Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUSH1402 H
Publication typeGrant
Application numberUS 07/950,617
Publication dateJan 3, 1995
Filing dateSep 24, 1992
Priority dateSep 24, 1992
Publication number07950617, 950617, US H1402 H, US H1402H, US-H-H1402, USH1402 H, USH1402H
InventorsSteven S. Chin, John A. Miller, Ramsis Gobran
Original AssigneeShell Oil Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hot melt adhesives
US H1402 H
Abstract
A linear styrene-isoprene-styrene block copolymer composition comprised of linear polymeric blocks wherein the block copolymer composition has a coupling efficiency of 25 to 82 percent, a polystyrene content of from 19 to 27 percent by weight, a polystyrene block molecular weight (peak polystyrene equivalent molecular weight as determined by gel permeation chromatography) of 12,000 to 18,000, and an overall molecular weight (peak polystyrene equivalent molecular weight as determined by gel permeation chromatography) of from 170,000 to 280,000. The invention also contemplates adhesive formulations comprising these block copolymer compositions and a tackifying resin.
Images(7)
Previous page
Next page
Claims(4)
We claim:
1. A linear styrene-isoprene-styrene block copolymer composition comprised of linear polymeric blocks, said block polymer composition characterized in that it has a coupling efficiency from 25 to 82%, a polystyrene content of from 19 to 17% by weight, a polystyrene block molecular weight of from 12,000 to 18,000 and an overall molecular weight of from 170,000 to 280,000, both molecular weights being peak polystyrene equivalent molecular weights as determined by gel permeation chromatography.
2. A hot melt adhesive comprising the block copolymer composition of claim 1 and a tackifying resin.
3. The block copolymer composition of claim 1 wherein the polystyrene content ranges from 19 to 26% by weight, the polystyrene block molecular weight ranges from 12,000 to 17,000 and the overall molecular weight ranges from 170,000 to 240,000, both molecular weights being peak polystyrene equivalent molecular weights as determined by gel permeation chromatography.
4. A hot melt adhesive comprising the block copolymer composition of claim 3 and a tackifying resin.
Description
BACKGROUND OF THE INVENTION

This invention relates to a novel block copolymer composition for use in adhesives. More particularly, it relates to linear styrene-isoprenestyrene block copolymer compositions comprised of linear polymeric blocks and adhesives made using such compositions.

It is known that a block copolymer can be obtained by an anionic copolymerization of a conjugated diene compound and an alkenyl arene compound by using an organic alkali metal initiator. Block copolymers have been produced which comprise primarily those having a general structure

A--B and A--B--A

wherein the polymer blocks A comprise thermoplastic polymer blocks of alkenyl arenes such as polystyrene, while block B is a polymer block of a conjugated diene such as polyisoprene. The proportion of the thermoplastic blocks to the elastomeric polymer block and the relative molecular weights of each of these blocks is balanced to obtain a rubber having unique performance characteristics. When the content of the alkenyl arene is small, the produced block copolymer is a so-called thermoplastic rubber. In such a rubber, the blocks A are thermodynamically incompatible with the blocks B resulting in a rubber consisting of two phases--a continuous elastomeric phase (blocks B) and a basically discontinuous hard, glass-like plastic phase (blocks A) called domains. Since the A--B--A block copolymers have two A blocks separated by a B block, domain formation results in effectively locking the B blocks and their inherent entanglements in place by the A blocks and forming a network structure.

These domains act as physical crosslinks anchoring the ends of many block copolymer chains. Such a phenomena allows the A--B--A rubber to behave like a conventional vulcanized rubber in the unvulcanized state and is applicable for various uses. For example, these network forming polymers are applicable for uses such as in adhesive formulations; as moldings of shoe soles, etc.; impact modifier for polystyrene resins and engineering thermoplastics; modification of asphalt; etc.

Different linear block copolymers exhibit different performances in adhesive formulations. Therefore, it requires some experimentation to determine the range of polymers which are useful for a particular adhesive application. For adhesive applications such as hot melt pressure sensitive adhesives, it is desirable that the polymer or the adhesive formulation containing it have the following characteristics: the viscosity of the neat polymer should range from 5,000 to 15,000 poise; the viscosity of the adhesive should be less than 20,000 poise at 43% wt. polymer content in the adhesive; the 180° peel of the adhesive formulation should be greater than 6.8 pli; the holding power to steel of the adhesive formulation should be at least 500 min., and the shear adhesion failure temperature (SAFT) to Mylar should be at least 70° C. The present invention provides polymers and adhesive formulations which will satisfy these performance requirements.

