Adhesive composition

Abstract

An adhesive composition is described, and more particularly, to an adhesive composition comprising 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, and at least one plasticizer selected from the group consisting of fatty alcohol ethoxylates, tristyrl phenol ethoxylates, alkyl ether sulfate, sulfosuccinates, polysorbates, glycerol esters, and combinations thereof, wherein the weight ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:1.

Description

Cross-references to related applications

[0001] This application claims the benefits of U.S. Provisional Application No. 63 / 560,841, filed March 4, 2024, and U.S. Provisional Application No. 63 / 567,159, filed March 19, 2024, both of which are incorporated herein by reference in their entirety and are part of this invention. Technical Field

[0002] This invention generally relates to an adhesive composition. More specifically, this invention relates to an adhesive composition comprising a hydrophilic adhesive, a hydrophobic adhesive, at least one surfactant, and at least one plasticizer. Specifically, this invention relates to a continuous phase hydrophilic adhesive, a dispersed phase hydrophobic adhesive, at least one surfactant, and at least one plasticizer selected from fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof, wherein the ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:1. Background Technology

[0003] Labels are an important aspect of information delivery, used to make products more identifiable and appealing to consumers. Typically, labels are made by applying an adhesive to a face stock. Attaching labels to containers is usually a simple process. However, in some situations, such as when bottles, vials, containers, or other items are removed from refrigerated environments, condensation tends to build up on their surfaces. This presents a challenge for traditional adhesives, as they do not adhere well to damp surfaces.

[0004] Therefore, customers had to wait for the surface to dry and heat up before they could successfully apply labels. Waiting for the surface to dry can be a tedious and time-consuming task, slowing down the production line. Previous solutions were not robust enough, only forming single-phase adhesives or using only a single adhesive.

[0005] Therefore, there is a need for novel adhesives and their preparation methods to improve adhesion performance in high-humidity environments. Summary of the Invention

[0006] An exemplary embodiment relates to a composition comprising: a continuous phase hydrophilic adhesive; a dispersed phase hydrophobic adhesive; at least one surfactant; and at least one plasticizer; said plasticizer being selected from fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof; wherein the ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:1. In this embodiment or other embodiments, the continuous phase hydrophobic adhesive is a pressure-sensitive adhesive. In this embodiment or other embodiments, the dispersed phase hydrophilic adhesive is a pressure-sensitive adhesive. In this embodiment or other embodiments, the dispersed phase hydrophobic adhesive comprises a polymer selected from polyisobutylene, polyacrylate, polymethacrylate, silicone, and combinations thereof. In this embodiment or other embodiments, the dispersed phase further comprises a solvent. In this embodiment or other embodiments, the solvent is water. In this embodiment or other embodiments, at least one light stabilizer is also included. In this embodiment or other embodiments, at least one rheology modifier is also included. In this or other embodiments, the continuous phase hydrophilic adhesive comprises at least one polymer or copolymer selected from: polyacrylic acid, polymethacrylic acid, copolymers comprising acrylic acid and at least one acrylic acid monomer, vinyl ether anhydride copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, polyethylene glycol copolymers, naturally occurring or naturally derived or synthetic water-soluble polymers and combinations thereof. In this or other embodiments, the weight ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 1:1. In this or other embodiments, the continuous phase hydrophilic adhesive comprises a solvent. In this or other embodiments, the solvent is a polar solvent. In this or other embodiments, the solvent is water. In this or other embodiments, the surfactant is a nonionic surfactant. In this or other embodiments, the nonionic surfactant is selected from fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof. In this embodiment or other embodiments, the ratio between the dispersed hydrophobic adhesive and the continuous hydrophilic adhesive is between about 5:95 and about 95:5. In this embodiment or other embodiments, the ratio between the dispersed hydrophobic adhesive and the continuous hydrophilic adhesive is between about 20:80 and about 80:20. In this embodiment or other embodiments, the particle size of the dispersed hydrophobic adhesive is between about 0.1 micrometers and about 20 micrometers. Attached Figure Description

[0007] Figure 1 Images showing the microstructure of hydrophilic / hydrophobic pressure-sensitive adhesive blends.

[0008] Figure 2 For hydrophilic: the wet adhesion of different blending ratios of hydrophobic and hydrophilic adhesives compared to standard adhesives.

