METHOD OF THERMOFORMING POLYOLEFIN RESIN

Abstract: A process for thermoforming a polyolefin resin sheet is provided having an aromatic aldehyde-polyhydric alcohol condensation product incorporated in the sheet to limit deformation of the sheet during the heating step.

Description: Description METHOD OF THERMOFORMING POLYOLEFIN RESIN BACKGROUND OF THE INVENTION This invention relates to thermoforming polyolefin resin, and in particular to resins which incorporate an aromatic aldehyde-polyhydric alcohol condensation product and an opacifying pigment Thermoforming polyolefin resins entails the steps of heating a sheet ofthe resin until it softens, stretching the softened sheet against a solid form and allowing the sheet to cool Heating the sheet is typically accomplished by infrared radiant heaters or by forced convection hot air ovens The sheet is transported through the heating zone while being suspended by pins mounted on bicycle-style chains running along the sides ofthe sheet Alternatively, the sheet may be suspended during transport by tenter-style clamps Polyolefin resins are semi-crystalline, that is, upon cooling they form amorphous regions and crystalline regions Because ofthe low mobility of polymer chains and the high cooling rates that are typically used to process polyolefins, polymer crystals usually form with varying degrees of crystalline perfection The crystalline regions act like physical cross-links that hold the polymer together The crystalline cross-links are the reason that most semi-crystalline polymers can be formed elastically at temperatures above the glass transition temperature ofthe polymer (T g ) When semi crystalline polymers are heated above T g the distribution in crystalline perfection causes the polymer to melt over a range of several degrees Less perfectly formed crystals have poor thermal stability and are the first to melt. When the first less perfect crystals melt, the physical cross-links begin to break down and the amorphous chains start to relax and flow. At this point the polymer has properties that are ideal for thermoforming, some physical structure exists, but the polymer is easily deformed. At slightly higher temperatures, all ofthe crystals melt, and the polymer deforms like a viscous liquid. One ofthe difficulties encountered in thermoforming resins is maintaining the resin temperature within the narrow processing window, whereby the resin is soft enough to be stretched and shaped, without the loss of the integrity of the sheet. Often under typical processing conditions, the sheet of resin sags or becomes rippled when it is heated. The deformations in the sheet may in turn lead to irregularities in the shaped articles made by the process, such as variations in weight and thickness, anisotropic thermal expansion and shrinkage. The deformation observed in the heated sheet and resulting irregularities may be exacerbated when resins having a relatively high melt flow index are employed. Consequently, resins having a melt flow index of from 1 to 2 are typically used. The aromatic aldehyde-polyhydric alcohol condensation products employed in the present invention have been incorporated in polyolefin resins as nucleating agents to improve the clarity of the resin. It has been proposed that the condensation products form a network of nucleation sites in the resin upon cooling. Upon crystallization, the resin forms fine spherulites which are smaller than the wavelength of visible light. A description ofthe nucleating agents may be found in Mannion US 5,310,950, and the references sited therein. The use of aromatic aldehyde-polyhydric alcohol condensation products as gelling agents for organic solvents is descπbed in Kobayashi et al , US 4,246,000 The condensation products are dissolved in a liquid fuel and castor oil mixture which is used to form a coal-in-oil suspension The condensation product helps prevent settling ofthe finely divided coal particles The aforementioned condensation products have also been employed as gelling agents in cosmetic sticks For example, Benfatto et al , US 5,376,363 describes a composition containing dibenzylidene sorbitol in an antiperspirant composition Additionally, the use of dibenzylidene sorbitol to improve the physical property of polyethylene, particularly to increase its tensile strength and raise its melting point, is disclosed in Hamada et al , JP 45-22008 (1970) A large share of thermoforming is performed with polyolefin resins containing an opacifying amount of pigment Since the resin is intended to be opaque, there has not been any motivation to incorporate the aromatic aldehyde-polyhydric alcohol condensation products or any other agents which improve resin clarity Furthermore, the potential benefits for the condensation products with regard to sheet stability during