Pressure sensitive hot melt adhesive for sanitary products.

SENSITIVE IN PRESSURE MELTING ADVERTISING PRODUCTS

PERSONAL HEALTH Background of the Invention

The present invention relates to pressure sensitive adhesive and more particularly formulations applied to a substrate in a hot or molten state and cooled to form a relative pressure sensitive adhesive. Consequently, the substrate may be adhered to another surface by the application of pressure and may subsequently be removed by traction from the surface.

In a particular embodiment the present invention relates to pressure-sensitive adhesive hot applied to the surface of absorbent articles and retained; body fluids as infants, menstrual absorbers and bandages. In the case of menstrual screens, for example, the screen has a side facing the garment and a side facing the body. The pressure sensitive adhesive is applied to the side as it faces the garment and glues the screen to the crotch underwear so that the screen remains in place for use. In such cases, it is of course desirable that the monitor be adhered to the underwear after being pressurized so that the screen is not displaced or detached under normal stresses. The causes are exerted on the adhesive by the usual means; On the other hand it is important to remove the monitor from the underwear after using it without: .. i i / iv ·· .. '· * »·' '' 'W · ···

<img file="GR78869B_D0001.tif" />

leave a residue on the underwear.

The technique is now complete formulation of pressure sensitive adhesive formulations for use in products absorbing body exudates as menstrual absorption screens. The foregoing may be broadly classified into two groups, namely the water-based adhesive systems and the so-called hot-melt systems. Several disadvantages have been addressed in the use of the prior systems in that they directly satisfy the previously mentioned criteria of persistent attachment and no residual removal. In particular, water-based systems have shown the problem of slow drying or slow polymerization. Basically, water-based systems initially require a high water content to have sufficient fluid flow characteristics to be applied to a substrate with high production speeds that are required for the economical manufacture of disposable products. as menstrual absorbers and baby patches. Unfortunately, the high water content gave the co-workers a long drying or freezing time which in turn slowed down the production process.

In an attempt to address this problem, the technique focuses on the so-called hot-melt pressure-sensitive adhesive systems, the main components of which are thermoplastic rubber polymers, which are combined with plasticizing oils, viscosifiers, oxidizing agents, viscosifiers, oxidizing agents. Hot melt adhesive formulations are for example in the US

PATENT No.4.136.699 issued January 30, 1979 to JACOLLINS ET AL. USPATENT No. 3,554,940 issued January 12, 1971 to M.ARAKAWA ET AL. U.S. Patent No. 3,917,607 issued to R .K. CROSSLAND ET AL on November 4, 1975, USPATENT No. 3,239,478 issued to HARLAN JR. in March 1966, USPATENT No.3-686.107 issued to T. Russell on August 22, 1972, US PATENT No. 3,862,068 issued January 21, 1975 to T. Russell; USPATENT No. 3-954,692 issued May 4, 1976 to REDOWNERY; USPATENT No. 3,935,338 issued January 27, 1976 to WJROBIN ET U.S. Patent No. 3,932,327 issued on January 13, 1976 to F. NAYLOR;

In each of the prior art suggestions for the proportion of components, the molecular weights and chemical nature of the various excipients are selected to produce an adhesive formulation having sufficient flow properties when heated to apply on a substrate and which can be cooled to a suitable temperature. adhesive that will bond these substrates to others with a sufficient degree of strength. Unfortunately, to date, these preceding suggestions, although representing improvements against the water-based pressure-sensitive adhesives, have at best been a compromise between durability and residual-free removal. Generally for achieving no residue removal, e.g. from underwear to

- - in the case of self-adhesive menstrual absorption monitors, the durability has waned.

Summary of the Invention It has now been discovered that a pressure sensitive melting glue can be provided or that it is made to order to remedy deficiencies in formulations; Those of the prior art, especially selected to exhibit certain rheological properties, are expressed in the desired yield criteria, i.e., residual binding and no residue removal.