[0009] definition As used in this invention, the term "tag" refers to a two-dimensional material, such as paper, fabric, plastic, or similar material, used to attach to an object and provide information and / or decoration. The tag can be any suitable shape or design, such as rectangular, square, circular, elliptical, triangular, polygonal, or irregular shapes. The tag may have sharp, rounded, or irregular edges and corners. The tag may be formed from the laminate described in this invention, with printed markings, such as pharmaceutical or RFID tags.

[0010] As used in this invention, the term "multilayer" in the context of a laminate construction refers to a face material coated with an adhesive and one or more additional layers. Non-limiting examples of such layers constituting the multilayer include protective layers, spacer layers, adhesive layers, layers containing optical components, metallic layers, barrier layers, release liner layers, adhesive layers, transparent layers, colored layers, white layers, reflective layers, fluid transport layers, strength-enhancing layers, topcoat layers, printing layers, printing-containing layers, marking layers, functional layers, and combinations thereof. The multilayer laminate construction obtained by this invention can be used in a variety of applications, including but not limited to graphic applications such as automotive and architectural films; reflective applications such as road and traffic signs, trains, and other commercial vehicles; and medical tapes, medical labels, pharmaceutical applications, RFID tags, or other labeling and packaging applications. Detailed Implementation

[0011] Exemplary embodiments of this invention relate to an adhesive composition and a method for preparing the same. The novel adhesive composition enables successful labeling even when condensation is present on the surface. This novel adhesive system is manufactured using advanced technology, allowing the adhesive to bond even on damp surfaces. The adhesive is specially formulated to be water-resistant, ensuring it will not be washed away or weakened upon contact with moisture. This breakthrough adhesive system not only saves time but also reduces the risk of label detachment, which can lead to labeling errors and other problems. Customers are very satisfied with this new invention because this adhesive allows them to label products more efficiently and effectively. With this new adhesive system, labeling is now effortless, enabling more efficient product labeling even when condensation is present on the surface.

[0012] One exemplary embodiment may relate to labels frequently purchased by pharmaceutical customers. These customers often remove millions of doses of vaccines from refrigerated environments and label them in dedicated temporary storage rooms. These storage rooms require long-term occupancy to allow moisture to evaporate. During this time, customers cannot remove any other vaccines to avoid the risk of cross-contamination or mislabeling. This represents costly downtime for customers, and a novel adhesive would save them money.

[0013] The two adhesive components are blended under high shear stress to form a stable emulsion. The emulsion is then applied to a surface material and dried in an oven to remove the solvent. The final product can be a roll of tape or a label. Further detailed instructions are provided herein to enable those skilled in the art to implement this process.

[0014] adhesives The laminate / construction described in this invention comprises one or more adhesives. The adhesive may be a pressure-sensitive adhesive, a non-pressure-sensitive adhesive, a hot-melt adhesive, or a combination thereof. In some embodiments, the adhesive is a pressure-sensitive adhesive. The pressure-sensitive adhesive may be any known pressure-sensitive adhesive. In some embodiments, the pressure-sensitive adhesive is a solvent-based adhesive, an emulsion adhesive, or a non-emulsion adhesive. In some embodiments, the pressure-sensitive adhesive is an emulsion adhesive. Hot-melt pressure-sensitive adhesives may also be used. The adhesive may be acrylic or any other useful adhesive having the modulus and adhesive properties required for the laminate and / or coating surface material. In some embodiments, the adhesive should have sufficient modulus to prevent the adhesive from being extruded from the laminate or article during processing.

[0015] Exemplary pressure-sensitive adhesives can be found in: (1) Encyclopedia of Polymer Science and Engineering, Vol. 13, Wiley-Interscience (New York, 1988); (2) Polymer Science and Technology, Vol. 1, Interscience (New York, 1964); (3) Pressure-sensitive adhesives as described in U.S. Patents Nos. 5,164,444, 5,183,459, and 5,264,532 (all granted to Bernard) and 5,385,965 (granted to Bernard et al.); (4) combinations thereof. The pressure-sensitive adhesive may be solvent-based or water-based. Conventional pressure-sensitive adhesives, including acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, and silicone pressure-sensitive adhesives, can be used in the laminates / constructs described in this invention. In one embodiment, the pressure-sensitive adhesive comprises an acrylic emulsion adhesive.

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

[0017] The vinyl ester typically contains about 2 to about 12 carbon atoms, or 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 tert-carbonate, etc., wherein vinyl acetate is preferred. In some embodiments, the content of the vinyl ester is about 15% to about 35% by weight, or about 20% to about 25% by weight.

