KR20070021119A - Silicone pressure sensitive adhesive and articles - Google Patents

Abstract

The present invention is directed to a pressure sensitive adhesive composition comprising an unreactive mixture of polydiorganosiloxane polyurea copolymer, diluent and silicate tackifying resin. Such compositions are useful for articles such as medical devices.

Description

SILICONE PRESSURE SENSITIVE ADHESIVE AND ARTICLES

Field of invention

The present invention is directed to a pressure sensitive adhesive composition comprising an unreactive mixture of polydiorganosiloxane polyurea copolymer, diluent and silicate tackifying resin. Such compositions are useful in articles such as medical devices.

Background of the Invention

Various compositions based on polydiorganosiloxane polyurea copolymers are disclosed.

U. S. Patent No. 5,580, 915 discloses a silicone adhesive composition having excellent rapid, peel and cohesive adhesion. Generally, the adhesive composition is a reaction mixture of silicone fluid, silicone polymer gum and silanol-containing siloxane resin comprising functional groups capable of reacting with silanol and silanol-type groups, optionally adding a solvent and a curing catalyst.

EP 0 667 382 A1 discloses silicone pressure sensitive adhesives comprising thermoplastic multi-segmented copolymers.

WO 97/40103 discloses a composition comprising a silicone fluid, a silicone-urea segmented copolymer and up to about 30% by weight silicate tackifying resin.

WO 03/052019 discloses pressure sensitive adhesives and methods, wherein the adhesive comprises a silicone tackifying resin and a polydiorganosiloxane polyurea copolymer. The adhesion of such adhesives is improved by using processing aids such as plasticizers.

Although various compositions are disclosed, the related arts have advantages in the compositions, and are particularly well suited for medical applications where adhesives adhere to the skin during use.

Summary of the Invention

In one embodiment, the invention is directed to a medical device comprising an article, such as a substrate, and a pressure sensitive adhesive composition disposed on the substrate. The adhesive composition comprises an unreactive mixture of polydiorganosiloxane polyurea copolymer, greater than 10 wt% diluent and greater than 30 wt% silicate tackifying resin.

In another embodiment, the present invention relates to an article comprising a substrate, a tie layer composition disposed on the substrate and a pressure sensitive adhesive composition disposed on the connection layer. The tie layer composition and the adhesive composition comprise a common base polymer and a common tackifying resin. The tie layer composition further comprises a reinforcing material. In certain embodiments, the linking layer comprises a polydiorganosiloxane polyurea copolymer, silicate tackifying resin, and polymer fibers.

In each embodiment of the invention, it is preferred that the diluent and resin of the adhesive do not comprise functional groups that react with the components of the adhesive. In addition, the polydiorganosiloxane polyurea copolymer is preferably substantially free of reactive end groups. The diluent is preferably a silicone fluid. Diluents are typically present in amounts ranging from about 20% to about 50% by weight. The diluent preferably has a weight average molecular weight of less than 50,000 g / mol. The content of the silicate tackifying resin is typically less than about 60% by weight. The adhesive preferably has a storage modulus at about 25 ° C. of about 1 × 10 ⁵ Pa or less. In addition, the initial peel force of the adhesive from the polypropylene is about 3 g / linear inch (2.54 cm) to 200 g / linear inch (2.54 cm).

Detailed description of the invention

The present invention relates to an adhesive composition and an article, such as a substrate and a medical device comprising a pressure sensitive adhesive disposed on the substrate. The adhesive composition comprises an unreactive mixture of one or more polydiorganosiloxane polyurea copolymers, more than 10 weight percent of one or more diluents, and more than 30 weight percent of one or more silicate tackifying resins.

Pressure sensitive adhesive (PSA) compositions are suitable to those skilled in the art for (1) strong and permanent tack, (2) subacupressure adhesion, (3) sufficient ability to remain adherent to the adherend, and (4) sufficient to be cleanly removable from the adherend. It is known to have properties including cohesive strength. Materials known to work well as PSAs are polymers designed and formulated to exhibit the necessary viscoelasticity that yields a proper balance of cohesion, peel adhesion and shear retention. Getting the right balance of these properties is not a simple process.

As used herein, medical device refers to an article comprising one or more substrates and an adhesive composition. In use, the adhesive composition is temporarily bonded to (eg, human) skin. The pressure sensitive adhesives of the present invention are transdermal drug delivery devices, as well as tapes and tabs used to hold a number of medical applications, such as tapes, bandages, dressings, drapes, bow tapes, adhesive medical devices such as sensors, electrodes and ostomy devices. Useful at The adhesive can also be used in protective and decorative face masks.

By using the appropriate type and content of the polydiorganosiloxane polyurea copolymer (s), silicate tackifying resin (s) and diluent (s) as described herein, the adhesive has a "soft" contact nature. It is felt and has a gel-like viscosity. The softness of the adhesive can be characterized as having at least some degree in certain tests. For example, softness can be specified by dynamic mechanical analysis. As an example of the adhesive composition of this invention, the storage elastic modulus (G ') in 25 degreeC is about 1 * 10 <^5> Pa or less. It is preferable that storage elastic modulus (G ') in 25 degreeC is about 1 * 10 <^4> Pa or less. The adhesive can have a storage modulus (G ′) of any integer between 1 × 10 ⁵ Pa and 1 × 10 ⁴ Pa. An advantage of the adhesive composition of the present invention is that the storage modulus exhibits a flat region at about 25 ° C. to 50 ° C., even at 100 ° C. In addition, adhesives exhibit adequate adhesion to (eg, human) skin in the case of adhesives for medical devices. Polypropylene test panels are often used to simulate adhesion to the skin. The adhesive composition preferably has a 180 ° peel adhesion to polypropylene by the test method described in the Examples below at least 3 g / linear inch (2.54 cm). Preferably the 180 ° peel adhesion to polypropylene is at least 5-10 g / linear inch (2.54 cm). The adhesive of the invention is advantageously less powerful. Thus, the 180 ° peel adhesion to polypropylene is less than 1,000 g / linear inch (2.54 inch), preferably less than 500 g / linear inch (2.54 inch) and more preferably less than 200 g / linear inch (2.54 cm) (Eg, less than 100 g / linear inch (2.54 cm)). Another advantage is that the adhesive can be applied back to the skin after removal. In addition, the adhesive can be peeled off cleanly without removing hair because of its flexibility.