SUMMARY OF THE INVENTION

The polymers which provide the above advantages and fall within the scope of the present invention are linear styrene-isoprene-styrene block copolymers. The polymers generally have a polystyrene content of from 19 to 27% by weight, a polystyrene block molecular weight of from 12,000 to 18,000, an overall molecular weight of from 170,000 to 280,000 and a coupling efficiency of 25 to 82%. However, in addition to those four parameters, the polymer must also satisfy the five performance requirements discussed above.

In a preferred embodiment of the present invention, the polymer performance requirements are neat polymer melt viscosity of from 6000 to 15,000 poise, an adhesive melt viscosity of less than 6000 poise, a 180° peel of greater than 6.8 pli, a holding power to steel of greater than 500 min. and an SAFT to Mylar of at least 70° C. The polymers which will satisfy these criterion have a polystyrene content of from 19 to 26% by weight, a polystyrene block molecular weight of from 12,000 to 17,000, an overall molecular weight of from 170,000 to 240,000 and a coupling efficiency of from 25 to 82.

DETAILED DESCRIPTION OF THE INVENTION

As is well known, polymers containing both aromatic and ethylenic unsaturation can be prepared by copolymerizing one or more polyolefins, particularly a diolefin, in this case isoprene, with one or more alkenyl aromatic hydrocarbon monomers, in this case styrene. The copolymers may, of course, be random, tapered, block or a combination of these, in this case block. The blocks in the copolymers of this invention are linear.

Polymers containing ethylenic unsaturation or both aromatic and ethylenic unsaturation may be prepared using free-radical, cationic and anionic initiators or polymerization catalysts. Such polymers may be prepared using bulk, solution or emulsion techniques. In any case, the polymer containing at least ethylenic unsaturation will, generally, be recovered as a solid such as a crumb, a powder, a pellet or the like. Polymers containing ethylenic unsaturation and polymers containing both aromatic and ethylenic unsaturation are, of course, available commercially from several suppliers.

Polymers of conjugated diolefins and copolymers of one or more conjugated diolefins and one or more alkenyl aromatic hydrocarbon monomers such as the present linear S-I-S block copolymer comprised of linear polymeric blocks are frequently prepared in solution using anionic polymerization techniques. In general, when solution anionic techniques are used, these S-I-S block copolymers are prepared by contacting the monomers to be polymerized simultaneously or sequentially with an organoalkali metal compound in a suitable solvent at a temperature within the range from about 150° C. to about 300° C., preferably at a temperature within the range from about -0° C. to 100° C. Particularly effective anionic polymerization initiators are organolithium compounds having the general formula:

RLin 

Wherein:

R is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical having from 1 to about 20 carbon atoms; and n is an integer of 1 to 4.

The concentration of the initiator can be regulated to control the molecular weight of the overall composition and of the polystyrene blocks. Generally, the initiator concentration is in the range of about 0.25 to about 50 millimoles per 100 grams of monomer. The required initiator level frequently depends upon the solubility of the initiator in the hydrocarbon diluent. The ratio of the initiator to the monomer determines the block size, i.e. the higher the ratio of initiator to monomer the smaller the molecular weight of the block.

In general, any of the solvents known in the prior art to be useful in the preparation of such polymers may be used. Suitable solvents, then, include straight- and branched-chain hydrocarbons such as pentane, hexane, heptane, octane and the like, as well as, alkyl-substituted derivatives thereof; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and the like, as well as, alkyl-substituted derivatives thereof; aromatic and alkyl-substituted aromatic hydrocarbons such as benzene, naphthalene, toluene, xylene and the like; hydrogenated aromatic hydrocarbons such as tetralin, decalin and the like; halogenated hydrocarbons, particularly halogenated aromatic hydrocarbons, such as chlorobenzene, chlorotoluene and the like; linear and cyclic ethers such as methyl ether, methyl ethyl ether, tetrahydrofuran and the like; ketones such as methyl ketone (acetone), methyl ethyl ketone, ethyl ketone (e-pentanone) and the like.

