Pressure sensitive adhesive compositions and elements made therefrom

Abstract

An adhesive element which exhibits excellent properties with respect to a variety of substrates, such as, skin, glass, fabric, paper, plastic, and other non-porous surfaces which is non-toxic, and non-sensitizing. The element exhibits high cohesive strength so that its integrity is maintained on removal from the substrate leaving no residues and is highly flexible so that total confirmation with the underlying shape of the substrate is maintained. The adhesive composition is the hydrolysis or esterification product of a methylvinyl ether/maleic anhydride co-polymer with an hydroxylated compound. Methods for preparation of the inventive adhesive element are disclosed.

Description

BACKGROUND OF THE INVENTION

I. Field of the Invention

This invention relates to adhesive compositions and methods for manufacture thereof, which compositions are easily formable to shape and are suitable for use in surgical, medical, and industrial applications.

II. Description of the Prior Art

Various adhesive compositions which are suitable for medical use and in particular, adapted to be used for ostomy appliances are disclosed in the patent literature. (See U.S. Pat. No. 4,393,080.) Generally, such compositions require resistance to erosion by moisture or other biological fluids, must exhibit good adherence to the human skin, and also must not be irritating. In addition, it is desired to have adhesive compositions for various industrial and medical applications, which are easily shaped so as to conform to the contours of the surface to which they are being applied and yet are simple to prepare.

Attempts to formulate such compositions utilizing mixtures of various polymers and hydroxyl-containing compounds, such as, Gantrez (a product of GAF Chemical Corporation composed of a co-polymer of methylvinyl ether and maleic anhydride), polyethylene oxide, ethoxylated alkyl phenol or nonyl phenol, e.g., Igepal, polyethylene oxide (GAF Chemical) are known. (See Japanese Patent 8805757, German Patent 3039542, and German Patent 2311746.) However, improvements in such adhesive elements are in constant demand, particularly, with respect to exhibiting the concomitant properties of good adhesion to the surface, ability to conform to the surface and yet absence of irritation in medical applications.

SUMMARY OF THE INVENTION

We have discovered an adhesive element which exhibits highly desirable properties with respect to the above-outlined requirements. In particular, we have discovered a method for making such an adhesive element by hydrolysing or esterifying a co-polymer of polymethylvinyl ether and maleic anhydride having the formula: ##STR1## wherein n is such that the weight average molecular weight is from about 2.times.10.sup.5 to 2.4.times.10.sup.6 to form a smooth paste. The paste may then be formed into the desired shape and heated for a period of time and temperature sufficient to form a gel. Upon cooling, a formed adhesive mass or element is obtained in the particular desired shape which is suitable for use in medicinal as well as other end uses.

DETAILED DESCRIPTION OF THE INVENTION

More particularly, we have discovered a variety of adhesive masses or elements which may be useful in many different medical devices and can be easily formed into desired shapes by reacting slurries of a first component comprising the methylvinyl ether/maleic anhydride co-polymer with a second component comprising an hydroxylated compound to hydrolyse or esterify the co-polymer.

Typically, the hydrolysis product would be the diacid whereas the esterification product may be the partial or full ester according to the following sequence: ##STR2## wherein R may be a wide variety of organic groups, e.g.,

alkyl polyethoxylates, aromatics, and fused aromatics, since the most important characteristic of the R-OH compounds is the hydroxyl group.

Depending upon the particular hydrolysing or esterification compounds used, the masses or elements may have varying degrees of tack, shear, and peel strength. Moreover, in a preferred embodiment, the masses can be formed within a container, which allows shaping of the element, which also provides packaging for the adhesive until its use.

Preferably, the methylvinyl ether/maleic anhydride co-polymer first component which is suitable for use in the present invention includes polymers wherein n is such that the weight average molecular weight is in the range from about 1.25.times.10.sup.6 to 2.4.times.10.sup.6 and most preferably, from about 1.08.times.10.sup.6 to 1.98.times.10.sup.6. A wide variety of such co-polymers are marketed under the trademark Gantrez (GAF Chemical Corporation).

The preferred materials for the first component are the long chain methylvinyl ether/maleic anhydride co-polymers wherein the maleic anhydride moiety in the polymer is intact, e.g., Gantrez S-97, and Gantrez AN-169.

