WO2015195602A1

WO2015195602A1 - Stretch releasable pressure sensitive adhesive compositions and articles

Info

Publication number: WO2015195602A1
Application number: PCT/US2015/035929
Authority: WO
Inventors: Mark D. Purgett; Marie Aloshyna Ep Lesuffleur; Michael B. RUNGE; Megan P. Lehmann; Justin M. BOLTON
Original assignee: 3M Innovative Properties Company
Priority date: 2014-06-17
Filing date: 2015-06-16
Publication date: 2015-12-23
Also published as: TW201605627A; WO2015195617A1; TW201610055A

Abstract

Some embodiments herein are related to stretch releasable pressure sensitive adhesive compositions and articles. In an embodiment, a stretch releasing adhesive article is included. The article can include a backing and a first pressure sensitive adhesive composition disposed on at least a portion of a first side of the backing. The first pressure sensitive adhesive composition can include one or more hydrocarbon block copolymers and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5. In an embodiment, a stretch releasing adhesive composition is included. In an embodiment, a method of making a stretch releasing adhesive article is included. In an embodiment, a method of using a stretch releasing adhesive article is included. Other embodiments are included herein.

Description

STRETCH RELEASABLE PRESSURE SENSITIVE ADHESIVE

COMPOSITIONS AND ARTICLES

Background

Architectural coatings are used on the interior and exterior of structures such as houses, apartments and office buildings. Other terms for architectural coatings are trade-sales paints, decorative coatings, building paints, and DIY (do it yourself) paints. Architectural coatings can also include are the semi-transparent and opaque stains for wood.

To satisfy the decorative and functional needs of their users, paints for home and commercial construction are formulated in a wide range of appearances, from flat or matte o shiny high-gloss with ranges of eggshell and semi-gloss in between. Exterior architectural coatings and wood stains must be formulated to withstand the rigors of wind, rain, and direct sunlight. Interior paints are generally used in a more benign environment, but one where surface flaws are more readily noticed, and where touch-up and washability are important.

Architectural coating formulations typically include pigments, polymers, wetting agents, dispersants, solvents and numerous other additives.

Frequently, there is a desire place objects on the surface of a wall or other structural element that is coated with an architectural coating. For example, decorative objects (pictures, posters, and the like) and utilitarian objects (calendars, clocks, attachment hooks, and the like) are commonly placed on the surface of a structural element that is coated with an architectural coating. In some cases, these objects can be affixed to a surface using a mechanical element such as a nail, a tack, a screw or the like. In other cases, an adhesive composition may be used to affix these objects. Regardless, being able to affix the object and have it stay in place on the structural element is a common expectation of end users.

Summary

Embodiments herein are related to stretch releasable pressure sensitive adhesive compositions and articles. In an embodiment, a stretch releasing adhesive article is included. The article can include a backing and a first pressure sensitive adhesive composition disposed on at least a portion of a first side of the backing. The first pressure sensitive adhesive composition can include one or more hydrocarbon block copolymers and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5. The first pressure sensitive adhesive composition can have a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value. In some embodiments, the stretch releasing adhesive article has a storage modulus of about 400,000 Pa or less at 25° C, as determined by dynamic mechanical analysis. In an embodiment, a stretch releasing adhesive composition is included. The stretch releasing adhesive composition can include one or more hydrocarbon block copolymers and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5. The stretch releasing adhesive composition can have a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value and a storage modulus of about 200,000 Pa or less at 25° C, as determined by dynamic mechanical analysis.

In an embodiment, a method of making a stretch releasing adhesive article is included. One method can include disposing a first pressure sensitive adhesive composition on at least a portion of a first side of a backing. The first pressure sensitive adhesive composition can include one or more hydrocarbon block copolymers; and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5. The first pressure sensitive adhesive composition can have a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value. The first pressure sensitive adhesive composition can have a storage modulus of about 400,000 Pa or less at 25° C, as determined by dynamic mechanical analysis.

In an embodiment, a method of using a stretch releasing adhesive article is included. The method can include contacting a stretch releasing adhesive article with an adherend coated with an architectural paint. In some embodiments the architectural paint can be one having VOC less than 5 g/L. The article can include a backing and a first pressure sensitive adhesive composition disposed on at least a portion of a first side of the backing. The first pressure sensitive adhesive composition can include one or more hydrocarbon block copolymers and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5. The first pressure sensitive adhesive composition can have a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value. The first pressure sensitive adhesive composition can have a storage modulus of about 400,000 Pa or less at 25° C, as determined by dynamic mechanical analysis.

This summary is an overview of some of the teachings of the present application and is not intended to be an exclusive or exhaustive treatment of the present subject matter. Further details are found in the detailed description and appended claims. Other aspects will be apparent to persons skilled in the art upon reading and understanding the following detailed description and viewing the drawings that form a part thereof, each of which is not to be taken in a limiting sense. The scope of the present invention is defined by the appended claims and their legal equivalents.

Brief Description of the Drawings

Embodiments may be more completely understood in connection with the following drawings, in which: FIG. 1 is a schematic cross-sectional view of an adhesive article in accordance with various embodiments herein.

FIG. 2A is a graph of the rheological properties of adhesive compositions tested herein.

FIG. 2B is a graph of the rheological properties of adhesive compositions tested herein.

While embodiments herein susceptible to various modifications and alternative forms, specifics thereof have been shown by way of example and drawings, and will be described in detail. It should be understood, however, that the embodiments are not limited to the particular embodiments described. On the contrary, the intention is to cover modifications, equivalents, and alternatives falling within the spirit and scope of that described herein.

Detailed Description

The formulations of architectural coatings have changed in recent years for various purposes including, in some cases, to reduce or eliminate volatile organic compounds (VOCs) and make the coatings deliverable via a water-based vehicle. Such formulations typically contain higher amounts of non-volatile compatibility enhancing compounds such as surfactants and polymers that can associate with both the pigment and the water phase to maintain the dispersion stability of the formulation, aid in coalescence during drying, or both. In addition, recent fashion trends in architectural coatings have shifted toward more saturated color palettes, which in turn require higher pigment content and thus more dispersion stabilizers as part of the formulations. An example of this includes deep base paints formulated for more saturated colors. In some instances, deep base paints have more than 2 ounces of pigment per quart. In some instances, deep base paints have more than 2.5 ounces of pigment per quart. In some instances, deep base paints have more than 2.1 or 2.2 or 2.3 or 2.4 or 2.5 or 2.6 or 2.7 or 2.8 or 2.9 or 3.0 ounces of pigment per quart. Also, modern architectural coatings have changed, in some cases, to accommodate formulations wherein the need for a separate primer layer is eliminated such as in the case of paint and primer-in-one coatings (or "combination paint/primers"). Adequate adherence to these deep base and/or combination paint/primer paints is often either challenging or not achievable with existing adhesives/products.

As a result of these recent formulation changes, painted surfaces have been found to be a highly complex, variable and dynamic mixture of components. Surfactants, dispersants, or other additives have in some cases been found to be mobile within the solidified coating and may "bloom" to the air-coating interface. In addition, at elevated relative humidity, surface polarity of many architectural coatings has been observed to both increase and become more heterogeneous. While not intending to be bound by theory, it is believed that this increase in polarity and heterogeneity is attributable to water sorption and concomitant dispersant/additive migration. These changes can be exacerbated in coatings having increased concentrations of mobile surfactants and other hydrophilic and amphiphilic compounds. Pressure sensitive adhesive compositions disposed on tape or other backings - that is, pressure sensitive adhesive tapes - have utility in bonding to architectural coatings for numerous applications. One uniquely challenging application of pressure sensitive adhesive tapes is the field of stretch-release products and adhesives. Stretch-release applications are where a product is designed to firmly adhere an article, such as a hook (to hold a picture or an article of clothing) or other decorative or utilitarian element, to a surface (an adherend), yet remove cleanly when pulled away from the architectural surface at a low angle. The clean removal aspect is so that a tacky and/or unsightly residue is not left behind on the surface after removal of the stretch release adhesive. During the process of stretch release removal, the adhesive layer must remain adhered to the tape backing as the backing is stretched, but must release from the surface (adherend).

The adhesive-adherend interface is susceptible to water ingress, the extent of which is dictated by ambient conditions as well as the chemical makeup of the adhesive and adherend. As noted above, adherends such as the newer generation architectural coating surfaces are complex and particularly susceptible to changes in polarity as a result of changes in temperature and humidity. Changes in polarity of the adherend can cause a change in the strength of the bond at the adhesive-adherend interface; the bond may increase or decrease in strength with changes in polarity of the adherend. An increased bond strength may cause failure of an adhesive to release cleanly from the adherend upon demand, while decreased bond strength may cause failure of an adhesive bond, particularly under appreciable load.

As such, the surface property complexities (wherein the polarity of the coating surface is heterogeneous and varies over a wide range depending on ambient temperature and humidity) of recent architectural coatings in combination with the special requirements of stretch release applications has made it enormously challenging to find adhesive compositions that perform satisfactorily and maintain consistent adhesion across a wide array of substrates including both recent architectural coatings and more traditional architectural coatings.

Embodiments herein include stretch releasable pressure sensitive adhesive compositions and stretch releasable adhesive articles made using the same that can perform satisfactorily with regard to new generations of architectural paints and coatings. Specifically, it has been found that terpene phenolic polar tackifiers with specific attributes (as described in greater detail below) can be used to form adhesive compositions (and articles made using the same) that provide a strong bond to modern architectural paints while still providing a sufficient level of tack and allowing for clean release. This finding is remarkable because other polar tackifiers have proven to be unsuitable.

Various embodiments will now be described in detail, wherein like reference numerals represent like parts and assemblies throughout the several views. Reference to various embodiments does not limit the scope of the claims attached hereto. Additionally, any examples set forth in this specification are not intended to be limiting and merely set forth some of the many possible embodiments for the appended claims. As used herein, the term "adhesive article" means an article having a pressure sensitive adhesive disposed on at least a portion thereof. An article is regularly or irregularly shaped, and has at least a portion thereof suitably situated for disposal of a pressure sensitive adhesive thereon. In some embodiments, "suitably situated for disposal of a pressure sensitive adhesive thereon" means substantially planar.

As used herein, the term "tape", "adhesive tape", "pressure sensitive adhesive tape" or "tape article" means an adhesive article wherein the article is a tape backing.

As used herein, the term "tape backing", "backing" or "backing layer" means a substantially planar film, layer, or article having two opposing major sides defining a thickness. In some

embodiments, the backing includes a film having a thickness of about 1 μηι to 1 cm, or about 10 μηι to 5 mm, or about 25 μηι to 1 mm, or an intermediate range such as 1 μηι to 25 μηι, or 10 μηι to 1 mm, and the like. In some embodiments, the backing includes a foam layer having a thickness of about 50 μηι to 1 cm, or about 100 μηι to 5 mm, or about 250 μηι to 2 mm, or about 500 μηι to 1 mm, or any intermediate range of thickness, such as 100 μηι to 500 μηι, 250 μηι to 1 mm, and the like. In some embodiments, the backing is extensible.

As used herein, the term "foam", "foam layer" or "foam backing" means a tape backing including a solidified thermoplastic polymer, the backing having an amount of gas bubbles entrapped therein.

As used herein, the term "layer" means a substantially planar film, sheet, or coating that is rigid or flexible, elastic or inelastic. In some embodiments, a first layer may be contiguous to one or more layers contacting one or both major sides thereof and substantially bonded thereto by coextrusion, extrusion coating, solvent coating, or lamination, and the like to form a multilayer construction. In some embodiments, a second layer is formed from a portion of a first layer by chemical alteration of the surface of the first layer.