The adhesive may be coated on any backing suitable for medical use, including porous and nonporous backings. The substrate (ie, backing) is preferably flexible and has a tear resistance. It is usual that the thickness of the base material is 0.0125 mm or more. In general, the thickness of the substrate is 3 mm or less. The substrate may have a basis weight of at least 5 g / m 2. In addition, it is common that a base weight is 200 g / m <2> or less.

Examples of suitable substrates include nonwoven or woven polymeric webs, polymeric films, hydrocolloids, foams, metal foils, paper and / or combinations thereof, and the like.

In certain embodiments, it is desirable to use a substrate (eg, a scrim) with open openings. The openings (ie gaps) in the porous substrate are of appropriate size and number to facilitate mechanical bonding of the adhesive and the backing. As a further advantage, such structures are typically highly breathable. Scrims typically include a plurality of warp members and a plurality of weft members that are woven or knitted together to form a scrim. The warp members extend longitudinally along the backing layer and are uniformly spaced apart from each other in the transverse direction. Weft members typically extend laterally along the backing layer at right angles to the warp members. It is also possible to use other open structures that are woven or nonwoven (eg, meltblown). In other embodiments, it is preferred to use a connecting layer between the adhesive and the backing as described below.

Examples of backing or support substrate materials include cotton, rayon, wool, hemp, jute, nylon, polyester, polyacetate, polyacrylic, alginate, ethylene-propylene-diene rubber, natural rubber, polyester, polyisobutylene Vinyl, polyamide, polystyrene, fiberglass, including polyolefins (e.g. polypropylene polyethylene, ethylene propylene copolymers and ethylene butylene copolymers), polyurethanes (including polyurethane foams), polyvinyl chloride and ethylene-vinyl acetate Papers from materials such as ceramic fibers and / or combinations thereof, various materials including natural or synthetic fibers, yarns and yarns, and the like.

In addition, the backing can provide stretch-relaxation. Stretch-relaxing refers to the nature of an adhesive article when the article is pulled from the surface, the article can be removed from the surface without leaving a significant visible residue. For example, film backings include high elasticity, including elastomeric and thermoplastic ABA block copolymers having a low rubber modulus, at least 200% below 2,000 pounds per square inch (13.8 MPa) and a longitudinal elongation at break of 50% rubber modulus. And high elastic compositions. Such a backing is described in US Pat. No. 4,024,312 to Korpman. Alternatively, the backing can be high elongation and substantially irreversible, such as those described in US Pat. No. 5,516,581 (Kreckel et al.).

The adhesive composition preferably comprises an unreactive mixture of at least one polydiorganosiloxane polyurea copolymer, at least one unreactive diluent and at least one silicate tackifying resin. In this preferred embodiment, the polydiorganosiloxane polyurea copolymer preferably comprises unreactive end groups. Unreactive mixtures are preferred because they exhibit stable adhesive properties even after aging. By stable adhesive properties it is meant to be cleanly removed from the (eg, human) skin and / or polypropylene substrate as described below without leaving sticky residue. Alternatively, for articles suitable for temporary use and with a shorter shelf life, the polydiorganosiloxane polyurea copolymer may optionally include end groups with ethylenic unsaturation.

As used herein, copolymer refers to a polymer comprising two or more different monomers, including terpolymers, quaternary copolymers, and the like. Preferred polydiorganosiloxane polyurea copolymers suitable for use in the preparation of the adhesives according to the invention are reaction products of at least one polyamine with at least one polyisocyanate and any polyfunctional chain extender such as organic amines and / or alcohols. Wherein the polyamine comprises at least one polydiorganosiloxane polyamine (preferably diamine). The molar ratio of isocyanate to amine is preferably from about 0.9: 1 to about 1.1: 1, more preferably from about 0.95: 1 to about 1.05: 1, most preferably from about 0.97: 1 to about 1.03: 1. That is, preferred polydiorganosiloxane polyurea copolymers suitable for use in the preparation of the pressure sensitive adhesives of the present invention include polydiorganosiloxane units, polyisocyanate residue units and optionally organic polyamine and / or polyol residue units. The polyisocyanate residue units and polyamine residue units preferably form less than 15% by weight, more preferably less than 5% by weight of polydiorganosiloxane polyurea copolymer. Polyisocyanate residues are polyisocyanate minus -NCO groups and polyamine residues are polyamine minus -NH ₂ groups. Polyisocyanate residues are linked to polyamine residues by urea linkages. Polyisocyanate residues are linked to polyol residues by urethane bonds. Examples of such segmented copolymers are disclosed in US Pat. No. 5,461,134 to Leir et al. And WO 96/34029, WO 96/35458 and WO 98/17726.

