Adhesive composition

Abstract

An adhesive composition is described herein. More particularly, an adhesive composition with a hydrophilic adhesive, a hydrophobic adhesive, at least one surfactant, and at least one plasticizer. Specifically, the adhesive is a blend of a continuous phase hydrophilic adhesive, a dispersed phase hydrophobic adhesive, at least one surfactant, at least one plasticizer selected from the group consisting of fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinate esters, polysorbates, glycerides and combinations thereof and wherein a weight ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:1.

Description

ADHESIVE COMPOSITIONCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Number 63 / 560,841 filed on March 4, 2024, and U.S. Provisional Application Number 63 / 567,159 filed March 19, 2024, which are both incorporated herein in their entirety.TECHNICAL FIELD

[0002] This disclosure generally relates to an adhesive composition. More particularly, this disclosure relates to an adhesive composition with a hydrophilic adhesive, a hydrophobic adhesive, at least one surfactant, and at least one plasticizer. Specifically, this disclosure relates a continuous phase hydrophilic adhesive, a dispersed phase hydrophobic adhesive, at least one surfactant, at least one plasticizer selected from the group consisting of fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinate esters, polysorbates, glycerides and combinations thereof and wherein a ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:1.BACKGROUND

[0003] Labels are an essential aspect of information delivery, and they are used to make products more identifiable and appealing to the consumer. They are often made by coating an adhesive on a facestock. Affixing labels on a container is generally a simple process. However, in certain cases, such as when bottles, vials, containers, or other items come out of refrigeration, the surfaces tend to accumulate condensation. This poses a challenge to traditional adhesives as they are unable to adhere properly to damp surfaces.

[0004] As a result, customers have had to wait until the surfaces dry up and warm up before applying labels successfully. The process of waiting for surfaces to dry can be a tedious and time-consuming task that can slow down production lines. Prior solutions have not been as robust only creating an adhesive in one phase or only a single adhesive.

[0005] As such, novel adhesives and methods of manufacture thereof are needed in order to promote adhesion in moisture rich environments.SUMMARY

[0006] Exemplary embodiments relate to a composition comprising: a continuous phase hydrophilic adhesive; a dispersed phase hydrophobic adhesive; at least one surfactant; and at least one plasticizer; selected from the group consisting of fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinate esters, polysorbates, glycerides and combinations thereof; and wherein a ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:1. This embodiment or other embodiments provide for the continuous phase hydrophobic adhesive is pressure sensitive. This embodiment or other embodiments provide for the dispersed phase hydrophilic adhesive is pressure sensitive. This embodiment or other embodiments provide for the dispersed phase hydrophobic adhesive comprises a polymer selected from the group consisting of polyisobutylene, polyacrylate, polymethacrylate, silicone, and combinations thereof. This embodiment or other embodiments provide for the dispersed phase further comprises a solvent. This embodiment or other embodiments provide for the solvent is water. This embodiment or other embodiments provide for at least one light stabilizer. This embodiment or other embodiments provide for at least one rheology modifier. This embodiment or other embodiments provide for the continuous phase hydrophilic adhesive comprises at least one polymer or copolymer selected from the group consisting of: polyacrylic acid, polymethacrylic acid, copolymer comprising acrylic acid and at least one acrylic monomer, vinyl-ether acid-anhydride copolymer, polyvinylpyrrolidone, polyethylene oxide, polyethylene glygol, and copolymers of polyethylene glycols, a naturally occurring or naturally existing or synthetic water soluble polymer, and combinations thereof. This embodiment or other embodiments provide for the ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 1:1. This embodiment or other embodiments provide for the continuous phase hydrophilic adhesive comprises a solvent. This embodiment or other embodiments provide for the solvent to be polar. This embodiment or other embodiments provide for the solvent to be water. This embodiment or other embodiments provide for the surfactant is a non-ionic surfactant. This embodiment or other embodiments provide for the non-ionic surfactant is a material selected from the group consisting of fatty alcohol ethoxylate, tristyrylphenol ethoxylate, alkyl ether sulfate, sulfosuccinate ester, polysorbate, glyceride, and combinations thereof. This embodiment or other embodiments provide for a ratio between the dispersed phase hydrophobic adhesive and the continuous phase hydrophilic adhesive is between about 5:95 and about 95:5. This embodiment or other embodiments provide for the ratio between the dispersed phase hydrophobic adhesive and the continuous phase hydrophilic adhesive is between about 20:80 and about 80:20. This embodiment or other embodiments provide for the particle size of the dispersed phase hydrophobic adhesive is between about 0.1 and about 20 microns.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 is a picture showing the microstructure of the hydrophilic / hydrophobic PSA blend.

[0008] Figure 2 is a wet stick of various blend ratios of hydrophilic:hydrophobic compared to standard adhesive.Definitions

[0009] As used herein, the term "label" means a two-dimensional piece of paper, fabric, plastic, or similar material configured to be attached to an object and giving information about it and / or decoration to it. The label may be any suitable shape or design, such as, for example, rectangular, square, circular, oval, triangular, multisided and irregular shapes. The label may have edges and corners that are sharp, rounded, or irregular. Labels may be formed from the laminates described herein with printed indicia thereon. Pharmaceutical or RFID tags and labels.