As used herein, the term "pressure sensitive adhesive" means a material that has tack, adheres with no more than finger pressure, requires no activation by any energy source, has sufficient adhesion when applied to an adherend to hold onto the adherend at the intended use angle and with the intended load, and has sufficient cohesive strength to be removed cleanly from the adherend.

As used herein, the term "tackifier" means a material that is part of a pressure sensitive adhesive as a rheological modifier to increase glass transition temperature, decrease modulus, increase tack, or a combination of two or more of these.

As used herein, the term "acid number" means the number of mg of potassium hydroxide (KOH) required to neutralize the acidic functionality present in 1 g of a tackifier compound.

As used herein, the term "hydroxyl number" means the number of mg KOH equivalent to the hydroxyl functionality present in 1 g of a tackifier compound.

As used herein, the term "adherend" means the surface to which an adhesive article is adhered by contacting the surface with a pressure sensitive adhesive disposed on the adhesive article. As used herein, the term "about" modifying, for example, the quantity of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity that can occur, for example, through typical measuring and handling procedures used for making compounds, compositions, concentrates or use formulations; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods, and like proximate considerations. The term "about" also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture. Where modified by the term "about" the claims appended hereto include equivalents to these quantities.

As used herein, the term "substantially free" with regard to a specified compound or material refers to a composition that may be free of that compound or material entirely, or may have a trace amount of that compound or material present, such as through unintended contamination or incomplete purification. A composition that has "substantially only" a provided list of components may consist of only those components, or have a trace amount of some other component present, or have one or more additional components that do not materially affect the properties of the composition. And a

"substantially planar" surface may have minor defects, or embossed features that do not materially affect the overall planarity of the film.

Polar Tackifiers

In various embodiments, the adhesive compositions include a polar tackifier, wherein the polar tackifier includes a phenolic moiety and is characterized by a hydroxyl value of between 20 and 130, in some cases between 20 and 90, in some cases between 40 and 80, in some case between 50 and 70, and in some cases between 55 and 65. The polar tackifier including a phenolic moiety can have an acid number of less than 0.5, in some cases less than 0.25, and in some cases about 0.

The phenolic moiety is an aromatic moiety having at least one hydroxyl group covalently bonded directly thereto; the simplest phenolic moiety is derived from the compound phenol (hydroxybenzene). In some embodiments, the phenolic moiety includes two or more aromatic rings bonded or fused together, either directly or through a linking group. In some embodiments the phenolic moiety has two or more hydroxyl groups bonded thereto. In some embodiments one or more additional substituents, such as alkyl groups, are present on the phenolic moiety. Blends of phenolic compounds are also suitably employed in the reactions leading to the terpene phenolic tackifiers useful in the pressure sensitive adhesives described herein.

Phenolic compounds include polyhydroxylated benzenes. Useful polyhydroxylated benzene compounds include dihydroxybenzenes and trihydroxybenzenes. Dihydroxybenzene compounds useful in reactions herein can include, in embodiments, hydroquinone (1,4-dihydroxybenzene), catechol (1,2- dihydroxybenzene), and resorcinol (1,3-dihydroxybenzene). Trihydroxybenzene compounds useful in reactions herein can include, in embodiments, phloroglucinol (1,3,5-trihydroxybenzene),

hydroxyhydroquinone (1,2,4-trihydroxybenzene), and pyrogallol (1,2,3-benzenetriol). In some embodiments, polyhydroxylated adducts of naphthalene are useful in the reactions herein; examples of such compounds include, in embodiments, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,6- dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and the like.

In some embodiments, hydroxylated and polyhydroxylated anthracene, phenanthrene, azulene, and the like are suitably employed in the reactions that form one or more terpene phenolics useful as tackifiers in the pressure sensitive adhesives herein. Bisphenols, such as bisphenol A and other compounds having non- fused multiple aromatic rings bonded via a linking group are also useful; it is not necessary for each aromatic ring to have a hydroxyl group as long as at least one aromatic ring has at least one hydroxyl group present bonded directly thereto.

Additionally, dimers, trimers, and oligomers of phenolic compounds and blends thereof are suitably employed in the reactions that form one or more terpene phenolics useful as tackifiers in the pressure sensitive adhesives herein. Such compounds include, for example, dimerized or oligomerized phenolic compounds formed via condensation with an aldehyde to result in methylene or methylol ether linking groups. Such compounds are widely used in the industry as precursors or prepolymers for phenol- formaldehyde resins. In some embodiments, both novalac and resole type precursors can be useful; however, in some such embodiments novalac precursors are preferred. In some embodiments the phenolic compound, or a blend of phenolic compounds, are pre-condensed or oligomerized. In somewhat more detail, a phenolic compound, or a combination of two or more phenolic compounds are combined with an amount of an aldehyde that is selected to provide the desired level of oligomerization, and an acidic or basic catalyst employed under conditions of mild heat, for example between 50° C and 100° C, to obtain the condensation products thereof. The oligomers thus formed have multiple reaction sites that are useful in subsequent steps in the formation of the tackifiers useful in the adhesive compositions herein, as will be readily recognized by one of skill. In some embodiments, suitable phenolic oligomers include naturally occurring oligomeric structures, such as tannic acid, humic acid, fulvic acid, and Quebracho extracts.

In some embodiments one or more additional substituents are present on one or more rings of the phenolic compounds. For example one or more alkyl, ether, halogen, amino, amido, imino, carbonyl, or other substituents, or a combination of two or more thereof, may be present as substituents bonded to the aromatic ring(s) of the phenolic compounds, or present as a substituent on an alkyl or alkenyl group bonded to the aromatic ring(s) of the phenolic compounds. In many embodiments, however, the one or more additional substituents substantially exclude or completely exclude acidic or potentially acidic moieties. In some embodiments, tackifiers used in the pressure sensitive adhesives are characterized by an acid number of less than about 0.5. In some embodiments, tackifiers used in the pressure sensitive adhesives herein are characterized by an acid number of less than about 0.4. In some embodiments, tackifiers used in the pressure sensitive adhesives are characterized by an acid number of less than about 0.3. In some embodiments, tackifiers used in the pressure sensitive adhesives are characterized by an acid number of less than about 0.25. In some embodiments, tackifiers used in the pressure sensitive adhesives are characterized by an acid number of less than about 0.2. In some embodiments, tackifiers used in the pressure sensitive adhesives are characterized by an acid number of less than about 0.1. In some embodiments, tackifiers used in the pressure sensitive adhesives herein are characterized by an acid number of about 0.

In some embodiments, carboxylate, sulfonate, phosphonate, and other groups are excluded from the group of additional substituents that may be present in any moiety bonded to the tackifiers useful in the pressure sensitive adhesives herein. Examples of suitable phenolic compounds having one or more additional substituents present thereon include various isomers of hydroxytoluene, orcinol (3,5- dihydroxytoluene) and 2,5-dimethyl resorcinol.

In some embodiments, phenolic compounds having more than one hydroxyl group, more than one aromatic group, and one or more additional substituents are suitably employed in the reactions that form one or more tackifiers that are useful in the pressure sensitive adhesives herein. Some examples of such compounds include 4,4'-((lE)-l-penten-4-yne- l,5-diyl)biscatechol, quercetin (2-(3,4-dihydroxyphenyl)- 3,5,7-trihydroxychromen-4-one), myricetin (3,5,7-trihydroxy-2-(3,4,5-trihydroxyphenyl)chromen-4-one), theaflavin (l,8-bis(3-alpha,5,7-trihydroxy-2-alpha-chromanyl)-5H-benzocyclohepten-5-one) and gossypol (7-(8-formyl-l,6,7-trihydroxy-3-methyl-5-propan-2-ylnaphthalen-2-yl)-2,3,8-trihydroxy-6-methyl-4- propan-2-ylnaphthalene- 1 -carbaldehyde).

Blends of two or more of any of the phenolic compounds described herein are useful in various embodiments to form the tackifiers useful in the pressure sensitive adhesive compositions herein. The use of any of the above alone or in combination is not particularly limited; rather, the selection and use thereof is suitably adjusted to result in the desired end product useful in one or more adhesive

compositions described herein or others that will be envisioned by one of skill.

The phenolic compounds as described above can be reacted with alkenyl compounds having at least 10 carbons, and no acidic moieties, to form the polar tackifiers useful in the adhesive compositions herein. The alkenyl compounds can be linear, branched, cyclic, or a combination thereof, and contain one or more unsaturated moieties that are reactive with a phenolic compound when catalyzed by an acid. One class of such alkenyl compounds is the terpenes. Terpenes are a class of hydrocarbons occurring widely in plants and animals, although synthetic versions are both available and useful herein. Empirically the terpenes are dimers, trimers, and higher oligomers of isoprene, or 2-methyl-l,3-butadiene. Isoprene has the formula CH2=C(CH3)-CH=CH2, or (CsHs); terpene compounds have the formula (CsH8)n where n is 2 or more. Terpenes can include one or more cyclic moieties. Terpenes are generally referred to in accordance with the number of isoprene units in the molecule: monoterpenes (CioHie) contain two isoprene units; sesquiterpenes (C15H24), three; diterpenes (C20H32), four; triterpenes (C30H48), six; and tetraterpenes (C40H64), eight. Monoterpenes, sesquiterpenes, and diterpenes are abundant in the essential oils of plants. Monoterpenes include a-pinene, its isomers β-pinene and γ-pinene, linalool, myrcene, limonene, carene, and camphene. Turpentine contains several monoterpenes. Sesquiterpenes include caryophyllene, zingiberene, humulene, cadinene, longifolene, cedr-8-ene, and farnesene. Diterpenes include ferruginol, cafestol, cembrene, sclarene, steviol, and taxadiene. Vitamin A is a diterpene derivative, as are the rosin acids. The triterpene squalene, obtainable from shark-liver oil, may be converted to cholesterol and many other steroids. The carotenes (α, β, γ, δ, ε, and ζ isomers, among others) are the best known tetraterpenes.

Terpene compounds are reacted with phenolic compounds to result in terpene phenolic tackifiers useful in the adhesive compositions herein. For the purposes of this disclosure, terpene phenolic tackifiers, or terpene phenolics, have at least one aromatic group bearing at least one hydroxyl group bound directly to the aromatic group; and at least one branched alkyl or alkenyl group bonded directly to an aromatic group. In some embodiments, the branched alkyl or alkenyl group is derived from an oligomer of isoprene. In some embodiments, the terpene phenolic has a single aromatic group having one or more hydroxyl groups and one or more branched alkyl or alkenyl group bonded directly thereto. In other embodiments, the terpene phenolic has more than one aromatic group having one or more hydroxyl groups and one or more branched alkyl or alkenyl group bonded directly to one or more aromatic groups.