As described in U.S. Pat. No. 4,096,203 the disclosure of which is herein incorporated by reference, usually the styrene is contacted with the initiator. Next, the living polymer in solution is contacted with isoprene. The resulting living polymer has a simplified structure A-B-Li. It is at this point that the living polymer is coupled.

There are a wide variety of coupling agents that can be employed. Any polyfunctional coupling agent which contains at least two reactive sites can be employed. Examples of the types of compounds which can be used include the polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides, and the like. These compounds can contain two or more types of functional groups such as the combination of epoxy and aldehyde groups, isocyanate and halide groups, and the like. Various other substituents which are inert in the treating reaction can be present such as hydrocarbon radicals as exemplified by the alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups and the alkoxy, aryloxy, alkythio, arylthio, and tertiary amino groups. Many suitable types of these polyfunctional compounds have been described in U.S. Pat. Nos. 3,595,941; 3,468,972, 3,135,716; 3,078,254, and 3,594,452, the disclosures of which are herein incorporated by reference. When the coupling agent has two reactive sites such as dibromoethane, the polymer will have a linear ABA structure. When the coupling agent has three or more reactive sites, such as silicon tetrachloride, the polymer will have a branched structure, such as (AB)n BA. Since the present block copolymers are linear, a coupling agent with two reactive sites must be used.

In the prior art, such as that exemplified by U.S. Pat. Nos. 3,595,941 and 3,468,972, the disclosures of which are herein incorporated by reference, the effort was always made to select the particular coupling agent or reaction conditions that resulted in the highest coupling efficiency. Lower coupling efficiencies are desired herein in order to produce adhesive compositions which adhere strongly to difficult to adhere substances such as polyolefins, e.g. polyethylene. Coupling efficiency is defined as the number of molecules of coupled polymer divided by the number of molecules of coupled polymer plus the number of molecules of uncoupled polymer. Thus, when producing an SIS linear polymer, the coupling efficiency is shown by the following relationship: ##EQU1## Coupling efficiency can be determined theoretically from the stoichiometric quantity of coupling agent required for complete coupling or coupling efficiency can be determined by an analytical method such as gel permeation chromotography. Typical prior art coupling efficiency is from about 80% to almost 100%. In U.S. Pat. No. 4,096,203, coupling efficiency is controlled from about 20% to about 80%, preferably about 30% to about 70%. It is also within the scope of the present invention to blend polymers from processes of differing coupling efficiency. For example, if a 60% efficiency is desired, then polymers from processes having an 80% efficiency and a 40% efficiency may be blended together or a 100% triblock may be blended with a 100% diblock in a 60:40 ratio.

This coupling efficiency is controlled by an number of methods. One method to reduce coupling efficency is to add less than the stoichiometric amount of coupling agent required for complete coupling of the polymers. Another means of reducing coupling efficiency is by the premature addition of a terminator compound. These terminators, such as water or alcohol, respond very quickly and could easily be employed to cut short complete coupling of the polymers. In addition, by performing the coupling reaction at elevated temperatures, such as above about 190° F., thermal termination of many of the living polymer groups (A-B-Li) occurs prior to coupling. The typical coupling conditions include a temperature of between about 150° and about 170° F. and sufficient pressure to maintain the reactants in a liquid phase.

Following the coupling reaction or when the desired coupling efficiency has been obtained, the product is neutralized such as by the addition of terminators, e.g., hydrogen, water, alcohol or other reagents, for the purpose of removing the lithium radical forming the nucleus for the condensed polymer product. The produce is then recovered such as by coagulation utilizing hot water or steam or both.