In particular, it has been discovered that adhesive formulation can be selected on the basis of readily available stress intensity analysis by identifying the rheological properties. substrate. It is now recognized that the adhesion process is relatively slow and that pressure is applied for a relatively long period of time and that elastic retention after applying such pressure may also require a long time. On the other hand, during the work of detachment, the tension is applied rapidly and the elastic retention must be accomplished within a short period of time. In other words, it is important that the viscous materials are radially selected for use as a hot-melting formulation to behave under dynamic stress conditions, as a relatively viscous material when they are under prolonged tension and have a long recovery time. At the same time, the viscous material must be selected to exhibit an elastic property when it is under dynamic stresses at high speed and when it has only a short recovery time.

According to the present invention the choice of a satisfactory adhesive can be made by performing an analysis of the rheological properties of the formulation by the use of readily available analytical instrument for characterizing viscoelastic materials, i.e. thermomechanical spectrometry. Basically, the instrument is designed to impose a selective pressure on the test specimen that is varied according to the temperature of the specimen by a method known in e.g. sinusoidally. The intensity associated with this pressure is sensed by the instrument, and the stress-pressure relationships are interpreted by an integrated microprocessor and are graphically related as the clock functions are temperature dependent such as the input coefficient and the input coefficient. known as TAN d. These parameters as a function of temperature are in fact proportional to these parameters as a function of time based on the known rheological principle of time-temperature superposition. Thus, the etine parameters produced by the thermomechanical spectrometer describe the stress-pressure properties of a given material under dynamic conditions.

It has been discovered that hot melt adhesive has some appearance; Critical parameters in the analysis with the thermomechanical spectrometer are extremely suitable for fulfilling the criteria of durable bonding and residual free removal and in relation to these criteria will exhibit substantial improvement over those known as hot melt preparations. . In particular, it has been found that the hot-melt adhesive composition must be selected to have a glass passage temperature;

<img file="GR78869B_D0002.tif" />

Furthermore, the formulation should emphasize the temperature difference between the glass temperature of the rubber phase 0 ° C and the flow temperature between 45 ° C and 55 ° C. 0 the coefficient of storage between the rubber phase glass passage temperature and the flow temperature shall be a monotonically reduced temperature function and shall have a value equal to the arithmetic mean between the tempered glass glass transition temperatures of 0.5 ° C and and 6.5X10 DYNES per CM². Furthermore the slope of the L0G₁₍-, the storage coefficient (in DYNES per CM) against the temperature (in ° C) must be at a temperature equal to the arithmetic mean of the glass transition temperature of the rubber phase and the flow temperature between - 0,005 and - 0,025.

It is to be understood that the above parameters are determined on the basis of the analysis of the mechanical spectrometer which is carried out under the conditions mentioned below.

Selected formulations should also be stable and not subject to degradation, e.g. by oxidizing for a considerable period of time. Thus, the formulation should not exhibit a significant decrease in viscosity when left in ambient air for ninety hours at a temperature of 7 ° C at 350 ° F (176.7 ° C).

It is needless to say that the radial components selected for a particular formulation meet the above rheological properties must also be compatible with the Eti: so that a homogeneous mixture can be prepared and maintained. In other words, the adhesive properties of the adipose mass of the adhesive formulation should not differ significantly from those of most of the mass.

When the above parameters are met, said glue has been found to combine high strength and removability and no residue to a degree higher than any known formulation while it can be stored in a molten state for a period of time.

The invention will be better understood by examining the description below in combination with the accompanying drawings against a typical rosological analysis produced by a thermomechanical spectrometer showing the storage coefficient, loss coefficient and TA. Detail or 2_X^e£ 2ⁱ£^e22222^oh2

As described above the present invention encompasses the selection from a wide variety of available viscoelastic polymer preparations, one particularly suitable for fulfilling the requirements of durable bonding and removable xat without further delay.

The viscoelastic polymer of choice as a major component in the formulation of the present invention is of the A-B-A copolymer type, and more particularly of the type where the block medium (i.e., section B) has a sialoliphin as e.g. ethylene and butylene copolymers. The final block (section A) contains polystyrene.

A wide variety of rubber copolymers is currently available from SHELL OIL COMPANY and is sold under the KRATON brand name and more specifically under the KRATON GH range of high-end KRATON G-polymer bulk polymers block.

For example there is KRATON G where the average molecular weights of each block A are between about 7000 and about 30,000 and the A-blocks can be about 10-50% by weight of the block copolymer. Within this wide range of available KRATON G type polymers, materials may be selected to provide a full range of adhesive rheological properties ranging from relatively elastic to relatively viscous flow property under stationary conditions and at a given temperature.