Conventional methods are employed to make the terpene phenolic tackifiers useful in the adhesive compositions herein. Some representative methods that are useful to form terpene phenolic tackifiers include those described in US Patent Nos. 3,347,935; 3,692,844; 3,976,606; 5,457, 175; and 6, 160,083; and EP 1504074. In some embodiments, the terpene phenolic tackifiers are 1 : 1 addition products of phenolic compounds with terpene compounds. In some such embodiments, the reaction is catalyzed by acidic or acid-forming catalysts. Using limonene and phenol as exemplary reagents for illustrative purposes only, the reaction proceeds via path a or path b below, typically resulting in a mixture of products A, B, C:

B C

Compound A is an aromatic ether, while compounds B and C are modified phenolics. In many embodiments reaction path b favors formation of product C over B. Only reaction path b results in residual hydroxyl functionality. The degree of selectivity of reaction path a over reaction path b, and thus the degree of hydroxyl functionality of the final product, is one factor that determines the utility of the terpene phenolic tackifiers that are useful in the adhesive compositions herein. It is important to note that a mixture of A, B, and C type products in a tackifier is acceptable: it is the total hydroxyl content of the tackifier, measured and expressed as the hydroxyl number, that is important for the tackifiers useful in the adhesive compositions herein. Measurement of hydroxyl number is discussed below.

In the reaction scheme pictured above, it is important to note that in some embodiments the reaction does not yield only the 1 : 1 addition reaction products as pictured. In some embodiments, two or more terpenes react with one phenolic compound. In other embodiments, two or more phenolic compounds react with one terpene. In embodiments where the phenolic compound has more than one site available for reaction with a terpene compound (in the case of phenol itself, there are 3 potential reactive sites), or where the terpene has more than one site available for reaction with a phenolic compound, X:Y phenolic compound : terpene compound reaction products can arise. For example, in embodiments 3: 1, 2: 1, 1 :2, 1 :3, or other reaction product ratios arise. This is particularly true where oligomeric phenolic compounds having multiple aromatic hydroxyls are employed as the phenolic compound starting material. In such embodiments, the relative amounts of 1 : 1 , 1 :2, or other reaction products present in a reaction mixture, or in a blend formed after the reaction, may be expressed as an average phenolic:terpene reaction product ratio such as e.g. 1 : 1.5,1.7: 1, 1 : 1.02, and the like. For the purposes of the terpene phenolic tackifiers useful in the adhesive compositions herein, such ratios are not particularly limited. In some embodiments, the average phenolic:terpene reaction product ratio is between about 2: 1 and 1 :2, or between about 1.5: 1 and 1 : 1.5.

In some embodiments, terpene phenolics useful in the adhesive compositions have average molecular weights of about 200 g/mol to 3000 g/mol, or about 250 g/mol to 1500 g/mol, or about 300 g/mol to 1000 g/mol, or about 300 g/mol to 800 g/mol, or about 400 g/mol to 800 g/mol, or about 500 g/mol to 700 g/mol. In some embodiments, terpene phenolics useful in the adhesive compositions have a polydispersity of about 1 to 3, or about 1 to 2, or about 1 to 1.5. In some embodiments, terpene phenolics useful in the adhesive compositions herein can have glass transition temperatures of about 40°C to 120°C, or about 50°C to 100°C. In some embodiments, terpene phenolics useful in the adhesive compositions herein have softening points of about 80°C to 170°C, or about 125°C to 170°C, or about 125°C to 140°C.

In various embodiments, terpene phenolic tackifiers that are useful in the adhesive compositions herein include those with an acid number that is very low. By way of example, in some embodiments terpene phenolic tackifiers used herein can have an acid number of less than about 0.5. In some embodiments terpene phenolic tackifiers used herein can have an acid number of less than about 0.25. In some embodiments terpene phenolic tackifiers used herein can have an acid number of less than about 0.1. In some embodiments terpene phenolic tackifiers used herein can have an acid number of about 0. Acid number is the number of mg of potassium hydroxide (KOH) required to neutralize the acid functionality in a 1 g aliquot of the tackifier compound. Various methods are employed by the skilled practitioner to determine acid number. In one typical procedure, a known amount of the tackifier is dissolved in organic solvent is titrated with a solution of KOH of known concentration, employing phenolphthalein as a color indicator. Other acid number tests include ASTM D 974 and ASTM D664. Included in the definition of "about 0" is an acid number that is very close to 0, such as 0.05, in order to account for minimal amounts of impurities or error in the testing measurements.

The terpene phenolic tackifiers can have a hydroxyl number between about 0 (such as for a nearly pure Compound A aromatic ether type reaction product shown above) and 220. In embodiments, terpene phenolic tackifiers that are useful in the adhesive compositions herein include those with a hydroxyl number in the range of about 20 to 130, or about 20 to 90, or about 30 to 80, or about 40 to 80, or about 50 to 70 or about 55 to 65. The hydroxyl number is defined as the number of mg KOH corresponding to the hydroxyl functionality in a 1 g aliquot of the tackifier compound. Various methods are employed by the skilled practitioner to determine hydroxyl number. The most frequently described method is conversion of the sample with acetic acid anhydride in pyridine with subsequent titration of the released acetic acid (also described in ASTM D 1957-86(2001) Standard Test Method for Hydroxyl Value of Fatty Oils and Acids (Withdrawn 2007)). Also widely employed is the method according to ASTM E 1899, wherein primary and secondary hydroxyl groups are converted with toluene-4-sulfonyl-isocyanate (TSI) into an acid carbamate, which is then titrated with tetrabutylammonium hydroxide (TBAH) in a nonaqueous medium.

In many embodiments, commercially available terpene phenolics are useful in the adhesive compositions herein. Terpene phenolic tackifiers are sold, for example, by the Arizona Chemical Company of Jacksonville, FL, under the trade name SYLVARES®; by MeadWestvaco Corporation of North Charleston, SC under the trade name DERTOPHENE®; and by the Yasuhara Chemical Company, Ltd. of Fuchu City, Japan under the trade name POLYSTER®. Specific tackifiers can include, but are not limited to, SYLVARES® TP 1 15, SYLVARES® TP 96, SYLVARES® TP 2019, POLYSTER® T130, POLYSTER® T100, POLYSTER® Tl 15, and POLYSTER® T80.

It will be understood that "phenolic tackifier" includes blends of two or more such tackifiers. Blends of two or more phenolic tackifiers are useful in some embodiments of the adhesive compositions herein. In some embodiments, the blends of phenolic tackifiers include blends of tackifiers differing solely in terms of molecular weight, degree of branching, or types of terpenes and/or phenolic compounds employed as starting materials to make the phenolic tackifiers. In other embodiments, the blends of phenolic tackifiers have more than one such difference.

Pressure Sensitive Adhesive Compositions

The pressure sensitive adhesive compositions herein can include a polar tackifier, such as those described above and at least one hydrocarbon block copolymer. In embodiments, the terpene phenolic tackifiers are present in the pressure sensitive adhesive compositions herein at about 5 wt% to 80 wt% based on the total weight of the composition, or about 10 wt% to 70 wt% based on the total weight of the composition, or about 15 wt% to 70 wt% based on the total weight of the composition, or about 20 wt% to 70 wt% based on the total weight of the composition, or about 30 wt% to 60 wt% based on the total weight of the composition, or about 40 wt% to 60 wt% based on the total weight of the composition, or about 5 wt% to 50 wt% based on the total weight of the composition, or about 10 wt% to 40 wt% based on the total weight of the composition, or about 15 wt% to 30 wt% based on the total weight of the composition.

The hydrocarbon block copolymers useful in the pressure sensitive adhesive compositions herein can include block copolymers that include substantially only hydrogen and carbon atoms. In some embodiments the hydrocarbon block copolymers useful in the adhesive compositions herein include discrete blocks wherein one block is substantially free of content from another block. In other embodiments the hydrocarbon block polymers include one or more blocks having measurable or even significant content attributable to another block; in such embodiments, the hydrocarbon block copolymers are referred to as "blocky". It will be understood that where hydrocarbon block copolymers are discussed herein, the discussion relates to both discrete block copolymers and blocky copolymers unless otherwise specified. In embodiments, the hydrocarbon block copolymers useful in the adhesive compositions herein include styrene -based block copolymers. Examples of useful styrene-based block copolymers include styrene-isoprene block copolymers, styrene-ethylene block copolymers, styrene-propylene block copolymers, styrene-butadiene block copolymers, styrene-ethylene-propylene block copolymers, and styrene-ethylene-butylene block copolymers. In embodiments, the styrene based block copolymers are diblock, triblock, or higher block copolymers. In various embodiments, the styrene based block copolymers are linear, branched or radial block copolymers. In some embodiments, the styrene component in the one or more styrene block copolymers ranges from about 15 wt% to 50 wt%, or about 20 wt% to 40 wt%.

In embodiments, "hydrocarbon block copolymer" includes blends of two or more such copolymers. Blends of two or more hydrocarbon block copolymers are useful in some embodiments of the adhesive compositions herein. In some embodiments, the blends of block copolymers include blends of polymers differing solely in terms of overall molecular weight, molecular weight of one or more blocks, degree of branching, chemical makeup of blocks, number of blocks, or molecular weight of block fractions. In other embodiments, the blends of block copolymers have more than one such difference. In some embodiments, a blend of substantially linear triblock copolymer blended with a substantially linear diblock copolymer is employed in the adhesive compositions herein. In some embodiments, a useful styrene -based block copolymer is a styrene -butadiene-styrene triblock copolymer. In some embodiments, a useful styrene -based block copolymer is a styrene-butadiene diblock copolymer. In some embodiments, a useful hydrocarbon block copolymer is a blend of a styrene-butadiene- styrene triblock copolymer (SBS) and a styrene-butadiene diblock copolymer (or styrene-butadiene rubber - SBR). In some such embodiments the ratio of triblock copolymer to diblock copolymer is about 90: 10 to 50:50; or about

80:20; or about 70:30 to 60:40. In some embodiments, a useful styrene based block copolymer is a blend of radial and branched copolymers, or of radial and linear polymers.

In some embodiments, the styrene -butadiene-styrene triblock copolymer is radially branched. It will be appreciated that typically preparation of radial branched polymers involves a post-polymerization step called "coupling". Various coupling agents can be used including, but not limited to, dihalo alkanes, silicon halides, siloxanes, multifunctional epoxides, silica compounds, esters of monohydric alcohols with carboxylic acids, (e.g., dimethyl adipate) and epoxidized oils. Exemplary SBS radial polymers made with silicon containing coupling agents can include, but are not limited to, DYNASOL® 41 1 or DYNASOL® 416. Exemplary SBS radial polymer having carbon-carbon bonds connecting the arms can include, but are not limited to, KRATON® D 1 184K and KRATON® D 1 116.

Commercially supplied hydrocarbon block copolymers useful in the pressure sensitive adhesive compositions herein include hydrocarbon block copolymers manufactured by Abbott Rubber Company, Inc. of Elk Grove Village, IL; National Rubber Corporation of Bethel Park, PA; GCP Industrial Products of Kitchener, Ontario, Canada; Seal Methods Inc. of Santa Fe Springs, CA; Newline Rubber Company of San Martin, CA; Jackson Flexible Products, Inc. of Jackson, MI; and STYRON® LLC of Berwyn, PA.

Particularly useful in some embodiments are styrene-butadiene block copolymers manufactured by Total S.A. of Paris, France under the trade name FINAPRENE® and Dynasol Elastomers of Houston, TX under the trade name SOLPRENE®.

The total amount of block copolymer included in the pressure sensitive adhesive compositions herein ranges from about 20 wt% to 90 wt% based on the total weight of the composition, or about 25 wt% to 80 wt% based on the total weight of the composition, or about 30 wt% to 70 wt% based on the total weight of the composition, or about 40 wt% to 60 wt% based on the total weight of the composition.