Preferred polydiorganosiloxane polyurea copolymers used in the preparation of the adhesives of the invention can be represented by repeating units of formula (I):

In the above formula, each R is independently an alkyl moiety (preferably containing 1 to 12 carbon atoms, which may be substituted for example with trifluoroalkyl or vinyl groups), vinyl moiety or higher alkenyl moiety ( Preferably it is represented by the formula -R ² (CH ₂ ) _a CH = CH ₂ , wherein R ² is-(CH ₂ ) _b -or-(CH ₂ ) _c CH = CH- and a is 1, 2 or 3 And b is 0, 3 or 6, c is 3, 4 or 5), a cycloalkyl moiety (preferably containing 6 to 12 carbon atoms), for example alkyl, fluoroalkyl or vinyl groups May be substituted), or an aryl moiety (preferably containing 6 to 20 carbon atoms, for example, may be substituted with an alkyl, cycloalkyl, fluoroalkyl or vinyl group), or R is fluorine-containing [US Pat. No. 5,236,997 to Fijiki, US Pat. No. 5,028,679 to Tere et al. Perfluoroalkyl groups as described above or perfluoroether-containing groups as described in US Pat. No. 4,900,474 (Terae et al.) And US Pat. No. 5,118,775 (Inomata et al.); Preferably at least 50% of the R moiety is a methyl moiety and the remainder is a monovalent alkyl or substituted alkyl moiety, alkenylene moiety, phenyl moiety, or substituted phenyl moiety having 1 to 12 carbon atoms;

Each Z is independently a multivalent moiety that is an arylene moiety, an aralkylene moiety, an alkylene moiety or a cycloalkylene moiety, each preferably having from 6 to 20 carbon atoms; Preferably Z is 2,6-tolylene, 4,4'-methylenediphenylene, 3,3'-dimethoxy-4,4'-biphenylene, tetramethyl-m-xylylene, 4, 4'-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylenecyclohexylene, 1,6-hexamethylene, 1,4-cyclohexylene, 2,2,4-trimethylhexylene and its Mixtures;

Each Y is independently a multivalent moiety that is an alkylene moiety (preferably having 1 to 10 carbon atoms), an aralkylene moiety or an arylene moiety, each preferably having 6 to 20 carbon atoms;

Each E is, independently, hydrogen, an alkyl moiety having 1 to 10 carbon atoms, phenyl, or a moiety that completes a ring structure comprising Y for forming a heterocycle;

Each A is independently oxygen or —N (G) —, wherein each G is independently a ring structure comprising hydrogen, an alkyl moiety having 1 to 10 carbon atoms, phenyl, or B to form a heterocycle To complete the part;

B is alkylene, aralkylene, cycloalkylene, phenylene, polyalkylene, polyalkylene oxide (e.g. polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polycaprolactone, polyethylene Adipate), copolymers, or mixtures thereof, or parts that complete a ring structure comprising A to form a heterocycle;

m is a number from 0 to about 1,000, preferably from 0 to about 25;

n is 1 or greater than 1 (preferably n is greater than 8); And

p is a number that is about 5 or more, preferably about 15 to about 2,000, more preferably about 70 to about 1,500, most preferably about 150 to about 1,500.

In the use of polyisocyanates when Z is a moiety with more than 2 functional groups and / or polyamine when B is a moiety with more than 2 functionalities, the structure of formula (I) is modified to reflect branching in the polymer backbone.

Different isocyanates in the reaction modify the properties of the polydiorganosiloxane polyurea copolymers in a number of ways. Diisocyanates useful in the process of the present invention can be represented by the formula:

OCN-Z-NCO

Any diisocyanate capable of reacting with a polyamine of formula III, in particular polydiorganosiloxane diamine, can be used in the present invention. Examples of such diisocyanates include aromatic diisocyanates such as 2,6-toluene diisocyanate, 2,5-toluene diisocyanate, 2,4-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, methylene Bis (o-chlorophenyl diisocyanate), methylenediphenylene-4,4'-diisocyanate, polycarbodiimide-modified methylenediphenylene diisocyanate, (4,4'-diisocyanato-3,3 ' , 5,5'-tetraethyl) diphenylmethane, 4,4'-diisocyanato-3,3'-dimethoxybiphenyl (o- dianisidine diisocyanate), 5-chloro-2,4-toluene Diisocyanates, 1-chloromethyl-2,4-diisocyanato benzene, aromatic-aliphatic diisocyanates such as m-xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, aliphatic diisocyanates such as 1, 4-diisocyanatobutane, 1,6- Diisocyanatohexane, 1,12-diisocyanatododecane, 2-methyl-1,5-diisocyanatopentane and cycloaliphatic diisocyanates such as methylenedicyclohexylene-4,4'-diisocyanate, 3- Isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 2,2,4-trimethylhexyl diisocyanate and cyclohexylene-1,4-diisocyanate and mixtures thereof; It is not limited to this.

Preferred examples of the diisocyanate include 2,6-toluene diisocyanate, methylenediphenylene-4,4'-diisocyanate, polycarbodiimide-modified methylenediphenyl diisocyanate, 4,4'-diisocyanato-3, 3'-dimethoxybiphenyl (-o- dianisidine diisocyanate), tetramethyl-m-xylylene diisocyanate, methylenedicyclohexylene-4,4'- diisocyanate, 3-isocyanatomethyl- 3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,6-diisocyanatohexane, 2,2,4-trimethylhexyl diisocyanate and cyclohexylene-1,4-diisocyanate .

The polydiorganosiloxane polyamines useful in the process of the invention are preferably diamines which can be represented by the formula:

In the above formula, each of R, Y, E and p is as defined above. In general, the number average molecular weight of the polydiorganosiloxane polyamines useful in the present invention is greater than about 700.

Preferred polydiorganosiloxane diamines (or referred to as silicone diamines) useful in the present invention are any that fall within the range of Formula III above, including those having a number average molecular weight in the range of about 5,000 to about 150,000. Polydiorganosiloxane diamines are described, for example, in US Pat. No. 3,890,269 (Martin), US Pat. No. 4,661,577 (JoLane et al.), US Pat. No. 5,026,890 (Webb et al.), US Pat. No. 5,214,119 (Leir et. al.), US Pat. No. 5,276,122 (Aoki et al.), US Pat. No. 5,461,134 (Leir et al.) and US Pat. No. 5,512,650 (Leir et al.).