When selecting a good viscous material, the person using it faces the problem of performing many empirical experiments before making a choice.

This problem is greatly aggravated when end-use is based on sticky behavior under different dynamic conditions such as e.g. the material considered in the selection of satisfactory viscoelastic material for use in menstrual absorption screen. Generally for such use, the glue formulation is applied by the manufacturer in a molten state facing the outer surface of the garment and is covered with a removable protective strip. 0 Using it, immediately before use, it removes the strip and presses the screen onto the inner surface of the crotch of a lingerie. The adhesive under the effect of this tension applied by the pressure of the screen in its position is deformed and flows to the surface irregularities of the garment attached thereto. Upon relaxation by the forceps, the adhesive assumes and, over time, reaches an iso-deformation condition that for any practical use is stable although it should be realized that it is likely to continue, though small. The ideal for maximizing bond strength is extremely slow recovery with low equilibrium low recovery.

Upon removal of the screen from the underwear, the wearer generally grasps the end of the screen and rapidly detaches the screen from the underwear, thus exercising rapidly in the adhesive. The ideal under such a rapid deformation condition is to recover from the resulting rapid deformation, i.e. to have the adhesive layer having sufficient cohesion strength to ensure a permanent removal from the garment.

The problem of the adhesive formulation is compounded by the fact that although a formulation may at a certain point exhibit approximately the same descriptive properties as described above, your ideal lollipop properties over time will have the same properties. polymers are degraded or oxidized by exposure to air. Then there is no assurance that performance can be maintained consistently during use.

It has now been discovered that the excruciatingly difficult task of selecting a good formulation from the wide range of KRATON G adhesive formulas has now been greatly facilitated by our discovery that the desired ideal behavior corresponds to a critical critical time. Further, the properties allowed us to define an adhesive cushion which in use greatly exceeds the in-use performance of any known prior art formulation.

The new adhesive formulation is characterized by some basic time-dependent rheological properties defining the use of thermomechanical spectrometry. This analysis is designed to describe the characteristics of viscoelastic material and to take into account the phase change between tension and pressure. By the principle of temperature overload, the time variable becomes proportional to the temperature variable or can be easily measured.

With an obvious degree of simplification, when a given intensity is applied as a function of time on viscoelastic material, the opposite strain or strain has the tendency to delay. function of intensity. So if the time-dependent unit? e (T) is a semiconductor function of time e.g.

e (T) = · e_M. nm (ωT) where is the range, T is the time, and ω is the angular velocity in RADIANS per unit time, then the corresponding elongated intensity s (T) will also be sinusoidal but there will be a delay delay at this angle. in order that:

σ (T) - σ_M. day (hT + d) that may be extended to:

<td colspan="2">σ (T) -c_M. plus dm (hT) 4 p_M. dd plus &lt;dT)</td>

<td>h_, Z p_M. they were d</td><td>nm (hT) 4 nsm plus (hT)</td>

<td>e_M G '(T)</td><td>+ e_M'G plus (hT)</td>

<td colspan="2">λ cms cms where G? - plus δ and G "- nd and</td>

where, for a given sample, at a given temperature, existing sinusoidal intensity at constant angular velocity, G and G will depend exclusively on time. The parameter G * is defined as the storage factor and G is defined as the loss factor. The ratio G / G * is defined as effects. On the basis of the above, it can be observed that the dynamic properties of an adhesive can be determined by determining the time-varying factors G ', G and effects. It takes a long time to get a full definition of these functions by experiment, and a time-dependent study is not practical. Fortunately, it has been found that the elongated functions have a direct proportion to the temperature-related functions in accordance with the well-known principle of temperature overlap (as discussed e.g. in RHEOLOG⁷Volume 2, Edited by FREDERICK R.EIRICH 1958 ACADEMIC PRESS INC. NY on page 67). In the simplest form of the principle curve of the functions and the LOG of the functions on the ordered against LOG_1Q of the time on the segmented 12 can be overlaid with an LOG indicative of the temperature without changing the characteristics of the curves. So long time equals high temperature and short time equals low temperature.