As discussed above, in order to achieve the desired advantages in ahesive formulations one of which is to make an excellent pressure sensitive adhesive, the polymer and adhesive must have the following performance characteristics: a neat polymer melt viscosity of 5,000 to 15,000 poise, an adhesive melt viscosity of less than 20,000 poise, a 180° peel of greater than 6.8 pli, a holding power to steel of at least 500 min. and an SAFT to Mylar of at least 70° C. In order to achieve these performance requirements, the polymer must have a polystyrene content of from 19-27% by weight because at lower styrene content the polymers are too soft to manufacture and at higher than 27% styrene content the polymers are too stiff to perform as base polymers for pressure sensitive adhesives. The polymer must have polystyrene block molecular weight of 12,000 to 18,000 because at less than 12,000 the adhesives have insufficient high temperature shear and at greater than 18,000 the adhesive melt viscosity is too high. The polymer must have an overall molecular weight of from 170,000 to 280,000 because at less than 170,000 the peel adhesion valves are low and at greater than 280,000 the adhesive melt viscosity is prohibitively high. The coupling efficiency of the polymer must be in the range from 25 to 82% because at less than 25% coupling efficiency the holding power of the adhesive is too low and at greater than 82% peel adhesion is low.

The polymer characteristic ranges were determined as follows. First, it was known from past experience that in order to achieve the five performance requirements, the coupling efficiency of the polymer had to be no less than 25%, the polystyrene block molecular weight had to be greater than 11,000 and the overall molecular weight had to be at least 170,000. These limitations were necessary in order to have sufficient holding power, SAFT and peel adhesion. Then, as described in the example, a number of polymer samples were made at varying polystyrene contents, polystyrene block molecular weight, overall molecular weights and coupling efficiencies. These polymers were used to make adhesive formulations which were then tested to determine if they met the five performance requirements. This data is shown in the tables in the Example. The data from Table 2 was then analyzed using regression equations to determine the ranges shown in Table 3 and the actual polymer characteristics shown in Table 4.

In order to achieve more stringent performance requirements, i.e. a neat polymer melt viscosity of less than 600 poise, an adhesive melt viscosity of 6000 to 15,000 poise, a 180° peel of greater than 6.8 pli, a holding power to steel of greater than 500 min. and an SAFT to Mylar of at least 70° C., it is necessary to operate within the area generally defined by a polystyrene content range of 19 to 26% by weight, a polystyrene block molecular weight of from 12,000 to 17,000, an overall molecular weight range of from 170,000 to 240,000 and a coupling efficiency range of from 25 to 82%.

The molecular weights described herein are polystyrene equivalent molecular weights. Molecular weights of linear polymers or unassembled linear segments of polymers such as mono-, di-, triblock, and etc., arms of star polymers before coupling are conveniently measured by Gel Permeation Chromatography (GPC), where the GPC system has been appropriately calibrated. Polymers of known molecular weight are used to calibrate and these must be of the same molecular structure and chemical composition as the unknown linear polymers or segments that are to be measured. For anionically polymerized linear polymers, the polymer is essentially monodisperse and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed.

Methods of controlling the molecular weights of the blocks and the overall polymer are quite well known. For instance, such are disclosed in U.S. Pat. Nos. 3,149,182, which states that the amount of monomer can be kept constant and different molecular weights can be achieved by changing the amount of catalyst or the amount of catalyst can be kept constant and different molecular weights can be achieved by varying the amount of the monomer, and in U.S. No. 3,231,635, the disclosures of which are herein incorporated by reference, and many others. A typical block copolymer composition within the scope of the present invention, having a coupling efficiency of 35%, polystyrene block molecular weight of 15,500, a polystyrene content of 22% and an overall molecular weight 200,000, was prepared by polymerizing styrene with sec-butyl lithium as initiator at a monomer to initiator molar ratio of 149, to 1 and then terminating the polymerization, polymerizing isoprene at a monomer to initiator molar ratio of 820 to 1 and then terminating the polymerization and finally polymerizing polystyrene again under the same conditions as before. Another typical block copolymer was made by blending a diblock polystyrene-polyisoprene polymer with a triblock polystyrene-polyisoprene-polystyrene copolymer.

It is necessary to add an adhesion promoting or tackifying resin that is compatible with the elastomeric conjugated diene block. A common tackifying resin is a diene-olefin copolymer of piperylene and 2-methyl-2butene having a softening point of about 95° C. This resin is available commercially under the tradename Wingtack 95 and is prepared by the cationic polymerization of 60% piperylene, 10% isoprene, 5% cyclopentadiene, 15% 2-methyl-2-butene and about 10% dimer, as taught in U.S. Pat. No. 3,577,398. Other tackifying resins of the same general type may be employed in which the resinous copolymer comprises 20-80 weight percent of piperylene and 80-20 weight percent of 2-methyl-2-butene. The resins normally have softening points (ring and ball) between 80° C. and about 115° C.