Polydiorganosiloxane polyamines are commercially available from Hughes America, Inc., of Shin-Etsu Silicones of America, Inc., Arknon, Ohio, USA, and Piscataway, NJ, USA. do. Preference is given to substantially pure polydiorganosiloxane diamines prepared as disclosed in US Pat. No. 5,214,119 to Leir et al. This high purity polydiorganosiloxane diamine is a reaction carried out in two steps, based on the weight of the total content of the cyclic organosiloxane, preferably anhydrous amino alkyl functional sila in an amount of less than 0.15% by weight. It is produced from the reaction of cyclic organosilanes and bis (aminoalkyl) disiloxanes using a nolate catalyst such as tetramethylammonium-3-aminopropyldimethyl silanolate. Particularly preferred polydiorganosiloxane diamines are prepared using cesium and rubidium catalysts and are disclosed in US Pat. No. 5,512,650 to Leir et al.

Examples of polydiorganosiloxane polyamines useful in the present invention include polydimethylsiloxane diamine, polydiphenylsiloxane diamine, polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxane diamine, polydiethylsiloxane diamine, polydivinylsiloxane diamine, Polyvinylmethylsiloxane diamine, poly (5-hexenyl) methylsiloxane diamine and copolymers and mixtures thereof, and the like, but is not limited thereto.

The polydiorganosiloxane polyamine component used to prepare the polydiorganosiloxane polyurea segmented copolymers of the present invention provides a means to control the elastic modulus of elasticity of the resulting copolymer. In general, high molecular weight polydiorganosiloxane polyamines provide copolymers with low modulus, while low molecular weight polydiorganosiloxane polyamines provide polydiorganosiloxane polyurea segmented copolymers with high modulus.

When the polydiorganosiloxane polyurea segmented copolymer composition comprises any organic polyamine, such optional component provides another means of changing the elastic modulus of elasticity of the copolymer of the present invention. The type and molecular weight of the organic polyamine as well as the concentration of the organic polyamine will determine how it affects the modulus of elasticity of the polydiorganosiloxane polyurea segmented copolymer comprising these components.

Examples of organic polyamines useful in the present invention include polyoxyalkylene diamines such as D-230, D-400, D-2000, D-4000, DU-700, available from Huntsman Chemical Corporation, Salt Lake City, Utah, USA. , ED-2001 and EDR-148, polyoxyalkylene triamines such as T-3000 and T-5000 sold by Huntsman Chemical Corporation, polyalkylene diamines such as Dupont, Wilmington, Delaware, USA DYTEK A and DYTEK EP, 1,4-bis (3-aminopropyl) piperazine from Aldrich Chemical Company, Milwaukee, WI, (3,3'-diamino-N-methyl-di Propylamine) and mixtures thereof, but are not limited thereto.

The nature of the isocyanate moieties in the polydiorganosiloxane polyurea copolymer affects the stiffness and flow properties, and also affects the properties of the mixture. Isocyanate residues generated from diisocyanates such as tetramethyl-m-xylylene diisocyanate, 1,12-dodecane diisocyanate and dianisidine diisocyanate which form crystalline urea are methylenedicyclohexylene-4,4 More rigid when using polydiorganosiloxane polyurea copolymers than those prepared from '-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and m-xylylene diisocyanate It provides a mixture that can be large.

If desired, crosslinking agents can be used, for example Si-H-containing formulations can be used to crosslink the curable polydiorganosiloxane polyurea copolymers or photoinitiators can be used in free radical curable polydiorganosiloxane urea copolymers. have. In addition, there may be additional curing agents such as silicon hydride addition curing agents, peroxide curing agents and photocuring agents such as triazines. When such components are used, their content is appropriate for the intended purpose and is typically used at a concentration of about 0.1% to about 5% by weight of the total weight of the polymerizable composition. Crosslinking can also be carried out using electron beam spinning if necessary.

Alternatively, although less preferred, the polydiorganosiloxane polyurea copolymer may comprise reactive end groups. For example, the polydiorganosiloxane polyurea copolymer may have the same formula as Formula III as described above, except that it has an ultraviolet (UV) curable end group represented by Formula IV instead of a hydrogen end group:

In the above formula, X is a group having ethylenic unsaturation;

Q is a divalent linking group; And

r is an integer of 0-1.

Regardless of whether the end groups of the polydiorganosiloxane polyurea copolymer (s) are UV curable or unreactive, the polydiorganosiloxane polyurea copolymers generally have a molar ratio of diamine: diisocyanate from about 1.0: 0.95 to It is created to remain within the 1.0: 1.05 range. By the use of relatively high molecular weight diamines combined in about 1: 1 molar ratio, the resulting polydiorganosiloxane polyurea copolymers have a high molecular weight.

The adhesive of the present invention may comprise a mixture of one or more polydiorganosiloxane polyurea copolymers described above. For example, the adhesive may comprise a mixture of two polydiorganosiloxane polyurea copolymers, each having unreacted end groups, where the first copolymer has a higher molecular weight than the second copolymer. Have As another example, the adhesive may comprise a mixture of two polydiorganosiloxane polyurea copolymers, wherein the first copolymer comprises end group (s) having ethylenic unsaturation and a second airborne The coalescence includes unreactive end groups.

The polydiorganosiloxane polyurea copolymer can be produced by any of a variety of known methods including solvent-based and solvent-free methods. Examples of solvent-based methods are described in Tyagi et al., "Segmented Organosiloxane Copolymers: 2. Thermal and Mechanical Properties of Siloxane Urea Copolymers", Polymer , Vol. 25, December, 1984 and US Pat. No. 5,214,119 to Leir et al. Suitable solvents include organic solvents which are unreactive with polyisocyanates and which completely maintain the reactants and products in solution through polymerization. Common organic solvents include those that can have a combination of polar and nonpolar properties, and mixtures of polar and nonpolar solvents can be used. Examples of preferred organic solvents include polar aprotic solvents, chlorinated solvents, ethers, aromatic hydrocarbons, aliphatic hydrocarbons and alcohols. Examples thereof include heptane, toluene, xylene, methyl ethyl ketone, 2-propanol, t-butanol, tetrahydrofuran, isoamyl alcohol, chloroform, dichloromethane, dimethyl formamide and the like and combinations thereof. Examples of solvent free methods are described in WO 96/34029, WO 96/35458 and WO 98/17726.

