Patent Grant
7550528
This invention relates to a composition comprising a functionalized C3-C40 olefin polymer. This invention further relates to functionalized olefin polymers, as well as processes to produce and use functionalized olefin polymers including applications as adhesives, tie layers, primers, compatibility agents, and the like.
Olefin based polymers are widely used in various applications due to their being chemically inert, having low density, and low cost. Applications include adhesives, tie layers, films, fibers, and combinations thereof.
Olefin based polymers may be formed into various films, which may be laminated to, coated on, or co-extruded with various substrates. The film and the substrate may be combined with other materials to form a structure having a plurality of layers, each layer having a specific purpose. Packaging laminates, for example, may comprise a plurality of layers, such as a configurationally rigid core layer of paper or paperboard, an outer liquid-tight layer, an oxygen gas barrier such as a mid-layer of aluminum foil, and/or other layers depending on application needs.
To provide effective adhesion, it is important that good bonding strength or intimate integrity between the layers be achieved for most applications. However, relatively non-polar olefin based polymers do not normally adhere well to substrates which are more polar.
In addition, the set time of an adhesive may need to be within limits consistent with a proposed end use. Tailoring of an adhesive set time however may be accomplished at the expense of other attributes of an adhesive. For example, while inclusion of various forms of wax (e.g., polyethylene wax) may reduce a set time of an adhesive, the inclusion of a wax may also reduce or destroy adhesive properties in particular temperature ranges, and/or to particular substrates, especially polar substrates.
Adhesives are typically not heat stable, especially with respect to color over a period of time when the adhesive is heated at or above its melting point. Stability issues related to thermal degradation, including those related to bond strength and color body formation at elevated temperatures, may render various adhesives unfit for a variety of end uses.
There thus remains a need for an adhesive that will intimately bond to both polar and non-polar substrates, preferably one that exhibits a superior durability of bond strength under various temperature conditions at particular set times and in the presence of aggressive products, and that is heat stable at elevated temperatures.
This invention relates to a composition comprising a functionalized C3 to C40 olefin polymer comprising at least 50 mol % of one or more C3 to C40 olefins and having: a) a Dot T-Peel of 1 Newton or more on Kraft paper; b) an Mw of 10,000 to 100,000; and c) a branching index (g′) of 0.98 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 60,000, or a branching index (g′) of 0.95 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 100,000. This invention further relates to such functionalized C3 to C40 olefin polymers blended with other polymers. In a preferred embodiment the functionalized C3 to C40 olefin polymer is blended with the same or different non-functionalized C3 to C40 olefin polymer comprising at least 50 mol % of one or more C3 to C40 olefins and having: a) a Dot T-Peel of 1 Newton or more on Kraft paper; b) an Mw of 10,000 to 100,000; and c) a branching index (g′) of 0.98 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 60,000, or a branching index (g′) of 0.95 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 100,000.
By “functionalized C3 to C40 olefin polymer” is meant that the C3 to C40 olefin polymer is contacted with a functional group, and optionally a catalyst, heat, initiator, or free radical source to cause all or part of the functional group to incorporate, graft, bond to, physically attach to, and or chemically attach to the C3 to C40 olefin polymer. By “functional group” is meant any compound with a weight average molecular weight of 1000 or less that contains a heteroatom and or an unsaturation. Preferably the functional group is a compound containing a heteroatom, such as maleic anhydride. Preferred functional groups include organic acids, organic amides, organic amines, organic esters, organic anhydrides, organic alcohols, organic acid halides (such as acid chlorides, acid bromides, etc.) organic peroxides, and the like.
For ease of reference the functionalized C3 to C40 olefin polymer may be abbreviated as F-POA and a C3 to C40 olefin polymer that has NOT been functionalized may be referred to as a POA.
For the purposes of this invention and the claims thereto and for ease of reference, when a polymer is referred to as comprising an olefin, the olefin present in the polymer is the polymerized form of the olefin.
In a preferred embodiment, this invention relates to a composition comprising:
1) 0.5 to 99 weight % (preferably 1 to 75 weight %, more preferably 1.5 to 40 weight %, preferably 2 to 20 weight %, preferably 2.5 to 10 weight %) of a functionalized C3 to C40 olefin polymer comprising at least 50 mol % of one or more C3 to C40 olefins and having: a) a Dot T-Peel of 1 Newton or more on Kraft paper; b) an Mw of 10,000 to 100,000; and c) a branching index (g′) of 0.98 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 60,000, or a branching index (g′) of 0.95 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 100,000.
2) 99 to 1 weight % (preferably 99 to 25 weight %, more preferably 98.5 to 60 weight %, preferably 98 to 80 weight %, preferably 97.5 to 90 weight %) of one or more additional polymers different from the functionalized C3 to C40 olefin polymer,
based upon the weight of the additional polymer(s) and the functionalized C3 to C40 olefin polymer.
In a preferred embodiment the additional polymer comprises one or more C3 to C40 olefin polymer comprising at least 50 mol % of one or more C3 to C40 olefins and having: a) a Dot T-Peel of 1 Newton or more on Kraft paper; b) an Mw of 10,000 to 100,000; and c) a branching index (g′) of 0.98 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 60,000, or a branching index (g′) of 0.95 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 100,000.
In a preferred embodiment this invention relates to a blend comprising F-POA and between 1 and 90 weight % tackifier, preferably between 5 and 75 weight %, more preferably between 10 and 60 weight %, more preferably between 15 and 50% of tackifier, based upon the weight of the blend, and between 10 and 99 weight % of the F-POA, preferably between 95 and 25 weight %, more preferably between 40 and 90 weight %, more preferably between 85 and 50% of the F-POA.
In another preferred embodiment this invention relates to a blend comprising F-POA, POA and between 1 and 90 weight % tackifier, preferably between 5 and 75 weight %, more preferably between 10 and 60 weight %, more preferably between 15 and 50% of tackifier, based upon the weight of the blend, and between 10 and 99 weight % of F-POA and POA, preferably between 95 and 25 weight %, more preferably between 40 and 90 weight %, more preferably between 85 and 50%.
In a preferred embodiment comprising POA and F-POA, the POA and the F-POA may include the same olefin polymer or blend of olefin polymers which is/are functionalized to become the F-POA, which are then blended with POA. In another embodiment, the olefin polymer or blend of olefin polymers of the POA may be different from the olefin polymer or blend of olefin polymers functionalized to become the F-POA. In still another embodiment, the olefin polymer or blend of olefin polymers of the POA may be the exact same olefin polymer or blend of olefin polymers that has been functionalized to become the F-POA. In yet another embodiment, the F-POA may include functionalized analogs of the exact same olefin polymer or blend of olefin polymers as is in the POA. Preferably, the POA comprises the exact same olefin polymer as the F-POA, which has been functionalized with maleic anhydride.
C3 to C40 Olefin Polymers (POA's)
Preferred C3 to C40 olefin polymers (also called “POA's” or “POA polymers”) useful in this invention are those described in U.S. Ser. No. 10/686,951, filed Oct. 15, 2003 and U.S. Ser. No. 10/687,508, filed Oct. 15, 2003, which are incorporated by reference herein. In particular, pages 23 to 91 of U.S. Ser. No. 10/686,951 and pages 22 to 168 of U.S. Ser. No. 10/687,508 provide specific instruction on how to produce the C3 to C40 olefin polymers useful herein. In general preferred POA's comprise a polypropylene prepared utilizing two or more catalysts (typically metallocene catalysts), wherein one catalyst is selected as being capable of producing essentially atactic polypropylene (aPP), and the other metallocene catalyst is selected as being capable of producing isotactic polypropylene (iPP) under the polymerization conditions utilized. Preferably, under the polymerization conditions utilized, incorporation of aPP and iPP polymer chains may occur within the in-reactor blend such that an amount of amorphous polypropylene present in the POA polymer is grafted to isotactic polypropylene, represented herein as (aPP-g-IPP) and/or such that an amount of isotactic polypropylene present in the POA polymer is grafted to amorphous polypropylene, represented herein as (iPP-g-aPP).
Preferred POA's useful in this invention include olefin polymer comprising one or more C3 to C40 olefins, preferably propylene, and less than 50 mole % of ethylene, having:
Preferred POA's useful in this invention include olefin polymers comprising one or more C3 to C40 olefins, preferably propylene, and less than 50 mole % of ethylene, having:
In an embodiment, the g′ may be 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less when measured at the Mz of the polymer.
In another embodiment the POA may have a peak melting point (Tm) between 40 and 250° C., or between 60 and 190° C., or between 60 and 150° C., or between 80 and 130° C. In some embodiments the peak melting point is between 60 and 160° C. In other embodiments the peak melting point is between 124-140° C. In other embodiments, the peak melting temperature is between 40-130° C.
In another embodiment the POA may have a viscosity (also referred to a Brookfield Viscosity or Melt Viscosity) of 90,000 mPa·sec or less at 190° C. (as measured by ASTM D 3236 at 190° C.); or 80,000 or less, or 70,000 or less, or 60,000 or less, or 50,000 or less, or 40,000 or less, or 30,000 or less, or 20,000 or less, or 10,000 or less, or 8,000 or less, or 5000 or less, or 4000 or less, or 3000 or less, or 1500 or less, or between 250 and 6000 mPa·sec, or between 500 and 5500 mPa·sec, or between 500 and 3000 mPa·sec, or between 500 and 1500 mPa·sec, and/or a viscosity of 8000 mPa·sec or less at 160° C. (as measured by ASTM D 3236 at 160° C.); or 7000 or less, or 6000 or less, or 5000 or less, or 4000 or less, or 3000 or less, or 1500 or less, or between 250 and 6000 mPa·sec, or between 500 and 5500 mPa·sec, or between 500 and 3000 mPa·sec, or between 500 and 1500 mPa·sec. In other embodiments the viscosity is 200,000 mPa·sec or less at 190° C., depending on the application. In other embodiments the olefin polymer may have a viscosity of about 50,000 mPa·sec or less, depending on the application.
In another embodiment the POA may also have a heat of fusion of 70 J/g or less, or 60 J/g or less, or 50 J/g or less; or 40 J/g or less, or 30 J/g or less, or 20 J/g or less and greater than zero, or greater than 1 J/g, or greater than 10 J/g, or between 20 and 50 J/g.
In another embodiment the oPOA may also have a Shore A Hardness (as measured by ASTM 2240) of 95 or less, 70 or less, or 60 or less, or 50 or less, or 40 or less or 30 or less, or 20 or less. In other embodiments, the Shore A Hardness may be 5 or more, 10 or more, or 15 or more. In certain applications, such as packaging, the Shore A Hardness is preferably about 60-70.
In still another embodiment the POA may have a Mz/Mn of 2 to 200, preferably 2 to 150, preferably 10 to 100.
In another embodiment the POA may have a Shear Adhesion Fail Temperature (SAFT—as measured by ASTM 4498) of 200° C. or less, or of 40° C. to 150° C., or 60° C. to 130° C., or 65° C. to 110° C., or 70° C. to 80° C. In certain embodiments SAFT's of 130° C. to 140° C. may be preferred.
In another embodiment the POA may have a Dot T-Peel of between 1 Newton and 10,000 Newtons, or 3 and 4000 Newtons, or between 5 and 3000 Newtons, or between 10 and 2000 Newtons, or between 15 and 1000 Newtons. As used herein, Dot T-Peel is determined according to ASTM D 1876, except that the specimen is produced by combining two 1 inch by 3 inch (2.54 cm×7.62 cm) Kraft paper substrate cut outs with a dot of adhesive with a volume that, when compressed under a 500 gram weight occupies about 1 square inch of area (1 inch=2.54 cm). Once made all the specimens are pulled apart in side by side testing (at a rate of 2 inches per minute) by a device which records the destructive force of the insult being applied. The maximum force achieved for each sample tested was recorded and averaged, thus producing the Average Maximum Force which is reported as the Dot T-Peel.
In another embodiment the POA may have a set time of several days to about 0.1 seconds or less, or 60 seconds or less, or 30 seconds or less, or 20 seconds or less, or 15 seconds or less, or 10 seconds or less, or 5 seconds or less, or 4 seconds or less, or 3 seconds or less, or 2 seconds or less, or 1 second or less.
In another embodiment the POA may have a Mw/Mn of 2 to 75, or 4 to 60, or 5 to 50, or 6 to 20.
In yet another embodiment, the POA may have an Mz of 1,000,000 or less, preferably 15,000 to 1,000,000, or 20,000 to 800,000, or 25,000 to 350,000.
In another embodiment the POA may also have a strain at break (as measured by ASTM D-1708 at 25° C.) of 50 to 1000%, preferably 80 to 200%. In some other embodiments the strain at break is 100 to 500%.
In another embodiment, the POA has a tensile strength at break (as measured by ASTM D-1708 at 25° C.) of 0.5 MPa or more, alternatively 0.75 MPa or more, alternatively 1.0 MPa or more, alternatively 1.5 MPa or more, alternatively 2.0 MPa or more, alternatively 2.5 MPa or more, alternatively 3.0 MPa or more, alternatively 3.5 MPa or more.
In another embodiment, the POA also has a crystallization point (Tc) between 20° C. and 110° C. In some embodiments the Tc is between 70° C. to 100° C. In other embodiments the Tc is between 30° C. and 80° C. In other embodiments the Tc is between 20° C. and 50° C.
In some embodiments the POA may have a slope of −0.1 or less, preferably −0.15 or less, more preferably −0.25 or less in the trace of complex viscosity versus temperature (as measured by ARES dynamic mechanical spectrometer operating at a frequency of 10 rad/s, with a strain of 20% under a nitrogen atmosphere, and a cooling rate of 10° C./min) over the range of temperatures from Tc+10° C. to Tc+40° C. The slope is defined for use herein as a derivative of log (complex viscosity) with respect to temperature.
In another embodiment the POA has a Tc that is at least 10° C. below the Tm, preferably at least 20° C. below the Tm, preferably at least 30° C. below the Tm, more preferably at least 35° C. below the Tm.
In another embodiment some POA's described above may have a melt index ratio (I10/I2) of 6.5 or less, preferably 6.0 or less, preferably 5.5 or less, preferably 5.0 or less, preferably 4.5 or less, preferably between 1 and 6.0. (I10 and I2 are measured according to ASTM 1238 D, 2.16 kg, 190° C.).
In another embodiment some POA's described above may have a melt index (as determined by ASTM 1238 D,2.16 kg, 190° C. ) of 25 dg/min or more, preferably 50 dg/min or more, preferably 100 dg/min or more, more preferably 200 dg/min or more, more preferably 500 dg/mn or more, more preferably 2000 dg/min or more. In another embodiment the POA has a melt index of 900 dg/min or more.
In another embodiment the POA may have a range of crystallization of 10 to 60° C. wide, preferably 20 to 50° C., preferably 30 to 45° C. in the DSC traces. In DSC traces where there are two or more non-overlapping peaks, then each peak has a range of crystallization of 10 to 60° C. wide, preferably 20 to 50° C., preferably 30 to 45° C. in the DSC traces.
In another embodiment the POA may have a molecular weight distribution (Mw/Mn) of at least 2, preferably at least 5, preferably at least 10, even more preferably at least 20.
In another embodiment the POA may have a unimodal, bimodal, or multimodal molecular weight distribution (Mw/Mn) distribution of polymer species as determined by Size Exclusion Chromatography (SEC). By bimodal or multimodal is meant that the SEC trace has more than one peak or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).
In another embodiment the POA may have an energy of activation of 8 to 15 cal/mol. Energy of activation being calculated using the relationships of complex viscosity and temperature over the region where thermal effects are responsible for viscosity increase (assuming an Arrhenius-like relationship).
In another embodiment the POA's utilized in this invention may have a crystallinity of at least 5%.
In another embodiment the POA's described above may also have one or more of the following:
Useful combinations of features include POA's having a Dot T-Peel of between 1 Newton and 10,000 Newtons, or 3 and 4000 Newtons, or between 5 and 3000 Newtons, or between 10 and 2000 Newtons, or between 15 and 1000 Newtons and:
1. an Mw of 30,000 or less, a peak melting point between 60 and 190° C., a Heat of fusion of 1 to 70 J/g, a branching index (g′) of 0.90 or less measured at the Mz of the polymer; and a melt viscosity of 8000 mPa·sec or less at 190° C.; or
2. an Mz of 20,000 to 500,000 and a SAFT of 60 to 150° C.; or
3. an Mz/Mn of 2-200 and a set time of 2 seconds or less; or
4. an Hf (heat of fusion) of 20 to 50 J/g, an Mz or 20,000-500,000 and a shore hardness of 50 or less; or
5. an Mw/Mn of greater than 1 to 50, a viscosity of 5000 or less mPa·sec at 190° C.; or
6. an Mw of 50,000 or less, a peak melting point between 60 and 190° C., a heat of fusion of 2 to 70 J/g, a branching index (g′) of 0.70 or less measured at the Mz of the polymer, and a melt viscosity of 8000 mPa·sec or less at 190° C.
In a preferred embodiment, the POA comprises amorphous, crystalline and branch-block molecular structures.
In a preferred embodiment the POA comprises at least 50 weight % propylene, preferably at least 60% propylene, alternatively at least 70% propylene, alternatively at least 80% propylene. In another embodiment the POA comprises propylene and 15 mole % ethylene or less, preferably 10 mole % ethylene or less, more preferably 9 mole % ethylene or less, more preferably 8 mole % ethylene or less, more preferably 7 mole % ethylene or less, more preferably 6 mole % ethylene or less, more preferably 5 mole % ethylene or less, more preferably 4 mole % ethylene or less, more preferably 3 mole % ethylene or less, more preferably 2 mole % ethylene or less, more preferably 1 mole % ethylene or less.
In another embodiment the POAcomprises less than 5 mole % of ethylene, preferably less than 4.5 mole % ethylene, preferably less than 4.0 mole % ethylene, alternatively less than 3.5 mole % ethylene, alternatively less than 3.0 mole % ethylene, alternatively less than 2.5 mole % ethylene, alternatively less than 2.0 mole % ethylene, alternatively less than 1.5 mole % ethylene, alternatively less than 1.0 mole % ethylene, alternatively less than 0.5 mole % ethylene, alternatively less than 0.25 mole % ethylene, alternatively 0 mole % ethylene.
In another embodiment the POA has a glass transition temperature (Tg) as measured by ASTM E 1356 of 5° C. or less, preferably 0° C. or less, preferably −5° C. or less, alternatively between −5° C. and −40° C., alternatively between −5° C. and −15° C.