The second component used to form the composition is an hydroxylated compound which serves to hydrolyse or esterify the polymer. Typical of such hydroxylated compounds are polyethoxylated fatty alcohols, oleyl alcohols, nonyl phenols, and octyl phenols. Others include polyethoxylated fatty alcohols, nonyl phenols, octyl phenols, polyethylene glycol, 1,3-butane diol, 1,4-butane diol, propylene glycol, 1,3-propane diol, and ethylene glycol.

The amount of the first component reactant used for the reaction is in the range from about 5 to 50 weight %. Preferred is from about 10 to 40 weight %, and most preferred is from about 15 to 35 weight %; all percentages being based on the total weight of the reactants.

The amount of hydroxylated compound used for the reaction in the present invention is in the range from about 5 to 50 weight % and preferably, from about 10 to 35 weight %, and most preferably, from about 15 to 30 weight % based on the total weight of the composition.

In addition, the composition may employ various additives, e.g., humectants, fillers, and the like.

Humectants are particularly useful since they serve to prevent the finally prepared element from drying out. Such humectants include non-ionic surfactants as well as certain compounds within the class of hydroxylated compounds which are useful to the second component, e.g., glycerol and polyethylene glycol. Thus, in this case, the second component may act as both a reactant and humectant.

The amount of humectant generally is in the range from about 5 to 50 weight %, preferably from about 15 to 35 weight %, and most preferably, from about 20 to 25 weight %, all weight percents being based on the total weight of the composition. Generally, the remainder of the reaction mixture is water.

The manner in which the inventive composition may be prepared is particularly advantageous. Generally, the methylvinyl ether/maleic anhydride co-polymer first component and hydroxylated compound second component, and water are reacted by admixing with stirring and heating to form a smooth paste. This reaction is generally carried out at a temperature from about 25.degree. to 95.degree. C. In a preferred embodiment, the hydroxylated compound, first component humectant (if used, and if different from the hydroxylated compound) are first mixed together with water. The mixture is warmed to a temperature in the range from about 25.degree. to 70.degree. C., preferably, from about 50.degree. to 70.degree. C., and, most preferably, about 60.degree. C., and then the methylvinyl ether/maleic anhydride copolymer first component is added with stirring. Normally, this admixing is carried out slowly, i.e., over a period of from about 15 to 20 minutes to ensure uniformity of the mixture and to form a smooth paste.

After the addition of the first component, the reaction mass is heated at a temperature and for a time period sufficient to effect completion of the reaction which it is generally evidenced by the formation of a cohesive, adhesive element. Generally the reaction is carried out at a temperature from about 70.degree. to 95.degree. C., preferably, from about 85.degree. to 95.degree. C., and most preferably, from about 90.degree. to 95.degree. C., for about 0.5 to 6 hours, preferably, from about 1 to 2 hours, and most preferably, for one hour. This heating should be carried out so as to assure a uniform temperature throughout the reaction mixture and avoid localized heating. Advantageously, the paste is placed in a mold having the desired shape of the element and the reaction is carried out in the mold thus producing a finished adhesive element having the desired shape.

Preferably, the inventive adhesive mass is formed by mixing the reactants (paste) in a flexible bag or container of a plastic film, e.g., polyethylene. The advantage is that the reaction may be formulated within the bag or enclosure, and then shaped while in the bag. The reactants in the shaped bag may be subjected to the reaction conditions and, upon cooling, the element is ready for use by removal from the bag at the time of use. Consequently, in essentially a series of simple steps, the adhesive can be formulated in a manner which allows it to be stored in its own packaging and one need only remove the mass from the packaging at the time of use.

EXAMPLES

The following are the chemical names of the trademark products used in the Examples:

Gantrez AN-119: a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 200,000 Gantrez AN-139: a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 1,000,000 Gantrez AN-169: a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 2,000,000 Antarox DM-970: dialkylnonyl phenol ethoxylate Pegol F-68: propylene oxide/ethylene oxide co-polymer with a ratio of 80/20 Pegol L-61: propylene oxide/ethylene oxide co-polymer with a ratio of 90/10 Emulphor ON-870: oleyl alcohol polyoxyethylated with 20 mols/mole of ethylene oxide Gafac LO-529: phosphate ester of ethoxylated nonylphenol Pegol 400: polyethylene glycol with a molecular weight of 400 Pegol 1450: polyethylene glycol with a molecular weight of 1450 Pegol 4000: polyethylene glycol with a molecular weight of 4000 Dextrin 30 AN 45: degraded starch Igepal CO-210: ethoxylated nonylphenol with a molecular weight of 286 Igepal CO-520: ethoxylated nonylphenol with a molecular weight of 440 Igepal CO-610: ethoxylated nonylphenol with a molecular weight of 528-572