The adhesive composition of the present invention comprises more than 30% by weight of one or more silicate tackifying resins to provide an appropriate level of adhesion to the skin. Typically the content of silicate tackifying resin is about 60% by weight or less. The content of the silicate tackifying resin is preferably 40% by weight or more. Any integer silicate tackifying resin content between the maximum and minimum values may be usefully used.

Examples of silicate tackifying resins useful in the present invention include the following structural units M (R ' ₃ SiO _1/2 units), D (R' ₂ SiO _2/2 units), T (R'SiO _3/2 units) and Q (SiO _4/2 unit) and a combination thereof. Typical examples include MQ silicone tackifying resins, MQD silicone tackifying resins and MQT silicone tackifying resins. It preferably has a number average molecular weight of about 100 to about 50,000, more preferably about 500 to about 15,000, and generally has a methyl substituent.

MQ silicone tackifying resins are copolymer silicone resins having R ′ ₃ SiO _1/2 units (“M” units) and SiO _4/2 units (“Q” units). Such resins are described, for example, in Encyclopedia of Polymer Science and Engineering , vol. 15, John Wiley & Sons, New York, (1989), pp. 265-270 and US Pat. No. 2,676,182 (Daudt et al.), US Pat. No. 3,627,851 (Brady), US Pat. No. 3,772,247 (Flannigan) and US Pat. No. 5,248,739 (Schmidt et al.). .

Certain MQ silicone tackifying resins are incorporated into the silica hydrosol capping process described in US Pat. No. 2,676,182 (Daudt et al.) As modified by US Pat. No. 3,627,851 (Brady) and US Pat. No. 3,772,247 (Flannigan). Can be generated by The method of modification of Daudt et al. Provides a solution of neutralized sodium silicate solution at a concentration of sodium silicate solution and / or a ratio of silicon-to-sodium in sodium silicate and / or generally lower than that described in Daudt et al. Limiting the time before capping. The neutralized silica hydrosol is stabilized with an alcohol such as 2-propanol and preferably capped with R ₃ SiO _1/2 siloxane units as soon as possible after neutralization. The level of silicon-bonded hydroxyl groups on the MQ resin is preferably less than about 1.5 wt%, more preferably up to about 1.2 wt%, even more preferably up to about 1.0 wt%, most preferably It is important that can be reduced to 0.8% by weight or less. This can be achieved, for example, by reacting hexamethyldisilazane with a silicone tackifying resin. This reaction can be catalyzed using, for example, trifluoroacetic acid. In addition, trimethylchlorosilane or trimethylsilylacetamide can be reacted with a silicone tackifying resin, and a catalyst is not essential in this case.

Suitable silicate tackifying resins are commercially available from suppliers such as Dow Corning, Midland, Michigan, General Electric Silicones, Waterford, NY, and Rhodia Silicones, Rock Hill, SC. Examples of particularly useful MQ silicone tackifying resins are sold under the trade names SR-545 and SR-1000, all of which are commercially available from General Electric Silicones, Waterford, NY. Such resins are generally supplied in organic solvents and can be used in the adhesives of the present invention as obtained.

The adhesive composition comprises more than 10% by weight of one or more unreactive diluents. Unreactive means that the diluent does not react with the silicate tackifying resin or polydiorganosiloxane polyurea copolymer (s) of the adhesive composition. Diluents do not react with these components during the manufacture of the adhesive, during the application of the adhesive to the substrate or under aging. Typically, the diluent is substantially free of reactive groups. Typically the content of the diluent is up to 50% by weight. The content of the silicate tackifying resin is preferably at least 20% by weight, more preferably at least 30% by weight. Any integer diluent content between the maximum and minimum can be used.

Useful unreactive diluents are miscible with the polydiorganosiloxane polyurea copolymer such that the diluents do not phase separate. Means for detecting phase separation (ie, forward) may be based on the presence of sticky residues remaining on the skin after removal of the medical device from the skin, or adhesive coated from a polypropylene test substrate (ie, further described in the Examples below). This is due to the presence of sticky residues upon removal of the substrate.

Preferred diluents typically have a number average molecular weight of at least about 150 g / mol, more preferably at least about 500 g / mol. The molecular weight of the diluent is preferably less than 100,000 g / mol, more preferably less than about 50,000 g / mol, and in certain embodiments, preferably less than about 30,000 g / mol. For content of at least about 40% by weight diluent, the molecular weight is preferably less than about 20,000 g / mol. The molecular weight of the diluent can be determined and reported by the supplier (e.g., General Electric Silicon, Waterford, NY). In certain embodiments, the molecular weight of the unreactive diluent is less than the molecular weight of the diamine used to prepare the polydiorganosiloxane polyurea copolymer.

Preferred unreactive diluents are silicone oils. Representative silicone oils include, but are not limited to, trialkylsiloxy terminated polydimethylsiloxanes, polyphenylmethylsiloxanes, polydialkylsiloxanes, as well as copolymers of such trialkylsiloxy terminated species.

Examples of other suitable diluents include hydrocarbon fluids, low molecular weight oligomers and oils. The selection of such other suitable diluents should be based on miscibility. In addition, in the case of medical devices care must be taken to select a diluent, such as mineral oil, which is not known as a skin irritant. If necessary, various combinations of diluents can be used.