In another embodiment the POA has an amorphous content of at least 50%, alternatively at least 60%, alternatively at least 70%, even alternatively between 50 and 99%. Percent amorphous content is determined using Differential Scanning Calorimetry measurement according to ASTM E 794-85.
In another embodiment the POA has a crystallinity of 40% or less, alternatively 30% or less, alternatively 20% or less, even alternatively between 10% and 30%. Percent crystallinity content is determined using Differential Scanning Calorimetry measurement according to ASTM E 794-85. In another embodiment, the POA's described herein have a percent crystallinity of between 5 and 40%, alternatively between 10 to 30%.
In another embodiment the POA may have a molecular weight distribution (Mw/Mn) of at least 1.5, preferably at least 2, preferably at least 5, preferably at least 10, even alternatively at least 20. In other embodiments the Mw/Mn is 20 or less, 10 or less, even 5 or less. Molecular weight distribution generally depends on the catalysts used and process conditions such as temperature, monomer concentration, catalyst ratio, if multiple catalysts are used, and the presence or absence of hydrogen. Hydrogen may be used at amounts up to 2 weight %, but is preferably used at levels of 50 to 500 ppm.
In another embodiment the POA may be found to have at least two molecular weights fractions present at greater than 2 weight %, preferably greater than 20 weight %, each based upon the weight of the polymer as measured by Gel Permeation Chromatography. The fractions can be identified on the GPC trace by observing two distinct populations of molecular weights. An example would be a GPC trace showing a peak at 20,000 Mw and another peak at 50,000 Mw where the area under the first peak represents more than 2 weight % of the polymer and the area under the second peak represents more than 2 weight % of the polymer.
In another embodiment the POA of this invention may have 20 weight % or more (based upon the weight of the starting polymer) of hexane room temperature soluble fraction, and 70 weight % or less, preferably 50 weight % or less of Soxhlet boiling heptane insolubles, based upon the weight of the polymer. Soxhlet heptane insoluble refers to one of the fractions obtained when a sample is fractionated using successive solvent extraction technique. The fractionations are carried out in two steps: one involves room temperature solvent extraction, the other soxhlet extraction. In the room temperature solvent extraction, about one gram of polymer is dissolved in 50 ml of solvent (e.g., hexane) to isolate the amorphous or very low molecular weight polymer species. The mixture is stirred at room temperature for about 12 hours. The soluble fraction is separated from the insoluble material using filtration under vacuum. The insoluble material is then subjected to a Soxhlet extraction procedure. This involves the separation of polymer fractions based on their solubility in various solvents having boiling points from just above room temperature to 110° C. The insoluble material from the room temperature solvent extraction is first extracted overnight with a solvent such as hexane and heptane (Soxhlet); the extracted material is recovered by evaporating the solvent and weighing the residue. The insoluble sample is then extracted with a solvent having higher boiling temperature such as heptane and after solvent evaporation, it is weighed. The insolubles and the thimble from the final stage are air-dried in a hood to evaporate most of the solvent, then dried in a nitrogen-purged vacuum oven. The amount of insoluble left in the thimble is then calculated, provided the tare weight of the thimble is known.
In another embodiment, the POA's may have a heptane insoluble fraction 70 weight % or less, based upon the weight of the starting polymer, and the heptane insoluble fraction has branching index g′ of 0.9 (preferably 0.7) or less as measured at the Mz of the polymer. In a preferred embodiment the composition may also have at least 20 weight % hexane soluble fraction, based upon the weight of the starting polymer. In another embodiment, the POA's may have a heptane insoluble fraction 70 weight % or less, based upon the weight of the starting polymer and a Mz between 20,000 and 5,000,000 of the heptane insoluble portion. In a preferred embodiment the composition also has at least 20 weight % hexane soluble fraction, based upon the weight of the starting polymer. In another embodiment the POA's have a hexane soluble portion of at least 20 weight %, based upon the weight of the starting polymer.
In another embodiment the POA comprises propylene and 15 mole % ethylene or less, preferably 10 mole % ethylene or less, more preferably 9 mole % ethylene or less, more preferably 8 mole % ethylene or less, more preferably 7 mole % ethylene or less, more preferably 6 mole % ethylene or less, more preferably 5 mole % ethylene or less, more preferably 4 mole % ethylene or less, more preferably 3 mole % ethylene or less, more preferably 2 mole % ethylene or less, more preferably 1 mole % ethylene or less.
In another embodiment the POA comprises less than 5 mole % of ethylene, preferably less than 4.5 mole % ethylene, preferably less than 4.0 mole % ethylene, alternatively less than 3.5 mole % ethylene, alternatively less than 3.0 mole % ethylene, alternatively less than 2.5 mole % ethylene, alternatively less than 2.0 mole % ethylene, alternatively less than 1.5 mole % ethylene, alternatively less than 1.0 mole % ethylene, alternatively less than 0.5 mole % ethylene, alternatively less than 0.25 mole % ethylene, alternatively 0 mole % ethylene.
For ease of reference the portion of the olefin polymer produced by one of the catalyst may have at least 10% crystallinity may also be referred to as the “semi-crystalline polymer” and the polymer produced by another of the catalyst may have a crystallinity of less than 5%, which may be referred to as the “amorphous polymer.”
In another embodiment of this invention the POA may have a characteristic three-zone complex viscosity-temperature pattern. The temperature dependence of complex viscosity was measured using ARES dynamic mechanical spectrometer operating at a frequency of 10 rad/s, with a strain of 20% under a nitrogen atmosphere, and a cooling rate of 10° C./min. The sample was first molten then gradually cooled down to room temperature while monitoring the build-up in complex viscosity. Above the melting point, which is typical of polymer processing temperature, the complex viscosity is relatively low (Zone I) and increases gradually with decreasing temperature. In zone II, a sharp increase in complex viscosity appears as temperature is dropped. The third zone (Zone III) is the high complex viscosity zone, which appears at lower temperatures corresponding to application (end use) temperatures. In Zone III the complex viscosity is high and varies slightly with further decrease in temperature. Such a complex viscosity profile provides, in hot melt adhesive applications, a desirable combination of long opening time at processing temperatures and fast set time at lower temperatures.
In a preferred embodiment, the POA's have less than 1 mol % ethylene, have at least 2 mol % (CH2)2 units, preferably 4 mol %, preferably 6 mol %, more preferably 8 mol %, more preferably 10 mol %, more preferably 12 mol %, more preferably 15 mol %, more preferably 18 mol %, more preferably 5 mol % as measured by Carbon 13 NMR as described below.
In an another embodiment, the POA's may have between 1 and 10 mol % ethylene, have at least 2+X mol % (CH2)2 units, preferably 4+X mol %, preferably 6+X mol %, more preferably 8+X mol %, more preferably 10+X mol %, more preferably 12+X mol %, more preferably 15+X mol %, more preferably 18+X mol %, more preferably 20+X mol %, where X is the mole % of ethylene, and the (CH2)2 units are determined by Carbon 13 NMR as described below.
In a preferred embodiment, the POA's may have less than 1 mol % ethylene, have an amorphous component (i.e., defined to be that portion of the polymer composition that has a crystallinity of less than 5%) which contains at least 3 mol % (CH2)2 units, preferably 4 mol %, preferably 6 mol %, more preferably 8 mol %, more preferably 10 mol %, more preferably 12 mol %, more preferably 15 mol %, more preferably 18 mol %, more preferably 20 mol % as measured by Carbon 13 NMR as described below.
In an another embodiment, the POA's may have between 1 and 10 mol % ethylene, have an amorphous component (which is defined to be that portion of the polymer composition that has a crystallinity of less than 5%) which contains at least 3+X mol % (CH2)2 units, preferably 4+X mol %, preferably 6+X mol %, more preferably 8+X mol %, more preferably 10+X mol %, more preferably 12+X mol %, more preferably 15+X mol %, more preferably 18+X mol %, more preferably 20+X mol %, where X is the mole % of ethylene, and the (CH2)2 units are determined by Carbon 13 NMR as described below.
Functionalized C3-C40 Olefin Polymers (F-POA's)
Any of the polymers described above as POA's may be functionalized and used as F-POA's. Typically, the POA is combined with a free radical initiator and a grafting monomer or other functional group (such as maleic acid or maleic anhydride) and is heated to react the monomer with the POA to form the F-POA.
As stated above, the present invention comprises a functionalized olefin polymer or blend of functionalized olefin polymers, also referred to herein as grafted olefin polymers. By functionalized (or grafted) it is meant that various functional groups are incorporated, grafted, bonded to, and/or physically or chemically attached to the polymer backbone of the POA being functionalized.
In one embodiment, functional groups are grafted onto the POA utilizing radical copolymerization of an functional group, referred to herein as graft copolymerization.
Examples of suitable functional groups include unsaturated carboxylic acids, esters of the unsaturated carboxylic acids, acid anhydrides, di-esters, salts, amides, imides, aromatic vinyl compounds hydrolyzable unsaturated silane compounds and unsaturated halogenated hydrocarbons. Preferred examples of unsaturated carboxylic acids and acid derivatives include, but are not limited to maleic anhydride, citraconic anhydride, 2-methyl maleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic anhydride and 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,&g, lo-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro(4.4)non-7-ene, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophtalic anhydride, norbom-5-ene-2,3-dicarboxylic acid anhydride, nadic anhydride, methyl nadic anhydride, himic anhydride, methyl himic anhydride, and x-methyl-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride (XMNA).
Examples of the esters of the unsaturated carboxylic acids include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
Hydrolyzable unsaturated silane compounds useful as functional groups herein may include radical polymerizable unsaturated group and an alkoxysilyl group or a silyl group in its molecule, such that the compound has a hydrolyzable silyl group bonded to a vinyl group and/or a hydrolyzable silyl group bonded to the vinyl group via an alkylene group, and/or a compound having a hydrolyzable silyl group bonded to an ester or an amide of acrylic acid, methacrylic acid or the like. Examples thereof include vinyltrichlorosilane, vinyltris(beta-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane monovinylsilane and monoallylsilane.
Examples of unsaturated halogenated hydrocarbons useful as functional groups herein include vinyl chloride and vinylidene chloride.
In a preferred embodiment, the POA is grafted with maleic anhydride (MA), to produce olefin grafted maleic anhydride (POA-g-MA), wherein the maleic anhydride is bonded to the polymer chain of the polymeric composition.
Preferable examples of the radical initiator used in the graft copolymerization include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, di-ti-butyl perphthalate, 2,5-dimethyl-2,5-di(t-butylperoxy)hexene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dilauryl peroxide and dicumyl peroxide.
The F-POA of the present invention may thus be obtained by heating the POA(s) and the functional group(s) in the presence of the radical initiator at, near, or above a decomposition temperature of the radical initiator.
In some embodiments, no particular restriction need be put on the amount of the functional group to be used, accordingly, conventional conditions for functionalizing, for example, an isotactic polypropylene, can be utilized with the POA's of this invention. Since in some cases the efficiency of the copolymerization is relatively high, the amount of the functional group may be small. In an embodiment, the amount of the functional group to be incorporated into the POA is preferably from about 0.001 to 50 wt % functional group with respect to the total amount of olefin polymer present, preferably from 0.005 to 40 weight %, preferably from 0.01 to 35 weight %, preferably from about 0.05 to about 30 weight %, more preferably from about 0.1 to about 25 weight %, preferably from about 0.5 to about 20 weight %, preferably from about 1.0 to about 15 weight %, preferably from about 1.5 to 10 weight %, preferably from about 2 to 5 weight %, preferably from about 2 to about 4 weight %. In a preferred embodiment, the amount of the maleic acid and/or maleic anhydride, preferably maleic anhydride, to be incorporated into the POA is preferably from about 0.001 to about 50 wt %, based upon the weight of the POA, preferably from 0.005 to 40 weight %, preferably from 0.01 to 35 weight %, preferably from about 0.05 to about 30 weight %, more preferably from about 0.1 to about 25 weight %, preferably from about 0.5 to about 20 weight %, preferably from about 1.0 to about 15 weight %, preferably from about 1.5 to 10 weight %, preferably from about 2 to 5 weight %, preferably from about 2 to about 4 weight %.
The radical initiator is preferably used in a ratio of from 0.00001 to 10 wt %, based on the weight of the functional group. The heating temperature depends upon whether or not the reaction is carried out in the presence of a solvent, but it is usually from about 50° C. to 350° C. When the heating temperature is less than 50° C., the reaction may be slow and thus efficiency may be low. When it is more than 350° C., decomposition of the POA may occur.
The F-POA may be functionalized with an functional group utilizing a solvent based functionalization process and/or utilizing a melt based functionalization process without a solvent. In the solvent based process, the reaction may be carried out using the POA in the form of a solution or a slurry having a concentration of from 0.1 to 50 wt % in the presence of a halogenated hydrocarbon compound having 2 to 20 carbon atoms, an aromatic compound, a halogenated aromatic compound, an alkyl substituted aromatic hydrocarbon, a cyclic hydrocarbon, and/or a hydrocarbon compound having 6 to 20 carbon atoms which is stable to the radicals.
The POA may also be functionalized in a process utilizing a melt based functionalization process without a solvent. Such a reaction may be carried out in the absence of the solvent in a device such as an extruder which can sufficiently produce physical contact between the POA, and the unsaturated monomer. In the latter case, the reaction is usually effected at a relatively high temperature, as compared with the reaction in the state of the solution.
Other methods for functionalizing POA's that may be used include, but are not limited to, selective oxidation, ozonolysis, epoxidation, and the like, both in solution or slurry (i.e., with a solvent), or in a melt (i.e., without a solvent) as described above.
In the present invention, the graft polymerization (grafting of the POA) may also be carried out in an aqueous medium. In this case a dispersant can be used, and examples of the dispersant include a saponified polyvinyl acetate, modified celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, and compounds containing an OH group such as polyacrylic acid and polymethacrylic acid. In addition, compounds which are used in a usual aqueous suspension polymerization can also be widely employed.
The reaction may be carried out by suspending the POA, the water-insoluble radical polymerizable monomer, the water-insoluble radical initiator and/or the dispersant in water, and then heating the mixture. Here, a ratio of water to the sum of the radical polymerizable monomer (i.e., the functional group) and the POA is preferably 1:0.1 to 1:200, more preferably 1:1 to 1:100. The heating temperature is such that the half-life of the radical initiator is preferably from 0.1 to 100 hours, more preferably from 0.2 to 10 hours, and it is preferably from 30° to 200° C., more preferably from 40° to 150° C. In the heating step, it is preferred that the mixture is stirred sufficiently so as to become in a suspension state. In this way, the F-PAO may be obtained in granular form.
A weight ratio of the water-insoluble monomer to the POA may preferably be from 1:01 to 1:10000, and a weight ratio of the radical initiator to the water-insoluble monomer may be from 0.00001 to 0.1. The ratio of the water-insoluble monomer in the F-POA depends upon its use, but the amount of the monomer may be from 0.1 to 200% by weight based on the weight of the POA present in the F-POA.
The F-POA preferably contains a desired amount of radical polymerizable functional group units in the range of from 0.1 to 50 wt % based on the weight of the POA in compliance with its intended use or application.
Furthermore, a compatibilizing effect within the inventive composition obtained by inclusion of the F-POA may be influenced by the level of grafting. In an embodiment, the POA may be functionalized to include about 0.001 wt % or greater of the functional group attached. The POA may also be functionalized grafted to a higher degree. The level of functionalization (e.g., the grafting level) may be less than about 50 wt %, preferably less than about 45 wt %, preferably less than about 40 wt %, preferably less than about 35 wt %, preferably less than about 30 wt %, preferably less than about 25 wt %, preferably less than about 20 wt %, preferably less than about 15 wt %, preferably less than about 10 wt %, preferably less than about 9 wt %, preferably less than about 8 wt %, preferably less than about 7 wt %, preferably less than about 6 wt %, preferably less than about 5 wt %, preferably less than about 4 wt %, preferably less than about 3 wt %, preferably less than about 2 wt %, preferably less than about 1.5 wt %, preferably less than about 1 wt %, preferably less than about 0.5 wt %.
The F-PAO may be a single POA which has been functionalized as described herein. In another embodiment, the F-POA of the present invention may be a blend of POA's which are functionalized together during a single process. The F-POA's of the present invention may also include a plurality of F-POA's which are combined after being individually functionalized, or any combination thereof.
In another aspect this invention provides the ability to produce adhesives that may be do not have to be further blended or modified.
Accordingly, this invention also further relates to a continuous process to prepare an F-PAO comprising the steps of:
1) combining monomer, optional solvent, catalyst and activator in a reactor system;
2) withdrawing PAO solution from the reactor system;
3) removing at least 10% solvent, if present, from the PAO solution;
4) quenching the reaction;
5) devolatilizing the PAO solution to form molten PAO;
6) combining at least a portion of the molten PAO with an functional group (preferably maleic anhydride) in the presence of a radical initiator at a temperature, and for a period of time sufficient to produce F-PAO;
7) combining F-PAO, optionally PAO, and optionally one or more additives (such as those described below) in a mixer, such as a static mixer, (in a preferred embodiment tackifer is not added or is added in amounts of less than 30 weight %, preferably less than 20 weight %, more preferably in amounts of less than 10 weight %), and mixing to produce the inventive compositon;
8) removing the composition from the mixer, and
9) pelletizing or drumming the composition;
where step 1) comprises any of the processes described herein for the production of PAO.
In another embodiment this invention relates to a continuous process to prepare an adhesive comprising:
1) combining monomer, optional solvent, catalyst and activator in a reactor system;
2) withdrawing PAO solution from the reactor system;
3) removing at least 10% solvent, if present, from the PAOsolution;
4) quenching the reaction;
5) devolatilizing the PAO solution to form molten PAO;
6) combining at least a portion of the molten PAO with an functional group in the presence of a radical initiator for a period of time sufficient to graft the functional group into the PAO to produce F-PAO;
7) combining the molten F-PAO, the PAO, and one or more additives in a mixer, such as a static mixer;
8) removing the polymer combination from the mixer; and
9) pelletizing or drumming the polymer combination.