In some embodiments, the adhesive compositions herein further include a non-polar tackifier. As defined herein, "non-polar tackifier" means a compound or mixture of compounds that function as tackifiers in an adhesive composition of the embodiments herein and do not include polar groups. While not being particularly limited otherwise, the non-polar tackifiers generally have a softening point between about 100°C and 135°C, or about 1 10°C to 120°C, and are compatible in mixtures with styrene block copolymers. In embodiments, the non-polar tackifiers are compatible in mixtures with the phenolic tackifiers. In embodiments, the non-polar tackifiers are compatible in mixtures with both a phenolic tackifier and a styrene block copolymer when these components are blended to form a pressure sensitive adhesive composition.

In embodiments, useful non-polar tackifiers include terpene tackifiers, also known as polyterpenes or terpene resins. Terpene tackifiers are dimers, trimers, higher oligomers, or polymers based on terpenes, such as monoterpenes, sesquiterpenes, diterpenes, and the like such as any of the terpenes described above. Terpene tackifiers are known to be compatible with many hydrocarbon block copolymers. In embodiments, commercially available terpene tackifiers useful in the pressure sensitive adhesive compositions herein include those manufactured by Yasuhara Chemical Company, Ltd. of Fuchu City, Japan; SUMMIT® Trade Pte Ltd. of Guangxi, China; and PINOVA® Inc. of Brunswick, GA under the trade name PICCOLYTE®. In some embodiments, styrenated terpene tackifiers are another type of non-polar tackifier useful in the pressure sensitive adhesive compositions herein. Styrenated terpenes include those sold by the Arizona Chemical Company of Jacksonville, FL. In some

embodiments, two or more non-polar tackifiers are included in the pressure sensitive adhesive compositions herein; where "non-polar tackifier" is used, it will be understood to mean one or more non- polar tackifiers.

The weight ratio of total block copolymer to total amount of tackifier in the pressure sensitive adhesive compositions herein is about 30:70 to 70:30, or about 35:65 to 65:30, or about 40:60 to 60:40, or about 50:50, or any such ratio there between, for example 35:65 to 40:60, or about 50:50 to 70:30, and the like. Where one or more non-polar tackifiers are included in the pressure sensitive adhesive compositions herein, the weight ratio of total phenolic tackifier to total non-polar tackifier is about 1 :99 to 99: 1 , or about 5:95 to 95:5, or about 10:90 to 90: 10, or about 15:85 to 85: 15, or about 20:80 to 80:20, or about

25:75 to 75:25, or about 30:70 to 70:30, or about 35:65 to 65:35, or about 40:60 to 60:40, or about 45:55 to 55:45, or about 50:50, or any ofthe ranges there between, such as 1 :99 to 5:95; or about 1 :99 to 90: 10; or about 75:25 to 55:45; or about 50:50 to 45:55, and the like.

The combined total block copolymer and total combined phenolic tackifier and non-polar tackifier, where employed, make up about 70 wt% to 100 wt% of the total weight of the adhesive compositions herein, or about 80 wt% to 98 wt% of the total weight of the adhesive compositions herein, or about 85 wt% to 95 wt% of the total weight of the adhesive compositions herein.

In some embodiments, the adhesive compositions herein include one or more additional components. The one or more additional components are, in various embodiments, a plasticizer, an anti- aging agent, an ultraviolet stabilizer, a colorant, a thermal stabilizer, an antimicrobial agent, a filler, a crosslinker, or another adjuvant or additive, and mixtures of two or more plasticizers, anti-aging agents, ultraviolet stabilizers, colorants, thermal stabilizers, antimicrobial agents, fillers, adjuvants, or additives. In some embodiments, the combined additional components make up about 0 wt% to 30 wt% of the total weight of the pressure sensitive adhesive compositions herein, or about 2 wt% to 20 wt% of the total weight of the pressure sensitive adhesive compositions herein, or about 5 wt% to 15 wt% of the total weight of the adhesive compositions herein. In some embodiments, where an additional component is a plasticizer, various mineral or vegetable oils or mixtures thereof are employed.

In various embodiments, pressure sensitive adhesive compositions herein can include an antioxidant. While not intending to be bound by theory, it is believed that antioxidants can be useful to prevent oxidation reactions from affecting components of the compositions. Oxidation of components can lead to various negative effects including, but not limited, to color changes, changes in molecular weight of polymeric components, rheological changes, changes in tack, changes to release properties, and the like.

Antioxidants can include various agents including, but not limited to, phenols (including but not limited to hindered phenolics and bisphenolics), mercaptan group containing compounds (including, but not limited to thioethers, thioesters, and mercapto-benzimidazoles), di-hydroquinolines, hydroquinones, lactates, butylated paracresols, amines, unsaturated acetals, fluorophosphonites, phosphites, and blends of these. It will be appreciated that these groups are not exclusive in some cases. By way of examples, a phenolic compound could also have a mercaptan group.

Examples of phenolic antioxidants can include, but are not limited to ETHANOX® 330,

ETHANOX® 702, CYANOX® 425, CYANOX® 2246, CYANOX® 1790, ULTRANOX® 276, HOSTANOX® 03, ISONOX® 129, ISONOX® 132, NAUGARD® BHT, NAUGARD® 76 and NAUGARD® 10, NAUGARD® SP, NAUGARD® 529, TOPANOL® CA, TOPANOL® CA-SF and TOPANOL® 205, IRGANOX® 1010, IRGANOX® 1035, IRGANOX® 1076, IRGANOX® 1098, IRGANOX® 245, IRGANOX® 31 14, and IRGANOX® 565.

Examples of mercaptan group containing antioxidants can include, but are not limited to, IRGANOX® 1726 and IRGANOX® 1520 L.

Other mercaptan group containing antioxidants, in the form of thioether antioxidants, can include, but are not limited to, IRGANOX® PS800 and IRGANOX® PS802.

Other mercaptan group containing antioxidants, in the form of thioester antioxidants, can include, but are not limited to, CYANOX® LTDP, CYANOX® STDP, CYANOX® MTDP, CYANOX® 1212, and CYANOX® 71 1.

Examples of fluorophosphonite antioxidants can include, but are not limited to, ETHANOX®

398.

Examples of phosphite antioxidants can include, but are not limited to, WESTON 619,

HOSTANOX® PAR 24, WYTOX® 312 and NAUGARD® P, NAUGARD® 524, Irgafos 126, and Irgafos 168

Further examples of antioxidants can include, IRGANOX® 1330, IRGANOX® 1425,

IRGANOX® 1425 WL, IRGANOX® 245 DW, IRGANOX® 5057, IRGANOX® B 1 171, IRGANOX® B 215, IRGANOX® B 225, IRGANOX® B 501 W, IRGANOX® B 900, IRGANOX® E 201,

IRGANOX® L 06, IRGANOX® L 101 , IRGANOX® L 107, IRGANOX® L 109, IRGANOX® L 1 15, IRGANOX® L 1 18, IRGANOX® L 135, IRGANOX® L 150, IRGANOX® L 55, IRGANOX® L 57, IRGANOX® L 64, IRGANOX® L 67, IRGANOX® L 74, IRGANOX® MD-1024, IRGANOX® ML- 81 1, IRGANOX® ML-820, IRGANOX® ML-840, IRGANOX® PS 802 FL, and IRGANOX® XT 500.

In some embodiments, the antioxidant specifically has hydroxyl and/or hydroperoxide decomposing ability.

In some embodiments, the amount of the antioxidant used is greater than about 0.01 wt. %, 0.05 wt. %, 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, 0.4 wt. %, 0.5 wt. %, 1.0 wt. %, 1.5 wt. %, or greater than 2.0 wt. %. In some embodiments, the amount of the antioxidant used is less than about 5 wt. %, 4 wt. %, 3 wt. %, 2.5 wt. %, 2 wt. %, 1.5 wt. %, or 1.0 wt. %, 0.8 wt. %, or 0.5 wt. %. In some embodiments, the amount of the antioxidant used can be in a range wherein any of the preceding numbers can form the lower bound or higher bound of the range wherein the higher bound is higher than the lower bound. In some embodiments, the amount of the antioxidant can be in a range of about 0.10 wt. % to about 2.0 wt. %.

In some embodiments the pressure sensitive adhesive compositions herein have a glass transition temperature (Tg) of 15°C or less, 10°C or less, or 5°C or less as measured by dynamic mechanical analysis, and determined as the tan δ (delta) peak parameter at a frequency of lHz and a temperature ramp rate of 3°C. In some embodiments, the Tg of the composition measured using this technique is between about -30°C and about 15°C, or between about -25° C and about 15° C, or between about -25° C and about 10° C, or between about -25°C and about 0°C, or between about -20°C and about 0°C, or between about - 15°C and about 0°C, or between about - 10°C and about -5°C, or in some cases about -8°C.

In some embodiments the pressure sensitive adhesive compositions herein are further characterized by storage modulus (G') of about 400,000 Pa or less at 25°C, as measured by dynamic mechanical analysis. In some embodiments, the storage modulus (G') is about 380,000 Pa or less at 25°C. In some embodiments, the storage modulus (G') is about 360,000 Pa or less at 25°C. In some

embodiments, the storage modulus (G') is about 340,000 Pa or less at 25°C. In some embodiments, the storage modulus (G') is about 80,000 Pa or more at 25°C. In some embodiments, the storage modulus (G') is about 100,000 Pa or more at 25°C. In some embodiments, the storage modulus (G') is about 120,000 Pa or more at 25°C. For example, in some embodiments, G' of the pressure sensitive adhesive compositions herein is between about 100,000 Pa to about 400,000 Pa at 25°C, or between about 150,000 Pa to 300,000 Pa at 25°C.

It will be appreciated that many different combinations of components and their relative amounts can be used to form pressure sensitive adhesive compositions herein. However, as a non-limiting example of how the components can be used to form an exemplary composition, the following table shows a specific example of a composition in accordance with various embodiments herein.

Pressure Sensitive Adhesive Articles and Methods of Making

The adhesive composition of the embodiments herein can be disposed on at least a portion of a surface of an article to form an adhesive article. FIG. 1 shows a schematic cross-sectional view of a portion of an adhesive article 100 in accordance with various embodiments herein. The adhesive article 100 includes a backing 102, a layer of an adhesive composition 104 disposed on the back, and a release liner 106 disposed on the opposite side of the adhesive composition from the backing.

In some embodiments, the adhesive article is a tape article, or adhesive tape. A tape backing is a substantially planar film or layer having two major opposing sides defining a thickness there between and a shape defined by one or more edge portions. The shape of the tape backing defined by the one or more edge portions may be regular or irregular; regular shapes include rectilinear and curvilinear type shapes. In some embodiments tape backings are rectilinear wherein edge portions further define a length and width. The length and width of rectilinear adhesive articles is not limited and is dictated solely by the intended end use. The thickness of the tape backing is not particularly limited, however, in some embodiments, the thickness of the tape backing is between about 1 μηι and 1 cm, or between about 25 μηι and 5 mm, or between about 50 μηι and 1 mm. In some embodiments, the backing includes a film having a thickness of about 1 μηι to 1 cm, or about 10 μηι to 5 mm, or about 25 μηι to 1 mm, or an intermediate range such as 1 μηι to 25 μηι, or 10 μηι to 1 mm, and the like. In some embodiments, the backing includes a foam layer having a thickness of about 50 μηι to 1 cm, or about 100 μηι to 5 mm, or about 250 μηι to 2 mm, or about 500 μηι to 1 mm, or any intermediate range of thickness, such as 100 μηι to 500 μηι, 250 μηι to 1 mm, and the like. In some embodiments, the foam density is 0.05 g/cm³ to 0.25 g/cm³, and the backing has a thickness of about 0.2 mm to 5 mm.