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

[0019] The unsaturated acid typically contains about 2 to about 12 carbon atoms, or about 2 to about 6 carbon atoms. Examples of unsaturated acids include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, etc. In some embodiments, the content of the unsaturated acid is up to 5% by weight, or about 1% by weight to about 3% by weight.

[0020] In an exemplary embodiment, the coating weight of the adhesive can be from 2 to 100 gsm.

[0021] A common characteristic of all pressure-sensitive adhesives is their poor adhesion to damp surfaces, particularly wet and cold surfaces. Previous attempts have failed to address moisture on substrate surfaces for various reasons. In one exemplary embodiment, a novel and practical adhesive system method is provided that exhibits strong adhesion to damp and / or wet surfaces.

[0022] The exemplary embodiments of the present invention comprise multi-component blends, namely: a hydrophobic pressure-sensitive adhesive, a hydrophilic pressure-sensitive adhesive, and subsequent blends of these two systems, which, upon drying, produce a pressure-sensitive adhesive with a microstructure capable of wet adhesion. Each component and process has been extensively optimized and studied to determine which categories of materials can be used to obtain optimal performance.

[0023] Specifically, the hydrophobic pressure-sensitive adhesive has two main functions: first, to displace water from the substrate surface; and second, to wet the surface and form an adhesive bond with the substrate once the water is absorbed by another component. In addition to its special function of wet adhesion, the hydrophobic pressure-sensitive adhesive must also have adhesion to normal, non-damp surfaces. To meet these requirements, various polymer types can be used, including polyisobutylene, polyacrylate, polymethacrylate, or silicone-based polymers. These can be selected from polyacrylic acid, polymethacrylic acid, copolymers containing acrylic acid and at least one acrylic acid monomer, vinyl ether anhydride copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, polyethylene glycol copolymers, naturally occurring or naturally derived or synthetic water-soluble polymers, and combinations thereof. Optionally, other additives, such as plasticizers, light stabilizers, or other rheology modifiers, may also be included in these base polymers. Furthermore, the hydrophobic pressure-sensitive adhesive may be optionally dispersed in water or dissolved in any other combination of solvents, or formulated as a 100% solids content formulation according to the desired implementation.

[0024] Specifically, the hydrophilic pressure-sensitive adhesive has two main functions: absorbing water from the substrate surface and wetting the substrate and forming adhesive bonds once the water is replaced by another component. In addition to its special function of wet adhesion, the hydrophilic pressure-sensitive adhesive must also have adhesion to normal, non-damp surfaces. To meet these requirements, various polymer types can be used, including polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid with other acrylic monomers, vinyl ether anhydride copolymers, polyvinylpyrrolidone, etc. For these polymers, plasticizers are typically added to further enhance adhesive properties. Plasticizers can be selected from a variety of categories, including but not limited to fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof. These plasticizers can also act as surfactants in the blending step. The weight ratio of hydrophilic polymer to plasticizer can be from 1:4 (polymer:plasticizer) to 4:1, with some embodiments having a ratio of 1:1 (polymer:plasticizer) to 1:4. Other additives may also include light stabilizers. These hydrophilic pressure-sensitive adhesives can be dissolved or dispersed in polar solvents, water, or any other combination of solvents, or formulated as 100% solids content according to the desired implementation.

[0025] Finally, the hydrophobic and hydrophilic pressure-sensitive adhesives need to be combined into a hydrophobic / hydrophilic composite pressure-sensitive adhesive. The mixing of the two polymers requires a surfactant. In one exemplary embodiment, the surfactant may be a nonionic surfactant. In another embodiment, a variety of surfactants may be included, including but not limited to: fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof. Specific combination methods will be discussed in the section on methods below.

[0026] The weight ratio of hydrophobic to hydrophilic materials can cover a wide range of formulations. In a complete formulation of one embodiment, the ratio can range from 5:95 to 95:5 (hydrophilic:hydrophobic). In other embodiments, the ratio can be from 1:9 to 1:1. In further embodiments, the ratio can be from 1:4 to 2:3. Specific tests and ratios for particular embodiments can be found in the examples below.

[0027] The mixture of materials should produce a microstructure that is not only conducive to adhesion to conventionally dry surfaces but also to wet surfaces. A microstructure conducive to wet adhesion has both a continuous phase and a dispersed phase, wherein the continuous phase is a hydrophilic pressure-sensitive adhesive and the dispersed phase is a hydrophobic pressure-sensitive adhesive. The particle size of the hydrophobic pressure-sensitive adhesive is preferably on the order of 0.1 to 20 micrometers, and a wide particle size distribution is also acceptable. Figure 1 A specific microstructure obtained in accordance with the proportions described in this invention is shown.