[0010] As used herein, the term "multilayer" means, with respect to laminate construction, the adhesive coated face material with one or more additional layers. Non-limiting examples of such layers to make up the multilayer include protective layers, spacing layers, adhesive layers, optical componentcontaining layers, metallic layers, barrier layers, release liners, tie coat layers, clear layers, color layers, white layers, reflective layers, fluid transfer layers, strength promoting layers, topcoats, print receptive layers, print containing layers, indicia layers, functional layers, and the like as well as combinations thereof. The resultant multilayer laminate construction described herein can be used for a variety of applications including, but not limited to, graphics applications, such as automobile and architectural wraps; reflective applications, such as road and traffic signs, trains and other commercial vehicles, etc.; and, medical tapes, medical labels, pharmaceutical applications, RFID tags and labels, or other label and packaging applications.DETAILED DESCRIPTION

[0011] Exemplary embodiments herein are directed towards an adhesive composition and methods of manufacture of the same. The novel adhesive composition allows for successful label application even when condensation is present on the surface. The new adhesive system is made using state-of-the-art technology, which makes it possible for the adhesive to bond with the surface even when it is moist. The adhesive is specially formulated to be water-resistant, ensuring that it will not wash away or weaken when exposed to moisture. This breakthrough adhesive system not only saves time, but it also reduces the risk of labels falling off, which could lead to incorrect labeling and other issues. The customers are delighted with this new invention, as it enables them to label their products more efficiently and effectively. Withthis new adhesive system, labeling is now a breeze, and product labeling can be done in a much more efficient manner, even with condensation present on the surface.

[0012] One exemplary embodiment can relate to a label frequently purchased by pharmaceutical customers. These customers frequently bring millions of vaccines out of refrigeration to be labeled in dedicated staging rooms. The rooms are tied up for an extended period of time to allow for the moisture to evaporate. During this time, the customers cannot bring out any other vaccine for risk of cross contamination or mislabeling. This is expensive downtime for the customer, and the new adhesive will save money for the customer.

[0013] The two adhesive components are blended under high shear to form a stable emulsion. Next, the emulsion is coated on the facestock and the solvent dried in an oven. The final product could be a roll of tape or a label. Further details are discussed herein for enablement for one skilled in the art.Adhesives

[0014] The laminates / constructs described herein contain one or more adhesives. The adhesive(s) can be a PSA, a non-pressure sensitive adhesive, a hot-melt adhesive, or combinations thereof. In some embodiments, the adhesive is a PSA. The PSA may be any known PSA. In some embodiments, the PSA is a solvent type adhesive, an emulsion type adhesive, or non-emulsion type adhesive. In some embodiments, the PSA is an emulsion adhesive. Hot melt PSAs may also be used. The adhesive may be acrylic or any other useful adhesive which has the modulus and adhesive properties needed for the laminates and / or adhesive coated facestocks. In certain embodiments, the adhesive should have a modulus sufficient to prevent the adhesive squeezing out of the laminate or article during processing.

[0015] Exemplary PSAs may be found in (1) Encyclopedia of Polymer Science and Engineering, Vol. 13, Wiley-lnterscience Publishers (NewYork, 1988); (2) Polymer Science and Technology, Vol. 1, Interscience Publishers (New York, 1964); (3) those described in U.S. Pat. Nos. 5,164,444; 5,183,459; and 5,264,532, all issued to Bernard, and U.S. Pat. No. 5,385,965, issued to Bernard et al; and (4) combinations thereof. The PSAs may be a solvent based or may be a water based adhesive. Conventional PSAs, including acrylic-based PSAs, rubber-based PSAs and silicone-based PSAs may be used in the laminates / constructs described herein. In one embodiment, the pressure sensitive adhesive contains an acrylic emulsion adhesive.

[0016] In some embodiments, the pressure sensitive adhesive is prepared by polymerizing alkyl acrylates, vinyl esters, diesters of dicarboxylic acids and unsaturated acids. The alkyl acrylates typically contain from about 2 to about 12, or from about 4 to about 8 carbon atoms in the alkyl group. Examplesof alkyl acrylates include, but are not limited to, ethyl, n-butyl, hexyl, 2-ethylhexyl, and isooctyl acrylates, with 2-ethylhexyl acrylate preferred. In one embodiment, the alkyl acrylates are present in an amount of at least about 35%. In some embodiments, the alkyl acrylates are present in an amount from about 35% to about 60% by weight.

[0017] The vinyl esters typically have from about 2 to about 12, or from about 4 to about 8 carbon atoms in the alkyl group. Examples of vinyl esters include, but are not limited to, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate and the like, with vinyl acetate being preferred. In some embodiments, the vinyl esters are present in an amount from about 15% to about 35% or from about 20% to about 25% by weight.