The adhesive tapes of the embodiments herein include at least a tape backing and a pressure sensitive adhesive of the embodiments herein, wherein the adhesive is coated on at least a portion of one major side of the tape backing. In some embodiments, a portion of one major side of the tape backing is coated with the adhesive composition of the embodiments herein. In other embodiments, portions of both major sides of the tape backing are coated with an adhesive composition, wherein the adhesives on the two major sides are the same or different compositions and at least one such adhesive composition is an adhesive composition of the embodiments herein. In some embodiments, a portion of a first major side of a tape backing is coated with an adhesive composition of the embodiments herein and a portion of a second major side of the tape backing is coated with a second pressure sensitive adhesive, wherein the second pressure sensitive adhesive is not an adhesive composition of the invention. In some

embodiments, a portion of a first major side of a tape backing is coated with a pressure adhesive composition of the embodiments herein and a portion of a second major side of the tape backing is also coated with a pressure adhesive composition of the embodiments herein. In some such embodiments, the first and second major sides of the tape backing are coated with the same pressure adhesive composition of the invention; in other such embodiments, the first and second major sides of the tape backing are coated with the different pressure sensitive adhesive compositions herein, wherein the differences include coating thickness, chemical composition, or both.

In embodiments where a second major side of the tape backing is coated with a second pressure sensitive adhesive, the composition of the second pressure sensitive adhesive is not particularly limited and is dictated by the intended end use. Representative examples of compositions suitable for the second layer of pressure sensitive adhesive include the pressure sensitive adhesive compositions described in U.S. Patent Nos. 6,569,521 ; 6,403,206; 6,231,962; and 5,516,581, all of which are incorporated herein by reference in their entirety. The second pressure sensitive adhesive is disposed on the tape backing using any suitable means for the adhesive selected, and is disposed at any suitable thickness as dictated by the intended end use of the adhesive article. In embodiments, the pressure sensitive adhesive compositions herein are coated and/or laminated onto the tape backing to form a coated layer disposed on one or more portions of one or more major surfaces thereon. In embodiments, the adhesive compositions herein are blended in a solvent or mixture of solvents to form a solution or dispersion of the adhesive components therein, and the blend is coated onto a liner or a major side of a tape backing; coating is followed by removal of the solvent or mixture thereof. In embodiments, the adhesive components are blended in the solvent until they appear to form a homogeneous blend; the blend is coated onto the liner or tape backing using conventional solvent coating techniques such as knife coating, die coating, bar coating, slot coating, brush coating, dip coating, spray coating, and the like. After coating, the solvent is removed to result in an adhesive layer. In some embodiments, heat, forced air, or both are employed to remove the solvent. After drying, in embodiments where the adhesive layer is coated on a liner, the liner can then be laminated to the tape backing; in some such embodiments, the laminating includes addition of pressure, heat, or both. In some embodiments, the thickness of the adhesive layer is about 1 μηι to 1 mm thick, or about 10 μηι to 500 μηι thick, or about 15 μηι to 250 μηι thick, or about 25 μηι to 100 μηι thick. In some embodiments, the pressure sensitive adhesive compositions herein are coated at about 1 wt% to 90 wt% solids in the solvent or solvent mixture, or about 10 wt% to 80 wt% solids in the solvent or solvent mixture, or about 20 wt% to 70 wt% solids in the solvent or solvent mixture, or about 30 wt% to 60 wt% solids in the solvent or solvent mixture. In embodiments, suitable solvents for mixing and coating the pressure sensitive adhesive compositions herein include aromatic, aliphatic, cycloaliphatic, and aralkyl compounds, as well as ketones, aldehydes, alcohols, or esters that are liquids at least between about 20°C to 85°C and dissolve or disperse the components of the pressure sensitive adhesive composition sufficiently to form a suitably homogeneous coating on the adhesive article at the targeted coating temperature. In some embodiments, heptane, cyclohexane, benzene, toluene, xylene, naphthalene, acetone, methyl ethyl ketone, acetaldehyde, propionaldehyde, ethyl acetate, isopropyl alcohol, butyl alcohol, and the like, and mixtures thereof, are suitable coating solvents.

After removal of solvent, the pressure sensitive adhesive composition of the embodiments herein is a substantially planar coated layer disposed on one or more portions of one or more major sides of a backing. In embodiments, the thickness of the pressure sensitive adhesive layer is about 1 μηι to 1 mm thick, or about 10 μηι to 500 μηι thick, or about 25 μηι to 300 μηι thick, or about 25 μηι to 200 μηι thick, or about 25 μηι to 100 μηι thick. In some embodiments, the layer of pressure sensitive adhesive composition is substantially continuous. In other embodiments, the layer of pressure sensitive adhesive composition is discontinuous. In some such embodiments, the layer is present as e.g., dots or stripes. In some such embodiments the discontinuous coating is present as a pattern or is randomly distributed throughout on the coated backing surface.

In some embodiments, the backing included in the adhesive article of the embodiments herein is a single layered backing; in other embodiments it is a multilayered backing. A single layered backing is formed from a single polymer, or a mixture of two more types of polymers, or a mixture of one or more polymers and one or more additional materials such as, for example, fillers, crosslinkers, colorants, stabilizers, or adjuvants. Where a backing is multilayered, each layer is formed from a single polymer, or a mixture of two more types of polymers, or a mixture of one or more polymers and additional materials such as, for example, fillers, crosslinkers, colorants, stabilizers, or adjuvants. In embodiments a single layered backing or one or more layers of a multilayered backing are porous, microporous, perforated, or a combination thereof. The relative thicknesses of the layers are not limited and are dictated in some embodiments by functionality. For example, in some embodiments the surface of a film is treated by flame treatment, air corona treatment, nitrogen corona treatment, or some other surface treatment to impart better adhesion of the pressure sensitive adhesive layer when coated thereon. In such

embodiments, the adhesive backing has a single-molecular layer or near single-molecular layer on the surface thereof corresponding to the flame treated material. In other embodiments, a layer of primer is coated from a liquid composition to form a dried layer less than 1 μηι thick on the surface of the adhesive backing, or in some embodiments 1 to 10 μηι thick; the primer is a material that improves adhesion of the pressure sensitive adhesive layer to the adhesive backing. In still other embodiments, the adhesive backing is extrusion coated or coextruded with one or more additional layers of resin to impart interlayer adhesion; such layers are often referred to as "tie layers." Tie layers are layers containing material that has acceptable interlayer adhesion to both the layer onto which it is deposited and the layer that is deposited on top of it; such tie layers provide sufficient interlayer adhesion for the selected application. A tie layer is present, in some embodiments, between coextruded layers of the backing; in other embodiments, the tie layer is extruded onto an exposed surface and provides adhesion between the pressure sensitive adhesive and the backing. Multilayered films are coextruded, laminated, or otherwise assembled to form a cohesive composite adhesive backing.

Suitable tape single layer and multilayer adhesive backings can be formed from a variety of thermoplastic polymers. Representative examples of suitable thermoplastic polymers include polyolefins such as polyethylene, polypropylene, polybutylene, ethylene-propylene copolymers, linear low-density polyethylene, high density polyethylene, ultrahigh density polyethylene, and the like; polyvinyl chloride, polyvinyl acetate, ethylene/acrylate copolymers, ethylene/methacrylate copolymers, ethylene/vinyl acetate copolymers, acrylonitrile/butadiene/styrene copolymers, polyurethanes, polyamides, polyamides, polyesters, polycarbonates, as well as mixtures and copolymers thereof. In some embodiments, a natural material such as paper is employed to form a suitable adhesive backing; composites or mixtures of paper and one or more thermoplastics are employed in some embodiments to form an adhesive backing suitable for use with the pressure sensitive adhesives of the embodiments herein. In some embodiments, a particularly useful adhesive backing film includes ethylene -vinyl acetate copolymer.

The adhesive articles of the embodiments herein are useful to adhere to an adherend. In some embodiments, the adhesive article is a stretch release adhesive article. Stretch release tapes are those that adhere to the adherend with a selected load applied to the article, for a selected period of time, and then release cleanly from the adherend by stretching the tape. The adhesive backing of a stretch release tape exhibits an elongation at break that is sufficiently high such that the backing is not ruptured prior to removal of the adhesive article from the adherend surface. In such adhesive articles, the adhesive backing must be capable of reaching at least about 50% elongation without breaking, such as about 50% to 1200% elongation, or about 100% to 1000% elongation, or about 100% to 600% elongation without breaking. In some embodiments, the backing has a tensile strength at break sufficiently high so that the backing will not rupture prior to being stretched and removed from an adherend at an angle of 35° or less. In some embodiments the adhesive backing has a Young's modulus of about 1000 pounds per square inch (PSI) (6894.7 kPa) to 72,500 PSI (499,865.8 kPa), or about 2500 PSI (17,236.8 kPa) to 50,000 psi (499,865.8 kPa), or about 3000 PSI (20,684.1 kPa) to 30,000 PSI (206,841 kPa), or about 5000 PSI (34,473.5 kPa) to 30,000 PSI (206,841 kPa).

In some embodiments, the article can exhibit a shear strength of greater than 7,500 minutes under conditions of a relative humidity of greater than 75% when adhered to an adherend and subjected to a load of at least 1 kg applied in a direction parallel to the surface of the adherend. In some embodiments, the article can exhibit a shear strength of greater than 10,000 minutes under conditions of a relative humidity of greater than 75% when adhered to an adherend and subjected to a load of at least 1 kg applied in a direction parallel to the surface of the adherend. In some embodiments, the article can exhibit a shear strength of greater than 15,000 minutes under conditions of a relative humidity of greater than 75% when adhered to an adherend and subjected to a load of at least 1 kg applied in a direction parallel to the surface of the adherend. In some embodiments, the article can exhibit a shear strength of greater than 20,000 minutes under conditions of a relative humidity of greater than 75% when adhered to an adherend and subjected to a load of at least 1 kg applied in a direction parallel to the surface of the adherend. In some embodiments, the article can exhibit a shear strength of greater than 25,000 minutes under conditions of a relative humidity of greater than 75% when adhered to an adherend and subjected to a load of at least 1 kg applied in a direction parallel to the surface of the adherend. In various embodiments, these shear strengths can be achieved even when the adherend is coated with an architectural paint having VOC less than 100, 50, or even less than 5 g/L.

Additionally, the stretch release tapes of the embodiments herein exhibit a relatively high initial resistance to shearing stress. When sufficient force is applied to overcome this resistance, the adhesive backing begins to yield while the adhesive elongates and releases from the adherend. The stretching angle of the stretch release pressure-sensitive adhesive articles of the embodiments herein is significantly or substantially parallel to the surface of adherend; in embodiments, the stretching angle is 35 degrees or less, less than 35 degree, 30 degrees or less, or even 10 degrees or less from the adherend surface. In some embodiments, the stretch release tapes of the embodiments herein exhibit an elastic recovery of 50% or less after being stretched, for example about 0% to 50% elastic recovery, or about 5% to 40% elastic recovery, or about 10% to 30% elastic recovery.

In embodiments, the stretch release articles (and or adhesives) of the embodiments herein can release cleanly from an adherend surface when stretched at an angle of about 35° or less from the adherend surface; that is, no visible adhesive or tape residue is visible on the adherend surface after release.

