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1. (WO1995033794) ADHESIFS SENSIBLES A LA PRESSION
Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

TITLE: PRESSURE SENSITIVE ADHESIVE

This is a continuation-in-part of Application Serial No. 08/134,924 which is a division application of U.S. Serial No. 07/977,580 now issued as U.S. Patent No. 5,274,036.
1. Field of Invention
This invention relates to novel pressure sensitive adhesive compositions formed of a combination of liquid and solid rubbers for providing adhesive properties .
2. Description of the Related Art
Pressure-sensitive adhesives are materials which have tac properties at room temperature. The pressure-sensitive adhesive firmly adheres to a variety of dissimilar surfaces without the need of more than finger or hand pressure. It is known that the adhesive should also be formed of a composition with sufficient internal strength to prevent leaving a residue of the adhesive on the application surface after the adhesive has been removed. The problems of providing excellent skin adhesion and having the ability to be applied to a variety of surfaces at a wide temperature range has persisted in conventional rubber based adhesives.
The properties of pressure sensitive adhesive depend primarily on the viscoelastic nature of the adhesive. Prior art conventional rubber based
adhesives are formed from two major ingredients:
elastic rubber and resinous tackifier. The rubber provides the elastic component and the resin the viscous component. For any given adhesive the
tackifying resin determines the viscoelastic behavior and the final properties of the adhesive and, thus, is a vital part of the adhesive. The tackifying resins constitute an important, and even essential, raw material in formulating rubber based pressure sensitive adhesives. Handbook of Adhesives. Third Edition, page 644, edited by Irving Skeist, Handbook of Pressure Sensitive Adhesive Technology. Second Edition by
Donatas Satas page 261, 527. Typically, conventional tackifiers have the criteria that the glass transition temperature (Tg) of the tackifier is higher than the Tg value of the base elastomer. Conventional tackifiers are brittle glassy solids having Tg values above room temperature, typically in the range of about 30-60°C. Typically, conventional tackifiers are present in an amount of greater than 50% by weight of the rubber components for improving tack properties.

A typical pressure-sensitive adhesive is described in U.S. Patent No. 4,335,026. In this adhesive, natural or synthetic rubber is used with a solid tackifier resin to impart to the rubber tackiness properties. The tackifier resin can be formed of a solid polyterpene or solid rosins and mixtures thereof. The solid tackifier comprises from about 30% to about 50% by weight of the total composition.
U.S Patent No. 4,037,016 describes an
adhesive composition comprising an admixture of at least one of natural and synthetic rubber with a tackifying resin containing carbon-to-carbon
unsaturation therein. The content of the resin is about 60 to about 140 parts by weight of the
composition.
U.S. Patent No. 3,402,220 describes a mixture of two rubbers having different hardness and solubility characteristics. A soft elastomeric uncured copolymer is mixed with a minor amount of a relatively hard elastomeric cured copolymer. The mixture is used for caulking or sealing of containers and is not used for pressure sensitive adhesives.
U.S. Patent No. 3,917,607 describes an adhesive composition including a blend of a
hydrogenated block copolymer, a tackifier resin
compatible with one of the polymer blocks and a high softening point resin compatible with another type of the polymer blocks. The adhesive contains between 25 to 300 parts by weight of the tackifying resin.
Of possible general relevance to the
invention are U.S. Patent Nos.: 3,484,405; 4,335,026 and 4,699,938 describing blends of rubbers and
tackifying resins.
SUMMARY OF INVENTION
Briefly described, the present invention comprises a pressure-sensitive adhesive formed of a liquid rubber and a solid rubber. Preferably, liquid rubber and solid rubber are used in a weight ratio of solid to liquid rubber of about 1:0.5 to about 1:7 by weight. The solid rubber and the liquid rubber have similar Tg values.
It has now been discovered that novel pressure sensitive adhesives can be made using rubbers only which are substantially free of the resins used in conventional adhesives. In an alternative embodiment, a minor amount of tackifier resin can be used in the adhesive of the present invention without substantially affecting the superior properties of the present invention over conventional ones. An amount of tackifier resin up to about 20 percent by weight of the rubber components can be added to the composition of the present invention to modify the adhesive
properties.
In accordance with the teachings of the invention, solid rubbers useful in forming the pressure sensitive adhesive include elastomers such as SBR natural rubber, block copolymers based on styrene butadiene, styrene isoprene, styrene ethylene-butylene and styrene ethylene propylene. Liquid rubbers useful in this invention are synthetic liquid isoprene rubber, depolymerized natural rubber, carboxy1 terminated synthetic liquid isoprene-styrene rubber, hydroxyl terminated synthetic liquid isoprene rubber,
hydrogenated liquid isoprene rubber, liquid isoprene-styrene copolymer, liquid isoprene-butadiene and liquid butadiene-styrene copolymer. Additional liquid rubbers useful in forming the pressure sensitive adhesive of the present invention are liquid polybutadiene, liquid hydrogenated butadiene, liquid styrene-ethylene-butylene and liquid styrene-ethylene-propylene.
It has also been discovered that the addition of an endblock phase associating resin which is defined as a reinforcing resin to the solid rubber block copolymer and liquid rubber composition provides improved hold properties without affecting the tack. The reinforcing resin is not a tackifying resin.