[0018] The diesters of the dicarboxylic acids include alkyl esters of unsaturated diacids, such as maleic acid or anhydride and fumaric acids. The alkyl group generally contains from about 2 to about 20, or from about 4 to about 16, or from about 6 to about 12 carbon atoms. Examples of diesters of diacids include, but are not limited to, butyl, octyl fumarate; hexyl, decyl maleate; di-2-ethylhexyl maleate; dibutyl fumarate; and di-2-ethylhexyl fumarate and mixtures thereof. In some embodiments, the diesters of diacids are present in an amount from about 20% to about 35% by weight.

[0019] The unsaturated acids generally contain from about 2 to about 12, or from about 2 to about 6 carbon atoms. Examples of the unsaturated acids include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, and the like. In some embodiments, the unsaturated acids are present in an amount up to 5% or from about 1% to about 3% by weight.

[0020] In exemplary embodiments, the coat weight of adhesives may be between 2 and 100 gsm.

[0021] A commonality of all pressure sensitive adhesives is the poor adhesion to wet surfaces, particularly wet and cold surfaces. Previous approaches have been unsuccessful due to a multitude of reasons, and therefore are unable to manage water on substrate surfaces. In an exemplary embodiment, a novel and practical method for an adhesive system that has strong adhesion to moist and / or wet surfaces.

[0022] The exemplary embodiment described herein comprises a multiple component blend, namely: a water displacing hydrophobic PSA, a water absorbing hydrophilic PSA, and a subesequent blend of the two systems that upon drying produces a PSA with a microstructure that enables wet-stick. Each of the components and processes has been extensively optimized and studied to determine which classes of materials can be used to give optimal properties.

[0023] Specifically referring to the hydrophobic PSA, the primary function of which is two-fold, first to displace the water on the surface of the substrate, and second once the water is absorbed by the othercomponent to be able to wet the surface and form an adhesive bond with the substrate. In addition to the specialty function of the wet-stick, the hydrophobic PSA must have adhesion to normal, non-moist surfaces. To satisfy these requirements a variety of polymer types can be used, including polyisobutylenes, polyacrylates, polymethacrylates, or silicone based polymers. They may be chosen from the group of polyacrylic acid, polymethacrylic acid, copolymer comprising acrylic acid and at least one acrylic monomer, vinyl-ether acid-anhydride copolymer, polyvinylpyrrolidone, polyethylene oxide, polyethylene glygol, and copolymers of polyethylene glycols, a naturally occurring or naturally existing or synthetic water soluble polymer, and combinations thereof. Included within these base polymers optionally can include other additives, such as plasticizers, light stabilizers, or other rheology modifiers. Additionally, the hydrophobic PSA may optionally be dispersed in water or dissolved in any other combination of solvents, or be a 100% solids formulation depending on the desired implementation.

[0024] Specifically referring to the hydrophillic PSA, the primary function of which is also two fold, to absorb the water on the surface of the substrate, and once the water is displaced by the other component to be able to wet the substrate and form an adhesive bond. In addition to the specialty function of the wet-stick, the hydrophilic PSA must have adhesion to normal, non-moist surfaces. To satisfy these requirements a variety of polymer types can be used including polyacrylic acids, polymethacrylic acids, copolymers of acrylic acid and other acrylic monomers, vinyl-ether acid-anhydride copolymers, polyvinylpyrrolidone, among others. With these polymers, a plasticizer is generally added to further enhance the adhesive properties. Plasticizers can be selected from a variety of classes, including but not limited to fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinate esters, polysorbates, glycerides, and combinations thereof, among others. These plasticizers may also act as surfactants for the blending step. The weight ratio of hydrophilic polymer to plasticizer can range from 1:4 polymerplasticizer to 4:1, with some embodiments being between 1:1 polymer:plasticizerto 1:4 ratio. Other additives can also include light stabilizers. These hydrophilic PSA's may be dissolved or dispersed in a polar solvent, water, or dissolved in any other combination of solvents, or be in a 100% solids formulation depending on the desired implementation.

[0025] Finally, it is needed to combine the hydrophobic and hydrophilic pressure sensitive adhesives into a combination hydrophobic / hydrophilic pressure sensitive adhesive. Mixing of the two polymers requires a surfactant. In one exemplary embodiment the surfactant may be a non-ionic surfactant. In another embodiment, there can include many classes of surfactants, including, but not limited to: fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinate esters, polysorbates,glycerides, and combinations thereof, among others. Specific methods of combination will be discussed below with respect to methods.

[0026] A weight ratio of hydrophobic to hydrophilic material can encompass a wide range of formulations. In complete formulation in one embodiment the range of ratios may encompass 5:95 to 95:5 hydrophilic:hydrophobic. In other embodiments the ratio can be 1:9 to 1:1. While in further embodiments the ratio may be 1:4 to 2:3. Specific testing and ratios for certain embodiments may be found in the examples below.