The pressure sensitive adhesives of the present invention may comprise one or more additives. For example, dyes or pigments may be added as colorants; Electrically and / or thermally conductive compounds may be added such that the adhesive is conductive and / or thermally conductive or antistatic, and antioxidants and bacteriostatics may be added, UV light stabilizers and light absorbers such as hindered amines Light stabilizers (HALS) may be added to stabilize the PSA against UV degradation and to block certain UV wavelengths from passing through the article. Examples of other additives include adhesion promoters, fillers, adhesion promoters, glass or ceramic microbubbles, foamed polymer microspheres, non-foamed polymer microspheres, foaming agents, polymers and other property modifiers such as clays, flame retardants and compatibilizers. . Such additives may be used in various combinations in amounts of about 0.05% to about 3% by weight based on the total weight of the adhesive composition.

The adhesive composition may be applied to a suitable release liner or directly onto a substrate (e.g. tape backing) by a wide variety of methods including solution coating, solution spraying, hot melt coating, extrusion, coextrusion, lamination, pattern coating, etc. to produce an adhesive stack. Applicable to

Commercial liners include liners with fluorosilicone release coatings, such as the tradename “Dow Corning SYL-OFF Q2-7785” available from Dow Corning Corporation, Midland, Mich .; The trade name "X-70-029NS" sold by Shin-Etsu Silicones of America, Inc., Torrens, California, USA; Trade name “S TAKE-OFF 2402” available from Release International, Bedford Park, Illinois, USA.

Articles of the invention may comprise additional layers such as primers, barrier coatings, connecting layers and combinations thereof. Priming of the layer (s) includes a priming step, such as chemical or mechanical priming. In the case of nonporous backings that lack mechanical bonding with the backing or are inadequate, it is preferred to include a connecting layer between the pressure sensitive adhesive compositions in the backing.

The connecting layer preferably comprises the same base polymer and resin (eg, common) as the adhesive composition, and further includes a reinforcing material. Preferred reinforcements are polymer fibers. Suitable examples of polymer fibers include polyolefins (eg, polyethylene copolymers, terpolymers and quaternary copolymers; polypropylene copolymers), polyamides, polyesters, copolyesters, and the like.

The reinforcement is not significantly affected by the adhesive composition. In particular, the reinforcement is not plasticized by the diluent of the adhesive composition and therefore does not appear to have substantially reduced mechanical properties. The tie layer composition typically contains substantially no diluent. In addition, the connecting layer may comprise a diluent at a concentration significantly lower than the concentration of the adhesive. One or more reinforcing agents may be used in which the connecting layer consisting of polydiorganosiloxane polyurea copolymer (s), silicate tackifying resin (s) and polyolefin fibers is combined with an adhesive composition comprising the same polymer and resin. It is anticipated that the use of a tie layer comprising a common base polymer and resin combined may likewise be used with other types of pressure sensitive adhesive compositions (eg, thermoplastic block copolymers).

The objects and advantages of the present invention are further illustrated by the following examples, but the specific materials recited in these examples and their contents as well as other conditions and details should not be considered as unduly limiting the invention. . All contents given in tape preparation and examples are by weight unless otherwise indicated.

The components used in the examples are described in Table I below.

Abbreviation / Tradename Explanation SR-545 60% solids solution of MQ resin in toluene, sold under the trade name SR-545 by GE Silicones, Waterford, NY, USA DC 2-7066 60% solids solution of MQ resin in toluene, marketed under the trade name DC 2-7066 from Dow Coatings, Midland, Mich. DMS-T11 Silicone fluids available from Gelest Incorporated, Tully Town, PA DMS-T15 Silicone fluids available from Gelest Incorporated, Tully Town, PA DMS-T21 Silicone fluids available from Gelest Incorporated, Tully Town, PA DMS-T25 Silicone fluids available from Gelest Incorporated, Tully Town, PA DMS-T31 Silicone fluids available from Gelest Incorporated, Tully Town, PA DMS-T35 Silicone fluids available from Gelest Incorporated, Tully Town, PA DMS-T46 Silicone fluids available from Gelest Incorporated, Tully Town, PA DMS-T51 Silicone fluids available from Gelest Incorporated, Tully Town, PA H-MDI Methylenedicyclohexylene-4,4'-diisocyanate sold by Bayer, Pittsburgh, Pennsylvania, under the trade designation DESMODUR W H12MDI. IPDI Isophorone diisocyanate commercially available from Olin Chemicals Company, Stamford, Connecticut, USA POE 10 Ultra low density linear poly (ethylene-co-octene) ATTANE 4202 available from Dow Chemical Company, Midland, Michigan, USA DYTEK A Organic diamines available from DuPont, Wilmington, Delaware, USA IEM 2-isocyanatoethyl methacrylate, available from Aldrich Chemical Company, Milwaukee, WI. PDMS Diamine Prepared by the procedure described in Example 2 of US Pat. No. 5,512,650. SPU Elastomer Silicone Polyurea Elastomers Prepared as Shown in the Examples

Test method

180 ° peel adhesion

This peel adhesion test was described in ASTM D 3330-90 using a polypropylene (PP) substrate or high density polyethylene (HDPE) commercially available from Aeromat Plastics, Burnsville, Minn., Instead of the stainless steel substrate described in the test. Similar to the test method.

The adhesive coating on the aminated-polybutadiene primed polyester film of polyethylene terephthalate with a 38 μm thick PET film was cut into 1.27 cm × 15 cm strips. Each strip was then bonded to a 10 cm by 20 cm, clean, solvent-cleaned polypropylene panel by one pass on the strip using a 2 kg roller. After the bonded assembly was held at room temperature for about 1 minute, 2.3 m / min using an IMASS slip / peel tester (Model 3M90, available from Instruments Incorporated, Strongsville, OH). 90 inches / minute) or 30.5 cm / minute (12 inches / minute) were tested for 180 ° peel adhesion over a 5 second data collection time. Two samples were tested and the reported peel adhesion values were the average of the peel adhesion values from each of the two samples, and the failure mode was recorded as adhesive on PP or flocculant or adhesive on PET.