In a particularly preferred embodiment, this invention relates to a continuous process to make an adhesive comprising:
1) selecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 20% or less (preferably 5% or less) under selected polymerization conditions;
2) selecting a second catalyst component capable of producing polymer having an Mw of 100,000 or less and a crystallinity of 20% or more (preferably 40% or more) at the selected polymerization conditions;
3) contacting, in a solvent and in a reaction zone under the selected polymerization conditions, the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins, and, optionally one or more diolefins;
4) at a temperature of greater than 70° C., preferably greater than 100° C.;
5) at a residence time of up to 120minutes, (preferably 60 minutes or less);
6) wherein the ratio of the first catalyst to the second catalyst is from 1:1 to 50:1;
7) wherein the activity of the catalyst components is at least 50 kilograms of polymer per gram of the catalyst components; and wherein at least 20% of the olefins are converted to polymer;
8) withdrawing olefin polymer solution from the reaction zone;
9) removing at least 10% solvent from the olefin polymer solution;
10) quenching the reaction;
11) devolatilizing the olefin polymer solution to form molten olefin polymer;
12) combining at least a portion of the molten olefin polymer with an functional group in the presence of a radical initiator at a temperature, and for a period of time sufficient to produce the functionalized olefin polymer (e.g., to graft the functional group into the olefin polymer);
13) combining the molten functionalized olefin polymer, the olefin polymer, and one or more additives in a mixer, such as a static mixer to produce the inventive composition;
14) removing the olefin polymer combination (the composition) from the mixer; and
15) pelletizing or drumming the composition.
In a particularly preferred embodiment, this invention relates to a continuous process to make an adhesive comprising:
1) selecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 20% or less (preferably 5% or less) under selected polymerization conditions;
2) selecting a second catalyst component capable of producing polymer having an Mw of 100,000 or less and a crystallinity of 20% or more (preferably 40% or more) at the selected polymerization conditions;
3) contacting, in a solvent and in a reaction zone under the selected polymerization conditions, the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins, and, optionally one or more diolefins;
4) at a temperature of greater than 70°0 C., preferably greater than 100° C.;
5) at a residence time of 120 minutes or less, preferably 60 minutes or less;
6) wherein the ratio of the first catalyst to the second catalyst is from 1:1 to 50:1, preferably 1:1 to 30:1;
7) wherein the activity of the catalyst components is at least 50 kilograms of polymer per gram of the catalyst components; and wherein at least 50% of the olefins are converted to polymer;
8) withdrawing olefin polymer solution from the reaction zone;
9) removing at least 10% solvent from the olefin polymer solution;
10) quenching the reaction;
11) forming molten olefin polymer
12) combining at least a portion of the molten olefin polymer with an functional group in the presence of a radical initiator at a temperature and for a period of time sufficient to produce the functionalized olefin polymer;
13) combining the molten functionalized olefin polymer, the olefin polymer, and one or more additives in a mixer, such as a static mixer and mixing to produce a composition;
14) removing the composition from the mixer; and
15) pelletizing or drumming the composition.
In a particularly preferred embodiment, this invention relates to a continuous process to make an adhesive comprising
1) selecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 20% or less, (preferably 5% or less) under selected polymerization conditions;
2) selecting a second catalyst component capable of producing polymer having an Mw of 100,000 or less and a crystallinity of 20% or more (preferably 40% or more) at the selected polymerization conditions;
3) contacting, in a solvent and in a reaction zone under the selected polymerization conditions, the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins, and, optionally one or more diolefins;
4) at a temperature of greater than 70° C., preferably greater than 100° C.;
5) at a residence time of 120 minutes or less, preferably 60 minutes of less;
6) wherein the ratio of the first catalyst to the second catalyst is from 1:1 to 50:1, preferably from 1:1 to 30:1;
7) wherein the activity of the catalyst components is at least 50 kilograms of polymer per gram of the catalyst components; and wherein at least 50% of the olefins are converted to polymer;
8) withdrawing olefin polymer solution from the reaction zone;
9) removing at least 10% solvent from the olefin polymer solution;
10) quenching the reaction;
11) forming molten olefin polymer
12) combining at least a portion of the molten olefin polymer with an functional group in the presence of a radical initiator for a period of time sufficient to produce the functionalized olefin polymer;
13) combining the molten functionalized olefin polymer, the olefin polymer, and one or more additives in a mixer, such as a static mixer and mixing to produce the inventive composition;
14) removing the inventive olefin polymer combination from the mixer; and
15) pelletizing or drumming the inventive olefin polymer combination.
Blending of Functionalized Olefin Polymers
The F-PAO may be mixed or blended with (i.e., in combination with, an admixture of, and the like) one or more other polymer. Preferred polymers include olefin homopolymers or copolymer containing no graft component, a different graft component, or a similar graft component at a different level of inclusion, and/or the like, to achieve a final composition with a desired level of adhesion for a particular end use or process.
In an embodiment, the olefin homopolymer or copolymer to be bleded with the F-POA may also be an alpha-olefin homopolymer or copolymer containing no graft component. If desired, the alpha-olefin homopolymers may have various molecular weight characteristics, may be random and/or block copolymers of alpha-olefins themselves. Examples of the alpha-olefin include ethylene and alpha-olefins having 4 to 20 carbon atoms in addition to propylene. The homopolymers and copolymers of these alpha-olefins can be manufactured by various known methods, and may be commercially available under various trade names.
In a preferred embodiment the F-POA is combined with one or more other polymers, including but not limited to, thermoplastic polymer(s) and/or elastomer(s).
By thermoplastic polymer(s)” is meant a polymer that can be melted by heat and then cooled with out appreciable change in properties. Thermoplastic polymers typically include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile-butadiene-styrene resins, polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrile resins, styrene maleic anhydride, polyimides, aromatic polyketones, or mixtures of two or more of the above. Preferred polyolefins include, but are not limited to, polymers comprising one or more linear, branched or cyclic C2 to C40 olefins, preferably polymers comprising propylene copolymerized with one or more C3 to C40 olefins, preferably a C3 to C20 alpha olefin, more preferably C3 to C10 alpha-olefins. More preferred polyolefins include, but are not limited to, polymers comprising ethylene including but not limited to ethylene copolymerized with a C3 to C40 olefin, preferably a C3 to C20 alpha olefin, more preferably propylene and or butene.
By elastomers is meant all natural and synthetic rubbers, including those defined in ASTM D1566). Examples of preferred elastomers include, but are not limited to, ethylene propylene rubber, ethylene propylene diene monomer rubber, styrenic block copolymer rubbers (including SI, SIS, SB, SBS, SIBS and the like, where S=styrene, I=isobutylene, and B=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutylene and para-alkylstyrene, halogenated copolymers of isobutylene and para-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, polybutadiene rubber (both cis and trans).
In another embodiment, the F-POA is combined with one or more of isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935 g/cm3) linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/cm3), very low density polyethylene (density 0.90 to less than 0.915 g/cm3), medium density polyethylene (density 0.935 to less than 0.945 g/cm3), high density polyethylene (density 0.945 to 0.98 g/cm3), ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols and/or polyisobutylene.
In a preferred embodiment the F-POA is combined with metallocene polyethylenes (mPE's) or metallocene polypropylenes (mPP's). The mPE and mPP homopolymers or copolymers are typically produced using mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high pressure or gas phase. The catalyst and activator may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted. Several commercial products produced with such catalyst/activator combinations are commercially available from Exxon Chemical Company in Baytown, Texas under the tradenames EXCEED™, ACHIEVE™ and EXACT™. For more information on the methods and catalysts/activators to produce such homopolymers and copolymers see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA 129,368; U.S. Pat. No. 5,264,405; EPA 520,732; WO 92 00333; U.S. Pat. No. 5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495 375; EPA 500 944; EPA 570 982; WO91/09882; WO94/03506 and U.S. Pat. No. 5,055,438.
In a preferred embodiment the F-POA is present in the in the above blends, at from 10 to 99 weight %, based upon the weight of the polymers in the blend, preferably 20 to 95 weight %, even more preferably at least 30 to 90 weight %, even more preferably at least 40 to 90 weight %, even more preferably at least 50 to 90 weight %, even more preferably at least 60 to 90 weight %, even more preferably at least 70 to 90 weight %.
In the process utilized for producing the F-POA no particular restriction need be put on a mixing manner, accordingly, the raw materials may be mixed uniformly by means of a Henschel mixer or the like and then may be melted, mixed and molded into pellets by an extruder or the like. The blends described herein may be formed using conventional techniques known in the art such that blending may be accomplished using one or more static mixers, in-line mixers, elbows, orifices, baffles, or any combination thereof. It is also possible to utilize a Brabender mixer by which mixing and melting are carried out simultaneously, and after the melting, the material can be directly molded into films, sheets, or the like.
In a preferred embodiment, the weight to weight ratio of POA to F-POA (preferably POA-g-MA), is in the range of about 1:1000 to 1000:1. In another preferred embodiment the weight to weight ratio of F-POA (preferably POA-g-MA) to POA, is preferably 1:100 or less, about 1:50 or less, about 1:20 or less, about 1:10 or less, about 1:5 or less, about 1:4 or less, about 1:3 or less, about 1:2 or less, or about 1:1. In another embodiment the weight to weight ratio of the F-POA to the POA may be about 100:1, about 50:1, about 20:1, about 10:1, about 5:1, about 4:1, about 3:1, or about 2:1.
The composition comprising the F-POA, blends of F-POA's and/or an admixture of POA and F-POA, as produced herein, may be used directly as an adhesive, or may be blended, mixed and/or combined with other components to form an adhesive formulation.
Tackifiers may be used with the compositions of the present invention. Examples of suitable tackifiers, include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, hydrogenated rosin acids, and hydrogenated rosin esters. In some embodiments the tackifier may be hydrogenated.
In other embodiments, the tackifier may be non-polar. (Non-polar meaning that the tackifier is substantially free of monomers having polar groups. Preferably, the polar groups are not present, however if they are present, they are preferably not present at more that 5 weight %, preferably not more that 2 weight %, even more preferably no more than 0.5 weight %.) In some embodiments the tackifier may have a softening point (Ring and Ball, as measured by ASTM E-28) of 80° C. to 150° C., preferably 100° C. to 130° C. In another embodiment the resins is liquid and has a R and B softening point of between 10 and 70° C.
The tackifier, if present in the composition, may comprise about 0.1 to about 80 wt %, based upon the weight of the composition, more preferably 2 to 40 weight %, even more preferably 3 to 30 weight %.
Preferred hydrocarbon resins for use as tackifiers or modifiers include:
The resins obtained after polymerization and separation of unreacted materials, can be hydrogenated if desired. Examples of preferred resins include those described in U.S. Pat. No. 4,078,132; WO 91/07472; U.S. Pat. No. 4,994,516; EP 0 046 344 A; EP 0 082 726 A; and U.S. Pat. No. 5,171,793.
Crosslinking Agents
In another embodiment the composition of this invention may further comprises a crosslinking agent. Preferred crosslinking agents include those having functional groups that can react with the acid or anhydride group. Preferred crosslinking agents include alcohols, multiols, amines, diamines and/or triamines. Particular examples of crosslinking agents useful in this invention include polyamines such as ethylenediamine, diethylenetriamine, hexamethylenediamine, diethylaniinopropylamine, and/or menthanediamine.
Of the F-POA's of the present invention, a copolymer in which an hydrolyzable unsaturated silane is grafted can be utilized as a starting material for a crosslinked polypropylene or a crosslinked propylene copolymer. In this case, the hydrolyzable unsaturated silane units may be present in the functionalized olefin polymer preferably in an amount of from 0.1 to 50% by weight, more preferably from 0.1 to 10% by weight based on the olefin polymer.
The composition may then be heated in the presence of water. In order to effectively form the crosslinking with the aid of water, a catalyst may also be added. Examples of suitable catalysts include hydroxides and/or oxides of alkaline metals and alkaline earth metals, ammonia, amines, organic and inorganic acids, salts thereof, alkoxysilicons, and silicon hydrides. In some cases, the catalysts may be used directly without any additional treatment. The amount of the catalyst is usually from 0.001 to 1 wt %, based on the weight of the functionalized olefin polymer. A temperature at which the above-mentioned composition may be heated in the presence of water is from about 50° C. to 200° C., preferably from 80° C. to 120° C. Water may be in the form of steam, or the composition may be immersed into boiling water.
In the thus crosslinked olefin polymer, the ratio of the boiling xylene-insoluble component to this olefin polymer is preferably from 5 to 100% by weight.
In another embodiment, the composition comprising a F-POA on which hydrolyzable unsaturated silane is grafted can be blended with a phenolic antioxidant, a sulfide hydroperoxide decomposer and a polyvalent amine to prepare a water-crosslinkable composition.
Many kinds of phenolic antioxidants are known and commercially available. A preferred example of a phenolic antioxidant is a substituted phenol such as 2,6-di-t-butylphenol in which a hydrogen atom at 2 and/or 6 position is substituted by an alkyl residue. Typical examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, vitamin E, 2-t-butyl-6-(3′-t-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,2′-methylene-bis(4-methyl-6-t-butylphenyl), 2,2′-methylene-bis(4-ethyl-6-t-butyl-phenol), 2,2′-methylene-bis(6-cyclohexyl-4-methylphenol), 1,6-hexanediol-bis([3-(3,5-di-t-butyl[4-hydroxyphenyl])] propionate and pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)] propionate.
A preferable example of the sulfide hydroperoxide decomposer is an ester of a thioether, and typical examples of the commercially available sulfide hydroperoxide decomposer include diesters of 3,3′-thiodipropionic acid and higher alcohols such as lauryl alcohol, tridecyl alcohol and stearyl alcohol.
Examples of the polyvalent amine include melamine, its derivatives, a hydrazide compound such as oxalic acid-bis(benzylidenehydrazide) and a triazole compound such as 3-(N-salicyloyl)amino-1,2,4-triazole.
The amount of each of these additives to be added is such that the weight ratio of the additive to the F-POA is preferably 1/1000 to 1/100000, more preferably 1/500 to 1/10000.
No particular restriction is put on the mixing manner of the functionalized olefin polymer and the stabilizer, which may be dry mixed utilizing, for example, a Henschel mixer, followed by melting and/or granulation.
In another embodiment, phosphite additives are substantially absent from the blends of this invention. Preferably the phosphites are present at less than 1000 ppm, preferably less than 500 ppm, more preferably less than 100 ppm.
To the above-mentioned composition, there can be added a neutralizing agent such as calcium stearate, magnesium hydroxide, aluminum hydroxide or hydrotalcite, and a nucleating agent such as a salt of benzoic acid, sodium-2,2′-methylene-bis(4,6-di-t-butylphenyl) phosphate and benzyl sorbitol, and the like, in addition to the above-mentioned stabilizer.
Additives
In another embodiment, a composition comprising the polymer product of this invention may further comprise typical additives known in the art such as fillers, antioxidants, adjuvants, adhesion promoters, oils, and/or plasticizers. Preferred fillers include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay and the like. Preferred antioxidants include phenolic antioxidants, such as Irganox 1010, Irganox, 1076 both available from Ciba-Geigy. Preferred oils include paraffinic or napthenic oils such as Primol 352, or Primol 876 available from ExxonMobil Chemical France, S.A. in Paris, France. Preferred plasticizers include polybutenes, such as Parapol 950 and Parapol 1300 formerly available from ExxonMobil Chemical Company in Houston Texas. Other preferred additives include block, antiblock, pigments, processing aids, UV stabilizers, hindered amine light stabilizers, UV absorbers, neutralizers, lubricants, surfactants and/or nucleating agents may also be present in one or more than one layer in the films. Preferred additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calcium sterate, carbon black, low molecular weight resins and glass beads. Preferred adhesion promoters include polar acids, polyaminoamides (such as Versamid 115, 125, 140, available from Henkel), urethanes (such as isocyanate/hydroxy terminated polyester systems, e.g. bonding agent TN/Mondur Cb-75(Miles, Inc.), coupling agents, (such as silane esters (Z-6020 from Dow Corning)), titanate esters (such as Kr-44 available from Kenrich), reactive acrylate monomers (such as sarbox SB-600 from Sartomer), metal acid salts (such as Saret 633 from Sartomer), polyphenylene oxide, oxidized polyolefins, acid modified polyolefins, and anhydride modified polyolefins.
In another embodiment the composition may include less than 3 wt % anti-oxidant, less than 3 wt % flow improver, less than 10 wt % wax, and or less than 3 wt % crystallization aid.
Other optional components that may be combined with the adhesive composition as disclosed herein include plasticizers, and/or other additives such as oils, surfactants, fillers, color masterbatches, and the like. Preferred plasticizers include mineral oils, polybutenes, phthalates and the like. Particularly preferred plasticizers include phthalates such as di-iso-undecyl phthalate (DIUP), di-iso-nonylphthalate (DINP), dioctylphthalates (DOP) and/or the like. Particularly preferred oils include aliphatic naphthenic oils.
Other optional components that may be combined with the polymer product of this invention are low molecular weight products such as wax, oil or low Mn polymer, (low meaning below Mn of 5000, preferably below 4000, more preferably below 3000, even more preferably below 2500). Preferred waxes include polar or non-polar waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, and wax modifiers. Preferred waxes include ESCOMER™ 101. Preferred functionalized waxes include those modified with an alcohol, an acid, a ketone, an anhydride and the like. Preferred examples include waxes modified by methyl ketone, maleic anhydride or maleic acid. Preferred oils include aliphatic napthenic oils, white oils, or the like. Preferred low Mn polymers include polymers of lower alpha olefins such as propylene, butene, pentene, hexene and the like. A particularly preferred polymer includes polybutene having an Mn of less than 1000. An example of such a polymer is available under the trade name PARAPOL™ 950 from ExxonMobil Chemical Company. PARAPOL™ 950 is a liquid polybutene polymer having an Mn of 950 and a kinematic viscosity of 220cSt at 100° C., as measured by ASTM D 445. In some embodiments the polar and non-polar waxes are used together in the same composition.
In some embodiments, however, wax may not be desired and may thus be present at less than 10 weight %, preferably less than 5 weight %, more preferably less than 1 weight %, more preferably less than 0.5 weight %, based upon the weight of the composition.
In another embodiment the composition of this invention may have less than 30 weight % total of any combination of additives described above, preferably less than 25 weight %, preferably less than 20 weight %, preferably less than 15 weight %, preferably less than 10 weight %, preferably less than 5 weight %, based upon the total weight of F-POA, POA and other polymers present.