[0027] The mixture of the materials should produce a microstructure that is conducive to not only regular dry surface adhesion, but also should adhere to wet surfaces. A microstructure that is conducive to wet stick is having both a continuous phase and a dispersed phase, wherein the continuous phase is the hydrophilic PSA and the dispersed phase is the hydrophobic PSA. The particle size diameter of the hydrophobic PSA is preferably on the order of 0.1 to 20 microns, with a wide distribution of particles also being possible. Figure 1 illustrates a specific microstructure obtained consistent with ratios herein.

[0028] If one were to flip the phases, i.e. wherein the continuous phase is the hydrophobic PSA and the dispersed phase is the hydrophillic PSA, the same properties would not occur. Specifically, it is required that there is an absorption of moisture and clearing the surface of standing water which allows for greater adhesion properties described herein.Release Liners

[0029] In some embodiments, the laminates described herein may include one or more release liner(s). The liner may have a first side, a second side opposed to the first side, a first edge, and a second edge opposed to the first edge. The liner may be any useful liner which provides necessary support and release properties. The liner may be made of, or from, a variety of materials including, but not limited to, paper or polymer film liners. In one embodiment, the caliper of the paper is sufficient to die cut the resulting laminate or article. For example, liner calipers can range from about 10 pm to 200 pm for PET liners. In one embodiment, the liner has lay flat properties. In some embodiments, the liner has a machine glaze or finish. In some embodiments, the liner has a silicone hold out layer. The hold out layer provides adhesion between the release coating and the release liner. The silicone holdout layer also prevents the silicone release coating from soaking into the liner.

[0030] In some embodiments, the release liner includes a liner having a release coating. The release coating of the release liner provides a releasable bond with the PSA or other adhesive. The release coating may be any composition which provides a desired releasable bond strength.

[0031] In one embodiment, the release coating is a silicone release coating. The release coating can be prepared by curing silicone polymers in the presence of a control release agent. In some embodiments, the control release agent is a copolymer of a monofunctional silicone unit of the formula R3SiOi / 2and tetrafunctional silicone units SiO4 / 2wherein R is an alkyl or alkenyl group. In one embodiment, the alkyl or alkenyl groups contain from about 1 to about 12, or from about 1 to about 6 carbon atoms. Non-limiting examples of alkyl and alkenyl groups include methyl, ethyl, propyl, butyl, hexyl, ethenyl, propenyl, butenyl and hexenyl groups.

[0032] The control release agent is typically reacted with a polysiloxane. The polysiloxane may be any polysiloxane which is useful in forming a release coating. Examples of useful polysiloxanes include, but are not limited to, vinyl terminated, hydroxy terminated and epoxy terminated polysiloxanes. In one embodiment, the polysiloxane is a functional polydialkyl siloxane, wherein the alkyl group contains from about 1 to about 6 carbon atoms. The alkyl groups independently include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl groups or mixtures thereof. In one embodiment, the alkyl or alkenyl group contains from 1 to about 12, or from 1 to about 6 carbon atoms. The polysiloxane typically has a viscosity average molecular weight of greater than 300,000 centipoise (cps). In another embodiment, the polysiloxane has a viscosity molecular weight from about 300,000 to about 1,000,000 or more. The polysiloxane may be represented by the formula (I):RO((Si(R)2O)x)-Si)-R (I) wherein each R is independently as defined above and x is an integer.

[0033] In some embodiments, the release coating is prepared with a cross linking agent. In some embodiments, the cross linking agent is a reactive polysiloxane, such as a polydialkyl or polyhydroalkyl siloxane. The alkyl groups are the same as those described above.

[0034] The release coating may be applied in a solvent, solvent-less or emulsion form. The release coating may be cured by any known curing process, e.g. thermal, radiation, etc., to form the release coating. The curing may be catalyzed by silicone soluble complexed compounds of Group VIII transition metals, such as platinum.

[0035] Commercially available release agents include, but are not limited to, GE SS-4335, a silicone release agent in unreactive solvent. Commercially available polysiloxanes include, but are not limited to, GE SS-4331, a vinyl terminated polydimethyl siloxane. Commercially available linking agents include, but are not limited to, GE SS-4300C, a polymethyvinyl siloxane. Exemplary catalysts include, but are not limited to, SS-8010 catalyst in toluene. These materials are available commercially fromMomentive Performance Materials, Inc. Similar silicone products are available under the tradename Syl- off from Dow Corning Corporation.