The pressure sensitive adhesives of the present invention can be substantially resin free or can contain a minor amount of tackifier resin.
Superior results have been obtained for human skin applications and for general applications including cold weather and oily surface applications.
Preferably, the adhesives can be coated by a hot melt process on a substrate without employing a solvent. Improved results and a reduction of
manufacturing costs have been obtained by using a solvent-less process for applying the coating.

DETAILED DESCRIPTION OF THE INVENTION
In accordance with the principals of this invention, pressure sensitive adhesives having improved characteristics are formed by combining a solid rubber and a liquid rubber. It is known that solid rubber alone is not tacky enough to produce pressure sensitive adhesions. It has now been found that the addition of liquid rubber imparts to the solid rubber a degree of adhesiveness and tackiness which was conventionally achieved by the addition of substantial amounts of tackifying resins.
A pressure sensitive adhesive is formed by adding together a liquid rubber and a solid rubber in a weight ratio of about 1:0.5 to about 1:7 by weight of solid rubber to liquid rubber. The amount of liquid rubber used is varied for the desired degree of adhesiveness and tackiness of the pressure sensitive adhesive. Most preferably, a weight ratio of about 1:1.0 to about 1:4.0 by weight of solid rubber to liquid rubber is used for adhesion to skin.
Solid rubbers useful in practice of this invention include conventional diene elastomers such as natural rubber, neoprene, and block co-polymers based on styrene-butadiene, styrene-isoprene, styrene
ethylene-butylene or styrene ethylene propylene. Also, a low styrene synthetic copolymer of butadiene and styrene, commonly called SBR, can be used as a solid rubber.
The thermoplastic elastomeric component may consist essentially of linear or radial A-B-A block copolymers or mixtures of these A-B-A block copolymers with simple A-B block copolymers. However, the
proportion of A-B block copolymers in the mixture of A-B-A and A-B block copolymers should not exceed about 90% by weight and lower percentages normally would be used. Elastomeric components useful for practice of the present invention are described in U.S. Patent No. 4,662,874 which is hereby incorporated by reference.
The A-B-A block copolymers are of the type which consist of A-blocks (end blocks) derived, i.e., polymerized or copolymerized, from styrene or styrene homologs; and B-blocks (center blocks) derived from conjugated dienes, such as isoprene or butadiene, or from lower alkenes, such as ethylene and butylene.
Small proportions of other monomers also may enter into the block copolymers themselves. The individual A-blocks have a number average molecular weight of at least about 6,000, preferably in the range of about 8,000-30,000, and the A-blocks constitute about 5-50 percent, preferably about 10-30 percent, by weight of the block copolymer. The number average molecular weight of the B-blocks for linear A-B-A block
copolymers preferably is in the range of about 45,000-180,000 and that of the linear copolymer, itself, preferably is in the range of about 75,000-225,000.