Other adhesions promoting resins whcih are also useful in the compositions of this invention include hydrogenated rosins, esters of ronsins, polyterpenes, terpenephenol resins and polymerized mixed olefins. To obtain good thermo-oxidative and color stability, it is preferred that the tackifying resin be a saturated resin, e.g., a hydrogenated dicyclopentadiene resin such as Escorez® 5000 series resin made by Exxon or a hydyrogenated polystyrene or polyalphamethylstyrene resin such as Regalrez® resin made by Hercules.

The amount of adhesion promoting resin employed varies from about 20 to about 400 parts by weight per hundred parts rubber (phr), preferably between about 100 to about 350 phr.

The selection of the particular tackifying agent is, in large part, dependent upon the specific block copolymer employed in the respective adhesive composition. In the manufacture of disposable articles such as diapers, sanitary napkins and bed pads, there is the additional consideration of having a substantially white or clear adhesive composition.

The adhesive composition of the instant invention may contain plasticizers, such as rubber extending plasticizers, or compounding oils or liquid resins. Rubber compounding oils are well-known in the art and include both high saturates content oils and high aromatics content oils. Preferred plasticizers are highly saturated oils, e.g. Tufflo® 6056 oil made by Arco. The amounts of rubber compounding oil employed in the invention composition can vary from 0 to about 100 phr, and preferably between about 0 to about 60 phr.

Optional components of the present invention are stabilizers which inhibit or retard heat degradation, oxidation, skin formation and color formation. Stabilizers are typically added to the commercially available compounds in order to protect the polymers against heat degradation and oxidation during the preparation, use and high temperature storage of the adhesive composition.

Addition stabilizers known in the art may also be incorporated into the adhesive composition. These may be for protection during the life of the disposable article against, for example, oxygen, ozone and ultraviolet radiation. However, these additional stabilizers should be compatible with the essential stabilizers mentioned herein-above and their intended function as taught herein.

The adhesive compositions of the present invention are typically prepared by blending the components at an elevated temperature, preferably between about 130° C. and about 200° C., until a homogeneous blend is obtained, usually less than three (3) hours. Various method of blending are known to the art and any method that produces a homogeneous blend is satisfactory.

The preferred use for these compositions is in pressure sensitive adhesives. However, it is useful in other applications such as diaper tab tape adhesives.

EXAMPLES

A number of polymers were prepared for use in the following experiments. These polymers and their characteristics are identified in Table 1 below.

              TABLE 1______________________________________Polymer IdentificationSample ID    PSC (wt. %) PS Block  Molecular Weight______________________________________A        22.5        16,500    210,400B        19.6        14,600    216,100C        25.5        17,300    192,500D        25.3        15,200    170,600E        22.0        15,500    202,500F        25.0        16,800    191,000G        22.0        15,500    202,500______________________________________

These polymers were styrene-isoprene-styrene triblock copolymers. Styrene isoprene diblock copolymers were made with the same characteristics and blended with the triblock to produce blends with varying coupling efficiencies.

The polymers were then used in an adhesive formulation and the performance of the adhesive formulation was determined. The adhesive formulation used was: 39.8% wt. polymer, 54.2% wt. Escorez 1310LC tackifying resin (a hydrocarbon resin), 5.6% wt. SHELLFLEX® 371 oil and 0.4% wt. Irganox 1010 antioxidant. The performance of the various polymers in this adhesive formulation was determined and the results are shown in Table 2 below. The melt viscosity was measured in centipoise (cps) by using a Brookfield Thermocell viscometer at 350° F. The SAFT (M) Mylar was measured by 1"×1" Mylar to Mylar lap joint with a 0.23 kg weight. SAFT measures the temperature at which the lap shear assembly fails under load. The molecular weights (styrene equivalent) were determined by gel permeation chromatography as the peak molecular weight of the main species. The polystyrene content was determined by nuclear magnetic resonance spectroscopy. Holding Power (HPST) is the time required to pull a standard area (1/2in. ×1/2 in.) of tape from a standard steel test surface under a standard load, in shear at 2° antipeel (Pressure Sensitive Tape Council Method No. 7). Peel was determined by PSTC Test No. 1.