[0036] It will be understood that the present subject matter is not limited to any of the noted release coatings or agents, and instead includes nearly any release coating or agent suitable for the intended end use application. Furthermore, although the present subject matter has been described in association with release liners, it will be appreciated that appropriately configured carrier films and other members could be used instead of release liners.Face Material

[0037] Suitable face materials include, but are not limited to, synthetic papers such as polyolefin type and polystyrene type; various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyurethane, polymethacrylate and polycarbonate. Additional examples of suitable face materials include paper and cardboard. The face material may be, or may include, a multilayer polymeric sheet. The multi-layers may be coextruded, or the multi-layers may be laminated together. In one embodiment, the face material includes both co-extruded multi-layers and laminated multi-layers. In addition, a white opaque film may be formed by adding a white pigment to one or more of the aforementioned synthetic resins and used as the face material. In one embodiment, a foamed film is used as the face material. The foamed film may be formed by a conventional foaming operation. In another embodiment, the face material may be a laminated body formed by combining a plurality of single layered sheets composed of the above listed materials. Examples of such a laminated body may include the combination of cellulose fiber paper with synthetic paper, and a laminated body of combined cellulose fiber paper with a plastic film or sheet. In another suitable embodiment, the face material includes coated and uncoated papers, metalized papers, aluminum foil, laminated paper and paper with a polymeric material extruded onto the surface of the paper. In certain versions, the face material can be coated with a liquid absorbent material. The selected face material may be porous or semi-porous. The face material may exhibit certain visibility characteristics such as opaqueness, color, and / or brightness. The face material may include water or other liquid absorbency properties. The face material may be electrically conductive and / or include electrically conductive coatings or regions. A wide array of commercially available face materials can be used such as for example those available under the designation TESLIN.

[0038] The thickness of the face material is optionally determined with reference to application specific criteria. Such criteria may include the desired end use. In one embodiment, the sheet thickness isin a range of from about 10 pm to about 300 pm. In another embodiment, the sheet thickness is in a range of from about 20 pm to about 200 pm. In still another embodiment, the sheet thickness is in a range of from about 30 pm to about 150 pm. Optionally, a primer treatment or a corona discharging treatment or a plasma treatment may be used on the face material to increase a bonding strength between the face material and a dried topcoat composition to be formed on a surface of the face material.

[0039] In certain embodiments described herein, the face material exhibits one or more functions or functional characteristics. For example, the face material may be selected to enable or promote an indication such as a visual indication of a liquid, outgassing such as directing or allowing flow of air or gas across a thickness of the face material, water or liquid retention within the face material, electrical discharge or conductivity of the face material, chemical delivery across a thickness of the face material, passage of sound across a thickness of the face material, and / or combinations of these functions or characteristics.Optional Layers

[0040] The adhesive coated face material and / or laminates described herein can include one or more additional layers or components. Non-limiting examples of such layers include protective layers, tie coat layers, clear layers, color layers, white layers, reflective layers, fluid transfer layers, strength promoting layers, topcoats, print receptive layers, print containing layers, indicia layers, functional layers, and the like.Laminate Properties

[0041] The laminates described herein may have specific and useful properties or functionalities.In some embodiments, the techniques described herein enable formation of laminates in which transfer, propagation, and / or migration of liquid, gas, sound waves, electrical current, and / or other agents or elements can occur and is controlled across or through the laminate in a Z-direction. The reference to "Z- direction" as made herein refers to a direction across a thickness dimension of a laminate or portion thereof, and thus references to "X-direction" and / or "Y-direction" refer to directions perpendicular to the Z-direction and correspond to width and length dimensions of the laminate.

[0042] Non-limiting representative examples of laminates having certain functionalities which are provided by the present subject matter include liquid indicator laminates, outgassing laminates, water absorbent laminates, sound channeling laminates, electrically conductive laminates, and laminates havingcombinations of these functionalities and / or laminates having combinations of one or more of these functionalities and additional functionalities.

[0043] For example, a liquid indicator laminate can be produced such that the speed of the indicator color change is linked to the facestock selection and porous adhesive properties. A discontinuous structure, such as resulting from pores in the adhesive layer or region(s), can allow, for example, liquid to channel through the discontinuous adhesive from one side of the adhesive to the other side and create a permanent discoloration when a dye or other agent in a functional coating in the laminate is dissolved.

[0044] In one embodiment, a liquid indicator laminate is provided. The speed or rate of the indicator color change is linked to the facestock properties such as for example absorbency of liquid, and porosity of the pattern adhesive in the Z-direction. The indication typically is irreversible and can be measured by color change or by a simple visual comparison.

[0045] The discoloration of a face or region of the laminate can be measured and quantified by optical change, such as by CIE Lab or by a simple visual comparison. The discoloration can be permanent or nonpermanent. The discoloration can also be temporary and revert to an initial state after passage of a period of time. In some embodiments, the period of time is predetermined.

[0046] This phenomenon of transport through discontinuities in an adhesive in the Z-direction can be implemented in other label applications and particularly pressure sensitive adhesive labels, such as for example, labels for outgassing substrates such as by air channeling in the Z-direction, moist substrate labeling such as by liquid channeling in the Z-direction, electrical discharge in the Z-direction, chemical delivery from one layer to another in the Z-direction, and / or sound channeling in the Z-direction. This phenomenon enables passage, transfer, and / or migration of a medium or agent from one side of an adhesive region of a laminate, to another side of the adhesive region. Although medium penetration or transport is noted as being in the Z-direction, it will be understood that the present subject matter is not limited to such and may also include penetration / transport in the X-direction and / or Y-direction.