The number average molecular weight of the radial A-B-A copolymers preferably is in the range of about 125,000-400,000. The designation A-B-A includes what are sometimes called A-B-C block copolymers wherein the end blocks are different from one another but both are derived from styrene or styrene homologs. This applies both to linear and radial block copolymers. The term "linear block copolymer" (or copolymers) includes branched A-B-A.
The radial A-B-A polymers useful in this invention are of the type described in U.S. Patent NO.

3,281,383 and conform to the following general formula: (A-B)_X1 wherein A is a thermoplastic block polymerized from styrene or styrene homologs, B is an elastomeric block derived from conjugated dienes or lower alkenes, as indicated above, X is an organic or inorganic connecting molecule with a functionality of 2-4 as described in U.S. Patent No. 3,281,383 or possibly with a higher functionality as described in the article entitled "New Rubber is Backed by Stars" appearing on page 35 of the June 11, 1975 issue of Chemical Week "n" then is a number corresponding to the functionality of X. It will be appreciated that other methods such as sequential processing and multifunctional initiation can be used to form other block polymers which can be used with the teachings of the present invention.
The A-B block copolymers useful for this invention are of the type described in U.S. Patent Nos. 3,519,585 and 3,787,531 and comprise A and B-blocks derived from the monomers described hereinbefore in connection with the A-B-A copolymers.
Liquid rubbers useful in this invention are synthetic liquid isoprene rubber, depolymerized natural rubber, carboxyl terminated synthetic liquid isoprene-styrene rubber, hydroxyl terminated synthetic liquid isoprene rubber, hydrogenated liquid isoprene rubber, liquid isoprene-styrene copolymer, liquid isoprene- butadiene and liquid butadiene-styrene copolymer.
Liquid rubbers also useful in this invention are liquid polybutadiene, liquid hydrogenated butadiene, liquid styrene-ethylene-butylene and liquid styrene-ethylene-propylene.
The liquid rubbers have a number average molecular weight of about 10,000 to about 75,000 and are compatible with the solid rubber used in the composition. Preferably, the liquid rubbers have a glass transition temperature of less than -50 "C, on a melt viscosity at 38 °C of between 300-15,000 poises. The liquid rubbers can be modified for improved
adhesive compatibility and for improved vulcanization properties. It will be appreciated that other liquid rubbers known in the art could be useful with the teachings of the present invention.
Pressure sensitive adhesives of the present invention can be adapted to be vulcanized or cross-linked so as to render the pressure sensitive adhesive composition more resistent to elevated temperatures and to solvents while retaining a balance of adhesion and cohesion properties enabling the composition to remain tacky and pressure sensitive. Ultraviolet, high energy radiation or heat curing with any conventional diene elastomer curing system can be used.

Other curing agents that can be used in the present invention are sulfur, peroxide, isocyanate and aluminum isopropylate. Examples of sulfur bearing accelerators are benzothiazyl disulfide, known as methyl and ethyl tuads, selenium
diethyldithiocarbamate, commercially available as Selenac, dipentamethylene thiuram hexasulfide,
commercially available as Sulfads and 4.4
dithiodiomorpholine, commercially available as Vannax A. Examples of peroxides are organic peroxides such as 2.5 bis (tert-butyl-peroxy) -2 , 5 dimethylene hexane. Preferably, an oil soluble heat reactive phenol formaldehyde resin is used as a curing agent by using about 5-40 parts of phenol formaldehyde resin with about per 100 of solid rubber. Preferably, 10-25 parts of phenol formaldehyde resin is used per 100 parts of solid rubber.
The resin curing agents mentioned above are combined with accelerators. Conventional accelerators such as zinc resinate or alkaline fillers, as disclosed in U.S. Patent No. 3,625,752, or acid accelerators, such as disclosed in U.S. Patent No. 3,231,419, can be used with the pressure sensitive adhesive and resin curing agents of the present invention. Preferably, zinc resinate is used as an accelerator and in amounts less than 40 parts to 100 of the solid rubber.