The thermomechanical spectrometer employs the principle of time-temperature overlap by replacing historical temperature in place of historical time. When used, the test specimen is positioned between two parallel plates and an intensity is imposed such that it can be selected to vary semiconductorally as a function of temperature. The temperature is controlled during the test using gas in an ambient chamber. The oscillation frequency can be selected as an arbitrary constant value. The spectrometer has a switch which detects the torque and the normal force produced by the pressure at the pressure. The detected forces are translated by the use of the microcomputer embedded in the spectrometer into causal intensities in the order that they are translated by the logic of the microcomputer into the clock functions G ', G and so on.

The accompanying drawing illustrates the clock functions. Temperature functions (as a proportion of time) calculated from the analysis of the thermomechanical spectrometer for adhesive formulation meet the prescribed criteria of the present invention. As shown in Figure 2, the temperature is very different. (short time increases) compared to high temperatures (long time additions). Specifically, the material changes from the glassy state to a rubber elastic state and subsequently to a viscous flow state as the temperature rises below Tm above Tr.

Some rosological properties can be defined by these factors. Therefore the temperatures at which the coefficient reaches its maximum is defined as the glass transition temperature of the rubber phase of the formulation i.e. the glass transition temperature of the central block T Τ. The temperature at which the coefficient G reaches its second maximum is the flow temperature T. Between T_G and the temperature field referred to herein as the Rubber Plateau Area (PLATEAU).

It has been found that if the adhesive formulation based on the AB-A-KRATON G polymer is selected based on the occurrence of some of the above described rheological properties fluctuating in a narrow field, then the desired end-use criteria for durable adhesion (e.g. the balance can be paid, provided that you make a further choice when selecting a formulation that retains these properties at the expected shelf life of the selected formulation.

Particularly on the basis of the parameter described herein for the analysis of the mechanical spectrometer it has been found that the passage temperature of the rubber phase glass (T preference varies between 0 ° C and 10 ° C. The temperature of the tempered rubber temperature range rubber phase and flow temperature (T._rshould extend between 45 ° C and 55 ° C. The storage factor G 'shall be monotonically reduced temperature function and shall have a value for the greater part of the PLATEAU rubber range between 3.5 X 1 and 6.5 X 10 DYNES a CM². In particular, C should have a value between 3.5 X 10 ^ and 6.5 X 10 ^ DYNES per CM²At the arithmetic mean temperature Tf and Tp ie at temperature (Tfp) / 2 where T_G and Tr are given in degrees Celsius. Further to the arithmetic mean temperature the LOG coefficient_1Q θ * versus temperature (where G is expressed in DYNES / CM² and the temperature at ° C) should have a slope D (LOG ^ qG ') / D (T) ranging between 0.005 and -0.025.

It is equally important that the selected formulation be able to maintain the above-mentioned rheological properties throughout the expected storage time and in use. It has been found that the formulation will have this characteristic if the selection is made based on the appearance of the formulation with almost no viscosity reduction when left in ambient air for ninety hours at 35 ° F (176.7 ° C). By virtually no reduction in viscosity it is understood that the viscosity immediately after the ninety hour period is not less than about 95% of the original viscosity and preferably 97% by measuring the viscosity using the BROOKFIELD 15 viscosity.

Example_1

The first set of adhesive preparations having the following compositions:

<td>INGREDIENT</td><td>Weight% Part</td><td>per 100 parts regulatory</td>

<td>Sample 1</td><td></td><td></td>

<td>KRATON G 1652</td><td> 20,0</td><td>100, no</td>

<td>ARKON P-85</td><td> 52,4</td><td> 262,0</td>

<td>TUFFLO 6054</td><td> 25,6</td><td> 128,0</td>

<td>what₂</td><td> 1,0</td><td> 5,0</td>

<td>Ethyl 330</td><td> 1,0</td><td> 5,0</td>

<td>Sample 2</td><td></td><td></td>

<td>KRATON G 1657</td><td> 25,0</td><td> 100,0</td>

<td>ARKON P-85</td><td> 52,1</td><td> 208,0</td>

<td>TUFFLO 6056</td><td> 20,9</td><td> 84,0</td>

<td>What0₂</td><td> 1,0</td><td> 5,0</td>

<td>Ethyl 330</td><td> 1 0</td><td> 5.0</td>

<td>Sample 3</td><td></td><td></td>

<td>KRATON G 1652 -</td><td> 19,8</td><td> 1 00</td>

<td>ESCOREZ 528TH</td><td> 59,5</td><td> 300</td>

<td>SHELLFLEX 371</td><td> 19,8</td><td> 100</td>

<td>Butyl zinc</td><td> 0,6</td><td> 3</td>

<td>Ethyl 330</td><td> 0,3</td><td> 2</td>

<td colspan="2">Rubber polymers of the series</td><td>KRATON G is copoly-</td>

<td>parts of block AB with</td><td colspan="2">final polystyrene and central group</td>