[0047] In some embodiments, the laminates described herein include a layer or region of a secondary adhesive. The secondary adhesive is typically utilized to adhere the laminate to a substrate of interest. The secondary adhesive may contain one or more adhesives which are the same or different than the adhesive of the patterned or porous adhesive. Description of representative examples of secondary adhesives are provided herein. In such an adhesive configuration, the primary adhesive may be coated onto the facestock, the secondary adhesive may be coated onto the release liner, and the coated adhesive and release liner may be laminated together such that the primary and secondary adhesives are in direct contact with each other. Alternatively, or additionally, both the primary and secondary adhesive may becoated on the facestock or the release liner, then laminated together. It is contemplated that the layering of the primary and secondary adhesive relative to the facestock and the release liner may be either facestock, primary adhesive, secondary adhesive, and release liner or facestock, secondary adhesive, primary adhesive, release liner. Regardless of the order of primary and secondary adhesive, it is contemplated that at least one of the primary and secondary adhesive is patterned, taking into consideration that the other adhesive may be continuous.

[0048] In some embodiments, an array of different arrangements of layers and components may be utilized. In some embodiments using the patterned adhesive, e.g., the layer of discontinuous adhesive, that layer is disposed between a functional facestock and a liner or functional layer. And in the liquid indicator laminates, the patterned adhesive may be disposed between the functional facestock and the layer or region of functional agent that is sensitive to liquid passing through the laminate. And, in the liquid indicator laminates, the layer or region of the functional agent may be disposed between the patterned adhesive and the carrier layer.

[0049] Utilization of the techniques and features described herein enable production of adhesive laminates and / or adhesive coated face materials with fluid / air management characteristics, controlled removability, and / or unique thermal and / or electrical conductivity. In addition, use of these techniques and features enable reductions in materials, e.g., adhesives, and thus enable cost savings. However, it will be understood that the present subject matter includes the adhesive coated face materials and laminates described herein which are formed by other methods than the methods described herein.Top Coat Formulation and Application

[0050] In exemplary embodiments discussed herein, the top coat coating is deposited on the substrate by any suitable method. In embodiments, the suitable method includes any suitable coating technology. Embodiments include depositing the coating on the substrate by any suitable liquid deposition method. Without limitation, examples of suitable methods include bath coating, spray coating, slot coating, spin coating, curtain coating, gravure coating, reverse gravure print coating, reverse roll coating, knife over roll (i.e., gap) coating, metering (Meyer) rod coating, air knife coating, or any combinations thereof. Bath coating includes immersion or dip in the aqueous solution. In an embodiment, the coating is deposited by bath in the aqueous solution. In other embodiments, the coating is deposited by spray of the aqueous solution.Methods

[0051] Having discussed various components of the apparatus, exemplary methods and methodologies of operation will be discussed. Exemplary embodiments provide for method comprising: providing a water displacing hydrophobic adhesive; providing a water absorbing hydrophilic adhesive; providing at least one surfactant; providing at least at plasticizer selected from the group consisting of fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinate esters, polysorbates, glycerides and combinations thereof; blending a portion of the hydrophobic adhesive and the hydrophilic adhesive, the at least one surfactant, and the at least one plasticizer; and dispersing the hydrophobic adhesive in a continuous phase hydrophilic adhesive resulting in hydrophobic adhesive particle sizes between about 0.1 and about 20 microns. This embodiment or another can provide a first solvent for the hydrophobic adhesive; and providing a second solvent for the hydrophilic adhesive.

[0052] Specific methods for combining via blending the adhesives of the exemplary embodiments can include, but are not limited to standing overhead stirring with pitch blade or a cowles blade, centripetal speed mixing, or high-pressure homogenizing. This combining or mixing will occur with enough time or vigor to emulsify each PSA in its required phase. Additionally, mixing must be done until there is a particle size diameter of the hydrophobic PSA is preferably on the order of 0.1 to 20 microns, with a wide distribution of particles also being possible. The resultant blend is coated on a facestock and if used, any solvent, is dried in an oven. The final product could be a roll of tape or a label. The final product could then be attached to a moist surface or substrate without the need to dry the substrate or surface prior to application.

[0053] Having properly mixed the adhesives, example formulations were obtained with various ratios in order to show various properties, specifically, the wet stick tack values in N. These may be seen in Figure 2 and are discussed in additional detail below. A surface was prepared with a level of moisture in order to sufficiently simulate a wet environment for application. Resultant values were then obtained by measuring the tack value as shown on the graph. All samples were prepared in an identical way. Namely, exposing a substrate vessel, namely a glass bottle containing water into a refrigerator. Then, the bottles were taken out of the refrigerated environment and allowed to sit out for a prescribed period of time in order to develop moisture on the outside. Then, a facestock with the exemplary adhesive was attached to the moist substrate. Tack values were then obtained. Alternatively, a mister unit could be used to simulate the condensation. Further, a given level of temperature and humidity could be present in the room such as 25C and 40% humidity. The adhesives were all coated between 13-20 gsm.ExamplesComparative Example A