                                  TABLE 2__________________________________________________________________________Polymer Performance  REQUIREMENTS  MV    MV  (Polymer)        (Adhesive)              PEEL                  HPST SAFT(M)  (Poise)        (Poise)              (pli)                  (min)                       (°C.)Sample    C.E.  5000-15000        <20,000              >6  50   65    REQ. MET__________________________________________________________________________A   10  3717x        3490  5.5x                    18x                        60x  NoA   30 6526  8930  8.2 3891 78    YesA   50 11460 22860x              10.0                   7000+                       86    NoB   10  3804x         840  5.8x                    15x                        65x  NoB   30 6397  2160  8.1 1259 82    YesB   50 10760 5530  10.1                   7000+                       88    YesC   10  3283x        5990  5.6x                    42x                       68    NoC   30 5870  15330 7.7  7000+                       84    YesC   50 10496 39240x              8.8  7000+                       89    NoD   10  2770x        1310  5.4x                    30x                        60x  NoD   30  4722x        3360  7.6 4634 77    NoD   50 8051  8590  8.8  7000+                       84    YesE   10  3461x        1680  5.6x                    22x                        63x  NoE   30 5942  4300  8.2 2718 82    YesE   50 10199 11000 8.5 5696 86    YesF   10  3231x        4760  --  --   --    NoF   30 5712  10890 --  --   --    YesG   35 6801  5440  8.8 5905 84    Yes__________________________________________________________________________ x denotes failure to meet requirements

As described previously, past experience shows that in order to meet the five polymer performance characteristics, the polymer must have a coupling efficiency of at least 25, a polystyrene block molecular weight of 12,000 or greater, a polystyrene content of 19 to 27% and an overall molecular weight to greater than 170,000. Using this information and the data from Table 2, a regression analysis reveals that in order to obtain the viscosity requirements and the adhesive test requirements, the coupling efficiences for polymers of A-F must fall within the ranges shown in Table 3 below:

                                  TABLE 3__________________________________________________________________________Summary of Polymer Parameter LimitsViscosity RequirementsMV1            MV2  Adhesive Test Reguirements(poise)        (poise)               CE >/= 25                      PS > 11M                            Mw > 170MSample    5-15M      <20000               Overall CE Range__________________________________________________________________________A   21 </= CE </= 59          CE < 47               25 </= CE < 47B   21 </= CE </= 62          CE < 77               25 </= CE < 77C   25 </= CE </= 62          CE < 35               25 </= CE < 35D   33 </= CE </= 73          CE < 67               33 </= CE < 67E   24 </= CE </= 64          CE < 62               25 </= CE < 62F   25 </= CE </= 63          CE < 42               25 </= CE < 42__________________________________________________________________________

Further work with this regression analysis yields the data shown ion Table 4 below.

              TABLE 4______________________________________PSC       PS Block Mw Mol. Wt.(wt. %)   (M)         (Ms)      C.E. Range (%)______________________________________1    19.5     12          178.6   35-822    19.5     13          193.5   30-743    19.5     14          208.3   25-674    19.5     15          223.2   25-595    19.5     16          238.1   25-526    19.5     17          253.0   25-397    19.5     18          267.9   25-258    20.5     13          183.3   33-779    20.5     14          197.4   27-7010   20.5     15          211.5   25-6311   20.5     16          225.6   25-5412   20.5     15          239.7   25-3913   20.5     17          253.8   25-2514   21.5     18          174.1   35-7915   21.5     13          187.5   30-7316   21.5     14          200.9   25-6617   21.5     16          214.3   25-5418   21.5     17          227.7   25-3919   21.5     18          241.1   25-2520   22.5     14          178.5   32-7521   22.5     15          191.5   28-6822   22.5     16          204.0   25-5423   22.5     17          216.8   25-3924   22.5     18          229.5   25-2525   23.5     14          170.3   34-7726   23.5     15          182.4   30-7127   23.5     16          194.6   26-5428   23.5     17          206.8   25-3929   23.5     18          218.9   25-2530   24.5     15          174.3   32-7131   24.5     16          186.0   28-5532   24.5     17          197.6   25-3933   24.5     18          209.2   25-2534   25.5     16          178.0   30-5535   25.5     17          189.1   26-4036   25.5     18          200.2   25-25______________________________________

Table 5 and these more stringent performance requirements. This regression analysis yields the coupling efficiency ranges shown in Table 6 and the polymer data points shown in Table. 7.