the heating step and facilitation ofthe use of high melt flow index resins has not been recognized SUMMARY OF THE INVENTION Therefore, the objects ofthe present invention include providing a method of thermoforming polyolefin resin with less variation in weight and thickness, less anisotropic expansion and shrinkage and less overall shrinkage, providing a method with a greater range of operating temperatures for the heating step, providing a method m which the sheet of resin is heated while being supported by its side edges, providing a process which has a minimum of sheet deformation or distortion, providing a process which may employ resins having a relatively high melt flow index; and providing a method of thermoforming opacified resins. Accordingly a method is provided having the steps of incorporating a condensation product of two moles of aromatic aldehyde and one mole of penta-or hexahydric alcohol and an opacifying amount of a pigment into the resin; forming a resin into a sheet; heating the sheet to a temperature above the softening temperature and below the melt temperature ofthe resin: shaping the softened sheet into an article; and cooling the shaped article. In an alternative embodiment ofthe invention a polyolefin resin having a melt flow index of 2.5 to 15, preferably 2.75 to 4.5, and the aforementioned condensation product incorporated therein, is employed in the thermoforming process. The resin may or may not be opaque. In addition to meeting the above objectives, the present invention has the features and advantages of extending the processing window ofthe heating step by several degrees centigrade and increasing the elasticity of the resin during the heating step, thereby enhancing the sheet integrity. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph ofthe storage modulus of polypropylene, both with and without bis(3,4-dimethylbenzylidene) sorbitol acetal, over a temperature range of 140 to 170°C. DETAILED DESCRIPTION OF THE INVENTION Without limiting the scope ofthe invention the preferred embodiments and features are set forth. Unless otherwise indicated, all parts and percentages are by weight and conditions are ambient, i.e. one atmosphere of pressure and 25 °C and the molecular weight is based on mean (number) averages. Unless otherwise specified, aliphatic hydrocarbons are from 1-12 carbons atoms in length, cycloaliphatic hydrocarbons comprise from 3-8 carbon atoms and aromatic compounds are single and fused double- ring unsaturated hydrocarbons. All ofthe US patents, and other references cited in the specification are hereby incorporated by reference. The process of thermoforming polyolefin resin is well known to those skilled in the art and is described in detail in Throne, "Thermoforming" (ISBN 3-446-14699-7) Hanser Publishers, Munich (1987). Briefly the typical thermoforming process steps are clamping, heating, shaping, cooling and trimming. The polyolefin resin is provided in sheets which are generally categorized as "thin-gauge" (sheet thickness less than 0.25 mm) and "thick-gauge" (sheet thickness greater than 0.25 mm). For most applications, the sheet thickness ranges from 0.25 mm to 12 mm, preferably 0.5 mm to 2.5 mm. The sheet may be heated by infrared radiant heater, forced convection hot air ovens, or a combination of radiant and convection heating Contact heating, where the sheet is placed against a heated plate, is used in a specialized thermoforming area referred to as trapped sheet forming. The sheet is heated to a temperature above the softening temperature and below the melt temperature of the resin. The softening temperature is characterized by the onset of melting in the amorphous stage; the melt temperature is characterized by melting of substantially all the crystal regions. The melt temperature may be determined by Differential Scanning Calorimeter (DSC) or by an oven "sag test", by observing when the sheet begins to sag uncontrollably The precise operating temperatures will depend upon the individual resin used Polypropylene homopolymer may be heated to a temperature of 141 ° to 164°C preferably 153 ° to 159°C Polypropylene random copolymer (RCP) 3% ethylene content may be heated to a temperature of 125° to 150°C, preferably 133 ° to 145°C, but the temperature will vary significantly depending upon the ethylene content Once the sheet is heated to the desired temperature it is shaped into an article by molding The basic moid configuration are the male mold, female mold and matched mold (die forming) The sheet may be pre-stretched prior to molding with air pressure or a mechanical assist known as a plug The sheet is held in the mold and cooled sufficiently foi the resin to maintain its desired shape The sheet may be trimmed in the mold or in a separate trimming apparatus Examples of polyolefin resins