[0054] A PSA which is commercially available under the designation Fasson® S692N. The S692N adhesive is an acrylic emulsion-based adhesive obtainable from Avery Dennison in Mentor, Ohio, USA. Generally, this adhesive is a polymeric blend of butyl acrylate and 2-ethyl hexyl acrylate monomers with various tackifiers and processing acids. This Comparative Example of a single adhesive system shows a wet stick tack value of approximately IN.Example 1 - HA: 4-17 (20:80)

[0055] A blend of a hydrophillic adhesive of this disclosure and a hydrophobic adhesive of this disclosure was obtained with the blend containing 20% hydrophillic adhesive and 80% hydrophobic adhesive. The tack value was seen around 7.5N.Example 2 - 11A: 4-17 (30:70)

[0056] A blend of a hydrophillic adhesive of this disclosure and a hydrophobic adhesive of this disclosure was obtained with the blend containing 30% hydrophillic adhesive and 70% hydrophobic adhesive. The tack value was seen around 7.5N.Example 3 - 11A: 4-17 (50:50)

[0057] A blend of a hydrophillic adhesive of this disclosure and a hydrophobic adhesive of this disclosure was obtained with the blend containing 50% hydrophillic adhesive and 50% hydrophobic adhesive. The tack value was seen around 8N.Example 4 - 14A: 4-17 (20:80)

[0058] A blend of a hydrophillic adhesive of this disclosure and a hydrophobic adhesive of this disclosure was obtained with the blend containing 20% hydrophillic adhesive and 80% hydrophobic adhesive. The tack value was seen around 7.5N.Example 5 - 14A: 4-17 (30:70)

[0059] A blend of a hydrophillic adhesive of this disclosure and a hydrophobic adhesive of this disclosure was obtained with the blend containing 30% hydrophillic adhesive and 70% hydrophobic adhesive. The tack value was seen around 8N.Example 6 - 14A: 4-17 (50:50)

[0060] A blend of a hydrophillic adhesive of this disclosure and a hydrophobic adhesive of this disclosure was obtained with the blend containing 50% hydrophillic adhesive and 50% hydrophobic adhesive. The tack value was seen around 8.5N.Example 7 - Glass Tack vs. PP Tack vs. Moist Tack

[0061] Various samples were coated at 20 microns in a standard coating process. The samples include a control adhesive (A), a hydrophilic polymer adhesive ( B), a hydrophobic polymer adhesive (C), a blend of 30:70 of the hydrophobic and hydrophillic adhesive (D). The looptack of these materials was tested on glass and polypropylene and measured in Newtons. The minimum shear (in N) was also measured on a 25mm x 25mm x 1kg test. The moist tack was then measured by spraying a controlled amount of moisture onto a substrate and testing again similar to the tack tests with respect to glass and polypropylene (PP). The results are summarized in the table below.Table 10062] As means of a brief summary, it can be seen that all had acceptable values of tack on glass while the blend (D) remained the highest. The tack value on the PP was unacceptably low for the hydrophillic polymer adhesive (B) but acceptable for the remaining. The shear of A and B are similar, but D exceeded them both. Further, the moist tack of the hydrophobic polymer adhesive (B) performed the best, but the blend (D) performed very well. As a whole, the tack to both glass and PP, with high shear and acceptable moist glass tack, only the blend performed well over these four tests.Example 8 - Pharmaceutical Simulation Example

[0063] Samples were applied to wet and moist surfaces to glass vials. These glass vials were removed from refrigeration and applied while rotating the vials. There is a first control adhesive (AA), a second control adhesive (BB), a pharmaceutical adhesive (CC), a first blend of the hydrophobic and hydrophillic adhesive at a ratio of 75:25(DD), and a second blend of the hydrophobic and hydrophillic adhesive at a ratio of 70:30 (EE). The samples were applied every minute and then qualitatively describedwhere a 1 is no adhesion or no 'grab' and where a 5 is perfect adhesion and a good 'grab'. The results are summarized in Table 2, below.Table 2Time out of Refrigeration (minutes)

[0064] As can be seen, the blend works better for application to moist glass substrates.

[0065] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0066] The articles "a" and "an," as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean "at least one." The phrase "and / or," as used herein in the specification and in the claims (if at all), should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with "and / or" should be construed in the same fashion, i.e., "one or more" of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the "and / or" clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to "A and / or B", when used in conjunction with open-ended language such as "comprising" can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc. As used herein in the specification and in the claims, "or" should be understood to have the same meaning as "and / or" as defined above. For example, when separating items in a list, "or" or "and / or" shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including morethan one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as "only one of" or "exactly one of," or, when used in the claims, "consisting of," will refer to the inclusion of exactly one element of a number or list of elements. In general, the term "or" as used herein shall only be interpreted as indicating exclusive alternatives (i.e. "one or the other but not both") when preceded by terms of exclusivity, such as "either," "one of," "only one of," or "exactly one of." "Consisting essentially of," when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0067] As used herein in the specification and in the claims, the phrase "at least one," in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of A and B" (or, equivalently, "at least one of A or B," or, equivalently "at least one of A and / or B") can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0068] An embodiment is an implementation or example of the present disclosure. Reference in the specification to "an embodiment," "one embodiment," "some embodiments," "one particular embodiment," or "other embodiments," or the like, means that a particular feature, structure, or characteristic described in connection with the embodiments is included in at least some embodiments, but not necessarily all embodiments, of the invention. The various appearances "an embodiment," "one embodiment," "some embodiments," "one particular embodiment," or "other embodiments," or the like, are not necessarily all referring to the same embodiments.