Preferably, the zinc resinate as an accelerator is added in the amount of 5 to 25 parts to 100 parts of rubber.
The pressure sensitive adhesives of this invention can include small amounts of other materials such as tackifier, antioxidants, heat stabilizers, pigments, oils, ultraviolet absorbers, and the like. Typical antioxidants are 2.5 ditertiary amyl
hydroquinone and ditertiary butyl cresol. Also, conventional heat stabilizers such as the zinc salts of alkyl dithiocarbonates can be used in the present invention. Also, the particulate mixture of this invention can include fillers such as zinc oxide, aluminum hydrate, clay, calcium carbonate, carbon black, titanium dioxide, and others.
It has surprisingly been found that the addition of endblock associating reinforcing resins which are not tackifying resins to the adhesive of the present invention provides further improved tack, adhesion and hold properties to the adhesive. The endblock associating resins predominately associate with the end blocks of the block copolymer and are substantially incompatible with the middle blocks of the block copolymer. Preferably, the block copolymer has a configuration of A-B-A with the endblocks derived from styrene or styrene homologs and the B blocks derived from isoprene, butadiene and ethylene-butylene.
The endblock associating resin is compatible with the A blocks and is substantially incompatible with the B
blocks. Preferably, the properties of the endblock 5 associating resin used in the adhesive is about 3% to
about 20% by weight of the total weight of the block
copolymer solid rubber and the liquid rubber. Most
preferably, the endblock associating resin is used in
an amount of about 5% to about 15% by weight of the

10 total rubber components. Endblock associating resins
useful in this invention are alphamethyl styrene
manufactured by Hercules as Kristalex Series, vinyl
toluene alphamethyl styrene manufactured by Hercules as
Piccotex Series, Coumarone indene resin manufactured by

15 Neville Chemical Company as Nevindene LX Series,
alkylaryl resin manufactured by Hercules as Picovax AP
Series, alkylaromatic polyindene manufactured by
Hercules as Piccovax 133 Series and polystyrene resins.
It will be appreciated that other known end block
20 associating resins could be used in the present
invention.
A minor amount of tackifier resin can be
added to the composition of the present invention
without affecting the improved properties of the
25 adhesive. Preferably, the tackifier resin can be added

« in an amount of about 3% to about 20% by weight of the total rubber components.
Tackifier resins useful for practice of the present invention are hydrocarbon resins, polyterpene resin and rosin esters. Examples of tackifier resins are synthetic tackifier resin polymerized mainly from a mixture of piperylene and isoprene and manufactured by Goodyear Tire and Rubber as Wingtack 95, a terpine resin polymer of beta pinene manufactured by Harwick Standard Chemical Company as Piccolyte S-115 and a glycerol ester of hydrogenated rosin solid by Hercules and known as Staybelite Ester #10.
The following examples are given only by way of illustration and are not intended to limit the scope of the invention in any way.
Table A gives the adhesive composition formulations for examples I-VII. In the examples, all proportions are expressed in parts per one hundred parts by weight of the solid elastomeric component unless otherwise indicated.

TABLE A
Examples

Ingredients II III IV V VI VII

Solid Rubber
Kraton 1112 100 100 100 100 Kraton D 1320
100
Kraton 1657 100 Kraton 1102 100
Liquid Rubber
Kuraray LIR 310 200 400 600 200

200
Kuraray LIR 50 300
Kuraray 290 300 Schenectady SP 1044 35 Zirex 25

Typical Skin adhesion
gm/inch 168 336 112 392 84 210 150
With respect to the foregoing examples, the following comments are made with respect to a number of ingredients listed in the examples.
The Thermoplastic solid rubbers designated as "Kraton" are offered commercially from Shell Chemical Company.
"Kraton 1112" is a linear styrene-isoprene-styrene (SIS) copolymer containing approximately 14% of styrene and with approximately 35% diblock.