The composition of this invention or formulations thereof may then be applied directly to a substrate or may be sprayed thereon. The composition may be molten, or heated to a semisolid state prior or during application. Spraying is defined to include atomizing, such as producing an even dot pattern, spiral spraying such as Nordson Controlled Fiberization or oscillating a stretched filament like may be done in the ITW Dynafiber/Omega heads or Summit technology from Nordson. The compositions described herein may be applied using melt blown techniques as well. Melt blown techniques are defined to include the methods described in U.S. Pat. No. 5,145,689 or any process where air streams are used to break up filaments of the extrudate and then used to deposit the broken filaments on a substrate. In general, melt blown techniques are processes that use air to spin hot melt adhesive fibers and convey them onto a substrate for bonding. Fibers sizes can easily be controlled from 20-200 microns by changing the melt to air ratio. Few, preferably no, stray fibers are generated due to the inherent stability of adhesive melt blown applicators. Under UV light the bonding appears as a regular, smooth, stretched dot pattern. Atomization is a process that uses air to atomize hot melt adhesive into very small dots and convey them onto a substrate for bonding.
Heat Stability
The compositions of the present invention preferably are heat stable, by which is meant that the Gardner color (as measured by ASTM D-1544-68) of the composition that has been heated to 180° C. for 48 hours, does not change by more than 7 Gardner units when compared to the Gardner color of the initial composition. Preferably, the Gardner color of the composition after heatingto 180° C. for 48 hours does not change by more than 6, more preferably 5, still more preferably 4, still more preferably 3, still more preferably 2, still more preferably 1 Gardner color unit, as compared to the initial composition prior to being heated. In a preferred embodiment, the F-POA is heat stable, by which is meant that the Gardner color (as measured by ASTM D-1544-68) of the F-POA that has been heated to 180° C. for 48 hours, does not change by more than 7 Gardner units when compared to the Gardner color of the initial F-POA. Preferably, the Gardner color of the F-POA after heatingto 180° C. for 48 hours does not change by more than 6, more preferably 5, still more preferably 4, still more preferably 3, still more preferably 2, still more preferably 1 Gardner color unit, as compared to the initial F-POA prior to being heated.
It has been discovered that free acid groups present in the composition may result in reduced heat stability. Accordingly, in a preferred embodiment, the amount of free acid groups present in the F-POA is less than about 1000 ppm, more preferably less than about 500 ppm, still more preferably less than about 100 ppm, based on the total amount of F-POA present.
In an embodiment, the composition may comprise F-POA in which at least a portion has been washed with an organic solvent, with an aqueous solution, with an acidic solution, with a basic solution, or a combination thereof, prior to incorporation of the F-POA into the final composition. Likewise, the entire composition may also be washed once formed.
In a preferred embodiment, the acid value of the F-POA, after washing with an aqueous solution, differs from the acid value of the F-POA prior to washing by less than about 10%, preferably by less than about 5%, more preferably by less than about 1% as determined by ASTM D-94-02
In a preferred embodiment, the F-POA comprises maleic anhydride, and the acid value of the F-POA, after washing with an aqueous solution, may differ from the acid value of the F-POA prior to washing by less than about 10%, preferably by less than about 5%, more preferably by less than about 1% as determined by ASTM D 94-02.
In another embodiment, the F-POA comprises an unsaturated group comprising a carbonyl group (preferably maleic anhydride), and peaks measured in the infrared spectrum of the composition attributable to free acid content (e.g., —OH stretch, C═O stretch, and the like) are reduced in peak height by less than about 20%, preferably less than about 10%, more preferably less than about 5%, still more preferably less than about 1%, as compared to the same peaks in an infra red spectrum of the composition measured essentially the same way after the composition has been devolatilized by heating at 180° C. for 30 minutes.
Lamination Melt Coating
The compositions of this invention may be used in any adhesive application, including but not limited to, disposables, packaging, laminates, pressure sensitive adhesives, tapes labels, wood binding, paper binding, non-wovens, road marking, reflective coatings, and the like.
In a preferred embodiment the adhesives of this invention can be used for disposable diaper and napkin chassis construction, elastic attachment in disposable goods converting, packaging, labeling, bookbinding, woodworking, and other assembly applications. Particularly preferred applications include: baby diaper leg elastic, diaper frontal tape, diaper standing leg cuff, diaper chassis construction, diaper core stabilization, diaper liquid transfer layer, diaper outer cover lamination, diaper elastic cuff lamination, feminine napkin core stabilization, feminine napkin adhesive strip, industrial filtration bonding, industrial filter material lamination, filter mask lamination, surgical gown lamination, surgical drape lamination, and perishable products packaging.
One or more of the embodiments of the compositions described above may be applied to any substrate. Preferred substrates include wood, paper, cardboard, plastic, thermoplastic, rubber, metal, metal foil (such as aluminum foil and tin foil), metallized surfaces, cloth, non-wovens (particularly polypropylene spun bonded fibers or non-wovens), spunbonded fibers, cardboard, stone, plaster, glass (including silicon oxide (SiOx) coatings applied by evaporating silicon oxide onto a film surface), foam, rock, ceramics, films, polymer foams (such as polyurethane foam), substrates coated with inks, dyes, pigments, PVDC and the like or combinations thereof.
Additional preferred substrates include polyethylene, polypropylene, polyacrylates, acrylics, polyethylene terephthalate, or any of the polymers listed above as suitable for blends.
Any of the above substrates, and/or the polymers of this invention, may be corona discharge treated, flame treated, electron beam irradiated, gamma irradiated, microwaved, or silanized.
The adhesives produced herein, when coated in some fashion between two adherends, preferably perform such that the materials are held together in a sufficient fashion compared to a standard specification or a standard adhesive similarly constructed. In so doing, the inventive composition may be utilized as a surface primer, as a tie layer, as an adhesion promoter, as a hot melt adhesive, as a compatiblizer, or the like.
The compositions of this invention may be used in any adhesive application described in WO 97/33921 in combination with the polymers described therein or in place of the polymers described therein.
The compositions of this invention, alone or in combination with other polymers and or additives, may also be used to form hook and loop fasteners as described in WO 02/35956.
In a particularly preferred embodiment the compositions of this invention are used as adhesives in low temperature (less than 0° C.) applications.
In a particularly preferred embodiment the compositions of this invention are used as adhesives in high temperature (more than 40° C.) applications.
In a particularly preferred embodiment the compositions of this invention are used as adhesives in applications requiring both high and low temperature performance (such as freezer to microwave applications or cardboard storage boxes for use in non-climate controlled wharehouses).
In a preferred embodiment this invention relates to:
Molecular weights (number average molecular weight (Mn), weight average molecular weight (Mw), and z-average molecular weight (Mz)) were determined using a Waters 150 Size Exclusion Chromatograph (SEC) equipped with a differential refractive index detector (DRI), an online low angle light scattering (LALLS) detector and a viscometer (VIS). The details of the detector calibrations have been described elsewhere [See T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001)].
The SEC with three Polymer Laboratories PLgel 10 mm Mixed-B columns, a nominal flow rate 0.5 cm3/min, and a nominal injection volume 300 microliters was common to both detector configurations. The various transfer lines, columns and differential refractometer (the DRI detector, used mainly to determine eluting solution concentrations) were contained in an oven maintained at 135° C.
The LALLS detector used was a model 2040 dual-angle light scattering photometer (Precision Detector Inc.). Its flow cell, located in the SEC oven, uses a 690 nm diode laser light source and collects scattered light at 15° and 90°. The 15° output was used herein. The signal generated was sent to a data acquisition board (National Instruments) that accumulates readings at a rate of 16 per second. The lowest four readings were averaged, and the proportional signal was sent to the SEC-LALLS-VIS computer. The LALLS detector was placed after the SEC columns, and before the viscometer.
The viscometer was a high temperature Model 150R (Viscotek Corporation) having four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity for the solution flowing through the viscometer was calculated from these outputs. The viscometer was inside the SEC oven, positioned after the LALLS detector but before the DRI detector.
Solvent for the SEC experiment was prepared by adding 6 grams of butylated hydroxy toluene (BHT) as an antioxidant to a 4 liter bottle of 1,2,4 Trichlorobenzene (TCB) (Aldrich Reagent grade) and waiting for the BHT to solubilize. The TCB mixture was then filtered through a 0.7 micron glass pre-filter and subsequently through a 0.1 micron Teflon filter. There was an additional online 0.7 micron glass pre-filter/0.22 micron Teflon filter assembly between the high pressure pump and SEC columns. The TCB was then degassed with an online degasser (Phenomenex, Model DG-4000) before entering the SEC.
Sample solutions were prepared by placing the dry polymer sample in a glass container, adding the desired amount of TCB, then heating the mixture at 160° C. with continuous agitation for about 2 hours. All quantities were measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units were 1.463 g/ml at room temperature and 1.324 g/ml at 135° C. The injection concentration ranged from 1.0 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
Prior to running each sample the DRI detector and the injector were purged. Flow rate in the apparatus was then increased to 0.5 ml/minute, and the DRI was allowed to stabilize for 8-9 hours before injecting the first sample. The argon ion laser was turned on 1 to 1.5 hours before running samples by running the laser in idle mode for 20-30 minutes and then switching to full power in light regulation mode.
The branching index was measured using SEC with an on-line viscometer (SEC-VIS) and are reported as g′ at each molecular weight in the SEC trace. The branching index g′ is defined as:
where ηb is the intrinsic viscosity of the branched polymer and ηl is the intrinsic viscosity of a linear polymer of the same viscosity-averaged molecular weight (Mv) as the branched polymer. ηl=KMvα, K and α were measured values for linear polymers and should be obtained on the same SEC-DRI-LS-VIS instrument as the one used for branching index measurement. For polypropylene samples presented in this invention, K=0.0002288 and α=0.705 were used. The SEC-DRI-LS-VIS method obviates the need to correct for polydispersities, since the intrinsic viscosity and the molecular weight were measured at individual elution volumes, which arguably contain narrowly dispersed polymer. Linear polymers selected as standards for comparison were of the same viscosity average molecular weight, monomer content and composition distribution. Linear character for polymer containing C2 to C10 monomers is confirmed by Carbon-13 NMR according to Randall (Rev. Macromol. Chem. Phys., C29 (2&3), p. 285-297). Linear character for C11 and above monomers was confirmed by GPC analysis using a MALLS detector. For example, for a copolymer of propylene, the NMR should not indicate branching greater than that of the co-monomer (i.e. if the comonomer is butene, branches of greater than two carbons should not be present). For a homopolymer of propylene, the GPC should not show branches of more than one carbon atom. When a linear standard was desired for a polymer where the comonomer is C9 or more, protocols described by T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001) were used in determining standards. In the case of syndiotactic polymers, the standard was selected to have a comparable amount of syndiotacticity as measured by Carbon 13 NMR.
Peak melting point (Tm), peak crystallization temperature (Tc), heat of fusion and crystallinity were determined using ASTM E 794-85. Differential scanning calorimetric (DSC) data was obtained using a TA Instruments model 2920. e.g., samples weighing approximately 7-10 mg were sealed in aluminum sample pans. The DSC data was recorded by first cooling the sample to −50° C. and then gradually heating it to 200° C. at a rate of 10° C./minute. The sample was kept at 200° C. for 5 minutes before a second cooling-heating cycle was applied. Both the first and second cycle thermal events were recorded. Areas under the curves were measured and used to determine the heat of fusion and the degree of crystallinity. The percent crystallinity is calculated using the formula, [area under the curve (Joules/gram)/B(Joules/gram)]* 100, where B is the heat of fusion for the homopolymer of the major monomer component. These values for B were obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999. A value of 189 J/g (B) was used as the heat of fusion for 100% crystalline polypropylene. For polymers displaying multiple melting or crystallization peaks, the highest melting peak was taken as peak melting point, and the highest crystallization peak was taken as peak crystallization temperature.
The glass transition temperature (Tg) was measured by ASTM E 1356 using a TA Instruments model 2920.
Melt Viscosity was determined according to ASTM D-3236, which is also referred to herein as “viscosity” and/or “Brookfield viscosity”. Melt viscosity profiles were measured at a temperature from 120° C. to 190° C. using a Brookfield Thermosel viscometer and a number 27 spindle unless otherwise noted.
Adhesive Testing
The samples were prepared consistent with testing of adhesives, in particular, hot melt adhesives, by using the olefin polymers or blending the olefin polymers, functionalized olefin polymers, additives, tackifier, wax, antioxidant, and other ingredients or components under mixing at elevated temperatures to form fluid melt. The mixing temperature varied from about 130 to about 190° C. Adhesive test specimens were created by bonding the substrates together with a portion (e.g., a dot) of molten adhesive and compressing the bond with a 500-gram weight until cooled to room temperature (i.e., about 25° C.). The dot size was controlled by the adhesive volume such that in most cases the compressed disk which formed gave a uniform circle just inside the dimensions of the substrates. Once a construct has been produced, it was be subjected to various insults in order to assess the effectiveness of the bond.
Once a bond fails to a paper substrate the effectiveness of the bond was quantified by estimating the area of the adhesive dot that retained paper fibers as the construct failed along the bond line. This estimate is referred to herein as the percent substrate fiber tear. An example of good fiber, after conditioning a sample for 15 hours at −12° C. and attempting to destroy the bond, would be an estimate of 80-100% substrate fiber tear. It is likely that 0% substrate fiber tear under those conditions would signal a loss of adhesion.
Substrate fiber tear: The specimens were prepared using the same procedure as that described above. For low temperature fiber tear test, the bond specimens were placed in a freezer or refrigerator to obtain the desired test temperature. For substrate fiber tear at room temperature, the specimens were aged at ambient conditions. The bonds were separated by hand and a determination made as to the type of failure observed. The amount of substrate fiber tear is expressed herein as a percentage.
Dot T-Peel was determined according to ASTM D 1876, except that the specimen was produced by combining two 1 inch by 3 inch (2.54 cm×7.62 cm) substrate cut outs with a dot of adhesive with a volume that, when compressed under a 500-gram weight occupied about 1 square inch of area (1 inch=2.54 cm). Once all the specimens were made, each were pulled apart in a side by side testing arrangement at a rate of 2 inches per minute by a machine that records the destructive force of the insult being applied. The maximum force achieved for each sample tested was recorded and averaged, thus producing the average maximum force which is reported as the Dot T-Peel.
Peel Strength (modified ASTM D1876): Substrates (1×3 inches (25×76 mm)) were heat sealed with adhesive film (5 mils (130 μm) thickness) at 135° C. for 1 to 2 seconds and 40 psi (0.28 MPa) pressure. Bond specimens were peeled back in a tensile tester at a constant crosshead speed of 2 in/min (51 mm/min). The average force required to peel the bond (5 specimens) apart was recorded.
Set time is defined for use herein as the time it takes for a compressed adhesive substrate construct to fasten together with enough adhesion so as to give substrate fiber tear when pulled apart, and thus the bond is sufficiently strong to remove the compression. The bond will likely still strengthen upon further cooling, however, it no longer requires compression. These set times were measured by placing a molten dot of adhesive on to a file folder substrate taped to a flat table. A file folder tab (1 inch by 3 inch (2.5 cm×7.6 cm)) was placed upon the dot 3 seconds later and compressed with a 500 gram weight. The weight was allowed to sit for about 0.5 to about 10 seconds. The construct thus formed was pulled apart to check for a bonding level sufficient to produce substrate fiber tear. The set time was recorded as the minimum time required for this bonding to occur. Standards of commercially available adhesives were used to calibrate this process.
SAFT (modified D4498) measures the ability of a bond to withstand an elevated temperature rising at 10° F. (5.5° C.) /15 min., under a constant force that pulls the bond in the shear mode. Bonds were formed in the manner described above on Kraft paper (1 inch by 3 inch (2.5 cm×7.6 cm)). The test specimens were suspended vertically in an oven at room temperature with a 500-gram load attached to the bottom. The temperatures at which the weight fell was recorded (when the occasional sample reached temperatures above the oven capacity >265° F. (129° C.) it was terminated and averaged in with the other samples at termination temperature).
Shore A hardness was measured according to ASTM D 2240. An air cooled dot of adhesive was subjected to the needle and the deflection was recorded from the scale.
Sample Preparation and Description
Two POA homopolypropylenes were produced according to the general procedures described in U.S. Ser. No. 10/868,951, filed Oct. 15, 2003. The catalysts used were di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafnium dimethyl and rac-dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl the activator used was N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate. The polymerization was run at 131° C. in hexane.) The polymer properties are listed in Table A.
Two blends of POA 12 were made. One where the POA-12 was functionalized with maleic anhydride and one without.
POA-12-g-MA
POA-12 was functionalized by dissolving 120 g of POA-12 polymer in toluene (polymer concentration is about 20 wt. %) to which 15 wt. % (based on polymer) of maleic anhydride was added. 2.5 wt % of 2,5-dimethyl-2,5-di(t-butylperoxyl)hexane was added and the reaction was heated to 139° C. and allowed to react for 4 hours. The method described by M. Sclavons et al. (Polymer, 41(2000), page 1989) was used to determine the MA content of the maleated polymer. Briefly, about 0.5 gram of polymer was dissolved in 150 ml of toluene at the boiling temperature. A potentiometric titration with tetra-butylammonium hydroxide using bromothymol blue as the color indicator was performed on the heated solution in which the polymer did not precipitate during the titration. The POA-12-g-MA was found to contain 1.41 weight % MA. Adhesion testing was then conducted on the POA-12-, POA-11, and POA-12-g-MA blended with other components. The data are as follows:
Escorez 5690 is a hydrogenated aromatic modified resin produced from dicyclopentadiene feedstock, exhibiting a ring and ball softening point of 130° C. available from ExxonMobil in Houston, Tex. C80 wax is Paraflint C80 propylene wax—which is a Fischer Tropsch fractionated wax, available from Moore and Munger.
As the data clearly shows, the inventive adhesive formulation dramatically improved the adhesion at −10° C. and −30° C.
All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby.