[0069] If this specification states a component, feature, structure, or characteristic "may","might", or "could" be included, that particular component, feature, structure, or characteristic is not required to be included. If the specification or claim refers to "a" or "an" element, that does not mean there is only one of the element. If the specification or claims refer to "an additional" element, that does not preclude there being more than one of the additional element.

[0070] As used herein in the specification and claims, including as used in the examples and unless otherwise expressly specified, all numbers may be read as if prefaced by the word "about" or "approximately," even if the term does not expressly appear. The phrase "about" or "approximately" may be used when describing magnitude and / or position to indicate that the value and / or position described is within a reasonable expected range of values and / or positions. For example, a numeric value may have a value that is + / -0. % of the stated value (or range of values), + / -!% of the stated value (or range of values), + / -2% of the stated value (or range of values), + / -5% of the stated value (or range of values), + / - 10% of the stated value (or range of values), etc. Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

[0071] Additionally, any method of performing the present disclosure may occur in a sequence different than those described herein. Accordingly, no sequence of the method should be read as a limitation unless explicitly stated. It is recognizable that performing some of the steps of the method in a different order could achieve a similar result.

[0072] In the claims, as well as in the specification above, all transitional phrases such as"comprising," "including," "carrying," "having," "containing," "involving," "holding," "composed of," and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases "consisting of" and "consisting essentially of" shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures.

[0073] In the foregoing description, certain terms have been used for brevity, clarity, and understanding. No unnecessary limitations are to be implied therefrom beyond the requirement of the prior art because such terms are used for descriptive purposes and are intended to be broadly construed.

[0074] Moreover, the description and illustration of various embodiments of the disclosure are examples and the disclosure is not limited to the exact details shown or described.

Claims

CLAIMSWhat is claimed is:

1. A composition comprising: a continuous phase hydrophilic adhesive; a dispersed phase hydrophobic adhesive; at least one surfactant; and at least one plasticizer; selected from the group consisting of fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinate esters, polysorbates, glycerides and combinations thereof; and wherein a weight ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:1.

2. The composition of claim 1, wherein the continuous phase hydrophobic adhesive is pressure sensitive.

3. The composition of claim 1, wherein the dispersed phase hydrophilic adhesive is pressure sensitive.

4. The composition of claim 1, wherein the dispersed phase hydrophobic adhesive comprises a polymer selected from the group consisting of polyisobutylene, polyacrylate, polymethacrylate, silicone, polybutadiene, styrene-butadiene copolymer, polyisoprene and combinations thereof.

5. The composition of claim 1, wherein the dispersed phase further comprises a solvent.

6. The composition of claim 5, wherein the solvent is water.

7. The composition of claim 1, further comprising at least one light stabilizer.

8. The composition of claim 1, further comprising at least one rheology modifier.

9. The composition of claim 1, wherein the continuous phase hydrophilic adhesive comprises at least one polymer or copolymer selected from the group consisting of: polyacrylic acid, polymethacrylic acid, copolymer comprising acrylic acid and at least one acrylic monomer, vinyl-ether acid-anhydride copolymer, polyvinylpyrrolidone, polyethylene oxide, polyethylene glygol, and copolymers of polyethylene glycols, a naturally occurring or naturally existing or synthetic water soluble polymer, and combinations thereof.

10. The composition of claim 1, wherein the weight ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 1:1.

11. The composition of claim 1, wherein the continuous phase hydrophilic adhesive comprises a solvent.

12. The composition of claim 11, wherein the solvent is polar.

13. The composition of claim 11, wherein the solvent is water.

14. The composition of claim 1, wherein the surfactant is a non-ionic surfactant.

15. The composition of claim 14, wherein the non-ionic surfactant is a material selected from the group consisting of fatty alcohol ethoxylate, tristyrylphenol ethoxylate, alkyl ether sulfate, sulfosuccinate ester, polysorbate, glyceride, and combinations thereof.

16. The composition of claim 1, wherein a weight ratio between the dispersed phase hydrophobic adhesive and the continuous phase hydrophilic adhesive is between about 5:95 and about 95:5.

17. The composition of claim 16, wherein the weight ratio between the dispersed phase hydrophobic adhesive and the continuous phase hydrophilic adhesive is between about 20:80 and about 80:20.

18. The composition of claim 1, wherein the particle size of the dispersed phase hydrophobic adhesive is between about 0.1 and about 20 microns.