[0028] If the reverse is true, i.e., the continuous phase is a hydrophobic pressure-sensitive adhesive and the dispersed phase is a hydrophilic pressure-sensitive adhesive, the same performance will not be achieved. Specifically, it is required to absorb moisture and remove surface water to achieve the superior adhesion performance described in this invention.

[0029] Release liner In some embodiments, the laminate of the present invention may include one or more release liner layers. The liner layer may have a first side, a second side opposite the first side, a first edge, and a second edge opposite the first edge. The liner layer may be any useful liner layer that provides the necessary support and release properties. The liner layer may be made of or derived from a variety of materials, including but not limited to paper or polymer film liner layers. In one embodiment, the paper thickness is sufficient to die-cut the resulting laminate or article. For example, for a PET liner layer, the liner layer thickness may range from about 10 µm to 200 µm. In one embodiment, the liner layer has lay-flat properties. In some embodiments, the liner layer has a machine-enameled or finished surface. In some embodiments, the liner layer has a silicone barrier layer. The barrier layer provides adhesion between the release coating and the release liner layer. The silicone barrier layer also prevents the silicone release coating from penetrating into the liner layer.

[0030] In some embodiments, the release liner comprises a liner having a release coating. The release coating of the release liner provides a peelable bond with pressure-sensitive adhesives or other adhesives. The release coating can be any composition that provides the desired peelable bond strength.

[0031] In one embodiment, the release coating is a silicone release coating. The release coating can be prepared by curing a silicone polymer in the presence of a controlled release agent. In some embodiments, the controlled release agent is of formula R3SiO. 1 / 2 Monofunctional silicone units and SiO 4 / 2 A copolymer of tetrafunctional silicone units, wherein R is an alkyl or alkenyl group. In one embodiment, the alkyl or alkenyl group contains about 1 to about 12 carbon atoms, or about 1 to about 6 carbon atoms. Non-limiting examples of alkyl and alkenyl groups include methyl, ethyl, propyl, butyl, hexyl, vinyl, propenyl, butenyl, and hexenyl.

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

[0033] In some embodiments, the release coating is prepared using a crosslinking agent. In some embodiments, the crosslinking agent is a reactive polysiloxane, such as a polydialkylsiloxane or a polyhydroalkylsiloxane. The alkyl group is the same as described above.

[0034] The release coating can be applied in solvent-based, solvent-free, or emulsion form. The release coating can be cured by any known curing method, such as thermosetting or radiation curing, to form the release coating. The curing can be catalyzed by silicone-soluble complexes 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 a non-reactive solvent. Commercially available polysiloxanes include, but are not limited to, GE SS-4331, a vinyl-terminated polydimethylsiloxane. Commercially available crosslinking agents include, but are not limited to, GE SS-4300C, a polymethylvinylsiloxane. Exemplary catalysts include, but are not limited to, SS-8010 catalyst in toluene. These materials are commercially available from Momentive Performance Materials, Inc. Similar silicone products are also available from Dow Corning Corporation under the trademark Syl-off.

[0036] It should be understood that this subject matter is not limited to any of the release coatings or release agents described above, but includes virtually any release coating or release agent suitable for the intended end-use application. Furthermore, although this subject matter has been described in conjunction with release liner, it should be understood that appropriately configured carrier films and other components may also be used in place of the release liner.

[0037] Surface material Suitable face materials include, but are not limited to, synthetic papers such as polyolefin and polystyrene types; various plastic films or sheets such as polyolefins, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyurethane, polymethacrylate, and polycarbonate. Other examples of suitable face materials include paper and paperboard. The face material can be or may include multilayer polymer sheets. The multilayers can be co-extruded or laminated together. In one embodiment, the face material includes both co-extruded and laminated multilayers. Furthermore, a white opaque film can be formed by adding a white pigment to one or more of the aforementioned synthetic resins and used as a face material. In one embodiment, a foamed film is used as the face material. The foamed film can be formed by conventional foaming operations. In another embodiment, the face material can be a laminate formed by combining multiple single-layer sheets composed of the aforementioned materials. Examples of such laminates may include a combination of cellulose fiber paper and synthetic paper, and a laminate of a combination of cellulose fiber paper and a plastic film or sheet. In another suitable embodiment, the face material includes coated and uncoated paper, metallized paper, aluminum foil, laminated paper, and paper with a polymer material extruded onto its surface. In some versions, the face material may be coated with a liquid-absorbing material. The selected face material may be a porous or semi-porous face material. The face material may exhibit certain visibility characteristics, such as opacity, color, and / or brightness. The face material may include water absorption or other liquid absorption properties. The face material may be a conductive face material and / or include a conductive coating or area. A variety of commercially available face materials can be used, such as those sold under the trade name TESLIN.

