorbent articles comprising a slow recovery stretch laminate|
|US7910795||Mar 9, 2007||Mar 22, 2011||Kimberly-Clark Worldwide, Inc.||Absorbent article containing a crosslinked elastic film|
|US7938921||May 10, 2011||Kimberly-Clark Worldwide, Inc.||Strand composite having latent elasticity|
|US7946765||May 24, 2011||The Glad Products Company||Shirred elastic sheet material|
|US8029488||Jan 26, 2006||Oct 4, 2011||The Procter & Gamble Company||Disposable pull-on diaper having a low force, slow recovery elastic waist|
|US8323257||Nov 20, 2008||Dec 4, 2012||The Procter & Gamble Company||Absorbent articles comprising a slow recovery stretch laminate and method for making the same|
|US8419701||Apr 16, 2013||The Procter & Gamble Company||Absorbent articles with stretch zones comprising slow recovery elastic materials|
|US9017305||Nov 10, 2011||Apr 28, 2015||The Procter Gamble Company||Elastomeric compositions that resist force loss and disintegration|
|US20030060788 *||Jul 24, 2001||Mar 27, 2003||Topolkaraev Vasily A.||Methods of making disposable products having humidity activated materials with shape-memory|
|US20050273071 *||Jun 3, 2005||Dec 8, 2005||Mckiernan Robin L||Absorbent articles comprising a slow recovery stretch laminate|
|US20050273072 *||Jun 3, 2005||Dec 8, 2005||Bryn Hird||Absorbent articles comprising a slow recovery elastomer|
|US20060008603 *||Sep 9, 2005||Jan 12, 2006||The Glad Products Company||Shirred elastic sheet material|
|US20060009339 *||Sep 9, 2005||Jan 12, 2006||The Glad Products Company||Shirred elastic sheet material|
|US20080003910 *||Oct 31, 2006||Jan 3, 2008||Kimberly-Clark Worldwide, Inc.||Latent elastic nonwoven composite|
|US20080108963 *||Nov 2, 2007||May 8, 2008||The Procter & Gamble Company||Absorbent Article With Handles Of Slow Recovery Material|
|US20080119102 *||Nov 22, 2006||May 22, 2008||Hughes Janis W||Nonwoven-film composite with latent elasticity|
|US20080119103 *||Nov 22, 2006||May 22, 2008||Wing-Chak Ng||Strand composite having latent elasticity|
|US20080221540 *||Mar 9, 2007||Sep 11, 2008||Kimberly-Clark Worldwide, Inc.||Absorbent article containing a crosslinked elastic film|
|US20100273012 *||Dec 19, 2008||Oct 28, 2010||Kuraray Co., Ltd.||Thermoplastic polymer composition and shaped article composed of the same|
|WO1993002137A1 *||Jul 22, 1991||Feb 4, 1993||The Dow Chemical Company||Compositions of vinylaromatic polymers and vinylidene chloride polymers|
|U.S. Classification||523/300, 525/281, 525/233, 524/572, 525/177, 524/467, 522/112, 264/230, 525/121, 524/575, 525/239, 524/545, 524/552, 525/106, 525/232, 525/215, 525/206, 522/111, 524/565, 524/588, 524/574, 525/104, 524/569, 524/579|
|International Classification||C08L23/02, C08L101/00, C08L23/34, C08L83/04, C08L21/00, C08L19/00, C08J3/24|
|Cooperative Classification||C08L21/00, C08J3/24, C08L91/06, C08L25/06, C08L23/06, C08L27/06, C08L83/00, C08L23/02, C08L19/003, C08L2312/00, C08L2310/00, C08L53/02, C08L83/04, C08L45/02, C08L23/0815, C08L9/02, C08L2205/02, C08G77/442, C08L63/00, C08L2205/035, C08L101/00, C08L91/00, C08L9/06, C08K5/14, C08G77/24, C08L2207/07, C08L23/34, C08L67/00, C08K3/22, C08L55/02, C08L11/00, C08G77/04|
|European Classification||C08L83/04, C08L19/00B, C08L83/00, C08L21/00, C08L9/06, C08L9/02, C08L23/02, C08L23/34, C08L27/06, C08L67/00, C08L53/02, C08L11/00, C08L55/02, C08L101/00, C08J3/24|