One useful type of adhesive backing for a stretch release tape is a conformable foam backing. Foam backings are particularly useful where the adhesive article will be used to adhere to an irregular surface, a textured surface, or the like. Examples of such irregular surfaces with which stretch release tapes are useful include irregularly textured interior painted wall finishes and textured vinyl wallpapers. In such applications, conformable foam backings provide the user with the ability to realize greater area of surface contact between the tape and the adherend. Useful foam adhesive backings for stretch release suitably conform to such surfaces with hand pressure. Some examples of useful foam backings for stretch release adhesive articles are described in U.S. Patent No. 6,231,962 and U.S. Patent Application No. 2008/0135159, the contents of which are incorporated herein in their entirety. In some embodiments, useful foam adhesive backings for stretch release have a density of about 0.05 g/cm³ to 0.25 g/cm³, or about 0.08 g/cm³ to 0.22 g/cm³, or about 0.12 g/cm³ to 0.20 g/cm³. In some embodiments, useful foam adhesive backings have a thickness of about 0.2 mm to 5 mm, or about 0.3 mm to 2 mm, or about 0.4 mm to 1 mm. In some embodiments a foam backing includes a single layer of foam or is a multilayer foam backing. Such single layer and multilayer foam backings are suitably formed using any of the above mentioned thermoplastic polymers. In some embodiments, multilayer foams are formed from foamed layers having the same or different properties, such as density, thickness, percent elongation, strength at break, or a combination thereof. In other embodiments, multilayer foams are formed from one or more foam layers and one or more thermoplastic film layers. The one or more thermoplastic film layers are suitably formed using any of the above mentioned thermoplastic polymers, and foam and film layers are suitably assembled to form a composite adhesive backing. In some embodiments, film and foam layers are coextruded, co-molded, laminated, extrusion coated, joined under pressure, joined through an adhesive layer, joined under heat, or a combination of two or more thereof. In some embodiments, a foam layer is sandwiched between two layers of film; a pressure sensitive adhesive composition of the embodiments herein is disposed on one or more portions of one or both film layers. In some such embodiments, the material used to make the foam is the same material present in the film. In other embodiments, a film layer is sandwiched between two foam layers; in some embodiments, a combination of film and foam layers form a composite layer with the ability to provide stretch release of the adhesive article.

Useful foam adhesive backings include polyethylene vinyl acetate copolymer foams available under the VOLEXTRA® and VOLARA® series of trade designations from Voltek, Division of Sekisui America Corporation of Lawrence, MA. Useful commercially available thermoplastic polymer films include, e.g., metallocene catalyzed linear low density polyethylene films available under the XMAX® series of trade designations and linear low density polyethylene films available under the MAXILENE® series of trade designations, both of which are available from Pliant Corporation (Chippewa Falls, Wis.).

In some embodiments, the adhesive articles of the embodiments herein include at least one liner disposed on the exposed surface of a layer of pressure sensitive adhesive composition to protect the adhesive composition until use. Liners are substantially planar films or layers having two opposing major sides defining a thickness, wherein at least one major side thereof contacts an adhesive layer of the adhesive article prior to use, and wherein the liner is removable by the user; and wherein upon removal, the liner includes substantially no adhesive. Examples of suitable liners include, e.g., paper such as kraft paper, polymer films such as polyethylene, polypropylene and polyester films, and combinations thereof. In embodiments, the liner is a release liner. In embodiments, a release liner is a liner wherein at least one major side thereof includes a release agent layer resulting from a release treatment to form a release liner. Examples of useful release agents include silicone (polydimethyl siloxane) or silicone copolymers such as silicone acrylates, silicone polyurethanes and silicone polyureas; fluorochemicals such as fluorosilicones or perfluoropolyethers; or other relatively low surface-energy compositions based on urethanes, acrylates, polyolefins, low density polyethylene, and the like, and combinations thereof. Suitable release liners and methods for treating liners are described in, e.g., U.S. Patent Nos. 4,472,480; 4,980,443; and 4,736,048, all of which are incorporated herein by reference in their entirety.

In some embodiments, a tape construction is formed by depositing an adhesive composition as described herein onto a liner. Depositing, in embodiments, can include solvent coating, coating of a liquid adhesive composition followed by curing, or extrusion coating. After depositing, the liner having adhesive disposed thereon is contacted to the tape backing. The adhesive is laminated to the tape backing by the act of contacting, or in some embodiments is joined under pressure, joined under heat, or a combination of two or more thereof. The liner then remains contacted to the adhesive until removed by a user. Upon removal of the liner, the adhesive remains contacted to the tape backing.

In some embodiments, the adhesive articles herein, liners used in conjunction with the adhesive articles, or both include various markings and indicia including, lines, brand indicia, and other information.

In some embodiments, the adhesive articles herein include a tab area. The tab of an adhesive article is defined as a portion of at least one major side thereof that does not adhere to the intended adherend. The tab of the adhesive article can exist in a variety of forms and is not particularly limited. In one embodiment, the tab is a portion of one or more major sides of the backing that is free of pressure sensitive adhesive composition. In other embodiments, the tab includes a cover layer that is adhered to and covers the pressure sensitive adhesive composition. In still other embodiments, the tab is a separate component that is affixed to a portion of the tape backing. In still other embodiments, the tab is created by detackifying a portion of a pressure sensitive adhesive composition residing on the tape backing, using any suitable method including applying powder such as calcium carbonate or titanium dioxide; exposure to radiation such as UV light or electron beam; or by coating a portion of an adhesive layer with varnish, ink, or another agent or combinations thereof.

In some embodiments, a method of making a stretch releasing adhesive article is included. The method can include disposing a first pressure sensitive adhesive composition on at least a portion of a first side of a backing. The first pressure sensitive adhesive composition can include one or more hydrocarbon block copolymers; and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5. The first pressure sensitive adhesive composition can have a glass transition temperature of about -25° C to 15° C , as determined by dynamic mechanical analysis of the tan δ peak value and a storage modulus of about 200,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

In some embodiments, a method of using a stretch releasing adhesive article is included. The method can include contacting a stretch releasing adhesive article with an adherend coated with an architectural paint. In some embodiments, the architectural paint can have VOC less than 5 g/L. In some embodiments, the architectural paint can be a deep base architectural paint and/or a combination paint/primer type architectural paint. The article can include a backing and a first pressure sensitive adhesive composition disposed on at least a portion of a first side of the backing. The first pressure sensitive adhesive composition can include one or more hydrocarbon block copolymers; and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5. The first pressure sensitive adhesive composition can have a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value and a storage modulus of about 200,000 Pa or less at 25° C, as determined by dynamic mechanical analysis.

Properties and Applications of the Adhesive Articles

The adhesive articles of the embodiments herein are useful as pressure sensitive adhesive tapes, that is, they are generally useful in any of the applications traditionally addressed by the use of a pressure sensitive adhesive tape. Various embodiments of adhesive articles herein are characterized by good adhesion to, and reliable, clean, damage-free release, debonding, or removal from, many adherend surface normally encountered in the vast array of adherends addressed by pressure sensitive adhesive tapes. The adhesive articles of the embodiments herein are further characterized by good adhesion to, and reliable, clean, damage-free release from, recent generations of architectural coatings over a range of expected humidity and temperature conditions. Recent generations of architectural coatings are characterized by an observed increase in measurable surface energy of the coating surface with elevated relative humidity. In some embodiments, recent generations of architectural coatings are characterized by factors including reduced volatile organic compounds (VOCs), eliminated VOCs, relatively high levels of surfactants that can associate with both the pigment and the water phase of the coating material, relatively high levels of polymers (including polymeric surfactants) that can associate with both the pigment and the water phase of the coating material, relatively high pigment content, or a combination of two or more such factors. In some embodiments, the architectural paint can have volatile organic content (VOC) of less than 250 g/L. In some embodiments, the architectural paint can have volatile organic content (VOC) of less than 100 g/L. In some embodiments, the architectural paint can have VOC of less than 50 g/L. In some embodiments, the architectural paint can have VOC less of than 5 g/L. In some embodiments, recent generations of architectural coatings are characterized by the inclusion of relatively large amounts of pigments and/or formulations that do not require a separate primer coating. In some embodiments, the architectural paint can be a deep base architectural paint and/or a combination paint/primer type architectural paint.

Recent generations of architectural coatings include both interior and exterior coatings intended for structures such as houses, apartments and office buildings. Recent generations of architectural coatings include trade-sales paints, decorative coatings, building paints, semi-transparent and opaque stains for wood, and DIY (do it yourself) paints. Recent generations of architectural coatings include a full commercial range of colors and finishes (high gloss, matte, and the like).

The adhesive articles of the embodiments herein are characterized by good adhesion to, and reliable, clean, damage-free release from, recent generations of architectural coatings over a full range of expected humidity and temperature conditions. In some embodiments, the release is stretch release carried out at an angle of about 35° or less from the surface of the adherend. In embodiments, adhesion to, and clean, damage-free release from, recent generations of architectural coatings is achieved while the tape is subjected to a load hung from the tape while the tape is adhered to a vertical adherend surface. In some such embodiments, the load is between about 1 g and 1 kg per cm² of tape surface adhered to the vertically situated adherend. In some such embodiments, the load is a static load hanging substantially vertically; in other embodiments, the load is applied at an angle from the vertical; in any of these embodiments, the load can be static or dynamic. Dynamic loads include those moved by e.g. wind or human action. In embodiments, adhesion to, and clean, damage-free release from, recent generations of architectural coatings while under load is further accomplished at relative humidities of 0% to 100%, including moderate humidity, defined as humidity of about 50%, or high humidity, defined as humidity of 70% or greater, further at temperatures between about 20°C and 40°C.

The pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful in a variety of applications, including mounting applications on surfaces such as painted wallboard, plaster, concrete, glass, ceramic, fiberglass, metal or plastic, wall hangings, organizers, holders, baskets, containers, decorations, e.g., holiday decorations, calendars, posters, dispensers, wire clips, body side molding on vehicles, carrying handles, signage applications, e.g., road signs, vehicle markings, transportation markings, and reflective sheeting. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for joining and assembly applications including, for example, adhering two or more containers, such as plastic or cardboard boxes, for later separation or to position the containers for further permanent separation. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for cushioning and sound deadening applications including, for example, cushioning materials for placement beneath objects, sound insulative sheet materials, and combinations thereof. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for closure applications including, for example, container closures such as closures for comestible containers, diaper closures, and surgical drape closures. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for vibration damping applications. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for sealing applications, for example for use in sealing gaskets for liquids, vapors, and dust. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for thermal insulation applications. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for labeling applications, for example removable labels such as notes, signage, price tags, and identification labels on containers. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for medical applications, for example bandages, wound care, or medical device labels such as in hospital settings. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for fastening applications, that is, fastening one object, for example an electrical cable, to another object, for example a desk or a book shelf. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for securing applications, for example fastening one or more components of a locking mechanism, such as a child safety lock, to a cabinet, electrical outlet, or toilet lid assembly. In some embodiments the pressure sensitive adhesive

compositions herein or the adhesive articles of the embodiments herein are useful in tamper-indicating applications. In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are useful for wire and cord organizers, holders, and clips.

In some embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are incorporated into larger articles or assemblies such as abrasive articles, polishing articles, pavement marking articles, traffic control articles, carpet and rug assemblies, automotive assemblies, medical device articles and assemblies, and the like; in some such embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are sacrificially - that is, temporarily - affixed to the article or assembly; in other embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are incorporated for the entirety of the use of the article or assembly.