[0038] The thickness of the sheet material may be determined with reference to specific application standards. These standards may include the desired end use. In one embodiment, the sheet thickness is in the range of about 10 μm to about 300 μm. In another embodiment, the sheet thickness is in the range of about 20 μm to about 200 μm. In yet another embodiment, the sheet thickness is in the range of about 30 μm to about 150 μm. Optionally, a primer treatment, corona discharge treatment, or plasma treatment may be applied to the sheet material to increase the adhesion strength between the sheet material and the dry topcoat composition to be formed on the surface of the sheet material.

[0039] In some embodiments described herein, the face material exhibits one or more functions or functional characteristics. For example, the face material may be selected to achieve or facilitate indication functions, such as visual indication of liquids; venting functions, such as guiding or allowing air or gas to flow through the thickness of the face material; water or liquid retention functions within the face material; electrical discharge or conductivity functions of the face material; chemical delivery functions through the thickness of the face material; sound propagation functions through the thickness of the face material; and / or combinations of these functions or characteristics.

[0040] Optional layer The coated surface material and / or laminate described in this invention may include one or more additional layers or components. Non-limiting examples of such layers include protective layers, primer layers, transparent layers, coloring layers, white layers, reflective layers, fluid transport layers, strength-enhancing layers, topcoats, printing layers, printing-inclusive layers, marking layers, functional layers, etc.

[0041] Laminate properties The laminates described in this invention may possess specific useful properties or functions. In some embodiments, the technology described in this invention enables the formation of laminates in which the transfer, propagation, and / or migration of liquids, gases, sound waves, electric currents, and / or other media or elements can occur in the Z direction and be controlled to pass through or through the laminate. The "Z direction" mentioned in this invention refers to the direction through the thickness dimension of the laminate or a portion thereof; therefore, the "X direction" and / or "Y direction" refer to directions perpendicular to the Z direction and correspond to the width and length dimensions of the laminate.

[0042] Non-limiting representative examples of laminates with certain functions provided in this topic include liquid indicator laminates, venting laminates, water-absorbing laminates, sound-guided laminates, conductive laminates, and laminates having combinations of these functions and / or laminates having one or more of these functions in combination with additional functions.

[0043] For example, liquid indicator laminates can be produced such that the rate of color change of the indicator is correlated with the choice of face material and the properties of the porous adhesive. For example, discontinuous structures created by pores in the adhesive layer or region can allow liquid to flow from one side of the adhesive through discontinuous adhesive channels to the other side, resulting in permanent color change when dyes or other reagents in the functional coating of the laminate dissolve.

[0044] In one embodiment, a liquid indicator laminate is provided. The rate or extent of the indicator's color change is correlated with surface material properties (e.g., liquid absorbency) and the porosity of the patterned adhesive in the Z-direction. The indication is typically irreversible and can be measured by color change or simple visual comparison.

[0045] Discoloration of a surface or region of a laminate can be measured and quantified by optical changes, for example, through CIE Lab or by simple visual comparison. The discoloration can be permanent or non-permanent. It can also be temporary, returning to its initial state after a period of time. In some embodiments, the time period is a predetermined time interval.

[0046] This phenomenon of transport via discontinuities in the Z-direction through the adhesive can be implemented in other labeling applications, particularly pressure-sensitive adhesive labels, such as labels for vented substrates via air guidance in the Z-direction, labels on damp substrates via liquid guidance in the Z-direction, discharge in the Z-direction, chemical delivery from one layer to another in the Z-direction, and / or acoustic guidance in the Z-direction. This phenomenon allows a medium or reagent to pass through, transfer, and / or migrate from one side of the adhesive region of the laminate to the other side. Although media penetration or transport is indicated as occurring in the Z-direction, it should be understood that the subject matter is not limited to this and may also include penetration / transport in the X and / or Y directions.