              TABLE 5______________________________________Polymer PerformanceREQUIREMENTS       MV1       (Poise) MV2   PEEL  HPST   STMYSam-        6M-     (Poise)                     (pli) (min)  (°C.)                                        REQ.ple  C.E.   15M     <6000 >6.8  >500   70    MET______________________________________A    10      3717x  3490  5.5x    18x   60x  NoA    30      6526   8930  8.2   3891   78    YesA    50     11460   22860x                     10.0   7000+ 86    NoB    10      3804x   840  5.8x    15x   65x  NoB    30      6397   2160  8.1   1257   82    YesB    50     10760   5530  10.1   7000+ 88    YesC    10      3283x  5990  5.6x    42x  68    NoC    30      5870x  15330x                     7.7    7000+ 84    NoC    50     10496   39240x                     8.8    7000+ 89    NoD    10      2770x  1310  5.4x    30x   60x  NoD    30      4722x  3360  7.6   4634   77    NoD    50      8051   8590  8.8    7000+ 84    YesE    10      3461x  1680  5.6x     22x  63x  NoE    30      5942x  4300  8.2   2718   82    NoE    50     10199   11000x                     8.5   5696   86    NoF    10      3231x  4760  --    --     --    NoF    30      5712x  10890x                     --    --     --    NoG    35      6801   5440  8.8   5905   84    Yes______________________________________ M: thousands x denotes failure to meet requirements MV1: Neat polymer viscosity at 350° F. MV2: Adhesive viscosity at 350° F. HPST: Holding Power to Steel STMY: SAFT to MYLAR PEEL: 180° peel adhesion

                                  TABLE 6__________________________________________________________________________Summary of Preferred Polymer Parameter LimitsMelt ViscosityMV1             MV2  Adhesive RequirementsPreferred(Poise)    (Poise)                Mw > 170M                       CE >/= 25                              PS > 12MSample6-15M      <6000                Preferred CE Range__________________________________________________________________________A    28 </= CE </= 59           CE < 22                NoneB    28 </= CE </= 62           CE < 51                33 </= CE < 51C    31 </= CE </= 62           CE < 10                NoneD    39 </= CE </= 73           CE < 42                39 </= CE < 42E    31 </= CE </= 64           CE < 37                31 </= CE < 37F    31 </= CE </= 63           CE < 17                None__________________________________________________________________________