This application is a continuation-in-part of U.S. Ser. No. 10/686,951, filed Oct. 15, 2003 which claims priority from U.S. Ser. No. 60/418,482, filed Oct. 15, 2002 and U.S. Ser. No. 60/460,714, filed Apr. 4, 2003. This application is also a continuation-in-part of U.S. Ser. No. 10/687,508, filed Oct. 15, 2003 which claims priority from U.S. Ser. No. 60/418,482, filed Oct. 15, 2002 and U.S. Ser. No. 60/460,714, filed Apr. 4, 2003.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1953104 | Hale-Church et al. | Apr 1934 | A |
| 3483276 | Mahlman | Dec 1969 | A |
| 3821143 | Cluff et al. | Jun 1974 | A |
| 3927166 | Tomoda et al. | Dec 1975 | A |
| 3954697 | McConnell et al. | May 1976 | A |
| 4178272 | Meyer, Jr. et al. | Dec 1979 | A |
| 4205021 | Morita et al. | May 1980 | A |
| 4210570 | Trotter et al. | Jul 1980 | A |
| 4217428 | McConnell et al. | Aug 1980 | A |
| 4361628 | Krueger et al. | Nov 1982 | A |
| 4476283 | Andersen | Oct 1984 | A |
| 4496698 | Adriaans et al. | Jan 1985 | A |
| 4510286 | Liu | Apr 1985 | A |
| 4525469 | Ueda et al. | Jun 1985 | A |
| 4547552 | Toyota et al. | Oct 1985 | A |
| 4600648 | Yazaki et al. | Jul 1986 | A |
| 4668752 | Tominari et al. | May 1987 | A |
| 4668753 | Kashiwa et al. | May 1987 | A |
| 4668834 | Rim et al. | May 1987 | A |
| 4673719 | Kioka et al. | Jun 1987 | A |
| 4675247 | Kitamura et al. | Jun 1987 | A |
| 4701432 | Welborn, Jr. | Oct 1987 | A |
| 4719260 | Stuart, Jr. et al. | Jan 1988 | A |
| 4725506 | Nagano | Feb 1988 | A |
| 4737548 | Kojima et al. | Apr 1988 | A |
| 4751121 | Kuhnel et al. | Jun 1988 | A |
| 4774144 | Jachec et al. | Sep 1988 | A |
| 4794096 | Ewen | Dec 1988 | A |
| 4822688 | Nogues | Apr 1989 | A |
| 4826939 | Stuart, Jr. | May 1989 | A |
| 4837271 | Brindopke | Jun 1989 | A |
| 4849487 | Kaminsky et al. | Jul 1989 | A |
| 4866023 | Ritter et al. | Sep 1989 | A |
| 4882406 | Cozewith et al. | Nov 1989 | A |
| 4892851 | Ewen et al. | Jan 1990 | A |
| 4897452 | Berrier et al. | Jan 1990 | A |
| 4929509 | Godfrey | May 1990 | A |
| 4935474 | Ewen et al. | Jun 1990 | A |
| 4937299 | Ewen et al. | Jun 1990 | A |
| 4939202 | Maletsky et al. | Jul 1990 | A |
| 4939217 | Stricklen | Jul 1990 | A |
| 4942096 | Abe et al. | Jul 1990 | A |
| 4950720 | Randall, Jr. et al. | Aug 1990 | A |
| 4960820 | Hwo | Oct 1990 | A |
| 4975403 | Ewen | Dec 1990 | A |
| 4981760 | Naito et al. | Jan 1991 | A |
| 5008356 | Ishimaru et al. | Apr 1991 | A |
| 5021257 | Foster et al. | Jun 1991 | A |
| 5035283 | Brücher et al. | Jul 1991 | A |
| 5036034 | Ewen | Jul 1991 | A |
| 5039614 | Dekmezian et al. | Aug 1991 | A |
| 5041251 | McCoskey et al. | Aug 1991 | A |
| 5047485 | DeNicola, Jr. | Sep 1991 | A |
| 5077129 | Schinkel et al. | Dec 1991 | A |
| 5089319 | Bothe | Feb 1992 | A |
| 5091352 | Kioka et al. | Feb 1992 | A |
| 5096743 | Schoenbeck | Mar 1992 | A |
| 5100963 | Lin | Mar 1992 | A |
| 5108680 | Menting et al. | Apr 1992 | A |
| 5114897 | Schell, Jr. et al. | May 1992 | A |
| 5115030 | Tanuka et al. | May 1992 | A |
| 5116881 | Park et al. | May 1992 | A |
| 5118566 | Wilhelm et al. | Jun 1992 | A |
| 5132157 | Asanuma et al. | Jul 1992 | A |
| 5147696 | Lansbury et al. | Sep 1992 | A |
| 5149579 | Park et al. | Sep 1992 | A |
| 5151474 | Lange et al. | Sep 1992 | A |
| 5152946 | Gillette | Oct 1992 | A |
| 5155080 | Elder et al. | Oct 1992 | A |
| 5155160 | Yeh et al. | Oct 1992 | A |
| 5155184 | Laurent et al. | Oct 1992 | A |
| 5171799 | Kioka et al. | Dec 1992 | A |
| 5175051 | Schloegl et al. | Dec 1992 | A |
| 5185398 | Kehr et al. | Feb 1993 | A |
| 5202361 | Zimmerman et al. | Apr 1993 | A |
| 5204037 | Fujii | Apr 1993 | A |
| 5209971 | Babu et al. | May 1993 | A |
| 5212247 | Asanuma et al. | May 1993 | A |
| 5216095 | Dolle et al. | Jun 1993 | A |
| 5218046 | Audureau et al. | Jun 1993 | A |
| 5218071 | Tsutsui et al. | Jun 1993 | A |
| 5219903 | Fujii et al. | Jun 1993 | A |
| 5219913 | Tomomatsu et al. | Jun 1993 | A |
| 5219968 | Shiomura et al. | Jun 1993 | A |
| 5225500 | Elder et al. | Jul 1993 | A |
| 5231126 | Shi et al. | Jul 1993 | A |
| 5232992 | Asanuma et al. | Aug 1993 | A |
| 5236649 | Hall et al. | Aug 1993 | A |
| 5236962 | Govoni et al. | Aug 1993 | A |
| 5244996 | Kawasaki et al. | Sep 1993 | A |
| 5246779 | Heimberg et al. | Sep 1993 | A |
| 5252659 | Koizumi et al. | Oct 1993 | A |
| 5271976 | Kondo et al. | Dec 1993 | A |
| 5272236 | Lai et al. | Dec 1993 | A |
| 5278216 | Asanuma et al. | Jan 1994 | A |
| 5278220 | Vermeire et al. | Jan 1994 | A |
| 5286564 | Cecchin et al. | Feb 1994 | A |
| 5292561 | Peiffer et al. | Mar 1994 | A |
| 5300361 | Vowinkel et al. | Apr 1994 | A |
| 5308817 | Reddy et al. | May 1994 | A |
| 5310584 | Jacoby et al. | May 1994 | A |
| 5314956 | Asanuma et al. | May 1994 | A |
| 5317036 | Brady, III et al. | May 1994 | A |
| 5317070 | Brant et al. | May 1994 | A |
| 5326824 | Asanuma et al. | Jul 1994 | A |
| 5332707 | Karayannis et al. | Jul 1994 | A |
| 5334677 | Razavi et al. | Aug 1994 | A |
| 5336746 | Tsutsui et al. | Aug 1994 | A |
| 5346773 | Simoens | Sep 1994 | A |
| 5350817 | Winter et al. | Sep 1994 | A |
| 5354619 | Babu | Oct 1994 | A |
| 5359102 | Inoue et al. | Oct 1994 | A |
| 5367022 | Kiang et al. | Nov 1994 | A |
| 5368919 | Robeson | Nov 1994 | A |
| 5369196 | Matsumoto et al. | Nov 1994 | A |
| 5373059 | Asanuma et al. | Dec 1994 | A |
| 5374685 | Asanuma et al. | Dec 1994 | A |
| 5374700 | Tsutsui et al. | Dec 1994 | A |
| 5397843 | Lakshmanan et al. | Mar 1995 | A |
| 5403667 | Simoens | Apr 1995 | A |
| 5410003 | Bai | Apr 1995 | A |
| 5412020 | Yamamoto et al. | May 1995 | A |
| 5414027 | DeNicola, Jr. et al. | May 1995 | A |
| 5416228 | Ewen et al. | May 1995 | A |
| 5430070 | Kono | Jul 1995 | A |
| 5434115 | Yamada et al. | Jul 1995 | A |
| 5439994 | Inoue et al. | Aug 1995 | A |
| 5441807 | Brandt et al. | Aug 1995 | A |
| 5455300 | Smith | Oct 1995 | A |
| 5455305 | Galambos | Oct 1995 | A |
| 5459217 | Todo et al. | Oct 1995 | A |
| 5459218 | Palackal et al. | Oct 1995 | A |
| 5464905 | Tsutsui et al. | Nov 1995 | A |
| 5468440 | McAlpin et al. | Nov 1995 | A |
| 5468560 | McPherson et al. | Nov 1995 | A |
| 5468807 | Tsurutani et al. | Nov 1995 | A |
| 5475075 | Brant et al. | Dec 1995 | A |
| 5476911 | Morini et al. | Dec 1995 | A |
| 5478646 | Asanuma et al. | Dec 1995 | A |
| 5478891 | Lakshmanan et al. | Dec 1995 | A |
| 5480848 | Geerts | Jan 1996 | A |
| 5480942 | Addeo et al. | Jan 1996 | A |
| 5483002 | Seelert et al. | Jan 1996 | A |
| 5500284 | Burgin et al. | Mar 1996 | A |
| 5504171 | Etherton et al. | Apr 1996 | A |
| 5504172 | Imuta et al. | Apr 1996 | A |
| 5512612 | Brown et al. | Apr 1996 | A |
| 5514460 | Surman et al. | May 1996 | A |
| 5516583 | Zhang et al. | May 1996 | A |
| 5516848 | Canich et al. | May 1996 | A |
| 5519091 | Tsutsui et al. | May 1996 | A |
| 5521251 | Satoh et al. | May 1996 | A |
| 5525689 | Tsutsui et al. | Jun 1996 | A |
| 5527846 | Christell et al. | Jun 1996 | A |
| 5529843 | Dries et al. | Jun 1996 | A |
| 5529850 | Morini et al. | Jun 1996 | A |
| 5529943 | Hong et al. | Jun 1996 | A |
| 5530054 | Tse et al. | Jun 1996 | A |
| 5532396 | Winter et al. | Jul 1996 | A |
| 5534473 | Welch et al. | Jul 1996 | A |
| 5534595 | Asanuma et al. | Jul 1996 | A |
| 5536773 | Yamada et al. | Jul 1996 | A |
| 5539056 | Yang et al. | Jul 1996 | A |
| 5539066 | Winter et al. | Jul 1996 | A |
| 5541260 | Pelliconi et al. | Jul 1996 | A |
| 5541262 | Brichta et al. | Jul 1996 | A |
| 5543373 | Winter et al. | Aug 1996 | A |
| 5547766 | Gobran | Aug 1996 | A |
| 5548007 | Asanuma et al. | Aug 1996 | A |
| 5548008 | Asanuma et al. | Aug 1996 | A |
| 5548014 | Tse et al. | Aug 1996 | A |
| 5552489 | Merrill et al. | Sep 1996 | A |
| 5554668 | Scheve et al. | Sep 1996 | A |
| 5556920 | Tanaka et al. | Sep 1996 | A |
| 5559165 | Paul | Sep 1996 | A |
| 5565533 | Galimberti et al. | Oct 1996 | A |
| 5565534 | Aulbach et al. | Oct 1996 | A |
| 5571613 | Schuhmann et al. | Nov 1996 | A |
| 5574082 | Keller et al. | Nov 1996 | A |
| 5576259 | Hasegawa et al. | Nov 1996 | A |
| 5576260 | Winter et al. | Nov 1996 | A |
| 5578743 | Ho et al. | Nov 1996 | A |
| 5579913 | Yamada et al. | Dec 1996 | A |
| 5585448 | Resconi et al. | Dec 1996 | A |
| 5585508 | K{umlaut over ( )}über et al. | Dec 1996 | A |
| 5587501 | Winter et al. | Dec 1996 | A |
| 5591785 | Scheve et al. | Jan 1997 | A |
| 5591817 | Asanuma et al. | Jan 1997 | A |
| 5594074 | Hwo et al. | Jan 1997 | A |
| 5594078 | Welch et al. | Jan 1997 | A |
| 5594080 | Waymouth et al. | Jan 1997 | A |
| 5594172 | Shirnohara | Jan 1997 | A |
| 5595827 | Yamada et al. | Jan 1997 | A |
| 5596052 | Resconi et al. | Jan 1997 | A |
| 5599881 | Xie | Feb 1997 | A |
| 5599885 | Kawasaki et al. | Feb 1997 | A |
| 5602223 | Sasaki et al. | Feb 1997 | A |
| 5605969 | Tsutsui et al. | Feb 1997 | A |
| 5610254 | Saguna et al. | Mar 1997 | A |
| 5612428 | Winter et al. | Mar 1997 | A |
| 5618369 | Peiffer et al. | Apr 1997 | A |
| 5618883 | Plamthottam et al. | Apr 1997 | A |
| 5621046 | Iwanami et al. | Apr 1997 | A |
| 5622760 | Leiss | Apr 1997 | A |
| 5629254 | Fukuoka et al. | May 1997 | A |
| 5631202 | Ewen | May 1997 | A |
| 5633010 | Chen | May 1997 | A |
| 5633018 | Stouffer et al. | May 1997 | A |
| 5639842 | Tsutsui et al. | Jun 1997 | A |
| 5641848 | Giacobbe et al. | Jun 1997 | A |
| 5643846 | Reddy et al. | Jul 1997 | A |
| 5648428 | Reddy et al. | Jul 1997 | A |
| 5652308 | Merrill et al. | Jul 1997 | A |
| 5658997 | Fukuoka et al. | Aug 1997 | A |
| 5661096 | Winter et al. | Aug 1997 | A |
| 5663232 | Seppanen et al. | Sep 1997 | A |
| 5663249 | Ewen | Sep 1997 | A |
| 5665469 | Brandt et al. | Sep 1997 | A |
| 5667902 | Brew et al. | Sep 1997 | A |
| 5670436 | Herrmann et al. | Sep 1997 | A |
| 5672668 | Winter et al. | Sep 1997 | A |
| 5677068 | Ghirardo et al. | Oct 1997 | A |
| 5683818 | Bolvari | Nov 1997 | A |
| 5684099 | Watanabe et al. | Nov 1997 | A |
| 5686533 | Gahleitner et al. | Nov 1997 | A |
| 5693730 | Küber et al. | Dec 1997 | A |
| 5693836 | Winter et al. | Dec 1997 | A |
| 5696045 | Winter et al. | Dec 1997 | A |
| 5696049 | Ikeyama et al. | Dec 1997 | A |
| 5698651 | Kawasaki et al. | Dec 1997 | A |
| 5700886 | Winter et al. | Dec 1997 | A |
| 5700895 | Kanda et al. | Dec 1997 | A |
| 5703172 | Watanabe et al. | Dec 1997 | A |
| 5703180 | Tsutsui et al. | Dec 1997 | A |
| 5705565 | Hughes et al. | Jan 1998 | A |
| 5705568 | Gahleitner et al. | Jan 1998 | A |
| 5705579 | Hawley et al. | Jan 1998 | A |
| 5705584 | Fukuoka et al. | Jan 1998 | A |
| 5709937 | Adams et al. | Jan 1998 | A |
| 5710223 | Fukuoka et al. | Jan 1998 | A |
| 5712323 | Braga et al. | Jan 1998 | A |
| 5714256 | DeLucia et al. | Feb 1998 | A |
| 5714426 | Tsutsui et al. | Feb 1998 | A |
| 5714427 | Winter et al. | Feb 1998 | A |
| 5716570 | Peiffer et al. | Feb 1998 | A |
| 5716698 | Schreck et al. | Feb 1998 | A |
| 5719235 | Zandona | Feb 1998 | A |
| 5719241 | Razavi et al. | Feb 1998 | A |
| 5723546 | Sustic | Mar 1998 | A |
| 5723640 | Fukuoka et al. | Mar 1998 | A |
| 5731362 | Scheve et al. | Mar 1998 | A |
| 5739220 | Shamshoum et al. | Apr 1998 | A |
| 5739225 | Tazaki et al. | Apr 1998 | A |
| 5739366 | Imuta et al. | Apr 1998 | A |
| 5741563 | Mehta et al. | Apr 1998 | A |
| 5741565 | Coosemans et al. | Apr 1998 | A |
| 5741868 | Winter et al. | Apr 1998 | A |
| 5747160 | Pinoca et al. | May 1998 | A |
| 5747405 | Little et al. | May 1998 | A |
| 5747620 | Machida et al. | May 1998 | A |
| 5747621 | Resconi et al. | May 1998 | A |
| 5753769 | Ueda et al. | May 1998 | A |
| 5753771 | Xie | May 1998 | A |
| 5756141 | Chen et al. | May 1998 | A |
| 5756169 | Peiffer et al. | May 1998 | A |
| 5756614 | Chien et al. | May 1998 | A |
| 5759469 | Asanuma et al. | Jun 1998 | A |
| 5760028 | Jadhav et al. | Jun 1998 | A |
| 5763349 | Zandona | Jun 1998 | A |
| 5763516 | Godfrey | Jun 1998 | A |
| 5767031 | Shamshoum et al. | Jun 1998 | A |
| 5767032 | Hokkanen et al. | Jun 1998 | A |
| 5767033 | Imuta et al. | Jun 1998 | A |
| 5767300 | Aulbach et al. | Jun 1998 | A |