which may be used in the thermoforming process of the present invention include polymers and copolymers of aliphatic mono-olefins containing from 2 to 6 carbon atoms, which have an average molecular weight of from about 10,000 to about 2,000,000, preferably from about 30,000 to about 300,000, such as polyethylene, linear low density polyethylene, polypropylene, crystalline ethylene/propylene copolymer (random or block), poly( 1 -butene) and polymethylpentene The polyolefins ofthe present invention may be described as semi- crystalline, basically linear, regular polymers which may be optionally contain side chains, such as are found in conventional low density polyethylene Preferably the polyolefin resm is polypropylene homopolymer or random copolymer The polyolefin resins ofthe present invention may include aliphatic polyolefins and copolymers made from at least one aliphatic olefin and one or more ethylenically unsaturated comonomers. Generally, the comonomers, if present, will be provided in a minor amount, e.g., about 10% or less or even about 5% or less, based upon the weight ofthe polyolefin. Such comonomers may serve to improve the mechanical and/or chemical properties ofthe polymer. Examples include acrylic acid, methacrylic acid, and esters ofthe same, vinyl acetate, etc. The present invention can accommodate a wide variety of polyolefin resins Accordingly, resins having a melt flow index of from 0.6 to 15 (0.6 MF to 15 MF) may be used, preferably from 1.8 MF to 4.5 MF. An advantage ofthe present invention is that while 1 MF to 2 MF resins are typically employed in thermoforming, now resins having a melt flow index of 2.5 or greater, preferably 2.75 to 4.5 may be employed to take advantage ofthe desirable performance characteristics of those resins. A condensation product of two moles of an aromatic aldehyde and one mole of a polyhydric alcohol, preferably a penta- or hexahydric alcohol such as xylitol or sorbitol respectively, is incorporated in the polyolefin resin prior to the resin being formed into a sheet. Examples of suitable aromatic aldehydes includes benzaldehyde and naphthaldehyde, which may be substituted with one or more substituent groups, such as alkyl, halo, alkoxy, poly(oxyalkylene), thioether Also included are substituents where the alkyl group forms a carboxylic ring with the aromatic aldehyde The condensation products of interest include di-acetals of sorbitol and xylitol having the general formula wherein p is 0 or 1, m and n are independently 0-3, R is, at each occurrence, independently selected from C,. 8 alkyl, C, 4 alkoxy, hydroxy, halogen, C,_ 6 alkylthio, C,. 6 alkylsulfoxy and a 4 or 6 membered alkyl group forming a carbocyclic ring with adjacent carbon atoms of the unsaturated parent ring Of particular interest are compounds where p is 1 and R is selected from C,. 3 alkyl, chlorine, bromine, thioether and a 4- membered alkyl group forming a carbocyclic ring with adjacent carbon atoms ofthe unsaturated parent ring Examples of compounds having utility herein include dibenzylidene sorbitol, dι(p-methylbenzylιdene) sorbitol, dι(o-methylbenzyhdene) sorbitol, dι(p-ethylbenzylιdene) sorbitol, bιs(dιmethylbenzylιdene) sorbitol, especially bιs(2,4-dιmethylbenyzhdene) sorbitol and bιs(3,4-dιmethylbenzyhdene) sorbitol, bιs(3,4-dιethylbenzylidene) sorbitol, bιs(5',6',7',8'-tetrahydro-2-naphthylιdene) sorbitol, bιs(tπmethylbenzylιdene) xylitol and bιs(tπmethylbenzylιdene) sorbitol Also within the scope ofthe present invention are compounds made with a mixture of aldehydes, including substituted and unsubstituted benzaldehydes, such as Kobayashi et al , US Pat No 4,532,280 and Kobayashi et al , US Pat No 4,954,291 The di-acetals of the present invention may be conveniently prepared by a variety of techniques known in the art Generally, such procedures employ the reaction of 1 mole of D-sorbitol or D-xyhtol with about 2 moles of an aldehyde in the presence of an acid catalyst The temperature employed in the reaction will vary widely depending on the characteristics, such as melting point, ofthe aldehyde or aldehydes employed as the starting material in the reaction Examples of suitable reaction medium are cyclohexane, or a combination of cyclohexane and methanol Water produced by the condensation reaction is distilled off Typically the mixture is allowed to react for several hours, after which the reaction is cooled, neutralized, filtered, washed, for example, with water or an alcohol, and then dried Representative processes for manufacturing the condensation products useful in the present invention are disclosed in Murai et al , US 3,721 ,682 and New Japan Company , Ltd , EP 0 497 976 Al The aromatic aldehyde-polyhydric alcohol condensation product may be conveniently added directly to the polyolefin resin duπng compounding or