<td>block copolymer</td><td>polyethylene -</td><td>polybutylene with</td>

varying molecular weights and varying percentages of polymeric / if terminal block groups as defined below.

W-- 16

ARKON P-85 is used in the above formulation as a viscosity resin and is a mixture of alicyclic, aliphatic, and unsaturated unsaturated aromatic compounds with 85 ° C softening points. The resin is sold by ARAKAW

RINSAN KAGAKU KUO KK HIGASHI-KU, OSAKASHI, Japan.

TUFFLO 6054 and TUFFLO 6056 are plasticizers sold by the ATLANTIC RICHFIELD OIL COMPANY and contain a mixture of paafafic, naphthenic and aromatic carbohydrates, with a weight of about 13% aromatic hydrocarbon and 5% argon based, respectively.

Ethyl 330 is an antioxidant sold by ET1 COPRORATION and contains 1,3,5-imimethyl-2,4,6 tris / 3,5-dithy-butyl-4-hydroxybenzyl) benzene.

The ESCOREZ 5280 is. EXXON CORPORATION and contains a mixture of short-chain alicyclic and aliphatic hydrocarbons and a small amount of monosubstituted aromatic hydrocarbons. The soft resin point is about 85 ° C.

SHELLFLEX 371 is a plasticizer available from SHELL OIL COMPANY and contains a mixture of paraffinic, naphthenic and aromatic hydrocarbons. The aromatic percentage by weight is about 34% in the gel-anther analysis.

Butyl Zinc is an antioxidant available from RTVANDERBILT COMPANY and contains zinc di-butyldithiocarbamate.

The above formulations are subjected to thermomechanical spectrometric analysis using xaucw'ur Spectrometer: provided by RHEOMETRICS INC. by UNION, NEW JERSEY. The geometric formula for the tests is parallel plates and the oscillation frequency is selected at 1.0 RADIANS per second. The results of the rheological analysis are given below in Table I.

The stability of the samples was tested by measuring the viscosity reduction, using a BROOKFIELD viscometer when the sample was subjected to 35 ° F for ninety hours. The results are reported in Table I.

The adhesive formulations are tested to determine their performance in use in relation to the properties of durable bonding and residual free removal. Mens absorption screen of the general structure of SURE AND NATURAL MAXISHIELD manufactured by PERSONAL PRODUCTS Co. MILLTOWN, NEW JERSEY is provided with a line of adhesive formulation of the present invention. The screen contains a generally rectangular absorbent body having a side facing the body and a side facing the garment. Protective chiller polyethylene tape adheres to the garment facing side of the absorbent body and is held in place by adhesive and wrap layer. The whole is then wrapped in a generally rectangular cover of nonwoven material. The edges of the unopened material; are parallel to the longitudinal edges of the screen overlapping the view to the thionic laundry. Rectangular line of the adhesive formulation of the¹is placed above the overlapping portions of the cover. The line has a length of six inches (15.24 cm) and a width of 3/4 of an inch 18 inches (1.9 cm). The weight of the applied adhesive formulation is 370 MILLIGRAMS per layer, evenly distributed with a weight distribution of about 12.7 MG / CM.

To test the adhesion strength of the adhesive, a Rapid Fabric Removal Test is performed using the TAG AND LABEL MANUFACTURERS INSTITUTE PEEL AND RELEASE TESTER manufactured by TESTING MACHINES INCORPORATED of AMITYVILLE, New York. Prior to the test, the menstrual absorption screen remains for 16 hours at 21 ° C and 65% relative humidity with a 80 gram per inch cotton woven in both 7 x 2 directions | inches of TEST FABRIC INC., MIDDLESEX, ME; JERSEY. After preparation, the cotton fabric is glued to the screen and the screen and fabric are pressed between two stainless steel plates for a minute with a maximum load of 150 POUNDS. Pressure is relaxed after about 80 minutes and after the system balances the cotton fabric detaches from the screen using TESTE; with a detachment rate of 1200 inches per minute and a nominal detachment angle of 180 °. The value is given in grams of maximum force per inch of width transversely in the release direction.