Igepal CO-630: ethoxylated nonylphenol with a molecular weight of 616

Igepal CO-720: ethoxylated nonylphenol with a molecular weight of 748

Igepal CO-880: ethoxylated nonylphenol with a molecular weight of 1540

Igepal CO-990: ethoxylated nonylphenol with a molecular weight of 4620

Igepal CA-630: ethoxylated nonylphenol with a molecular weight of 621

The following example illustrates the invention:

A variety of samples were obtained by using different amounts of water, glycerol, surfactant, and methyl-vinyl ether/maleic anhydride co-polymer. The indicated amount of water, glycerol, and surfactant were introduced to a glass beaker which was heated in a water bath to 60.degree. C. with stirring. The methylvinyl ether/maleic anhydride copolymer was added to this mixture with stirring. After a smooth paste was formed, the mixture was placed in a polyethylene 5".times.8" freezer bag (polyethylene thickness of 35-40 micrometers).

The bag was flattened lightly between two glass plates secured with elastic bands, the bag was sealed and immersed in a water bath at a temperature of about 90.degree. to 95.degree. C. for at least one hour. After heating, the bag was removed and cooled with tap water. The mass was sampled by cutting a strip from the edge and then removing one or both sides of the attached polyethylene film to provide the adhesive test piece.

Adhesion to various surfaces was tested by applying a 1/16 inch mass formed by the above-outlined procedure to skin, glass, paper, gauze dressing, applying slight finger pressure to attach and then attempting to remove the mass as indicated.

Values assigned, i.e., good, fair poor, where judged as follows:

good--masses remain adhered to the substrate and can only be removed by peeling from said substrate by applying some force fair--same procedure but mass easily removed with little applied force poor--same procedure but mass peels from substrate with little or no applied peeling force (literally falls off the substrate of its own weight).

Table I shows the compositions of 6 different formulations produced by the above-outlined method. Table II shows the properties of each of these formulations.

As can be seen from the following examples, depending on the relative amounts and specific compounds or reactants used within the scope of the classes of components described herein in accordance with the invention, a wide variety of tack and adhesive properties can be obtained which allows the element to be tailored for a particular end use.

TABLE I______________________________________INITIAL TRIAL FORMULATIONSRaw Sample Material 1 2 3 4 5 6______________________________________Gantrez AN-119 25 -- -- -- -- --Gantrez AN-169 -- 25 20 20 25 25Glycerol -- 5 20 20 25 25Pegol F-68 -- 25 -- 20 25 --Igepal CO-720 25 -- -- -- -- --Igepal DM-970 -- -- -- -- -- 25Water 30 35 -- -- 25 25______________________________________ TABLE II__________________________________________________________________________ Adhesion to skin Adhesion Skin- Skin- After Adhesion Adhesion to removal resealFormulation Initial 4 hours to glass to paper dressing properties properties__________________________________________________________________________1 good good -- -- -- -- --2 fair poor -- -- -- -- --3 poor poor -- -- -- -- --4 poor poor -- -- -- -- --5 fair poor -- -- -- -- --6 good good -- -- -- -- --These formulations were repeated at a later date when thesuccessful formulations produced equally satisfactory results__________________________________________________________________________

Tables III and IV show the compositions and properties of a variety of samples prepared using additional hydroxyl-containing polymers and compounds.