In embodiments the adhesive articles herein are provided in any useful form generally known in the art as useful for pressure sensitive adhesive tapes. Such forms include, without limitation, sheets, such as perforated sheets, rolls, discs, stacks, tablets, and combinations thereof. In some embodiments the adhesive articles of the embodiments herein are provided in suitable packaging including, without limitation, dispensers, bags, blister packs, boxes, and cartons.

In embodiments the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein are incorporated as part of a kit. Suitable kits include, in addition to the adhesive or adhesive article, one or more kit elements including, for example, hooks, connector systems, combinations thereof, and the like. In such kits, one or more kit elements are adapted for use with the pressure sensitive adhesive compositions herein or the adhesive articles of the embodiments herein. For example, in some embodiments a hook is adapted to receive an adhesive article of the embodiments herein on one side thereof; in some such embodiments, the adhesive article includes a pressure sensitive adhesive composition on both major sides thereof. In this way, the hook may be affixed to a wall or some other adherend such that the adhesive article is sandwiched between, and provides adhesion to, both the hook and the adherend. Advantageously, the pressure sensitive adhesive compositions herein and related articles can be easily and firmly adhered to an adherend and later removed cleanly and without damaging the adherend surface.

In particular, where the adherend includes a recent generation architectural coating, pressure sensitive adhesive compositions herein and related articles can advantageously remain firmly adhered under reasonably anticipated conditions of temperature and humidity. It is an advantage of the embodiments herein that such articles can apply a load of between 1 g/cm² and 1 kg/cm² to the adhesive/adherend interface and remain firmly adhered under all reasonably anticipated conditions of temperature and humidity. Further, in accordance with various embodiments, when such articles are later removed, upon demand, they can be cleanly removed without damaging the adherend surface. In embodiments where an adhesive article is a stretch release tape, removal upon demand is accomplished by stretching the tape at an angle of 35° or less from the adherend surface.

In various embodiments, the articles including pressure sensitive adhesive compositions herein can be removed from an adherend surface coated with an architectural paint such that less than 10% of the adherend surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of having a portion of the coating removed as observed visually with the unaided eye. In some embodiments, less than 5% of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of having a portion of the coating removed. In some embodiments, less than 2% of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of having a portion of the coating removed. In some embodiments, less than 1% of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of having a portion of the coating removed. In some embodiments, substantially none of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of having a portion of the coating removed.

In various embodiments, the articles including pressure sensitive adhesive compositions herein can be removed from an adherend surface coated with an architectural paint such that less than 10% of the adherend surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of a leftover residue from the pressure sensitive adhesive composition as observed visually with the unaided eye. In some embodiments, less than 5% of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of a leftover residue. In some embodiments, less than 2% of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of a leftover residue. In some embodiments, less than 1% of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of a leftover residue. In some

embodiments, substantially none of the surface area that is contacted with the pressure sensitive adhesive composition exhibits any signs of a leftover residue.

In various embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of time. Stability can include the substantial lack of detrimental changes resulting from oxidation reactions, including one or more of color changes, changes in molecular weight of polymeric components, rheological changes, changes in tack, and changes in release properties. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 2 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 4 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 6 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 8 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 10 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 12 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 18 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 24 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 36 weeks. In some embodiments, pressure sensitive adhesive compositions herein can exhibit stability for a period of greater 48 weeks.

The pressure sensitive adhesive compositions herein and adhesive articles of the embodiments herein are suitably applied to an adherend using any suitable method. One example of a useful method includes contacting the surface of the adherend with a first major side of a adhesive article, wherein said first major side includes a layer of a pressure sensitive adhesive composition of the embodiments herein; applying finger pressure or some other static or dynamic pressure along the length of the tape; optionally removing a release liner from the second major side of the adhesive article to expose a second layer of pressure sensitive adhesive; and contacting the second pressure sensitive adhesive to an article. Said article is a kit element, a larger article or assembly, or any of the articles useful in one or more applications such as those described above. In conjunction with application of a pressure sensitive adhesive composition of the embodiments herein or an adhesive article of the embodiments herein to an adherend, useful methods include application of heat, such as from a hair dryer, an oven, and the like, to the adherend or a adhesive article or the finished assembly or a combination of two or more thereof; cleaning the surface of the adherend to remove debris and dust; lately abrading the surface of the adherend to increase surface area; applying a static or dynamic pressure to the second layer of pressure sensitive adhesive.

While the embodiments herein are susceptible to various modifications and alternative forms, specifics thereof have been shown by way of examples as described below, and are described in detail above. It should be understood, however, that the embodiments herein are not limited to the particular embodiments described or exemplified. On the contrary, the intention is to cover modifications, equivalents, and alternatives falling within the spirit and scope of the embodiments herein. In various embodiments, the invention suitably comprises, consists essentially of, or consists of the elements described herein and claimed according to the claims. Additionally each and every embodiment of the invention, as described here, is intended to be used either alone or in combination with any other embodiment described herein as well as modifications, equivalents, and alternatives thereof falling within the spirit and scope of the invention.

Examples

Standard Procedures

Materials used in the various Examples below are shown in Tables 1, 2 and 3. Other test materials and general procedures are listed below.

Table 1. Material and sui lier information,

Material Description Supplier Acid Softening

Value Point, °C

SUPER ESTER W- Arakawa 19 125

Glycerin-Based Rosin Ester

125 Chemical

PENSEL® GB 120 Pentaerythritol-Modified Arakawa 16 120

Rosin Ester Chemical

Industries, Ltd.

PENSEL® GA 90 Glycerin-Based Rosin Ester Arakawa 10 90

Chemical

Industries, Ltd.

PICCOLYTE® A130 Polyterpene Resin Ashland Inc.

PICCOLYTE® A1 15 Polyterpene Resin Ashland Inc.

= Not available

Table 2. Material and supplier information.

= Not available

Table 3. Material and su lier information.

Pressure Sensitive Adhesive Formulations

Pressure sensitive adhesive compositions were prepared by adding all indicated components to glass jars in the indicated proportions. The jars were sealed and the contents thoroughly mixed by placing the jars on a roller at about 2-6 rpm for at least 24 h prior to coating.

Preparation of Adhesive Films

Pressure sensitive adhesive compositions were knife-coated onto a paper liner web having a silicone release surface. The paper liner web speed was 2.75 meter/min. After coating, the web was passed through an oven 1 1 meter long (residence time 4 minutes total) having three temperature zones. The temperature in zone 1 (2.75 meter) was 57° C; temperature in zone 2 (2.75 meter) was 71° C;

temperature in zone 3 (about 5.5 meter) was 82° C. Transfer adhesives were then stored at ambient conditions. The transfer adhesives were then laminated to film-foam-film composites and the desired size and geometry was die cut.

Test Adherends

Drywall panels (obtained from Materials Company, Metzger Building, St. Paul, MN) were painted with Behr PREMIUM PLUS ULTRA® Primer and Paint 2 in 1 Flat Egyptian Nile ("Behr FEN PPU") obtained from Behr Process Corporation of Santa Ana, CA).

Procedure for painting drywall with paints: a first coat of paint was applied to a drywall panel by paint roller, followed by air drying for 24 hours at ambient conditions. A second coat of paint was applied dried at ambient conditions for 24 hours. The panel was placed in a forced air oven set to 50°C for 7 days. Then the panel was stored at ambient conditions until use. Test Procedures

a. Shear Strength (ASTM D3654)

Shear strength was determined according to the ASTM D-3654 method. Specifically, adhesive formulations were laminated to both sides of a film- foam-film composite. ½" x ½" pieces were die cut and adhered to the test adherend. A 3" long 5/8" metalized PET film was adhered to the 2^nd adhesive side. A 6.8 kg roller was passed over the test adhesive at 12"/min. The samples were mounted in a vertical position and allowed to dwell for 60 min at 72°F 50% relative humidity before attaching a 1 kg load to the adhesive. Samples were hung until failure or until 25,000 minutes had elapsed (note that ASTM D3654 actually calls for 10,000 minutes as the limit).

b. Holding Power When Used in Combination with a Hook

A 2.75" x 5/8" strip with an adhesive area of 2.0" x 5/8" laminated to both sides of a film-foam- film composite was adhered to the test adherends by contacting the experimental adhesive side to the indicated test panel and rolling a 6.8 kg roller over the sample in 2 passes at 12"/min. A COMMAND® back plate was then adhered to the adhesive side opposing the test adherend and a medium utility hook available from the 3M Company of St. Paul, MN was connected to the back plate. The test assembly was mounted in a vertical position and allowed to dwell on the test substrate for 1 hour at the environmental condition to be tested. A 1.36 kg load was hung from the COMMAND® hook, and a time to failure was recorded. Six replicates were tested and the average was reported. Three samples were tested for each adhesive and the average time to failure of these samples was recorded.

c. Dynamic Mechanical Properties Test

To prepare samples for dynamic mechanical properties testing, adhesive layers 0.0762 mm thick were laminated using a Catena 35 GBC roll laminator, at T = 104.4 °C and speed = 0.71 mm/sec together until a total thickness of approximately 1.2- 1.4 mm was achieved. Circles of 8 mm diameter were cut with a die and these samples were mounted on 8 mm diameter stainless steel parallel plate fixture of Ares 2000 Ex (TA Instruments). The test procedure was a set of temperature sweeps in torque mode at angular frequency of 1 rad/sec. The first temperature range was from 25 °C to the lower temperature using 3 °C steps at 1 % strain until stress of 10000 Pa was achieved; the second temperature range was from this lower temperature to -65 °C using 3 °C steps with strain of 1% and stress of 10000 Pa; finally, the third temperature range from 25 °C to 150 °C was covered in 3 °C increments using a strain of 5 % and stress of 10000 Pa. Test Compositions

An adhesive composition was formed according to the procedure outlined above. Composition components are shown in Table 3.

Table 4. Control Adhesive Com osition Com onents

A list of adhesive formulations with commercially available tackifiers used for modification of the standard A8254 adhesive fonnulation shown above in Table 4 is given in Table 5 (formulations El- E13). CI is the formulation for standard non-modified A8254 adhesive.

Table 5. Adhesive Formulations

These compositions were then evaluated for holding power with a hook according the procedure described above on the "Behr FEN PPU" Paint at 75 % RH/RT. The data are presented in Table 6. Table 6. Holding Power with Hook Test on Behr FEN PPU 2 in 1 Paint

Adhesives E1-E8 that were modified with different types of rosin and rosin ester tackifiers did not pass the shear strength test. For this performance screening, 4 hours post-application dwell time was used. This prolonged dwell time allowed good wet-out to be obtained for adhesives with low tack and to select promising candidates. Adhesives E9-E13 (with TAMANOL® 901 and PINECRYSTAL® KE- 604) passed the shear strength test.

Rheological properties of these adhesives were then evaluated according to the procedures described above. Rheological properties of E9-E13 adhesives compared with standard A8254 adhesive (example CI) are shown in Figures 1A-2B. As can be seen from Figures 1A-2B, TAMANOL® 901 and PINECRYSTAL® KE-604 are not compatible with the polybutadiene phase when formulated as the only tackifier (examples E10, and E13, Figures 1A, 2A), their plateau modulus is increased and Tg is not sufficiently increased (no Tan delta max is observed in -10 - +5 °C temperature range). When these polar tackifiers were formulated with a polyterpene non-polar tackifier, PICCOLYTE® A135, (examples E9 and El 2, Figures IB and 2B), plateau modulus is decreased and Tan delta max is observed at 2 °C for E9 and -10 °C for El 2. However, all these adhesives compositions have low tack. It is believed that their shear performance was delivered by enabling chemistry across the interface. This example illustrates the difficulty of formulating an adhesive composition that provides all of the desired functional properties.