Dynamic Machine Analysis (DMA)

Storage (G ′) and loss (G ″) shear modulus was measured using a Rheometrics ARES flowmeter operating in a stress controlled oscillation mode. ARES flowmeters (available from TEI Instruments, Newcastle, Delaware, USA) included temperature control. For this purpose an 8 mm parallel plate surrounded by a forced air convection oven is provided.

Preparation of Adhesive Composition

I. Preparation of Silicone Polyurea Solution (SPU Elastomer)

In order to remove the absorbed carbon dioxide, 33,000 parts of PDMS diamine, degassed at 100 ° C. under reduced pressure, and an equimolar ratio of DYTEK A (1.86 parts) were placed in a reaction vessel. A mixture of toluene / 2-propanol (70/30 weight ratio) was added to produce a diamine mixture solution (1,693 g). The solution was then stirred at room temperature, 6.71 parts of H-MDI were added and the resulting mixture was stirred for 2 hours to yield a high molecular weight SPU elastomer solution (20% solids).

Silicone fluids having various molecular weights were used to create the adhesive compositions of the examples. The molecular weight of this fluid is shown in Table II below.

Example 1

70 parts of silicone fluid DMS-T11 and 150 parts of SPU elastomer solution (30 parts of solids) were mixed with 166.7 parts of silicone tackifier SR-545 (100 parts of solids) to produce a pressure sensitive adhesive (PSA). This PSA was diluted with 280 parts of toluene / isopropanol mixture (70/30 weight ratio) to give a PSA solution (30% solids). The PSA solution was then coated onto the PET film using a knife coater and the wet gap was adjusted to 8 mils. The coated PSA was dried at 70 ° C. for 20 minutes to make about 2 mils of PSA anhydrous film.

Example 2-7

Examples 2-7 were prepared in the same manner as in Example 1 except that silicone fluids having various molecular weights were used as shown in Table II below.

Example 8

80 parts of silicone fluid DMS-T11 and 100 parts of SPU elastomer solution (20 parts of solids) were mixed with 166.7 parts of silicone tackifier SR-545 (100 parts of solids) to produce a pressure sensitive adhesive (PSA). This PSA was diluted and coated as described in Example 1.

Example 9-13

Examples 9-13 were prepared in the same manner as in Example 8 except that silicone fluids having various molecular weights were used as described in Table II below.

Example number Silicone fluid Silicone Fluid Mw Silicone fluid (% by weight) SPU Elastomer (wt%) SR-545 solid (wt%) One DMS-T11 1,250 35 15 50 2 DMS-T15 3,780 35 15 50 3 DMS-T21 5,970 35 15 50 4 DMS-T25 17,250 35 15 50 5 DMS-T31 28,000 35 15 50 6 DMS-T35 49,350 35 15 50 7 DMS-T46 116,500 35 15 50 8 DMS-T11 1,250 40 10 50 9 DMS-T15 3,780 40 10 50 10 DMS-T21 5,970 40 10 50 11 DMS-T25 17,250 40 10 50 12 DMS-T31 28,000 40 10 50 13 DMS-T35 49,350 40 10 50

Samples were conditioned for 24 hours at 25 ° C./50% relative humidity prior to peel test. Examples 1-13 were tested for adhesive performance. The results of the peel force and failure mode obtained are shown in Table III below.

Example Peel force from PP panel (g / in) Failure Modes from PP Panels Failure mode from the skin One 13.6 adhesion Clean 2 23.2 adhesion Clean 3 24.2 adhesion Clean 4 32.2 adhesion Clean 5 35.6 adhesion Clean 6 124 Cohesion Low adhesion to the skin 7 28.8 Cohesion Very low adhesion to the skin 8 15.4 adhesion Clean 9 20.8 adhesion Clean 10 26.2 adhesion Clean 11 48.4 adhesion Clean 12 79.5 adhesion Sticky residue remaining 13 40.2 Cohesion More sticky residue

Fabrication of the connection layer

Silicone diamines were prepared by the procedure generally described in Example 2 of US Pat. No. 5,512,650, with a molecular weight of about 77,000 g / mol. This silicone diamine (14.96 parts) was placed in a glass reactor and mixed with 39.00 parts of toluene and 21.00 parts of 2-propanol. The resulting solution was then mixed with 25.00 parts of SR-545. The solution was stirred at room temperature and 0.04 parts of IPDI was added. After 6 hours, the solution was viscous. The resulting solution had a weight ratio of silicone polyurea: MQ resin of 50:50. This solution was cast on a liner and dried at room temperature to produce a solid connection layer intermediate sample.

Solid connection layer intermediate sample (225 g) for 10 minutes at 150 ° C. in a single screw extruder equipped with a 250 ml bowl mixer (C. Double U. Brabender Instruments, Inc., South Sea, New Jersey). Was hot melt mixed with 25 g of POE 10 resin to produce a homogeneous mixture. 3/4 inch marketed under the trade name "Haake Rheocord" by Hark, Karlsruhe, Germany, on a fluorinated silicone release liner sold by Roparex Inc., Bedford Park, Illinois, under the trade name "REXAM No. 20987". The connecting layer composition was hot melt coated to a thickness of 3 mils using a (1.9 cm) single screw extruder. The linking layer composition is transition coated onto the rayon nonwoven backing so that the backing is present on a medical tape sold under the trade name "Micropore" by 3M Company.

Example 14

PSA film is not PET but REXAM No. Except for coating over 20987 ", it was produced as in Example 1. The coated PSA was dried at 70 ° C. for 20 minutes to make the PSA anhydrous film approximately 2 mils thick. The dried adhesive film was then dried at room temperature. The medical tape was laminated to the tie layer / nonwoven backing structure.

Example 15 was prepared as in Example 14 except that the PSA film used was prepared as in Example 2.