provided as a resin concentrate, which is "let down" by blending with resin which does not contain the condensation product, prior to the resin being formed into a sheet The sheet of polyolefin resin may contain from 250 ppm to 20,000 ppm of the condensation product, preferably from 500 ppm to 4,000 ppm In addition to facilitating the use of relatively high melt flow index polyolefin resins, the present invention includes the use of polyolefin resins incorporating an aromatic aldehyde-polyhydric alcohol condensation product and an opacifying amount of a pigment Suitable pigments are disclosed in Gachter & Muller, "Plastics Additives," Third Edition (ISBN 3-446-15680-1) Hanser Publishers, Munich (1990) The pigments typically have a primary particle size range of from 0 01 to 1 micron Examples of suitable pigments include titanium dioxide, carbon black, lamp black, calcium carbonate, talc, and organic colored pigments, such as azo, phthalocyanine and anthraquinone pigments. The pigments are compounded into the resins by techniques well known to those skilled in the art, prior to formation ofthe polyolefin resin into a sheet The pigment is provided in sufficient concentration to opacify the resin, which may be characterized as having less than 10 percent light transmittance through a sheet of resin. By way of examples, concentrations of from 100 ppm to 40 weight percent, preferably 1,000 ppm to 2 weight percent ofthe pigment in the resin composition may be employed The invention may be further understood by reference to the following examples, but is not intended to be unduly limited thereby. EXAMPLE I The following example demonstrates that incorporation of the aromatic aldehyde-polyhydric alcohol condensation product in the resin increases the temperature range over which the softened resin sheet maintains elasticity during the thermoforming process. It is believed that the loss of elasticity results in wrinkling, puckering, and sagging ofthe sheet during the heating step, which in turn leads to irregularities and defects in articles shaped from the sheet. Rggins Resin A- 1 : polypropylene homopolymer (2MF) Resin A-2: polypropylene homopolymer (2MF) containing 1,900 ppm of bis (3,4-dimethylbenzylidene) sorbitol acetal. Resin B-l : polypropylene homopolymer (4MF) Resin B-2: polypropylene homopolymer (4MF) containing 2,300 ppm of bis (3,4-dιmethylbenzyhdene) sorbitol acetal Resin C-l polypropylene random copolymer (4MF) 3 percent ethylene content Resin C-2 polypropylene random copolymer (4MF) 3 percent ethylene content containing 2,300 parts per million ofthe bιs(3,4-dιmethylbenzylιdene) sorbitol acetal Resin D-l polypropylene random copolymer (12MF) 3 percent ethylene content Resin D-2 polypropylene random copolymer (12MF) 3 percent ethylene content containing 2,500 parts per million of the bιs(3,4-dιmethylbenzylιdene) sorbitol acetal All ofthe resin tested contained a commercial additive package of an antioxidant, lubricant and acid scavenger Method Viscoelastic measurements were made in oscillation mode using a TA Instruments CSL 2 500 Dynamic Mechanical Rheometer equipped with 4cm diameter parallel plates Isofrequency measurements were performed at either 0 1 Hz or 0 3 Hz while the sample was heated from 100° C to 170° C at either 2° C or 5° C per minute The strain was set to a nominal value of 1 % The Dynamic Mechanical Rheometer was used to measure the viscoelasticity properties of polypropylene while heating the polymer sample from the solid phase to the liquid phase Over the course ofthe investigation, it was determined that the storage modulus, G', is the viscoelastic function that is most closely related to the polymer structure The storage modulus, a measure ofthe energy that is stored elastically during the deformation of a viscoelastic material, is analogous to a spring constant. When the semi-crystalline polymer is heated above T g , the storage modulus remains nearly constant until the polymer begins to melt and the elasticity ofthe resin is substantially lost During the melting transition, the polymer structure melts away and G' decreases by several orders of magnitude The temperature at which elasticity is lost is referred to as the "onset" temperature The results ofthe experiment are presented below in Table 1 and in the graph in Figure 1 TABLE 1 The results demonstrate that the onset temperature, measured as the temperature at which G' begins to deviate significantly from the value of G' in the plateau region, is increased by incorporating the aromatic aldehyde-polyhydric alcohol condensation product in the resin The increase in temperature ranges from as little as 1 6° C to as much as 4 2° C It is believed that the condensation products form a network of nanometer-scale high aspect ratio fibers, that adds structure to the partially melted