| 5773129 | Wakamatsu et al. | Jun 1998 | A |
| 5773142 | Murschall et al. | Jun 1998 | A |
| 5773516 | Huffer et al. | Jun 1998 | A |
| 5773544 | Christell et al. | Jun 1998 | A |
| 5776851 | Küber et al. | Jul 1998 | A |
| 5777055 | Peiffer et al. | Jul 1998 | A |
| 5780168 | Satoh et al. | Jul 1998 | A |
| 5792549 | Wilkie | Aug 1998 | A |
| 5795941 | Cree et al. | Aug 1998 | A |
| 5795946 | Agarwal et al. | Aug 1998 | A |
| 5798175 | Tynan, Jr. et al. | Aug 1998 | A |
| 5804304 | Williams et al. | Sep 1998 | A |
| 5804524 | Reddy et al. | Sep 1998 | A |
| 5804623 | Hoffmann et al. | Sep 1998 | A |
| 5804665 | Watanabe et al. | Sep 1998 | A |
| 5807948 | Sugane et al. | Sep 1998 | A |
| 5817590 | Hasegawa et al. | Oct 1998 | A |
| 5817725 | Zandona | Oct 1998 | A |
| 5824753 | Naganuma et al. | Oct 1998 | A |
| 5827252 | Werenicz et al. | Oct 1998 | A |
| 5834393 | Jacobsen et al. | Nov 1998 | A |
| 5834538 | deHullu et al. | Nov 1998 | A |
| 5834562 | Silvestri et al. | Nov 1998 | A |
| 5840783 | Momchilovich et al. | Nov 1998 | A |
| 5840815 | Tsutsui et al. | Nov 1998 | A |
| 5843577 | Ouhadi et al. | Dec 1998 | A |
| 5844037 | Lundgard et al. | Dec 1998 | A |
| 5846558 | Nielsen et al. | Dec 1998 | A |
| 5846654 | Modrak | Dec 1998 | A |
| 5846896 | Ewen | Dec 1998 | A |
| 5846918 | Meijer et al. | Dec 1998 | A |
| 5847059 | Shamshoum et al. | Dec 1998 | A |
| 5849409 | Pinoca et al. | Dec 1998 | A |
| 5851610 | Ristey et al. | Dec 1998 | A |
| 5852100 | Sadatoshi et al. | Dec 1998 | A |
| 5852116 | Cree et al. | Dec 1998 | A |
| 5854354 | Ueda et al. | Dec 1998 | A |
| 5856400 | Matsumura et al. | Jan 1999 | A |
| 5856406 | Silvis et al. | Jan 1999 | A |
| 5858293 | Yoo | Jan 1999 | A |
| 5859088 | Peterson et al. | Jan 1999 | A |
| 5859139 | Addeo et al. | Jan 1999 | A |
| 5861211 | Thakkar et al. | Jan 1999 | A |
| 5861474 | Weller et al. | Jan 1999 | A |
| 5863665 | Kale et al. | Jan 1999 | A |
| 5863994 | DeNicola, Jr. et al. | Jan 1999 | A |
| 5866663 | Brookhart et al. | Feb 1999 | A |
| 5867316 | Carlson et al. | Feb 1999 | A |
| 5869555 | Simmons et al. | Feb 1999 | A |
| 5874505 | Saito et al. | Feb 1999 | A |
| 5874513 | Watanabe et al. | Feb 1999 | A |
| 5876855 | Wong et al. | Mar 1999 | A |
| 5880056 | Tsutsui et al. | Mar 1999 | A |
| 5880241 | Brookhart et al. | Mar 1999 | A |
| 5880323 | Brookhart, III et al. | Mar 1999 | A |
| 5882774 | Jonza et al. | Mar 1999 | A |
| 5882782 | Tsubone | Mar 1999 | A |
| 5883204 | Spencer et al. | Mar 1999 | A |
| 5883205 | Tsutsui et al. | Mar 1999 | A |
| 5886123 | Resconi et al. | Mar 1999 | A |
| 5886224 | Brookhart et al. | Mar 1999 | A |
| 5888607 | Seth et al. | Mar 1999 | A |
| 5888636 | Asanuma et al. | Mar 1999 | A |
| 5891946 | Nohara et al. | Apr 1999 | A |
| 5891963 | Brookhart et al. | Apr 1999 | A |
| 5891976 | Costa et al. | Apr 1999 | A |
| 5900294 | Murschall et al. | May 1999 | A |
| 5902848 | Burgin et al. | May 1999 | A |
| 5910136 | Hetzler et al. | Jun 1999 | A |
| 5910362 | Aratake et al. | Jun 1999 | A |
| 5911023 | Risch et al. | Jun 1999 | A |
| 5914079 | Peiffer et al. | Jun 1999 | A |
| 5914376 | Herrmann et al. | Jun 1999 | A |
| 5916974 | Song et al. | Jun 1999 | A |
| 5916988 | Tsutsui et al. | Jun 1999 | A |
| 5916989 | Brookhart, III et al. | Jun 1999 | A |
| 5916990 | Yanagihara et al. | Jun 1999 | A |
| 5919864 | Watanabe et al. | Jul 1999 | A |
| 5919983 | Rosen et al. | Jul 1999 | A |
| 5922823 | Sagane et al. | Jul 1999 | A |
| 5932157 | Dries et al. | Aug 1999 | A |
| 5936051 | Santi et al. | Aug 1999 | A |
| 5936053 | Fukuoka et al. | Aug 1999 | A |
| 5942451 | Daponte et al. | Aug 1999 | A |
| 5942569 | Simmons et al. | Aug 1999 | A |
| 5942586 | Herrmann et al. | Aug 1999 | A |
| 5945496 | Resconi et al. | Aug 1999 | A |
| 5947944 | Hetzler et al. | Sep 1999 | A |
| 5959046 | Imuta et al. | Sep 1999 | A |
| 5961782 | Luu et al. | Oct 1999 | A |
| 5969070 | Waymouth et al. | Oct 1999 | A |
| 5969217 | Rhodes | Oct 1999 | A |
| 5972490 | Crighton et al. | Oct 1999 | A |
| 5973078 | Pinoca et al. | Oct 1999 | A |
| 5973084 | Suga et al. | Oct 1999 | A |
| 5977251 | Kao et al. | Nov 1999 | A |
| 5977260 | Ciaccia et al. | Nov 1999 | A |
| 5983604 | Wilfong et al. | Nov 1999 | A |
| 5985193 | Harrington et al. | Nov 1999 | A |
| 5985426 | Wilkie | Nov 1999 | A |
| 5986024 | Wilson, Jr. | Nov 1999 | A |
| 5986651 | Reber et al. | Nov 1999 | A |
| 5990331 | Winter et al. | Nov 1999 | A |
| 5994437 | Lebez et al. | Nov 1999 | A |
| 5997981 | McCormack et al. | Dec 1999 | A |
| 5998547 | Hohner | Dec 1999 | A |
| 6002033 | Razawi et al. | Dec 1999 | A |
| 6004897 | Imuta et al. | Dec 1999 | A |
| 6005049 | Rebhan et al. | Dec 1999 | A |
| 6008262 | McKay et al. | Dec 1999 | A |
| 6017842 | Rosen et al. | Jan 2000 | A |
| 6028152 | Winter et al. | Feb 2000 | A |
| 6033514 | Davis et al. | Mar 2000 | A |
| 6034164 | Elspass et al. | Mar 2000 | A |
| 6034165 | Tomomatsu et al. | Mar 2000 | A |
| 6034259 | Brookhart et al. | Mar 2000 | A |
| 6040348 | Delaite et al. | Mar 2000 | A |
| 6040407 | Ishida et al. | Mar 2000 | A |
| 6040469 | Riedel et al. | Mar 2000 | A |
| 6042930 | Kelch et al. | Mar 2000 | A |
| 6045922 | Janssen et al. | Apr 2000 | A |
| 6046273 | Syed | Apr 2000 | A |
| 6048942 | Buehler et al. | Apr 2000 | A |
| 6054542 | Kojoh et al. | Apr 2000 | A |
| 6054544 | Finlayson et al. | Apr 2000 | A |
| 6057413 | Ima et al. | May 2000 | A |
| 6060139 | Peiffer et al. | May 2000 | A |
| 6060561 | Wolfschwenger et al. | May 2000 | A |
| 6060584 | Neely et al. | May 2000 | A |
| 6063482 | Peiffer et al. | May 2000 | A |
| 6063838 | Patnode et al. | May 2000 | A |
| 6069213 | Nemzek et al. | May 2000 | A |
| 6071598 | Peiffer et al. | Jun 2000 | A |
| 6077907 | Raetzsch et al. | Jun 2000 | A |
| 6080818 | Thakker et al. | Jun 2000 | A |
| 6084010 | Baetzold et al. | Jul 2000 | A |
| 6084041 | Andtsjo et al. | Jul 2000 | A |
| 6084048 | Hozumi et al. | Jul 2000 | A |
| 6086982 | Peiffer et al. | Jul 2000 | A |
| 6087459 | Miro et al. | Jul 2000 | A |
| 6090325 | Wheat et al. | Jul 2000 | A |
| 6090903 | Kataoka et al. | Jul 2000 | A |
| 6096843 | Saito et al. | Aug 2000 | A |
| 6100351 | Sun et al. | Aug 2000 | A |
| 6100353 | Lynch et al. | Aug 2000 | A |
| 6107422 | Wang et al. | Aug 2000 | A |
| 6107430 | Dubois et al. | Aug 2000 | A |
| 6107431 | Resconi et al. | Aug 2000 | A |
| 6110986 | Nozawa et al. | Aug 2000 | A |
| 6113996 | Amon et al. | Sep 2000 | A |
| 6114261 | Strelow et al. | Sep 2000 | A |
| 6114457 | Markel et al. | Sep 2000 | A |
| 6114477 | Merrill et al. | Sep 2000 | A |
| 6117962 | Weng et al. | Sep 2000 | A |
| 6121185 | Rosen et al. | Sep 2000 | A |
| 6121377 | Chien | Sep 2000 | A |
| 6121393 | Kioka et al. | Sep 2000 | A |
| 6121401 | Yamamoto et al. | Sep 2000 | A |
| 6121402 | Machida et al. | Sep 2000 | A |
| 6124231 | Fritze et al. | Sep 2000 | A |
| 6124400 | Chien | Sep 2000 | A |
| 6127484 | Cribbs et al. | Oct 2000 | A |
| 6140439 | Brookhart et al. | Oct 2000 | A |
| 6143683 | Shamshoum et al. | Nov 2000 | A |
| 6143825 | Beren et al. | Nov 2000 | A |
| 6143844 | Hokkanen et al. | Nov 2000 | A |
| 6143846 | Herrmann et al. | Nov 2000 | A |
| 6147174 | Holtcamp et al. | Nov 2000 | A |
| 6147180 | Markel et al. | Nov 2000 | A |
| 6150481 | Winter et al. | Nov 2000 | A |
| 6153549 | Hubscher et al. | Nov 2000 | A |
| 6156844 | Hashimoto et al. | Dec 2000 | A |
| 6156846 | Tsuruoka et al. | Dec 2000 | A |
| 6159888 | Welch et al. | Dec 2000 | A |
| 6162871 | Watanabe et al. | Dec 2000 | A |
| 6166161 | Mullins et al. | Dec 2000 | A |
| 6174930 | Agarwal et al. | Jan 2001 | B1 |
| 6174946 | Rubenacker et al. | Jan 2001 | B1 |
| 6174974 | Starzewski et al. | Jan 2001 | B1 |
| 6177190 | Gehlsen et al. | Jan 2001 | B1 |
| 6177377 | Chien | Jan 2001 | B1 |
| 6177526 | Fritze | Jan 2001 | B1 |
| 6177527 | Sishta et al. | Jan 2001 | B1 |
| 6180229 | Becker et al. | Jan 2001 | B1 |
| 6180732 | Ewen | Jan 2001 | B1 |
| 6184327 | Weng et al. | Feb 2001 | B1 |
| 6190760 | Nagai et al. | Feb 2001 | B1 |
| 6191241 | Starzewski et al. | Feb 2001 | B1 |
| 6197910 | Weng et al. | Mar 2001 | B1 |
| 6207606 | Lue et al. | Mar 2001 | B1 |
| 6207746 | Uchida et al. | Mar 2001 | B1 |
| 6207748 | Tse et al. | Mar 2001 | B1 |
| 6207750 | Lin et al. | Mar 2001 | B1 |
| 6207773 | Ting et al. | Mar 2001 | B1 |
| 6210764 | Hayes | Apr 2001 | B1 |
| 6211110 | Santi et al. | Apr 2001 | B1 |
| 6214447 | Nakagawa et al. | Apr 2001 | B1 |
| 6214948 | Zandona | Apr 2001 | B1 |
| 6214949 | Reddy et al. | Apr 2001 | B1 |
| 6214952 | Sadatoshi et al. | Apr 2001 | B1 |
| 6218457 | Fralich et al. | Apr 2001 | B1 |
| 6218488 | Schiggino et al. | Apr 2001 | B1 |
| 6218493 | Johnson et al. | Apr 2001 | B1 |
| 6221802 | Costa et al. | Apr 2001 | B1 |
| 6221981 | Jung et al. | Apr 2001 | B1 |
| 6225411 | Dang et al. | May 2001 | B1 |
| 6225432 | Weng et al. | May 2001 | B1 |
| 6228948 | Flaris et al. | May 2001 | B1 |
| 6238732 | Cameron et al. | May 2001 | B1 |
| 6245856 | Kaufman et al. | Jun 2001 | B1 |
| 6248829 | Fischer et al. | Jun 2001 | B1 |
| 6248832 | Peacock | Jun 2001 | B1 |
| 6248845 | Loveday et al. | Jun 2001 | B1 |
| 6251997 | Imai et al. | Jun 2001 | B1 |
| 6251998 | Medsker et al. | Jun 2001 | B1 |
| 6255246 | Devore et al. | Jul 2001 | B1 |
| 6255395 | Klosiewicz | Jul 2001 | B1 |
| 6255414 | Ittel et al. | Jul 2001 | B1 |
| 6255425 | Asanuma et al. | Jul 2001 | B1 |
| 6255426 | Lue et al. | Jul 2001 | B1 |
| 6258903 | Mawson et al. | Jul 2001 | B1 |
| 6262203 | Chien et al. | Jul 2001 | B1 |
| 6265512 | Siedle et al. | Jul 2001 | B1 |
| 6268062 | DeMeuse | Jul 2001 | B1 |
| 6268445 | McAdon et al. | Jul 2001 | B1 |
| 6268453 | Köppl et al. | Jul 2001 | B1 |
| 6271164 | Fritze et al. | Aug 2001 | B1 |
| 6271310 | Okayama et al. | Aug 2001 | B1 |
| 6271323 | Loveday et al. | Aug 2001 | B1 |
| 6274678 | Shinozaki et al. | Aug 2001 | B1 |
| 6277479 | Campbell et al. | Aug 2001 | B1 |
| 6277934 | Kondoh et al. | Aug 2001 | B1 |
| 6281289 | Maugans et al. | Aug 2001 | B1 |
| 6284814 | Gupta | Sep 2001 | B1 |
| 6284820 | Braga et al. | Sep 2001 | B1 |
| 6284857 | Shinozaki et al. | Sep 2001 | B1 |
| 6287658 | Cosentino et al. | Sep 2001 | B1 |
| 6287705 | Seta et al. | Sep 2001 | B1 |
| 6288189 | Brown et al. | Sep 2001 | B1 |
| 6291063 | Shah et al. | Sep 2001 | B1 |
| 6294611 | Takayanagi et al. | Sep 2001 | B1 |
| 6294632 | Shiraishi et al. | Sep 2001 | B1 |
| 6297301 | Erderly et al. | Oct 2001 | B1 |
| 6300398 | Jialanella et al. | Oct 2001 | B1 |
| 6300419 | Sehanobish et al. | Oct 2001 | B1 |
| 6300451 | Mehta et al. | Oct 2001 | B1 |
| 6303696 | Ushioda et al. | Oct 2001 | B1 |
| 6306970 | Dang et al. | Oct 2001 | B1 |
| 6310140 | Raetzsch et al. | Oct 2001 | B1 |
| 6310163 | Brookhart et al. | Oct 2001 | B1 |
| 6313184 | Sasaki et al. | Nov 2001 | B1 |
| 6319979 | Dubois et al. | Nov 2001 | B1 |
| 6319991 | Okayama et al. | Nov 2001 | B1 |
| 6319998 | Cozewith et al. | Nov 2001 | B1 |
| 6323151 | Siedle et al. | Nov 2001 | B1 |
| 6323284 | Peacock | Nov 2001 | B1 |
| 6323286 | Kuramochi et al. | Nov 2001 | B1 |
| 6325956 | Chaudhary et al. | Dec 2001 | B2 |
| 6326426 | Ellul | Dec 2001 | B1 |
| 6326427 | Birnbrich et al. | Dec 2001 | B1 |
| 6326444 | Lynch et al. | Dec 2001 | B2 |
| 6329313 | Fritze et al. | Dec 2001 | B1 |
| 6329454 | Krabbenborg | Dec 2001 | B1 |
| 6329468 | Wang | Dec 2001 | B1 |
| 6331590 | Herrmann et al. | Dec 2001 | B1 |
| 6331595 | Mitchell et al. | Dec 2001 | B1 |
| 6339109 | Day et al. | Jan 2002 | B1 |
| 6339136 | Huikku et al. | Jan 2002 | B1 |
| 6340703 | Kelly | Jan 2002 | B1 |
| 6340730 | Murray et al. | Jan 2002 | B1 |
| 6342574 | Weng et al. | Jan 2002 | B1 |
| 6346580 | Fujita et al. | Feb 2002 | B1 |
| 6348272 | Haveaux et al. | Feb 2002 | B1 |
| 6350791 | Feichtmeier et al. | Feb 2002 | B1 |
| 6350828 | Takaoka et al. | Feb 2002 | B1 |
| 6350829 | Lynch et al. | Feb 2002 | B1 |
| 6350830 | Göres et al. | Feb 2002 | B1 |
| 6352948 | Pike et al. | Mar 2002 | B1 |
| 6355747 | Rausch et al. | Mar 2002 | B1 |