Residual detachment is measured by five consecutive detachment tests as described above with the difference; * that the time between pressure relaxation and test is minus 80 minutes using the same cotton fabric in each case. and are reported as MG of glue per CM ^ of glue surface. —-- 19

Table I

<td></td><td> 1</td><td>SAMPLE 2</td>

<td>POLYMER RUBBER</td><td></td><td></td>

<td>Weight% Polymer in the Formulation</td><td> 20</td><td> 25</td>

<td>Weight% Polystyrene Finishes</td><td> 29</td><td> 14</td>

<td>Numerical average molecular weight</td><td> 98.000</td><td> 105-500 98-</td>

<td>Molecular weight average weight</td><td> 109,500</td><td> 135.700 109-</td>

<td>WATCHES</td><td></td><td></td>

<td>Glass transition temperature ° C (Te)</td><td> 8,0</td><td> 0,0</td>

<td>flow temperature ° C (Tp)</td><td> 63,0</td><td> 50,0</td>

<td>Tf-Tr ° C (ΔΊ)</td><td> 55,0</td><td> 50,0 ·;</td>

<td>(T._G+ T._p) / 2 TAV ° C</td><td> 35,5</td><td> 25,0</td>

<td>G, 'DYNES / CM² in TAV</td><td>4.0 X 10⁵</td><td>6.0 X 10⁵ 6,0</td>

<td>D (LOG_WG *) / D (T) in TAV</td><td> -0,0074</td><td> -0,0072 -0,!'</td>

<td>Stability</td><td></td><td></td>

<td>% viscosity reduction</td><td> ~0</td><td> “0 4</td>

<td>PERFORMANCE AGAINST USE</td><td></td><td></td>

<td>GM / IN Detachment Balance</td><td> 870</td><td> 800 7·:</td>

<td>M3 / CM residue² glue surface</td><td>none</td><td>no no</td>

<td>As summarized</td><td>in Table 1 above</td><td>, the rubber</td>

<td colspan="2">polymer showed a significant difference</td><td>to the chemist -</td>

<td>property like</td><td>its arithmetic mean</td><td>molecular weight, </td>

<td colspan="2">average molecular weight, and</td><td>the percent r?</td>

<td>final teams</td><td>polystyrene. Also the</td><td>percent</td>

<td colspan="2">of the rubber polymer in them</td><td>preparations for men</td>

<td>importantly</td><td colspan="2">field. However, the combination of the metallic</td>

give them formulations each of which is agreed upon by

T - -.....

of rheological properties to the teachings of the present invention. Further, each preparation conforming to the stability requirements of etins is set forth herein.

So the efficiency of using these glues is satisfactory. The detachment equilibrium strength in each case is at least 700 GM / IN, a value that assures safe retention in the position of e.g. of menstrual absorption screens. Durable adhesion was associated with virtually no transfer of adhesive to lingerie, and the combination of these properties has so far not been overshadowed by standard adhesive formulations of this type.

A COMPARATIVE EXAMPLE

To illustrate the advantages of the present invention,

<td>a series was prepared</td><td>comparative</td><td>sample</td><td>of the following compositions:</td>