polymer by thickening or gelling the amorphous regions Because of the added structure in the amorphous regions, loss of elasticity occurs at a much slower rate Consequently, wrinkling, puckering, and sagging ofthe sheet are easier to avoid during thermoforming EXAMPLE II The following example confirms the rheological date of Example I, using a Dynamic Mechanical Analyzer (DMA) to measure the strain or expansion of a polyolefin resm versus temperature at very low stress In addition to testing the resins of Example I, a resin containing an opacifying amount of titanium dioxide was also tested Resin Resin E-l Polypropylene Homopolymei (1 6MF) containing 10,000 ppm titanium dioxide Resin E-2 Polypropylene Homopolymei (1 6 MF) containing 10,000 ppm titanium dioxide and 1,900 ppm bιs(3,4-dιmethylbenzylιdene) sorbitol acetal Method The force exerted on a polyolefin resin sheet, which is pinned or clamped along its sides, while being heated during the thermoforming process was estimated to be from 0 5 to 2 5 newtons DMA was used in the creep recovery mode to model the stress seen by the sheet in a thermoforming oven The specimen sheet was first heated to 80° C then was clamped m the jaws ofthe DMA and the instrument was zeroed The sample was slowly heated under an oscillating force, which ranged from 0 9 to 1 newton until the transition from the elastic to the tensile flow state was observed The temperature at which the transition occurred was identified as the onset temperature The results are shown below in Table 2 TABLE 2 The results confirm that incorporation of the aromatic aldehyde-polyhydric alcohol condensation product increases the onset temperature at which the elasticity of the resin is substantially diminished This increase in the yield onset temperature is very significant because it widens the temperature region where the polypropylene exhibits desirable elastic properties from about 141° to 148° C with the homopolymer control to about 141° to 151° C with the homopolymer containing the sorbitol acetal In addition to widening the processing window by about 40%, this innovation enables the processor to form parts at a higher temperature which will allow for the production of parts with less internal stress The difference in absolute values for the onset temperature, between Example I and Example II, is a function of the nature ofthe testing apparatus and the geometry ofthe samples. EXAMPLE HI fComparativeϊ The following example demonstrates application of the sheet stabilizing technology to the thermoforming process to control part to part weight variation The example also includes a comparative test of a commercial nucleating agent for a polyolefin, which is outside the scope ofthe present invention Resin In addition to Resins A-l and A-2 from Example 1, a resin was prepared with the recommended loading of a phosphite based commercial nucleating agent available from Asahi Denka Kogyo (Japan), sold under the trade name NA-10 Resin A-3 polypropylene homopolymer (2MF) containing 900 ppm NA-10. Method Each resin formulation was extruded into a sheet and pressure formed into containers having a capacity of 325cc. The thermoforming equipment allowed eight containers to be molded simultaneously Next all ofthe containers from a particular mold were weighed and the standard deviation was calculated The results are compiled below in Table 3 TABLE 3 The results clearly demonstrate that there is less part to part weight variation when the thermoforming process is performed with a polyolefin resin having an aromatic aldehyde-polyhydric alcohol condensation product incorporated therein Furthermore, the results are consistent with the observations made during the trial, that is, after the heating step, the sheets without the control sheet and the sheet containing NA-10 had an uneven, rippled appearance, whereas the sheet ofthe present invention was flat prior to forming EXAMPLE IV The following example demonstrates application ofthe sheet stabilizing technology to the thermoforming process to produce parts which are less prone to shrinkage when they are "hot-filled " Resin Resin F-1 polypropylene homopolymer (4MF) Resin F-2 polypropylene homopolymer (4MF) containing 1 ,900 ppm bιs(3,4- dimethylbenzylidene) sorbitol acetal Resin G-l polypropylene random copolymer (4MF) 3 percent ethylene content Resin G-2: polypropylene random copolymer (4MF) 3 percent ethylene containing 1,900 ppm bis(3,4-dimethylbenzylidene) sorbitol acetal Method Each resin formulation was extruded into a sheet and pressure formed into drinking cups with a capacity of 200cc. Four cups were selected from each resin sample and the outer diameter ofthe cup was precisely measured at a height of 0 5 inches above the base. Next, the cup was filled with 150 to 160ml of water and heated in the