"Kraton D 1320" is a branched SIS block copolymer having 10 % styrene. It is readily radiation crosslinkable .
"Kraton 1657" is a linear styrene-ethylene-butylene-styrene copolymer. It has approximately 13% styren .
"Kraton 1102" is a linear styrene-butadiene-styrene copolymer. It has approximately 28% styrene.
The thermoplastic liquid rubbers in the above examples are products of Kuraray Co. Ltd., Tokyo, Japan.
"Kuraray LIR 310" is a liquid isoprene-styrene copolymer having a molecular weight of
approximately 30000.
"Kuraray LIR 50" is a liquid isoprene polymer having a molecular weight approximately 47000.
"Kuraray LIR 290" is a liquid hydrogenated isoprene polymer having a molecular weight of
approximately 25000.
"The Schenectady SP 1044" is a heat reactive octyl phenol formaldehyde resin supplied by Schenectady Chemical Company.
"Zirex" is zinc resinate commercially
available from Arizona Chemical Company and it
functions as an accelerator to heat reactive phenolic resin cures.

A predetermined constant pressure is applied to apply the tape to skin. Typical skin adhesion is measured by peeling the adhesive away from skin at 90° at a constant speed (by a force applied to the free end of a tape) .
The pressure sensitive adhesives can be used as free films or coated on a substrate. Also, the adhesives can be made into solvent cement or applied from hotmelt.
When a substrate is used, the adhesives are coated, such as by solvent, calendar or hotmelt
processes to the substrate. Suitable substrates can be film, foil, paper, cloth, foam or the like. When the pressure sensitive adhesive is solvent coated, the solid/liquid rubber composition is solvated in a suitable solvent like toluene prior to coating, followed by evaporation of the solvent. In a hotmelt process, the liquid is heated to a temperature of about 300°F in a heated kettle. The solid rubber is stirred into the liquid until smooth. Alternatively, solid rubber can be mixed with the liquid rubber in a single or twin screw extruder. A hotmelt coating is applied via roller, slot die, spray or any other convenient hotmelt coating method. The hotmelt process has the advantage of being ecology safe and being solvent free.

The coated substrates described above can be slit into desired widths to form pressure sensitive adhesive tapes or bandages. Each of the adhesives possesses superior finger tack, i.e., the ability to stick to the finger when the finger is pressed against the adhesive side of the tape. In fact, the tapes exhibit superior skin adhesion when adhered to other parts of the body and in general are able to adhere to oily surfaces. Thus, they are suited for a variety of applications where adhesion is desired despite the presence of some oil on the application surface.
EXAMPLES VTII-XII
Ingredients Control
VIII IX X XI