TABLE III______________________________________ALTERNATIVE HYDROXYL COMPOUNDSA trial series was next made to investigate the suitability of other--OH containing polymers and compounds.Raw Sample Material 7 8 9 10 11 12 13 14______________________________________Gantrez AN-169 25 25 25 25 25 25 25 25Water 25 25 25 17 34 34 25 34Glycerol 25 25 25 25 25 -- -- --Igepal CO-210 25 -- -- -- -- -- -- --Igepal CO-610 -- 25 -- -- -- -- -- --Pegol L-61 -- -- 25 -- -- -- -- --Pegol 1450 -- -- -- -- -- 25 -- --Dextrin 30 AN 45 -- -- -- -- -- -- -- 25______________________________________ TABLE IV__________________________________________________________________________ Adhesion to skin Adhesion Skin- Skin- After Adhesion Adhesion to removal resealFormulation Initial 4 hours to glass to paper dressing properties properties__________________________________________________________________________ 7 fair fair good -- -- easy -- 8 good good good good good -- -- 9 fair fair good -- -- -- --10 poor poor -- -- -- -- --11 good good good good good fair --12 good good good -- -- -- --13 poor poor -- -- -- -- --14 good good good -- -- poor poor__________________________________________________________________________

Tables V and VI show yet a further variety of samples in accordance with the present invention and the properties thereof.

TABLE V__________________________________________________________________________FORMULATIONIngredients 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31__________________________________________________________________________Gantrez AN-169 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 5Gantrez AN-139 -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- --Gantrez AN-119 -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- --Glycerol 25 25 25 25 25 25 25 25 25 25 25 25 25 25 50 25 10Water 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 10Igepal CO-210 -- 25 -- -- -- -- -- -- -- -- -- -- -- -- -- -- --Igepal CO-520 -- -- 25 -- -- -- -- -- -- -- -- -- -- -- -- -- --Igepal CO-630 -- -- -- 25 -- -- -- -- -- -- -- -- -- -- -- -- 15Igepal CO-880 -- -- -- -- 25 -- -- -- -- -- -- -- -- -- -- -- --Igepal CO-990 -- -- -- -- -- 25 -- -- -- -- -- -- -- -- -- -- --Igepal CA-630 -- -- -- -- -- -- 25 -- -- -- -- -- -- -- -- -- --Emulphor ON-870 -- -- -- -- -- -- -- -- 25 -- -- -- -- -- -- -- --Gafac LO-529 -- -- -- -- -- -- -- 25 -- -- -- -- -- -- -- -- --Pegol 400 -- -- -- -- -- -- -- -- -- -- -- 25 -- -- -- -- --Pegol 1450 -- -- -- -- -- -- -- -- -- -- 25 -- -- -- -- -- --Pegol 4000 -- -- -- -- -- -- -- -- -- 25 -- -- -- -- -- -- --Dextrin 30 AN 45 -- -- -- -- -- -- -- -- -- -- -- -- 25 -- -- -- --Sugar -- -- -- -- -- -- -- -- -- -- -- -- -- 25 -- -- --Propyleneglycol -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- 25 --Pegol F-68 25 -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- --Formulation 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31__________________________________________________________________________Ingredients 32 33 34 35 36 37 38 39 40 41 42 43 44__________________________________________________________________________Gantrez AN-169 6.6 13.3 15 5 6.6 13.3 15 15 15 -- -- -- --Gantrez AN-139 -- -- -- -- -- -- -- -- -- -- -- 25 25Gantrez AN-119 -- -- -- -- -- -- -- -- -- 25 25 -- --Glycerol 10 10 10 10 10 10 10 -- -- 25 25 25 25Water 10 10 10 10 10 10 10 12.5 20 25 25 25 25Igepal CO-210 -- -- -- -- -- -- -- -- -- -- -- -- --Igepal CO-520 -- -- -- -- -- -- -- -- -- -- -- -- --Igepal CO-630 13.3 6.6 5 -- -- -- -- 15 -- -- -- -- --Igepal CO-880 -- -- -- -- -- -- -- -- -- -- -- -- --Igepal CO-990 -- -- -- -- -- -- -- -- -- -- -- -- --Igepal CA-630 -- -- -- -- -- -- -- -- -- -- -- -- --Emulphor ON-870 -- -- -- -- -- -- -- -- -- -- -- -- --Gafac LO-529 -- -- -- -- -- -- -- -- -- -- -- -- --Pegol 400 -- -- -- -- -- -- -- -- -- -- -- -- --Pegol 1450 -- -- -- -- -- -- -- -- -- -- -- -- --Pegol 4000 -- -- -- -- -- -- -- -- -- -- -- -- --Dextrin 30 AN 45 -- -- -- 15 13.3 6.6 5 -- 15 -- 25 -- 25Sugar -- -- -- -- -- -- -- -- -- -- -- -- --Propyleneglycol -- -- -- -- -- -- -- -- -- -- -- -- --Pegol F-68 -- -- -- -- -- -- -- -- -- 25 -- 25 --Formulation 32 33 34 35 36 37 38 39 40 41 42 43 44__________________________________________________________________________ TABLE VI__________________________________________________________________________PROPERTIES Adhesion to skin Adhesion Skin- Skin- After Adhesion Adhesion to removal resealFormulation Initial 4 hours to glass to paper dressing properties properties__________________________________________________________________________15 Poor falls off None Good Good Poor Easy Poor16 Poor falls off None Good Poor Poor Easy None17 Good Good Good Good Good Difficult, Excellent pulls hairs18 Good Good Good Good Good Difficult, Excellent pulls hairs19 Poor None Good Good Good Easy Good20 Poor None Fair Fair Poor Easy Poor21 Good Good Good Good Good Difficult, Good22 None -- None None None -- --23 Poor None Good Good Good Easy Good24 Poor None Fair Good Fair Easy Fair25 Poor None Good Good Good Easy Good26 Fair None Good Good Poor Easy Poor27 Good None Good Good Good Fell off Good28 Good None Good Good Good Easy Good29 Good Good Good Good Good Firm/Easy Good30 Good Good Good Good Good Firm/Easy Good31 Not compatible, exudate present on surface.32 Good Good Good Good Good Strong, Good remove pulls hairs33 Good None Good Good Good Fell off Good34 Not practical formulation, too thick.35 Good Good Good Good Good Easy, but Good strong bond36 Good None Good Good Good Easy, but Good strong bond37 Good None Good Good Fair Fell off Good38 Good None Good Good Good Fell off Good39 Good; adhesion too high; not possible to remove from polyethylene!40 Good Good Good Good Good Strong Good but easy41 Good Good Good Good Good Strong Good but easy42 Good Good Good Good Good Strong Good but peels but easy43 Good None Good Good Good Easy Good44 Good Fair Good Good Good Easy Good__________________________________________________________________________