| 6359077 | Avgousti et al. | Mar 2002 | B1 |
| 6359095 | Winter et al. | Mar 2002 | B1 |
| 6362125 | Shamshoum et al. | Mar 2002 | B1 |
| 6365763 | Winter et al. | Apr 2002 | B1 |
| 6365779 | Devore et al. | Apr 2002 | B2 |
| 6368708 | Brown et al. | Apr 2002 | B1 |
| 6369175 | Ewen | Apr 2002 | B1 |
| 6369176 | Laughner et al. | Apr 2002 | B1 |
| 6376410 | Burkhardt et al. | Apr 2002 | B1 |
| 6376416 | Hirakawa et al. | Apr 2002 | B1 |
| 6380327 | Teasley | Apr 2002 | B1 |
| 6391974 | Ogawa et al. | May 2002 | B1 |
| 6395831 | Pelliconi et al. | May 2002 | B1 |
| 6399531 | Job et al. | Jun 2002 | B1 |
| 6403677 | Walker | Jun 2002 | B1 |
| 6403708 | Moriya et al. | Jun 2002 | B2 |
| 6403855 | Mertens | Jun 2002 | B1 |
| 6407168 | Sugita et al. | Jun 2002 | B1 |
| 6407177 | Shamshoum et al. | Jun 2002 | B1 |
| 6407189 | Herrmann | Jun 2002 | B1 |
| 6413899 | Dolle et al. | Jul 2002 | B1 |
| 6416699 | Gownder et al. | Jul 2002 | B1 |
| 6417240 | Park | Jul 2002 | B1 |
| 6417242 | Hughes et al. | Jul 2002 | B1 |
| 6417275 | Takayanagi et al. | Jul 2002 | B2 |
| 6420516 | Tau et al. | Jul 2002 | B1 |
| 6423793 | Weng et al. | Jul 2002 | B1 |
| 6423800 | Musgrave | Jul 2002 | B1 |
| 6426026 | Avgousti et al. | Jul 2002 | B1 |
| 6429274 | Siedle et al. | Aug 2002 | B1 |
| 6430898 | Remmers et al. | Aug 2002 | B1 |
| 6433087 | Ebner et al. | Aug 2002 | B1 |
| 6441094 | Cecchin et al. | Aug 2002 | B1 |
| 6444301 | Davidson et al. | Sep 2002 | B1 |
| 6448301 | Gaddam et al. | Sep 2002 | B1 |
| 6448302 | Dawson et al. | Sep 2002 | B1 |
| 6448358 | Siedle et al. | Sep 2002 | B2 |
| 6455614 | Jackson et al. | Sep 2002 | B1 |
| 6455630 | Rigosi et al. | Sep 2002 | B1 |
| 6455634 | Khandpur et al. | Sep 2002 | B1 |
| 6455643 | Harlin et al. | Sep 2002 | B1 |
| 6458877 | Ahmed et al. | Oct 2002 | B1 |
| 6465558 | Scheibelhoffer et al. | Oct 2002 | B2 |
| 6469110 | Harlin et al. | Oct 2002 | B1 |
| 6472473 | Ansems et al. | Oct 2002 | B1 |
| 6472477 | Kanzaki et al. | Oct 2002 | B2 |
| 6476135 | Bugada et al. | Nov 2002 | B1 |
| 6482907 | Wang et al. | Nov 2002 | B1 |
| 6486246 | Vion | Nov 2002 | B1 |
| 6489426 | Kawamoto et al. | Dec 2002 | B1 |
| 6492465 | Burkhardt et al. | Dec 2002 | B1 |
| 6495646 | Arthur et al. | Dec 2002 | B1 |
| 6500540 | Langohr et al. | Dec 2002 | B1 |
| 6503993 | Huovinen et al. | Jan 2003 | B1 |
| 6506839 | Nishihara et al. | Jan 2003 | B1 |
| 6506847 | Song | Jan 2003 | B1 |
| 6509107 | Ding et al. | Jan 2003 | B2 |
| 6509288 | Dorer et al. | Jan 2003 | B1 |
| 6511755 | Mochizuki et al. | Jan 2003 | B1 |
| 6512019 | Agarwal et al. | Jan 2003 | B1 |
| 6512050 | Kanamori et al. | Jan 2003 | B2 |
| 6515086 | Razavi | Feb 2003 | B1 |
| 6518327 | Dang et al. | Feb 2003 | B1 |
| 6518386 | Resconi et al. | Feb 2003 | B1 |
| 6521675 | Wu et al. | Feb 2003 | B1 |
| 6521693 | Saito et al. | Feb 2003 | B2 |
| 6525157 | Cozewith et al. | Feb 2003 | B2 |
| 6528448 | Jensen et al. | Mar 2003 | B1 |
| 6534608 | Peterson et al. | Mar 2003 | B2 |
| 6537478 | Grasmeder et al. | Mar 2003 | B1 |
| 6537652 | Kochem et al. | Mar 2003 | B1 |
| 6545072 | Tamura et al. | Apr 2003 | B2 |
| 6545099 | Shinozaki et al. | Apr 2003 | B2 |
| 6545108 | Moody et al. | Apr 2003 | B1 |
| 6548579 | Reski et al. | Apr 2003 | B2 |
| 6551955 | Diefenbach | Apr 2003 | B1 |
| 6555643 | Rieger | Apr 2003 | B1 |
| 6559211 | Zhao et al. | May 2003 | B2 |
| 6562886 | Minami et al. | May 2003 | B1 |
| 6562914 | Andtsjo et al. | May 2003 | B1 |
| 6569915 | Jackson et al. | May 2003 | B1 |
| 6569934 | Noel, III | May 2003 | B2 |
| 6569945 | Bugada et al. | May 2003 | B2 |
| 6569965 | Markel et al. | May 2003 | B2 |
| 6573344 | Hawley et al. | Jun 2003 | B1 |
| 6573350 | Markel et al. | Jun 2003 | B1 |
| 6573352 | Tatsumi et al. | Jun 2003 | B1 |
| 6576306 | Mehta et al. | Jun 2003 | B2 |
| 6576712 | Feldstein et al. | Jun 2003 | B2 |
| 6582828 | Kaschel | Jun 2003 | B1 |
| 6583076 | Pekrul et al. | Jun 2003 | B1 |
| 6583209 | Mehta et al. | Jun 2003 | B2 |
| 6583254 | Tsuji et al. | Jun 2003 | B2 |
| 6586531 | Washiyama et al. | Jul 2003 | B2 |
| 6586536 | Kelley | Jul 2003 | B1 |
| 6590006 | Park et al. | Jul 2003 | B2 |
| 6593407 | Haner et al. | Jul 2003 | B2 |
| 6593442 | Bidell et al. | Jul 2003 | B2 |
| 6596198 | Semen | Jul 2003 | B1 |
| 6596814 | Kim et al. | Jul 2003 | B2 |
| 6599985 | Fujii et al. | Jul 2003 | B2 |
| 6602598 | Simpson et al. | Aug 2003 | B1 |
| 6610785 | Cecchin et al. | Aug 2003 | B1 |
| 6613381 | Bredahl et al. | Sep 2003 | B1 |
| 6613816 | Mahdi et al. | Sep 2003 | B2 |
| 6620888 | Resconi et al. | Sep 2003 | B2 |
| 6620892 | Bertin et al. | Sep 2003 | B1 |
| 6624253 | Nakamura et al. | Sep 2003 | B2 |
| 6630559 | Shinozaki et al. | Oct 2003 | B2 |
| 6632885 | Morizono et al. | Oct 2003 | B2 |
| 6635715 | Cozewith et al. | Oct 2003 | B1 |
| 6635733 | Yahata et al. | Oct 2003 | B2 |
| 6639018 | Yunoki et al. | Oct 2003 | B2 |
| 6646019 | Perez et al. | Nov 2003 | B2 |
| 6646051 | Demain | Nov 2003 | B1 |
| 6649685 | Saito et al. | Nov 2003 | B2 |
| 6653385 | Wang et al. | Nov 2003 | B2 |
| 6657009 | Zhou | Dec 2003 | B2 |
| 6657025 | Blackmon et al. | Dec 2003 | B2 |
| 6660805 | Righettini et al. | Dec 2003 | B1 |
| 6664306 | Gaddam et al. | Dec 2003 | B2 |
| 6664309 | Svenningsen et al. | Dec 2003 | B2 |
| 6673870 | Owens et al. | Jan 2004 | B2 |
| 6677403 | Abe | Jan 2004 | B1 |
| 6686433 | Miro et al. | Feb 2004 | B1 |
| 6703457 | Van Baar et al. | Mar 2004 | B2 |
| 6709734 | Higashi et al. | Mar 2004 | B2 |
| 6710134 | Demain | Mar 2004 | B2 |
| 6713573 | Wenzel et al. | Mar 2004 | B2 |
| 6723769 | Miller et al. | Apr 2004 | B2 |
| 6727332 | Demain | Apr 2004 | B2 |
| 6730742 | Demain | May 2004 | B1 |
| 6734253 | Krabbenborg et al. | May 2004 | B2 |
| 6734270 | Minami et al. | May 2004 | B1 |
| 6747103 | Vestberg et al. | Jun 2004 | B1 |
| 6747114 | Karandinos et al. | Jun 2004 | B2 |
| 6750288 | Pradel | Jun 2004 | B2 |
| 6756098 | Zhou et al. | Jun 2004 | B2 |
| 6756463 | Ito et al. | Jun 2004 | B2 |
| 6758994 | Gownder et al. | Jul 2004 | B2 |
| 6759475 | Sakai et al. | Jul 2004 | B2 |
| 6759500 | Dolle et al. | Jul 2004 | B1 |
| 6770355 | Minami et al. | Aug 2004 | B1 |
| 6770714 | Ommundsen et al. | Aug 2004 | B2 |
| 6774069 | Zhou et al. | Aug 2004 | B2 |
| 6777067 | Speith-Herfurth et al. | Aug 2004 | B1 |
| 6777476 | Jeong et al. | Aug 2004 | B2 |
| 6777497 | Kanzaki et al. | Aug 2004 | B2 |
| 6780936 | Agarwal et al. | Aug 2004 | B1 |
| 6784250 | Kijima | Aug 2004 | B2 |
| 6784252 | Ramanathan et al. | Aug 2004 | B2 |
| 6784269 | Lin et al. | Aug 2004 | B2 |
| 6790922 | Rieger | Sep 2004 | B2 |
| 6797371 | Gehlsen et al. | Sep 2004 | B1 |
| 6797774 | Kijima | Sep 2004 | B2 |
| 6800669 | Thoen et al. | Oct 2004 | B2 |
| 6800681 | Ohkawa et al. | Oct 2004 | B2 |
| 6800700 | Sun | Oct 2004 | B2 |
| 6800703 | Reinking et al. | Oct 2004 | B1 |
| 6800706 | Kanamaru et al. | Oct 2004 | B1 |
| 6800710 | Pelliconi et al. | Oct 2004 | B2 |
| 6811886 | Speith-Herfurth et al. | Nov 2004 | B1 |
| 6815490 | Seelert et al. | Nov 2004 | B2 |
| 6815496 | Tasaka et al. | Nov 2004 | B2 |
| 6818698 | Kashikar | Nov 2004 | B1 |
| 6824721 | Albe et al. | Nov 2004 | B2 |
| 6825276 | Forte et al. | Nov 2004 | B2 |
| 6825280 | Hayakawa et al. | Nov 2004 | B1 |
| 6825292 | Reid | Nov 2004 | B2 |
| 6828022 | Bisleri et al. | Dec 2004 | B2 |
| 6833180 | Kodemura | Dec 2004 | B1 |
| 6833404 | Quinn et al. | Dec 2004 | B2 |
| 6841620 | Ansems et al. | Jan 2005 | B2 |
| 6844078 | Su et al. | Jan 2005 | B2 |
| 6855406 | Takayasu et al. | Feb 2005 | B2 |
| 6855411 | Su et al. | Feb 2005 | B2 |
| 6855424 | Fitts, Jr. et al. | Feb 2005 | B1 |
| 6855656 | Hosaka et al. | Feb 2005 | B2 |
| 6855777 | McLoughlin et al. | Feb 2005 | B2 |
| 6858667 | Flerlage et al. | Feb 2005 | B1 |
| 6858676 | Johoji et al. | Feb 2005 | B1 |
| 6858695 | Schmidt, Jr. et al. | Feb 2005 | B2 |
| 6858700 | Dahl et al. | Feb 2005 | B2 |
| 6861472 | Adedeji et al. | Mar 2005 | B2 |
| 6863989 | Dyatlov et al. | Mar 2005 | B1 |
| 6867252 | Tomomatsu et al. | Mar 2005 | B1 |
| 6867253 | Chen | Mar 2005 | B1 |
| 6872790 | Ewen | Mar 2005 | B2 |
| 6875816 | DeGroot et al. | Apr 2005 | B2 |
| 6878327 | Cooper et al. | Apr 2005 | B2 |
| 6878756 | Cinelli et al. | Apr 2005 | B2 |
| 6881793 | Sheldon et al. | Apr 2005 | B2 |
| 6884846 | Pradel | Apr 2005 | B2 |
| 6884851 | Gauthy | Apr 2005 | B2 |
| 6887941 | Zhou | May 2005 | B2 |
| 6887943 | Onoe et al. | May 2005 | B2 |
| 6890661 | Pradel | May 2005 | B2 |
| 6897261 | Machida et al. | May 2005 | B1 |
| 6905760 | Mukohara et al. | Jun 2005 | B1 |
| 6913834 | Kanamaru et al. | Jul 2005 | B2 |
| 6914085 | Delaite et al. | Jul 2005 | B2 |
| 6916892 | Tharappel et al. | Jul 2005 | B2 |
| 6924041 | Lee et al. | Aug 2005 | B2 |
| 6924342 | Stevens et al. | Aug 2005 | B2 |
| 6951683 | Blackwell | Oct 2005 | B2 |
| 6951900 | Blanchard et al. | Oct 2005 | B2 |
| 6964986 | Bachon et al. | Nov 2005 | B2 |
| 6984680 | Quinn | Jan 2006 | B2 |
| 6992121 | Peters et al. | Jan 2006 | B1 |
| 6992128 | Busch et al. | Jan 2006 | B2 |
| 6992146 | McLoughlin et al. | Jan 2006 | B2 |
| 6994763 | Austin | Feb 2006 | B2 |
| 6994915 | Pelliconi et al. | Feb 2006 | B2 |
| 6998431 | Albe | Feb 2006 | B2 |
| 7008990 | Raether et al. | Mar 2006 | B2 |
| 7019078 | Collina et al. | Mar 2006 | B1 |
| 7022763 | Matsugi et al. | Apr 2006 | B2 |
| 7022795 | Huffer et al. | Apr 2006 | B1 |
| 7022796 | Blackmon et al. | Apr 2006 | B2 |
| 7026055 | Hanyu et al. | Apr 2006 | B2 |
| 7026421 | Appleyard et al. | Apr 2006 | B2 |
| 7038000 | Vestberg et al. | May 2006 | B2 |
| 7041381 | Rasp et al. | May 2006 | B1 |
| 7056991 | Tharappel et al. | Jun 2006 | B2 |
| 7060754 | Stevens et al. | Jun 2006 | B2 |
| 7064160 | Zanka et al. | Jun 2006 | B2 |
| 7064163 | Shida | Jun 2006 | B2 |
| 7067196 | Pradel et al. | Jun 2006 | B2 |
| 7067585 | Wang et al. | Jun 2006 | B2 |
| 7078468 | Thorman | Jul 2006 | B2 |
| 7081299 | Richeson | Jul 2006 | B2 |
| 7081493 | Kawai et al. | Jul 2006 | B2 |
| 7087314 | Forte et al. | Aug 2006 | B2 |
| 7091277 | Rydin et al. | Aug 2006 | B2 |
| 7094463 | Haas et al. | Aug 2006 | B2 |
| 7094820 | Zhao et al. | Aug 2006 | B2 |
| 7101622 | Chang et al. | Sep 2006 | B2 |
| 7101926 | McMichael et al. | Sep 2006 | B2 |
| 7101929 | Zah et al. | Sep 2006 | B2 |
| 7105604 | Shimizu et al. | Sep 2006 | B2 |
| 7105609 | Datta et al. | Sep 2006 | B2 |
| 7109265 | Kucera et al. | Sep 2006 | B2 |
| 7109269 | Stevens et al. | Sep 2006 | B2 |
| 7112642 | Meesters et al. | Sep 2006 | B2 |
| 7115694 | Shimizu et al. | Oct 2006 | B2 |
| 7119154 | Coates et al. | Oct 2006 | B2 |
| 7122584 | Moriya et al. | Oct 2006 | B2 |
| 7122604 | Onoe et al. | Oct 2006 | B2 |
| 7125924 | Credali et al. | Oct 2006 | B2 |
| 7129292 | Kristen et al. | Oct 2006 | B1 |
| 7138173 | Wheatley et al. | Nov 2006 | B2 |
| 7141182 | Walters et al. | Nov 2006 | B2 |
| 7141300 | Yamamoto et al. | Nov 2006 | B2 |
| 7144542 | Holzer et al. | Dec 2006 | B2 |
| 7144925 | Burgun et al. | Dec 2006 | B2 |
| 7144939 | Dotson et al. | Dec 2006 | B2 |
| 7144959 | Kitahara | Dec 2006 | B2 |
| 7148305 | Stevens et al. | Dec 2006 | B2 |
| 7153906 | Akiyama et al. | Dec 2006 | B2 |
| 7160949 | Ota et al. | Jan 2007 | B2 |
| 7160950 | Mori et al. | Jan 2007 | B2 |
| 7169727 | Thorman | Jan 2007 | B2 |
| 7169827 | Debras et al. | Jan 2007 | B2 |
| 7169866 | Ostoja Starzewski et al. | Jan 2007 | B2 |
| 7169871 | Morini et al. | Jan 2007 | B2 |
| 7173099 | Minami | Feb 2007 | B1 |
| 7175906 | Longmore | Feb 2007 | B2 |
| 7183364 | Sita | Feb 2007 | B2 |
| 7186312 | Bolte et al. | Mar 2007 | B1 |
| 7189788 | Machida et al. | Mar 2007 | B2 |
| 7192902 | Brinen et al. | Mar 2007 | B2 |
| 7193003 | Oi et al. | Mar 2007 | B2 |
| 7193013 | Machida et al. | Mar 2007 | B2 |
| 7199204 | Haner et al. | Apr 2007 | B2 |
| 7201815 | Muvundamina | Apr 2007 | B2 |
| 7202296 | Muylem et al. | Apr 2007 | B2 |
| 7208436 | Dall'Occo et al. | Apr 2007 | B2 |
| 7208552 | Komoto et al. | Apr 2007 | B2 |
| 7211537 | Fujita et al. | May 2007 | B2 |
| 7214745 | Arai et al. | May 2007 | B2 |