[0047] In some embodiments, the laminate of the present invention includes an auxiliary adhesive layer or region. The auxiliary adhesive is typically used to adhere the laminate to a target substrate. The auxiliary adhesive may comprise one or more adhesives that are the same as or different from the patterned or porous adhesive. The present invention provides a description of representative examples of auxiliary adhesives. In this adhesive configuration, a primary adhesive is applied to a face stock, an auxiliary adhesive is applied to a release liner, and then the adhesive-coated liner and face stock are laminated together such that the primary adhesive and auxiliary adhesive are in direct contact with each other. Alternatively or additionally, both the primary adhesive and auxiliary adhesive may be applied to either the face stock or the release liner and then laminated together. It is contemplated that the lamination order of the primary adhesive and auxiliary adhesive relative to the face stock and release liner may be face stock, primary adhesive, auxiliary adhesive, release liner, or face stock, auxiliary adhesive, primary adhesive, release liner. Regardless of the order of the primary and auxiliary adhesives, it is contemplated that at least one of the primary and auxiliary adhesives is a patterned adhesive, while the other adhesive may be a continuous adhesive.

[0048] In some embodiments, different arrays of layers and components may be utilized. In some embodiments using patterned adhesives (e.g., discontinuous adhesive layers), the layer is disposed between the functional face material and the liner or functional layer. In liquid-indicating laminates, the patterned adhesive may be disposed between the functional face material and a functional agent layer or region sensitive to liquids passing through the laminate. In liquid-indicating laminates, the functional agent layer or region may be disposed between the patterned adhesive and the carrier layer.

[0049] The techniques and features described in this invention enable the production of adhesive laminates and / or coated surfaces with fluid / air management properties, controlled removability, and / or unique thermal and / or electrical properties. Furthermore, using these techniques and features can reduce the amount of materials such as adhesives, thereby saving costs. However, it should be understood that this subject matter includes coated surfaces and laminates formed by methods other than those described in this invention.

[0050] Topcoat formulation and application In the exemplary embodiments discussed in this invention, the topcoat is deposited on the substrate by any suitable method. In embodiments, the suitable method includes any suitable coating technique. Embodiments include depositing the coating on the substrate by any suitable liquid deposition method. Without limitation, examples of suitable methods include dip coating, spray coating, slot coating, spin coating, curtain coating, gravure coating, reverse gravure printing coating, reverse roll coating, doctor blade roll (i.e., gap) coating, metering bar coating, air knife coating, or any combination thereof. Dip coating includes immersion or soaking in an aqueous solution. In one embodiment, the coating is deposited by bathing in an aqueous solution. In other embodiments, the coating is deposited by spraying an aqueous solution.

[0051] method After discussing the various components of the device, exemplary methods and operating procedures will be discussed. An exemplary embodiment provides a method comprising: providing a hydrophobic adhesive; providing a hydrophilic adhesive; providing at least one surfactant; providing at least one plasticizer selected from fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof; blending a portion of the hydrophobic adhesive with the hydrophilic adhesive, the at least one surfactant, and the at least one plasticizer; and dispersing the hydrophobic adhesive in a continuous phase of the hydrophilic adhesive to obtain hydrophobic adhesive particles with a particle size between about 0.1 micrometers and about 20 micrometers. This embodiment or another embodiment may provide a first solvent for the hydrophobic adhesive and a second solvent for the hydrophilic adhesive.

[0052] Specific methods for combining adhesives of exemplary embodiments by blending may include, but are not limited to: vertical overhead stirring with paddles or Cowles blades, centripetal speed mixing, or high-pressure homogenization. This combination or mixing will be carried out for sufficient time or intensity to emulsify each pressure-sensitive adhesive in its desired phase. Furthermore, mixing must be performed until the particle size of the hydrophobic pressure-sensitive adhesive is preferably on the order of 0.1 to 20 micrometers, and a wide particle size distribution is also feasible. The resulting blend is applied to a surface material, and if a solvent was used, it is dried in an oven to remove the solvent. The final product may be a roll of tape or a label. The final product can then be attached to a damp surface or substrate without drying the substrate or surface prior to application.

[0053] After properly mixing the adhesive, sample formulations with different proportions were obtained to demonstrate various properties, specifically wet adhesion values ​​in Newtons (N). These can be found in [reference needed]. Figure 2 The process is further discussed in detail below. A surface with a certain moisture level was prepared to fully simulate the humid environment during application. The resulting values ​​were then obtained by measuring the adhesion strength values ​​as shown in the figure. All samples were prepared in the same manner: the substrate container (i.e., a glass bottle filled with water) was placed in a refrigerator. The bottle was then removed from the refrigerated environment and left outdoors for a specified time to allow moisture to form. The face stock with the exemplary adhesive was then applied to the damp substrate. The adhesion strength values ​​were then obtained. Alternatively, a sprayer unit can be used to simulate condensation. Furthermore, a given temperature and humidity level, such as 25°C and 40% humidity, may be present in the room. The coating weight of all adhesives was between 13 and 20 gsm.