              TABLE 7______________________________________PSC       PS Block Mw Mol. Wt.  C.E. Range (%)(wt. %)   (M)         (Ms)      Preferred______________________________________1    19.5     12          178.6   43-822    19.5     13          193.5   37-743    19.5     14          208.3   31-624    19.5     15          223.2   25-455    19.5     16          238.1   25-286    19.5     17          253.0   None7    19.5     18          267.9   None8    20.5     13          183.3   40-779    20.5     14          197.4   34-6210   20.5     15          211.5   29-4511   20.5     16          225.6   25-2812   20.5     17          239.7   None13   20.5     18          253.8   None14   21.5     13          174.1   43-7915   21.5     14          187.5   37-6216   21.5     15          200.9   32-4517   21.5     16          214.3   27-2918   21.5     17          227.7   None19   21.5     18          241.1   None20   22.5     14          178.5   40-6221   22.5     15          191.5   35-4522   22.5     16          204.0   None23   22.5     17          216.8   None24   22.5     16          229.5   None25   23.5     14          170.3   42-6226   23.5     15          182.4   37-4527   23.5     16          194.6   None28   23.5     17          206.8   None29   23.5     18          218.9   None30   24.5     15          174.3   39-4531   24.5     16          186.0   None32   24.5     17          197.6   None33   24.5     18          209.2   None34   25.5     16          178.0   None35   25.5     17          189.1   None36   25.5     18          200.2   None______________________________________
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3519585 *Apr 25, 1969Jul 7, 1970Morgan Adhesives CoPressure sensitive adhesive composition
US3681190 *May 7, 1970Aug 1, 1972Minnesota Mining & MfgPressure-sensitive adhesive tape
US3783072 *Nov 2, 1971Jan 1, 1974Johnson & JohnsonExtrusion process for pressure-sensitive adhesive sheets and tapes
US3784587 *Jul 31, 1972Jan 8, 1974Goodyear Tire & RubberAdhesive composition containing an a-b-a block copolymer,poly alpha-methyl styrene and a tackifying resin
US3787531 *May 24, 1971Jan 22, 1974Minnesota Mining & MfgPressure-sensitive adhesives comprising a block copolymer and a tackifier
US3932328 *Oct 17, 1973Jan 13, 1976Johnson & JohnsonHot melt adhesive composition and tape
US3984509 *Jun 30, 1975Oct 5, 1976Johnson & JohnsonExtrusion process for mixtures of elastomer particles and resin particles
US4028292 *May 23, 1974Jun 7, 1977Johnson & JohnsonHot melt adhesive
US4080348 *May 18, 1976Mar 21, 1978Johnson & JohnsonPressure sensitive, block polymers containing isoprene and styrene or derivatives, block polymers containing styrene and conjugated dienes or an olefin
US4096203 *Jul 30, 1976Jun 20, 1978Shell Oil CompanyProcess to control cohesive strength of block copolymer composition
US4136071 *May 18, 1976Jan 23, 1979Johnson & JohnsonThermoplastic elastomer and tackifier resin
US4622357 *Jul 9, 1984Nov 11, 1986Arakawa Kagaku Kogyo Kabushiki KaishaPressure-sensitive adhesive compositions
US4734447 *Sep 2, 1986Mar 29, 1988Sunstar Giken Kabushiki KaishaHot-melt adhesive
US4785043 *Sep 24, 1987Nov 15, 1988Nippon Oil Co., Ltd.Pressure-sensitive adhesive composition produced from a base block copolymer, a resinous tackifier, a naphthenic or parffinic mineral oil, and an aromatic synthetic oil
US5093406 *Dec 14, 1989Mar 3, 1992Avery Dennison CorporationUnsaturated elastomer and tackifier resin
US5118762 *Apr 11, 1990Jun 2, 1992Shell Oil CompanyBranching; linear polymeric blocks; molecular weight control; coupling agent; used in diapers
US5149741 *Sep 20, 1991Sep 22, 1992Findley Adhesives, Inc.Hot melt construction adhesives for disposable soft goods
CA686721A *May 19, 1964Phillips Petroleum CoShoe sole compositions
DE2432496A1 *Jul 4, 1974Jan 22, 1976Bostik GmbhSchmelzkleber auf butylkautschukbasis
EP0027606A1 *Oct 10, 1980Apr 29, 1981BASF AktiengesellschaftHot-melt adhesive based on non hydrogenated, linear ABC block polymers
GB888624A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6025071 *Oct 23, 1997Feb 15, 2000H.B.Fuller Licensing & Financing Inc.Removable grade hot melt pressure sensitive adhesive
US6433069 *Oct 22, 1998Aug 13, 2002H. B. Fuller Licensing & Financing Inc.Comprised of styrene and ethylene-propylene or ethylene-butylene block terpolymers; used in bookbinding and labeling
US6730737 *Dec 22, 1994May 4, 2004Kraton Polymers U.S. LlcComprising a crosslinked block copolymer based on a conjugated diene and a vinyl aromatic hydrocarbon, crosslinked with a polysiloxane
Classifications
U.S. Classification525/314
International ClassificationC09J193/04, C09J153/02, C08L53/02, C09J193/00
Cooperative ClassificationC09J193/00, C09J153/02, C09J193/04, C08L53/02
European ClassificationC09J193/00, C09J193/04, C09J153/02, C08L53/02
Legal Events
DateCodeEventDescription
Apr 26, 1994ASAssignment
Owner name: SHELL OIL COMPANY, TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHIN, STEVEN S.;MILLER, JOHN A.;GROBRAN, RAMSIS;REEL/FRAME:006969/0069
Effective date: 19920921