Claims

1. A method for forming a composition comprising mixing a first component of a copolymer having the formula ##STR3## wherein n is such that the average molecular weight of the copolymer is from about 2.times.10.sup.5 to 2.4.times.10.sup.6, with a second component selected from the group consisting of polyethoxylated fatty alcohols, nonyl phenols, octyl phenols, polyethylene glycol, 1,3-butane diol, 1,4-butane diol, propylene glycol, 1,3-propane diol, and ethylene glycol, wherein the amount of the first component is in the range from about 5 to 50 weight % and the amount of the second component is from about 5 to 50 weight %, based on the total weight of the composition, in the presence of water and reacting the mixture at a temperature and time period sufficient to hydrolyze or esterify the first component.

2. The method of claim 1 wherein the adhesive composition further comprises a humectant, which humectant is a compound other than the second component.

3. The method of claim 1 wherein the average molecular weight of the co-polymer is from about 1.25.times.10.sup.6 to 2.4.times.10.sup.6.

4. The method of claim 1 wherein the average weight of the co-polymer in the composition is from about 1.08.times.10.sup.6 to 1.98.times.10.sup.6.

5. A method for forming a composition by mixing a first component selected from the group consisting of polyethoxylated fatty alcohols, nonyl phenols, octyl phenols, polyethylene glycol, 1,3-butane diol, 1,4-butane diol, propylene glycol, 1,3-propane diol, and ethylene glycol, with water and maintaining said mixture at a temperature from about 25.degree. to 70.degree. C., adding a second component of a copolymer having the formula: ##STR4## wherein n is such that the average molecular weight of the copolymer is from about 2.times.10.sup.5 to 2.4.times.10.sup.6, to this mixture so as to form a uniform paste and heating the paste at a temperature of from about 70.degree. to 95.degree. C. in a mold having the desired shape of the ultimate element.

6. The method of claim 5 wherein the adhesive composition further comprises a humectant, which humectant is a compound other than the first component.

7. The method of claim 5 wherein the average molecular weight of the co-polymer is from about 1.25.times.10.sup.6 to 2.4.times.10.sup.6.

8. The method of claim 5 wherein the average weight of the co-polymer in the composition is from about 1.08.times.10.sup.6 to 1.98.times.10.sup.6.