[0054] Example Comparative Example A A commercially available pressure-sensitive adhesive, marketed under the name Fasson ® S692N. This S692N adhesive is an acrylic emulsion-based adhesive, available from Avery Dennison, Inc., Mentos, Ohio, USA. Typically, this adhesive is a polymer blend of butyl acrylate and 2-ethylhexyl acrylate monomers with various tackifiers and processing acids. Comparative examples of this single adhesive system show a wet adhesion strength of approximately 1 N.

[0055] Example 1–11A: 4-17 (20:80) A blend of the hydrophilic adhesive and the hydrophobic adhesive of the present invention is obtained, the blend containing 20% ​​hydrophilic adhesive and 80% hydrophobic adhesive. The adhesion strength is approximately 7.5 N.

[0056] Example 2–11A: 4-17 (30:70) A blend of the hydrophilic adhesive and the hydrophobic adhesive of the present invention is obtained, the blend containing 30% hydrophilic adhesive and 70% hydrophobic adhesive. The adhesion strength is approximately 7.5 N.

[0057] Example 3–11A: 4-17 (50:50) A blend of the hydrophilic adhesive and the hydrophobic adhesive of the present invention is obtained, the blend containing 50% hydrophilic adhesive and 50% hydrophobic adhesive. The adhesion strength is approximately 8 N.

[0058] Example 4–14A: 4-17 (20:80) A blend of the hydrophilic adhesive and the hydrophobic adhesive of the present invention is obtained, the blend containing 20% ​​hydrophilic adhesive and 80% hydrophobic adhesive. The adhesion strength is approximately 7.5 N.

[0059] Example 5–14A: 4-17 (30:70) A blend of the hydrophilic adhesive and the hydrophobic adhesive of the present invention is obtained, the blend containing 30% hydrophilic adhesive and 70% hydrophobic adhesive. The adhesion strength is approximately 8 N.

[0060] Example 6–14A: 4-17 (50:50) A blend of the hydrophilic adhesive and the hydrophobic adhesive of the present invention is obtained, the blend containing 50% hydrophilic adhesive and 50% hydrophobic adhesive. The adhesion strength is approximately 8.5 N.

[0061] Example 7 – Glass adhesion vs. PP adhesion vs. wet adhesion In a standard coating process, various samples were coated to a thickness of 20 micrometers. The samples included a control adhesive (A), a hydrophilic polymer adhesive (B), a hydrophobic polymer adhesive (C), and a blend of hydrophobic and hydrophilic adhesives in a 30:70 ratio (D). The ring adhesion strength of these materials was tested on glass and polypropylene (PP) and measured in Newtons. The minimum shear force (N) was also measured using a 25mm × 25mm × 1kg test. Wet adhesion strength was then measured by spraying a controlled amount of water onto the substrate and testing again, similar to the adhesion strength test for glass and polypropylene (PP). The results are summarized in the table below.

[0062] Table 1

[0063] In summary, all samples showed acceptable adhesion strength on glass, with blend (D) maintaining the highest. The hydrophilic polymer adhesive (B) exhibited unacceptably low adhesion strength on PP, but the remaining samples were acceptable. Shear forces were similar for A and B, but D surpassed both. Furthermore, the hydrophobic polymer adhesive (B) showed the best wet adhesion strength, but blend (D) performed exceptionally well. Overall, only the blend performed well in all four tests regarding adhesion to glass and PP, high shear force, and acceptable wet adhesion to glass.

[0064] Example 8 – Pharmaceutical Simulation Example Samples were applied to the moist and wet surfaces of glass vials. The vials were removed from refrigeration and applied while rotating them. First control adhesive (AA), second control adhesive (BB), pharmaceutical adhesive (CC), a first blend (DD) of hydrophobic and hydrophilic adhesives in a 75:25 ratio, and a second blend (EE) of hydrophobic and hydrophilic adhesives in a 70:30 ratio were present. Samples were applied once per minute, followed by qualitative description, where 1 indicates no adhesion or no "grip," and 5 indicates perfect adhesion and good "grip." The results are summarized in Table 2.