Another set of adhesive formulations with commercially available tackifiers was prepared (based on modification of the standard A8254 adhesive formulation shown above in Table 4) as shown in Table 7 (formulations E14-E43). Table 7. Adhesive Formulations

These compositions were then evaluated for holding power with a hook according the procedure described above on the "Behr FEN PPU" Paint at 75 % RH/RT. The data are presented in Table 8. Table 8.

The various embodiments described above are provided by way of illustration only and shouldot be construed to limit the claims attached hereto. It will be recognized that various modifications and changes may be made without following the example embodiments and applications illustrated and described herein, and without departing from the true spirit and scope of the claims.

It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing "a compound" includes a mixture of two or more compounds. It should also be noted that the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise.

It should also be noted that, as used in this specification and the appended claims, the phrase "configured" describes a system, apparatus, article, or other structure that is constructed or configured to perform a particular task or adopt a particular configuration. The phrase "configured" can be used interchangeably with other similar phrases such as arranged and configured, constructed and arranged, constructed, manufactured and arranged, and the like.

All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated by reference.

Claims

What is claimed is:

1. A stretch releasing adhesive article comprising:

a backing;

a first pressure sensitive adhesive composition disposed on at least a portion of a first side of the backing, the first pressure sensitive adhesive composition comprising

one or more hydrocarbon block copolymers; and

a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5.

2. The stretch releasing adhesive article of claim 1, the article exhibiting a shear strength of greater than 10,000 minutes under conditions of a relative humidity of greater than 75% when adhered to an adherend coated with an architectural paint having VOC less than 5 g/L and subjected to a load of at least 1 kg applied in a direction parallel to the surface of the adherend.

3. The stretch releasing adhesive article of any of the preceding claims, the article exhibiting damage free release and/or debonding after being adhered to an adherend coated with an architectural paint having VOC less than 5 g/L at a relative humidity of greater than 75%.

4. The stretch releasing adhesive article of any of the preceding claims, the article exhibiting damage free release and/or debonding after being adhered to an adherend coated with a deep base architectural paint.

5. The stretch releasing adhesive article of any of the preceding claims, the article exhibiting damage free release and/or debonding after being adhered to an adherend coated with a combination paint/primer type architectural paint.

6. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier comprising a terpene phenolic tackifier.

7. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier having a hydroxyl value of between 20 to 90.

8. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier having a hydroxyl value of between 50 and 70.

9. The stretch releasing adhesive article of any of the preceding claims, wherein the first pressure sensitive adhesive composition having a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value.

10. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier an acid value of less than about 0.25.

1 1. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier an acid value of about 0.

12. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier having a softening point of about 125 to about 170 degrees Celsius.

13. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier having a softening point of about 125 to about 140 degrees Celsius.

14. The stretch releasing adhesive article of any of the preceding claims, wherein the first pressure sensitive adhesive composition has a storage modulus of about 400,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

15. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier having a molecular weight of about 400 to about 800.

16. The stretch releasing adhesive article of any of the preceding claims, the polar phenolic tackifier having a molecular weight of about 500 to about 700.

17. The stretch releasing adhesive article of any of the preceding claims, further comprising a non- polar tackifier.

18. The stretch releasing adhesive article of claim 17, wherein the ratio of polar tackifier to non-polar tackifier is between about 50:50 to 10:90 by weight.

19. The stretch releasing adhesive article of claim 17, wherein the non-polar tackifier is a terpene resin tackifier.

20. The stretch releasing adhesive article of any of the preceding claims, the first pressure sensitive adhesive composition having a glass transition temperature of about -20° C to 10° C.

21. The stretch releasing adhesive article of any of the preceding claims, the first pressure sensitive adhesive composition having a glass transition temperature of about -15° C to 0° C.

22. The stretch releasing adhesive article of any of the preceding claims, the first pressure sensitive adhesive composition having a storage modulus of about 3500,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

23. The stretch releasing adhesive article of any of the preceding claims, the first pressure sensitive adhesive composition having a storage modulus of about 300,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

24. The stretch releasing adhesive article of any of the preceding claims, the first pressure sensitive adhesive composition having a storage modulus of about 250,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

25. The stretch releasing adhesive article of any of the preceding claims, wherein the block copolymer comprises styrene and butadiene blocks.

26. The stretch releasing adhesive article of any of the preceding claims, wherein the block copolymer comprises a blend of a radial block copolymer and a linear block copolymer.

27. The stretch releasing adhesive article of any of the preceding claims, wherein the block copolymer comprises a blend of a styrene-butadiene-styrene triblock copolymer and a styrene-butadiene diblock copolymer.

28. The stretch releasing adhesive article of any of the preceding claims, the backing having an elongation at break of about 50% to 1200% in at least one direction.

29. The stretch releasing adhesive article of any of the preceding claims, the backing having a tensile strength at break sufficiently high so that the backing will not rupture prior to being stretched and removed from an adherend at an angle of 35° or less.

30. The stretch releasing adhesive article of any of the preceding claims, wherein the backing is a foam backing.

31. The stretch releasing adhesive article of claim 30, wherein the foam backing has a foam density that is between about 0.05 g/cm³ to about 0.25 g/cm³, and the backing has a thickness of about 0.2 mm to 5 mm.

32. The stretch releasing adhesive article of any of the preceding claims, wherein the thickness of the pressure sensitive adhesive on at least a portion of one major side of the backing is about 1 μηι to 1 mm.

33. The stretch releasing adhesive article of any of the preceding claims, wherein the adhesive releases cleanly from the surface of an adherend when the tape is stretched at an angle of about 35° or less from the adherend surface.

34. The stretch releasing adhesive article of any of the preceding claims, wherein the adhesive releases from the surface of an adherend when the backing is stretched at an angle of about 35° or less from the adherend surface such that there are substantially no traces of the adhesive left behind on the surface of the adherend.

35. The stretch releasing adhesive article of claim 34, wherein after release, the backing has an elastic recovery of about 0% to 50%.

36. The stretch releasing adhesive article of any of the preceding claims, where the adherend is coated with an architectural paint having a volatile organic content of less than 250 g/L.

37. The stretch releasing adhesive article of any of the preceding claims, where the adherend is coated with an architectural paint having a volatile organic content of less than 100 g/L.

38. The stretch releasing adhesive article of any of the preceding claims, where the adherend is coated with an architectural paint having a volatile organic content of less than 50 g/L.

39. The stretch releasing adhesive article of any of the preceding claims, where the adherend is coated with an architectural paint having a volatile organic content of less than 5 g/L.

40. The stretch releasing adhesive article of any of the preceding claims, wherein the second major side of the backing comprises a second pressure sensitive adhesive disposed on at least a portion of thereof.

41. The stretch releasing adhesive article of claim 40, wherein the second pressure sensitive adhesive is the same as the first pressure sensitive adhesive.

42. The stretch releasing adhesive article of claim 40, wherein the second pressure sensitive adhesive is different than the first pressure sensitive adhesive.

43. The stretch releasing adhesive article of claim 40, further comprising a liner disposed on at least a portion of the second pressure sensitive adhesive.

44. The stretch releasing adhesive article of any of the preceding claims, further comprising a liner disposed on at least a portion of the first pressure sensitive adhesive.

45. The stretch releasing adhesive article of any of the preceding claims, further comprising a tab.

46. The stretch releasing adhesive article of any of the preceding claims, the first pressure sensitive adhesive further comprising from about 0.01 to about 5 wt. % of an antioxidant.

47. The stretch releasing adhesive article of claim 46, the antioxidant comprising a mercaptan group.

48. A stretch releasing adhesive composition comprising:

one or more hydrocarbon block copolymers; and

a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5; and

a non-polar tackifier;

the adhesive composition having a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value and a storage modulus of about 400,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

49. A method of making a stretch releasing adhesive article comprising:

disposing a first pressure sensitive adhesive composition on at least a portion of a first side of a backing, the first pressure sensitive adhesive composition comprising

one or more hydrocarbon block copolymers; and a polar phenolic tackifier comprising a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5; and

a non-polar tackifier;

the first pressure sensitive adhesive composition having a glass transition temperature of about - 25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value and a storage modulus of about 400,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

50. A method of using a stretch releasing adhesive article comprising:

contacting a stretch releasing adhesive article with an adherend coated with an architectural paint having VOC less than 5 g/L;

the stretch releasing adhesive article comprising

a backing;

one or more hydrocarbon block copolymers; and

a non-polar tackifier;

the first pressure sensitive adhesive composition having a glass transition temperature of about -25° C to 15° C, as determined by dynamic mechanical analysis of the tan δ peak value and a storage modulus of about 400,000 Pa or less at 25°C, as determined by dynamic mechanical analysis.

51. A stretch releasing adhesive article, comprising:

a backing; and

a first pressure sensitive adhesive composition disposed on at least a portion of a first side of the backing, the first pressure sensitive adhesive composition comprising one or more hydrocarbon block copolymers and a polar phenolic tackifier;

wherein the stretch releasing adhesive article exhibits damage free release and/or debonding after being adhered to an adherend coated with an architectural paint having VOC less than 250 g/L.

52. The stretch release adhesive article of claim 51, wherein the architectural paint has a VOC that is less than 100 g/L.

53. The stretch release adhesive article of claim 51, wherein the architectural paint has a VOC that is less than 50 g/L.

54. The stretch release adhesive article of claim 51, wherein the architectural paint has a VOC that is less than 5 g/L.

55. The stretch release adhesive article of any of claims 51-54, wherein the stretch releasing adhesive article exhibits damage free release and/or debonding after being adhered to the adherend at a relative humidity of greater than 50%.

56. The stretch release adhesive article of any of claims 51-55, wherein the stretch releasing adhesive article exhibits damage free release and/or debonding after being adhered to the adherend at a relative humidity of greater than 70%.

57. The stretch release adhesive article of any of claims 51-56, wherein the stretch releasing adhesive article exhibits damage free release and/or debonding after being adhered to the adherend at a relative humidity of greater than 75%.

58. The stretch release adhesive article of any of claims 51-57, wherein the stretch releasing adhesive article has a shear strength of greater than 10,000 minutes.

59. The stretch release adhesive article of any of claims 51-58, wherein the stretch releasing adhesive article has a shear strength of greater than 10,000 minutes under conditions of a relative humidity of greater than 75% when adhered to an adherend coated with an architectural paint having VOC less than 250 g/L and subjected to a load of at least 1 kg applied in a direction parallel to the surface of the adherend.

60. The stretch release adhesive article of any of claims 51-59, wherein a polar phenolic tackifier comprises a phenolic moiety and having a hydroxyl value of between 20 to 130 and an acid value of less than 0.5.

61. A stretch releasing adhesive article, comprising:

a backing; and

a first pressure sensitive adhesive composition disposed on at least a portion of a first side of the backing, the first pressure sensitive adhesive composition comprising one or more hydrocarbon block copolymers and a polar phenolic tackifier; wherein the tape article exhibits damage-free release and/or removal after being adhered to an adherend coated with at least one of a deep base architectural paint, a combination paint/primer, and/or a low or no VOC coating.