microwave oven until the water boiled for approximately one and a half minutes The cups were allowed to cool at room temperature for one hour Finally the outer diameter of each cup was measured at a height of 0 5 inches above the base The results are compiled below in Table 4 TABLE 4 The cups that were thermoformed from resin containing the aromatic aldehyde- polyhydric alcohol condensation product shrank substantially less than the controls It is believed that incorporation ofthe condensation products reduces deformation in the sheet prior to the sheet being shaped into an article, which results in less stress in the shaped article and less shrinkage when the article is filled with a hot fluid There are, of course, many alternative embodiments and modifications ofthe invention which are intended to be included within the scope of the following claims

Claims: What we claim is 1 A process for thermoforming a polyolefin resin, comprising the steps of (a) incorporating into the resin (i) the condensation product of two moles of an aromatic aldehyde and one mole of a penta- or hexahydric alcohol, and (ii) a pigment in an amount sufficient to opacify the resin, (b) forming the resin into a sheet, (c) heating the sheet of resin to a temperature above the softening temperature and below the melt temperature of the resin, (d) shaping the softened sheet into an article, and (e) cooling the shaped article. 2 The process of Claim 1 wherein the condensation product has the formula: wherein p is 0 or 1 , m and n are independently 0-3, R is, at each occurrence, independently selected from C,.g alkyl, C,. 4 alkoxy, hydroxy, halogen, C,. 6 alkylthio, C,. 6 alkylsulfoxy and a 4 or 6 membered alkyl group forming a carbocyclic ring with adjacent carbon atoms of the unsaturated parent ring 3. The process of Claim 2 wherein the polyolefin resin is selected from the group consisting of polypropylene homopolymer and random copolymer 4. The process of Claim 2 wherein the pigment is selected from the group consisting of titanium dioxide, carbon black, calcium carbonate, talc and colored organic pigments. 5 The process of Claim 4 wherein the resin is polypropylene homopolymer and the sheet of resin is heated to a temperature of from 153° to 159° C. 6 The process of Claim 4 wherein the resin is polypropylene random copolymer and the sheet of resin is heated to a temperature of from 133° to 145° C 7 The process of Claim 4 wherein the polyolefin resin is selected from the group consisting of polypropylene homopolymer and random copolymer 8 The process of Claim 3 wherein the pigment is titanium dioxide and the pigment is incorporated in the resin in a concentration of from 1 ,000 to 20,000 ppm 9 The process of Claim 3 wherein the resin has a melt flow index of from 2.5 to 15 10 The process of Claim 3 wherein the resin has a melt flow index of from 2 75 to 4.5. 1 1 A process for thermoforming a polyolefin resin, comprising the steps of (a) incorporating into the resin the condensation product of two moles of an aromatic aldehyde and one mole of a penta- or hexahydric alcohol, wherein the resin has a melt flow index of from 2 5 to 15, (b) forming the resin into a sheet, (c) heating the sheet of resin to a temperature above the softening temperature and below the melt temperature of the resin, (d) shaping the softened sheet into an article, and (e) cooling the shaped article The process of Claim 1 1 wherein the condensation product has the formula wherein p is 0 or 1, m and n are independently 0-3, R is, at each occurrence, independently selected from C,. 8 alkyl, C,. 4 alkoxy, hydroxy, halogen, C,. 6 alkylthio, C,. 6 alkylsulfoxy and a 4 or 6 membered alkyl group forming a carbocyclic ring with adjacent carbon atoms ofthe unsaturated parent ring The process of Claim 12 wherein the polyolefin resin is selected from the group consisting of polypropylene homopolymer and random copolymer The process of Claim 12 wherein the resin is polypropylene homopolymer and the sheet of resin is heated to a temperature of from 153° to 159° C The process of Claim 12 wherein the resin is polypropylene random copolymer and the sheet of resin is heated to a temperature of from 133° to 145° C The process of Claim 13 wherein the polypropylene resin has a melt flow index offrom 2 75 to 4 5 The process of Claim 16 wherein the resin is polypropylene homopolymer and the sheet of resin is heated to a temperature of from 153° to 159° C The process of Claim 16 wherein the resin is polypropylene random copolymer and the sheet of resin is heated to a temperature of from 133° to 145° C

Inventors: MANNION MICHAEL J, MEHL NATHAN A, MANNION, MICHAEL, J., MEHL, NATHAN, A.
Applicants: MILLIKEN RES CORP, MILLIKEN RESEARCH CORPORATION
Application year: 1997
Main classification: C08K5
IPC codes: B29C51, B29K23, C08K5, C08L23