<td>of:</td><td></td><td></td><td></td>

<td>INGREDIENT</td><td>Weight%</td><td>Parts Parts</td><td>those 100 rubber</td>

<td>Sample 4</td><td></td><td></td><td></td>

<td>KRATON G 1652</td><td> 15,0</td><td></td><td> 100</td>

<td>ARKNO N-85</td><td> 55,8</td><td></td><td> 372</td>

<td>TUFFLO 6054</td><td> 27,2</td><td></td><td> 181</td>

<td>What0₂</td><td> 1,0</td><td></td><td> 7</td>

<td>EHTYL 330</td><td> 1,0</td><td></td><td> 7</td>

<td>Sample 5</td><td></td><td></td><td></td>

<td>KRATON G 1650</td><td> 14,9</td><td></td><td> 100</td>

<td>ARKON P-85</td><td> 53,5</td><td></td><td> 359</td>

<td>TUFFLO 6054</td><td> 29,7</td><td></td><td> 199</td>

<td>T0₂</td><td> 1,0</td><td></td><td> 7</td>

<td>EHTYL 330</td><td> 1,0</td><td></td><td> 7</td>

Sample 6

KRATON G 1650

WINGTACK 95

OTHER

Sample 6 is a formulation available to the trader whose composition is not fully known. WINGTACK 95 is a viscosity resin available from GOODYEAR TIRE AND RUBBER COMPANY and contains a polymerized piperylene isoprene solid viscosity with a softening point of about 95 ° C.

<td>Samples are tested for</td><td colspan="2">clocks t</td><td>of property</td>

<td>stability and efficiency</td><td>at</td><td>»Useful</td><td>at the</td>

<td>arranged in Example I manner</td><td colspan="2">. Results</td><td>are given</td>

<td>below in Table 2</td><td></td><td></td><td></td>

<td>TABLE 2</td><td>SAMPLE</td><td></td><td></td>

<td></td><td></td><td> 5,</td><td> 6</td>

<td>POLYMER RUBBER</td><td></td><td></td><td></td>

<td>Weight% Polymer in the Formulation</td><td> 15,0</td><td> 14,9</td><td>unknown</td>

<td>Weight% polystyrene finishing groups</td><td> 29,0</td><td> 28</td><td> 28</td>

<td colspan="2">Numerical average molecular weight 98,000</td><td> 108.300</td><td> 108.300</td>

<td colspan="2">Average molecular weight 109,500</td><td> 123.900</td><td> 123.900</td>

<td>WATCHES</td><td></td><td></td><td></td>

<td>Glass transition temperature ° C (T ^)</td><td> 10,0</td><td> 6</td><td> 6</td>

<td>flow temperature ° C (T ^)</td><td> 60,0</td><td> 70,0</td><td> 90,0</td>

<td>TG-TF ° C (ΔT)</td><td>5th, o</td><td> 64,0</td><td> 84.0</td>

<td>(TGs TF) / 2 ° C (TAV)</td><td> 35,0</td><td> 38,0</td><td> 48,9</td>

<td>G ', DYNES / TAV</td><td>1.8X10⁵</td><td>2.7x1c⁵</td><td>4.0 X 10⁵</td>

<td>D (LOG_1OG ') / D (T) in TAV</td><td> • 0,0108</td><td> - 0,0</td><td> 0,0</td>

<td>Stability</td><td></td><td></td><td></td>

<td>% Viscosity reductions Performance in use</td><td> 0</td><td> “0</td><td>“Θ '</td>

<td>GM / IN Detachment Balance</td><td> 650,0</td><td> 130</td><td> &lt;120</td>

<td>MG / Crf residue; surface</td><td>6.9X10^-2</td><td>none</td><td>· X ' none</td>

As Table 2 shows, the percentage weight of rubber polymer, the percentage of final polystyrene groups, and the molecular weights of the polymer lie within the range of these parameter values. The percentages are given in Table I. However, the combinations are 4 to. and 6 in such a way as to give a rheological property outside the scope specified herein, and as shown in Table 2, result in performance in use that is far less satisfactory than the compositions of the samples 1-3 according to the invention.

In particular, sample 4 shows a storage factor G '>> which is less than the prescribed field of 3.5 X 10⁵ up to 6.5 X 10 ^ DYNES / CM² at the average temperature of the PLATEAU rubber, TAV. The result is that while the equilibrium value at detachment is at nearly satisfactory levels, the amount of residue is unacceptable.

Sample 5 implies an overly long PLATEAU RT temperature interval as well as a low G 'in TAV. Also the slope of the L0G function₁₀G 'versus T in TAV is very small. The results in use efficiency are the inadequate release equilibrium value.

Likewise, sample 7 shows a very high RT and a very small inclination. The result is again an insufficient detachment equilibrium value.

The sample also has the disadvantage of inadequate¹ godly that it showed a viscosity reduction of 30% when '$ a-,' * 5®