Example 16 was prepared as in Example 14 except that the used PSA film was prepared as in Example 3.

Example 17 was prepared as in Example 14 except the used PSA film was prepared as in Example 4.

Example 18 was prepared as in Example 14 except the used PSA film was prepared as in Example 5.

Example 19 was prepared as in Example 14 except that the PSA film used was prepared as in Example 6.

Example 20 was prepared as in Example 14 except that the used PSA film was prepared as in Example 7.

The laminated sample was conditioned for 24 hours at 25 ° C./50% relative humidity prior to the peel test. Peel force was measured and recorded along with failure mode as reported in Table IV below.

Example Peel force from PP panel (g / in) Failure Modes from PP Panels Failure mode from the skin 14 18.1 adhesion Clean 15 26.2 adhesion Clean 16 29.3 adhesion Clean 17 32.6 adhesion Clean 18 35.8 adhesion Clean 19 128.0 Cohesion Low adhesion to the skin 20 29.0 Cohesion Very low adhesion to the skin

Example 21

Into the reaction vessel, 14,000 parts of 7.50 parts of PDMS diamine and 33,000 parts of 7.50 parts of PDMS diamine were added. After mixing, 0.23 parts of IEM was added. 1.00 parts of photoinitiator, sold under the trade name "Darocur 1173" at Specialty Chemical Corporation, Terrytown, NY, were added to this mixture. It was mixed for 2 hours, and then 35.0 parts of polydimethylsiloxane, sold under the trade name “Rhodorsil Fluid 47V-500”, from Rhodia Incorporated, Rockville, SC, was added. After mixing, 50 parts of DC 2-7066 solution was added. It was mixed for 1 hour, then cast on PET and dried in an oven at 70 ° C. for 10 minutes to produce a film of 2 mils thick on drying. The Rexham release liner was then laminated to the dried PSA, and the laminated structure was placed under UV light for 30 minutes to cure the elastomer mixture. After curing was completed, the liner was removed and the sample was tested. The test results are as follows:

The cured adhesive composition was clean and slightly sticky with a finger touch (ie 1 in grades 1-3). Peel force from polypropylene was 8 g / linear inch (2.54 cm).

Patents, patent documents, and publications cited herein are hereby incorporated by reference in their entirety, as if each were individually cited. Various modifications and variations of the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. It is to be understood that the present invention is not to be unduly limited by the illustrative embodiments and examples described herein, which are intended to be limited only by the claims set out below.

Claims (27)

materials; And Pressure sensitive adhesive composition disposed on the substrate A medical device comprising: the adhesive composition comprising an unreactive mixture of polydiorganosiloxane polyurea copolymer, greater than 10 wt% diluent and greater than 30 wt% silicate tackifying resin. The medical device of claim 1, wherein the diluent is substantially free of functional groups that react with the polydiorganosiloxane polyurea copolymer and silicate tackifying resin of the adhesive composition. The medical device of claim 1, wherein the polydiorganosiloxane polyurea copolymer is substantially free of functional end groups. The medical device of claim 1 wherein the polydiorganosiloxane polyurea copolymer comprises end groups having ethylenic unsaturation. The medical device of claim 1 wherein the diluent is a silicone fluid. The medical device of claim 1, wherein the diluent is present in an amount of at least 20% by weight of the adhesive composition. The medical device of claim 6, wherein the content of the diluent is at least 30% by weight of the adhesive composition. The medical device of claim 6, wherein the content of the diluent is less than about 50% by weight. The medical device of claim 1 wherein the diluent has a number average molecular weight of less than 50,000 g / mol. The medical device of claim 1, wherein the diluent has a number average molecular weight of about 30,000 g / mol or less. The medical device of claim 1, wherein the silicate tackifying resin is present in an amount of less than about 60% by weight. The medical device of claim 1, wherein the polydiorganosiloxane polyurea copolymer is present in an amount ranging from about 10 wt% to about 20 wt%. The medical device of claim 1, further comprising a tie layer disposed between the substrate and the adhesive. The medical device of claim 13, wherein the tie layer composition comprises the same components as the adhesive and further comprises polymer fibers. The medical device of claim 1 wherein the adhesive has a loss modulus at about 25 ° C. of 1 × 10 ⁵ Pa or less. The medical device of claim 1 wherein the adhesive has a peel force from polypropylene of at least 3 g / linear inch (2.54 cm). The medical device of claim 1, wherein the adhesive has a peel force from polypropylene of at least about 10 g / linear inch. The medical device of claim 1 wherein the adhesive has a peel force from polypropylene of less than 200 g / linear inch. The medical device of claim 1, further comprising a scrim. The medical device of claim 1, further comprising a release liner that temporarily covers the adhesive. materials; A connection layer comprising a polydiorganosiloxane polyurea copolymer, a silicate tackifying resin and a polymer fiber disposed on the substrate; And Pressure sensitive adhesive composition disposed on the connecting layer Article comprising a. The article of claim 21, wherein the pressure sensitive adhesive comprises an unreactive diluent. The article of claim 21, wherein the polymer fibers are not plasticized by the unreactive diluent of the adhesive. A pressure sensitive adhesive composition comprising an unreactive mixture of a polydiorganosiloxane polyurea copolymer, more than 10 wt% plasticizer and more than 30 wt% silicate tackifying resin. An article comprising a substrate, a connection layer composition disposed on the substrate and a pressure sensitive adhesive composition disposed on the connection layer, the connection layer comprising an adhesive composition, the connection layer composition having a common base polymer and a common An article comprising a tackifying resin of and further comprising polymer fibers. The article of claim 25, wherein the pressure sensitive adhesive composition and the tie layer composition further comprise a common diluent, wherein the concentration of the diluent is greater in the adhesive composition than in the tie layer composition. The article of claim 25, wherein the tie layer is substantially free of diluent.