XII
Kraton 1112 100 100 100
100
Kuraray 310 200 400 600
Natural Rubber 100

Wingtack plus 100

100
Ethanox 300 2 2 2 2

2

Skin adhesion gms/inch
5 minutes 75 420 100 140

50
24 hours 168 336 112 56

28
A demonstration of improvements obtained by the practice of the present invention is shown by a comparison of examples VIII-XII. The pressure
sensitive adhesive compositions were subject to a skin adhesion test. Prior art natural rubber resin systems Example XI and XII lose adhesion to the skin within hours after application of between 44% - 60%. Examples VIII and X shows improved adhesion to the skin over time. Example IX indicates a reduced loss of adhesion of 20%.
EXAMPLE XIII
Ingredients Tq Value °C
Kraton 1112 -60
Kraton D 1320 -60
Kraton 1657 -50
Kraton 1102 -90
Kuraray LIR 310 -63
Kuraray LIR 50 -63
Kuraray LIR 290 -59
Tackifier (+)30° - (+) 60
The above table compares the Tg values for components of the pressure sensitive adhesive to a Tg value of a conventional tackifier.
The pressure sensitive adhesive of the present invention have advantageous surface wetting properties at low temperatures. The pressure sensitive adhesives of the present invention are useful below room temperature and at temperatures below -20 °C. The use of a tackifying resin in conventional adhesives limits the adhesive use at low temperatures. The Tg of tackifying resins is from +30 °C to +60 °C. The Tg of liquid rubbers is about -55 °C. The lower range of Tg values of the present invention allows for improved performance at low temperatures.
EXAMPLE XIV
Addition of a thermoplastic triblock solid rubber, such as Kraton D 1114X which is a 100 percent triblock with 19% styrene content with a diblock liquid rubber, such as Kuraray LIR 310, exhibits exceptionally stable properties. Styrene of the diblock combines with styrene in the triblock to form a non-migratory adhesive composition. Conventional rubber/resin compositions do not exhibit this property.
EXAMPLE XV
The compositions of the present invention exhibit superior skin wetting properties. When a coated tape of the adhesive of the present invention is adhered to the skin without using pressure to apply, the coated tape exhibits superior ability to stick to the skin compared to a conventional rubber resin composition.
EXAMPLE XVI
The pressure sensitive adhesive of the present invention comprised of synthetic solid and liquid rubbers has the advantage of being colorless and odorless. Conventional tackifiers impart a
yellow/brownish discoloration to the adhesive.
EXAMPLE XVII The pressure sensitive adhesive of the
present invention comprised of synthetic solid and
liquid rubbers has the advantage of being free from
impurities. Conventional resins obtained from natural 5 sources can include impurities.
«
EXAMPLE XVIII
An adhesive formulation with a sulfur
crosslinking agent of the present invention.

10 Ingredients Parts By Weight
Kraton 1112 100
Kuraray LR 50 200
Sulfads 1
Altax 1
15 Zinc Oxide 1
Irganox 1010 1

"Sulfads" is a commercially available agent
20 supplied by R.T. Vanderbilt.
"Altax" is Benzothiazyl Disulfide manufactured by
R.T. Vanderbilt.
"Irganox 1010" is an antioxidant manufactured by
Ciba-Geigy.
25

EXAMPLE XIV

« An adhesive formulation with a peroxide
30 curing system of the present invention.

Ingredients Parti3 Bv Weight
Kraton 1112 100
Kuraray LIR 310 200
DiCup 3
Irganox 1010 1. .5
"DiCup" is a Dicumyl Peroxide supplied by

Hercules, Inc.

EXAMPLE XV
An adhesive formulation with an aluminum isopropylate curing agent.
Ingredients Parts By Weight
Kraton 1112 100
Kuraray LIR 50 200
Aluminum Iscipropylate 2
Irganox 1010 1 1
EXAMPLES XVI -- XVIII
Table B gives the adhesive formulation for examples XVI-XVIII.
Table B

I Innggrreeddiieennttss X XVVII XVII
XVIII
Kraton 1112 100 100
100
Kuraray LIR 310 100 300
500
Piccotex 120 26 30
50
Irganox 2 2
2 The adhesive composition of this invention exhibits superior finger tack and skin adhesion. The pressure sensitive adhesives can also be applied to a variety of other surfaces at a wide temperature range. The pressure sensitive adhesives can be used in health care products for skin adhesion. Also, the pressure sensitive adhesives can be used in industrial
applications in which excellent tack, adhesion and hold characteristics are desired. Superior results have also been obtained for application of the adhesive in cold weather and for application of the adhesive on an oily surface. The pressure sensitive adhesive of the present invention can also be used in a drug delivery system. In this system, a drug can be compounded into the adhesive itself, or the adhesive can be a vehicle to attach a drug reservoir to the skin. The drug migrates from or through the adhesive to the skin. The adhesive of the present invention also has the
advantage of being useful for high hold applications.
While the invention has been described with reference to the preferred embodiment, this description is not intended to be limiting. It will be appreciated by those of ordinary skill in the art that
modifications may be made without departing from the spirit and scope of the invention.