| 7217455 | Valdez | May 2007 | B2 |
| 7217766 | Datta et al. | May 2007 | B2 |
| 7226880 | Potnis | Jun 2007 | B2 |
| 7226974 | Nishihara | Jun 2007 | B2 |
| 7229687 | Kinning et al. | Jun 2007 | B2 |
| 7232872 | Shaffer et al. | Jun 2007 | B2 |
| 7235191 | Schmidt et al. | Jun 2007 | B2 |
| 7235610 | Fujino et al. | Jun 2007 | B2 |
| 7235618 | Lin et al. | Jun 2007 | B2 |
| 7238759 | Stevens et al. | Jul 2007 | B2 |
| 7238846 | Janssen et al. | Jul 2007 | B2 |
| 7241844 | Bouhelal | Jul 2007 | B2 |
| 7247675 | Thomas et al. | Jul 2007 | B2 |
| 7250211 | Minami et al. | Jul 2007 | B1 |
| 7250470 | Stevens et al. | Jul 2007 | B2 |
| 7250471 | Stevens et al. | Jul 2007 | B2 |
| 7253234 | Mori et al. | Aug 2007 | B2 |
| 7262251 | Kanderski et al. | Aug 2007 | B2 |
| 7268185 | Shimojo et al. | Sep 2007 | B2 |
| 20010004662 | Bidell et al. | Jun 2001 | A1 |
| 20010007896 | Agarwal et al. | Jul 2001 | A1 |
| 20010016639 | Agarwal et al. | Aug 2001 | A1 |
| 20010031843 | Whiteker et al. | Oct 2001 | A1 |
| 20010034299 | Terry et al. | Oct 2001 | A1 |
| 20010044505 | Ford et al. | Nov 2001 | A1 |
| 20010044515 | Siedel et al. | Nov 2001 | A1 |
| 20010047064 | Sun | Nov 2001 | A1 |
| 20010053837 | Agarwal et al. | Dec 2001 | A1 |
| 20020007033 | Karandinos et al. | Jan 2002 | A1 |
| 20020010077 | Lue et al. | Jan 2002 | A1 |
| 20020013440 | Agarwal et al. | Jan 2002 | A1 |
| 20020016254 | Whiteker et al. | Feb 2002 | A1 |
| 20020040114 | Loveday et al. | Apr 2002 | A1 |
| 20020045054 | Uhara et al. | Apr 2002 | A1 |
| 20020049135 | Moody et al. | Apr 2002 | A1 |
| 20020061945 | Oates et al. | May 2002 | A1 |
| 20020064653 | Ladika et al. | May 2002 | A1 |
| 20020065192 | Mackenzie et al. | May 2002 | A1 |
| 20020086955 | Kendrick | Jul 2002 | A1 |
| 20020123538 | Zhou et al. | Sep 2002 | A1 |
| 20020124956 | Zhou | Sep 2002 | A1 |
| 20020132923 | Langohr et al. | Sep 2002 | A1 |
| 20030078350 | Weng et al. | Apr 2003 | A1 |
| 20030096896 | Wang et al. | May 2003 | A1 |
| 20040023037 | Baumert et al. | Feb 2004 | A1 |
| 20040034170 | Brant | Feb 2004 | A1 |
| 20040039117 | Kijima | Feb 2004 | A1 |
| 20040048984 | Weng et al. | Mar 2004 | A1 |
| 20040127614 | Jiang et al. | Jul 2004 | A1 |
| 20040138392 | Jiang et al. | Jul 2004 | A1 |
| 20040220336 | Abhari et al. | Nov 2004 | A1 |
| 20040220359 | Abhari et al. | Nov 2004 | A1 |
| 20040249046 | Abhari et al. | Dec 2004 | A1 |
| 20050020778 | DeGroot et al. | Jan 2005 | A1 |
| 20050065286 | DeGroot et al. | Mar 2005 | A1 |
| 20050187350 | Stevens et al. | Aug 2005 | A1 |
| 20050187351 | Stevens et al. | Aug 2005 | A1 |
| 20060025535 | Onoe et al. | Feb 2006 | A1 |
| Number | Date | Country |
|---|---|---|
| 2157806 | Mar 1997 | CA |
| 2407183 | Apr 2003 | CA |
| 2316614 | Oct 1973 | DE |
| 19960411 | Jul 2001 | DE |
| 19963585 | Jul 2001 | DE |
| 51114438 | Oct 1976 | EP |
| 0 033 220 | Aug 1981 | EP |
| 0 930 320 | Oct 1983 | EP |
| 0 115 434 | Aug 1984 | EP |
| 0 263 718 | Apr 1988 | EP |
| 0 248 708 | Oct 1988 | EP |
| 0 284 707 | Oct 1988 | EP |
| 0 319 043 | Jun 1989 | EP |
| 0 366 411 | May 1990 | EP |
| 0 387 691 | Sep 1990 | EP |
| 0 486 293 | Sep 1991 | EP |
| 0 459 264 | Dec 1991 | EP |
| 0 513 808 | Nov 1992 | EP |
| 0 515 132 | Nov 1992 | EP |
| 0 524 624 | Jan 1993 | EP |
| 0375730 | Jan 1993 | EP |
| 0 530 908 | Mar 1993 | EP |
| 0 536 104 | Apr 1993 | EP |
| 0 417 428 | Sep 1993 | EP |
| 0 577 581 | Jan 1994 | EP |
| 0 363 029 | Aug 1994 | EP |
| 0 612 768 | Aug 1994 | EP |
| 0 310 734 | Nov 1994 | EP |
| 0 647 246 | Nov 1994 | EP |
| 0 648 801 | Apr 1995 | EP |
| 0 653 433 | May 1995 | EP |
| 0 666 267 | Aug 1995 | EP |
| 0 557 718 | Oct 1995 | EP |
| 0 516 019 | Dec 1995 | EP |
| 0 564 596 | Feb 1996 | EP |
| 0 695 765 | Feb 1996 | EP |
| 0 516 018 | Mar 1996 | EP |
| 0 700 937 | Mar 1996 | EP |
| 0 593 083 | May 1996 | EP |
| 0 718 359 | Jun 1996 | EP |
| 0 719 829 | Jul 1996 | EP |
| 0 553 757 | Sep 1996 | EP |
| 0 733 652 | Sep 1996 | EP |
| 0 652 905 | Oct 1996 | EP |
| 0 747 430 | Dec 1996 | EP |
| 0 749 989 | Dec 1996 | EP |
| 0 773 238 | May 1997 | EP |
| 0 773 239 | May 1997 | EP |
| 0 791 607 | May 1997 | EP |
| 0 643 100 | Jul 1997 | EP |
| 0 527 221 | Sep 1997 | EP |
| 0 598 628 | Sep 1997 | EP |
| 0 620 257 | Sep 1997 | EP |
| 0 803 559 | Oct 1997 | EP |
| 0 812 854 | Dec 1997 | EP |
| 0 700 934 | Jan 1998 | EP |
| 0 661 300 | Mar 1998 | EP |
| 0 832 924 | Apr 1998 | EP |
| 0 646 604 | May 1998 | EP |
| 0 841 349 | May 1998 | EP |
| 0 842 955 | May 1998 | EP |
| 0 527 589 | Jun 1998 | EP |
| 0 563 917 | Jun 1998 | EP |
| 0 613 908 | Jul 1998 | EP |
| 0 948 432 | Jul 1998 | EP |
| 0 958 318 | Jul 1998 | EP |
| 0 857 735 | Aug 1998 | EP |
| 0 958 313 | Aug 1998 | EP |
| 0 958 314 | Aug 1998 | EP |
| 0 958 324 | Aug 1998 | EP |
| 0 864 593 | Sep 1998 | EP |
| 0 500 944 | Oct 1998 | EP |
| 0 573 120 | Nov 1998 | EP |
| 0 879 849 | Nov 1998 | EP |
| 0 977 666 | Nov 1998 | EP |
| 0 977 808 | Nov 1998 | EP |
| 0 788 521 | Dec 1998 | EP |
| 0 882 731 | Dec 1998 | EP |
| 0 889 089 | Jan 1999 | EP |
| 0 584 609 | Mar 1999 | EP |
| 0 627 447 | Apr 1999 | EP |
| 0 685 498 | May 1999 | EP |
| 0 696 303 | Jun 1999 | EP |
| 0 922 653 | Jun 1999 | EP |
| 1 040 140 | Jun 1999 | EP |
| 1 040 146 | Jun 1999 | EP |
| 1 044 225 | Jun 1999 | EP |
| 0 608 054 | Jul 1999 | EP |
| 1 049 730 | Jul 1999 | EP |
| 0 827 526 | Aug 1999 | EP |
| 0 747 403 | Sep 1999 | EP |
| 0 950 667 | Oct 1999 | EP |
| 0 953 581 | Nov 1999 | EP |
| 0 602 716 | Dec 1999 | EP |
| 0 423 101 | Jan 2000 | EP |
| 0 974 601 | Jan 2000 | EP |
| 0 909 284 | Feb 2000 | EP |
| 0 731 729 | Mar 2000 | EP |
| 0 909 283 | Mar 2000 | EP |
| 0 985 677 | Mar 2000 | EP |
| 0 719 797 | Apr 2000 | EP |
| 0 719 802 | May 2000 | EP |
| 0 769 505 | May 2000 | EP |
| 1 141 051 | Jun 2000 | EP |
| 0 586 168 | Jul 2000 | EP |
| 0889912 | Jul 2000 | EP |
| 1 031 580 | Aug 2000 | EP |
| 0 889 911 | Nov 2000 | EP |
| 1 050 558 | Nov 2000 | EP |
| 0 654 476 | Jan 2001 | EP |
| 1 077 244 | Feb 2001 | EP |
| 0 702 030 | Mar 2001 | EP |
| 1 081 203 | Mar 2001 | EP |
| 1 081 204 | Mar 2001 | EP |
| 0 882 069 | Apr 2001 | EP |
| 0 882 076 | Apr 2001 | EP |
| 1 238 035 | Apr 2001 | EP |
| 0 351 392 | May 2001 | EP |
| 0 882 077 | May 2001 | EP |
| 1 095 944 | May 2001 | EP |
| 1 095 951 | May 2001 | EP |
| 1 100 854 | May 2001 | EP |
| 0 824 113 | Jun 2001 | EP |
| 1 237 963 | Jun 2001 | EP |
| 1 252 231 | Jul 2001 | EP |
| 0 619 325 | Aug 2001 | EP |
| 1 023 379 | Aug 2001 | EP |
| 0 886 656 | Sep 2001 | EP |
| 1 144 533 | Oct 2001 | EP |
| 0 963 382 | Nov 2001 | EP |
| 1 153 944 | Nov 2001 | EP |
| 0 645 401 | Dec 2001 | EP |
| 0 707 010 | Dec 2001 | EP |
| 0 747 402 | Dec 2001 | EP |
| 0 821 748 | Dec 2001 | EP |
| 0 891 381 | Dec 2001 | EP |
| 1 118 637 | Dec 2001 | EP |
| 1 066 330 | Feb 2002 | EP |
| 1 181 979 | Feb 2002 | EP |
| 0 659 757 | Mar 2002 | EP |
| 1 197 500 | Apr 2002 | EP |
| 1 089 878 | May 2002 | EP |
| 1 231 236 | Aug 2002 | EP |
| 0 868 498 | Jan 2003 | EP |
| 1 295 925 | Mar 2003 | EP |
| 1 295 926 | Mar 2003 | EP |
| 1 165 622 | Apr 2003 | EP |
| 1396054 | Apr 1965 | FR |
| 1582841 | Oct 1969 | FR |
| 2323846 | Mar 1997 | GB |
| 56072033 | Jun 1981 | JP |
| 56109213 | Aug 1981 | JP |
| 57030774 | Feb 1982 | JP |
| 57076041 | May 1982 | JP |
| 58049736 | Mar 1983 | JP |
| 59159843 | Sep 1984 | JP |
| 59217709 | Dec 1984 | JP |
| 60011538 | Jan 1985 | JP |
| 01054010 | Mar 1989 | JP |
| 0 208 6676 | Mar 1990 | JP |
| 083336937 | Dec 1996 | JP |
| 11115127 | Apr 1999 | JP |
| 99349634 | Dec 1999 | JP |
| 199012839 | Apr 1989 | WO |
| 8912828 | Dec 1989 | WO |
| WO 9107472 | May 1991 | WO |
| WO 9220644 | Nov 1992 | WO |
| WO 9404625 | Mar 1994 | WO |
| 9407930 | Apr 1994 | WO |
| 9412193 | Jun 1994 | WO |
| 9413715 | Jun 1994 | WO |
| 9425498 | Nov 1994 | WO |
| 9425526 | Nov 1994 | WO |
| 199506556 | Mar 1995 | WO |
| WO 9510575 | Apr 1995 | WO |
| 9524449 | Sep 1995 | WO |
| 199532242 | Nov 1995 | WO |
| 9612744 | May 1996 | WO |
| 9613531 | May 1996 | WO |
| 9623010 | Aug 1996 | WO |
| 9623751 | Aug 1996 | WO |
| 9626967 | Sep 1996 | WO |
| 9627822 | Sep 1996 | WO |
| 9629460 | Sep 1996 | WO |
| 9637568 | Nov 1996 | WO |
| 9704271 | Feb 1997 | WO |
| 119710300 | Mar 1997 | WO |
| 9712919 | Apr 1997 | WO |
| WO 9720872 | Jun 1997 | WO |
| 9723577 | Jul 1997 | WO |
| 9726287 | Jul 1997 | WO |
| 9729138 | Aug 1997 | WO |
| 9733921 | Sep 1997 | WO |
| 9749738 | Dec 1997 | WO |
| 9802467 | Jan 1998 | WO |
| 9802471 | Jan 1998 | WO |
| 9803603 | Jan 1998 | WO |
| 9809996 | Mar 1998 | WO |
| 9823690 | Jun 1998 | WO |
| 9823699 | Jun 1998 | WO |
| 9829249 | Jul 1998 | WO |
| 9832784 | Jul 1998 | WO |
| 9833860 | Aug 1998 | WO |
| 9834965 | Aug 1998 | WO |
| 9834970 | Aug 1998 | WO |
| 9834971 | Aug 1998 | WO |
| 9834985 | Aug 1998 | WO |
| 9838374 | Sep 1998 | WO |
| 9841574 | Sep 1998 | WO |
| 9842780 | Oct 1998 | WO |
| 9846694 | Oct 1998 | WO |
| 9849229 | Nov 1998 | WO |
| 9852686 | Nov 1998 | WO |
| 9857998 | Dec 1998 | WO |
| WO 9901481 | Jan 1999 | WO |
| 9905152 | Feb 1999 | WO |
| 9910425 | Mar 1999 | WO |
| 9914046 | Mar 1999 | WO |
| 9914047 | Mar 1999 | WO |
| 9914262 | Mar 1999 | WO |
| 9919394 | Apr 1999 | WO |
| 9920664 | Apr 1999 | WO |
| 9920694 | Apr 1999 | WO |
| 9920701 | Apr 1999 | WO |
| 1023339 | Apr 1999 | WO |
| 9924516 | May 1999 | WO |
| 9929742 | Jun 1999 | WO |
| 9929743 | Jun 1999 | WO |
| 9929749 | Jun 1999 | WO |
| 9932272 | Jul 1999 | WO |
| 9932288 | Jul 1999 | WO |
| 9932525 | Jul 1999 | WO |
| 9937711 | Jul 1999 | WO |
| 9946348 | Sep 1999 | WO |
| 9954421 | Oct 1999 | WO |
| 9960060 | Nov 1999 | WO |
| 9961487 | Dec 1999 | WO |
| 9965949 | Dec 1999 | WO |
| 9967094 | Dec 1999 | WO |
| 0000565 | Jan 2000 | WO |
| 0001745 | Jan 2000 | WO |
| 0023483 | Apr 2000 | WO |
| 0029655 | May 2000 | WO |
| 0037514 | Jun 2000 | WO |
| 0044799 | Aug 2000 | WO |
| 0047592 | Aug 2000 | WO |
| 0050466 | Aug 2000 | WO |
| 0050475 | Aug 2000 | WO |
| 0058320 | Oct 2000 | WO |
| 0059721 | Oct 2000 | WO |
| 0069869 | Nov 2000 | WO |
| 0069963 | Nov 2000 | WO |
| 0075198 | Dec 2000 | WO |
| 0100257 | Jan 2001 | WO |
| 0100691 | Jan 2001 | WO |
| 0102444 | Jan 2001 | WO |
| WO 0100693 | Jan 2001 | WO |
| 0109200 | Feb 2001 | WO |
| 0114429 | Mar 2001 | WO |
| 0116189 | Mar 2001 | WO |
| 0118109 | Mar 2001 | WO |
| 0119609 | Mar 2001 | WO |
| 0123396 | Apr 2001 | WO |
| 0125296 | Apr 2001 | WO |
| 0127213 | Apr 2001 | WO |
| 0129096 | Apr 2001 | WO |
| 0132721 | May 2001 | WO |
| 0134665 | May 2001 | WO |
| 0140325 | Jun 2001 | WO |
| 0142322 | Jun 2001 | WO |
| 0142323 | Jun 2001 | WO |
| 0142350 | Jun 2001 | WO |
| 0144309 | Jun 2001 | WO |
| 0146274 | Jun 2001 | WO |
| 0146277 | Jun 2001 | WO |
| 0146278 | Jun 2001 | WO |
| 0148029 | Jul 2001 | WO |
| 0148034 | Jul 2001 | WO |
| 0148036 | Jul 2001 | WO |
| 0148037 | Jul 2001 | WO |
| 0148038 | Jul 2001 | WO |
| 0170878 | Sep 2001 | WO |
| 0174745 | Oct 2001 | WO |
| 0177193 | Oct 2001 | WO |
| 0181493 | Nov 2001 | WO |
| 0183498 | Nov 2001 | WO |
| 0183571 | Nov 2001 | WO |
| 0198374 | Dec 2001 | WO |
| 0198380 | Dec 2001 | WO |
| 0198381 | Dec 2001 | WO |
| WO 0196490 | Dec 2001 | WO |
| 0235956 | May 2002 | WO |
| 0236651 | May 2002 | WO |
| 02053668 | Jul 2002 | WO |
| 02053669 | Jul 2002 | WO |
| WO 02051931 | Jul 2002 | WO |
| 02074817 | Sep 2002 | WO |
| 1377613 | Sep 2002 | WO |
| 1412398 | Sep 2002 | WO |
| WO 02070572 | Sep 2002 | WO |
| WO 03091289 | Nov 2003 | WO |
| 2004037872 | May 2004 | WO |
| 2004046214 | Jun 2004 | WO |
| 2005023889 | Mar 2005 | WO |
| 2005035598 | Apr 2005 | WO |
| 2005087864 | Sep 2005 | WO |
| 2005095473 | Oct 2005 | WO |
| 1723184 | Oct 2005 | WO |
| 1727836 | Oct 2005 | WO |
| 2007002435 | Jan 2007 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20040220320 A1 | Nov 2004 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60418482 | Oct 2002 | US | |
| 60460714 | Apr 2003 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10686951 | Oct 2003 | US |
| Child | 10825349 | US | |
| Parent | 10687508 | Oct 2003 | US |
| Child | 10686951 | US |