[0065] Table 2 Time to remove from refrigerator (minutes)

[0066] It can be seen that the blend is more effective when applied to damp glass substrates.

[0067] All definitions defined and used in this invention should be understood to take precedence over dictionary definitions, definitions in documents incorporated by reference, and / or the general meaning of the defined terms.

[0068] The articles “a” and “an” used in this specification and claims, unless explicitly stated otherwise, shall be construed as meaning “at least one”. The phrase “and / or” (if any) used in this specification and claims shall be construed as meaning “any one or both” of so-called related elements, i.e., elements that exist jointly in some cases and separately in others. Multiple elements listed with “and / or” shall be interpreted in the same manner as “one or more” of so-called related elements. Other elements may optionally be present, whether related to or unrelated to those specifically identified by the “and / or” clause. Thus, as a non-limiting example, when used in conjunction with open-ended language such as “comprising,” reference to “A and / or B” may in one embodiment refer to only A (optionally including elements other than B); in another embodiment to only B (optionally including elements other than A); in yet another embodiment to both A and B (optionally including other elements); and so on. As used in this specification and claims, “or” shall be construed as having the same meaning as “and / or” as defined above. For example, when separating items in a list, “or” or “and / or” should be interpreted as inclusive, meaning it includes at least one, but also more than one, of several or a series of elements, and optionally includes additional unlisted items. Only terms that explicitly indicate the opposite, such as “only one” or “exactly one,” or when used in claims, “consisting of…” will refer to including exactly one of several or a series of elements. Generally, the term “or” as used herein should only be interpreted as indicating an exclusive alternative (i.e., “one or the other but not both”) when preceding exclusive terms such as “either,” “one of,” “only one,” or “exactly one”. “Substantially consisting of…” as used in claims should have its ordinary meaning in the field of patent law.

[0069] As used in this specification and claims, the phrase "at least one" when referring to a list of one or more elements should be understood to mean at least one element selected from any one or more elements in the list, but does not necessarily include each and every element specifically listed in the list, and does not exclude any combination of elements in the list. This definition also allows for the optional presence of other elements besides those specifically identified in the list of elements referred to by the phrase "at least one," whether related to or unrelated to those specifically identified elements. 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") in one embodiment may refer to at least one A, optionally including more than one A, with no B (and optionally including elements other than B); in another embodiment, it may refer to at least one B, optionally including more than one B, with no A (and optionally including elements other than A); in yet another embodiment, it may refer to at least one A, optionally including more than one A, and at least one B, optionally including more than one B (and optionally including other elements); and so on.

[0070] The embodiments are implementations or examples of the present invention. The references in the specification to "an embodiment," "an embodiment," "some embodiments," "a specific embodiment," or "other embodiments," etc., indicate that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least some, but not necessarily all, embodiments of the present invention. The various appearances of "an embodiment," "an embodiment," "some embodiments," "a specific embodiment," or "other embodiments," etc., do not necessarily refer to the same embodiment.

[0071] If this specification states that a component, feature, structure, or characteristic "may," "may," or "can" be included, then that particular component, feature, structure, or characteristic is not necessarily required to be included. If the specification or claims refer to "a" or "an" element, it does not mean that there is only one such element. If the specification or claims refer to "additional" element, it does not exclude the existence of more than one such additional element.

[0072] As used in this specification and claims, including in the embodiments, and unless otherwise expressly stated, all figures should be understood as if prefixed with the words “about” or “approximately,” even if this term is not explicitly stated. When describing size and / or location, the phrase “about” or “approximately” may be used to indicate that the described value and / or location is within a reasonable expected range of values ​​and / or locations. For example, numerical values ​​may have values ​​of + / -0.%, + / -1%, + / -2%, + / -5%, + / -10%, etc., of the stated value (or range of values). Any numerical range referenced in this invention is intended to include all subranges contained herein.

[0073] Furthermore, any method of the present invention may be performed in an order different from that described herein. Therefore, unless explicitly stated otherwise, any order of the methods should not be construed as limiting. It should be understood that performing some steps of the methods in a different order can achieve similar results.

[0074] In the claims and in the description above, all transitional phrases such as “comprising,” “including,” “with,” “having,” “containing,” “involving,” “holding,” “constituting,” etc., should be understood as open-ended, meaning including but not limited to. Only the transitional phrases “constituting of” and “constituting substantially of” should be closed or semi-closed transitional phrases, respectively, as specified in the U.S. Patent and Trademark Office Patent Examination Procedure Manual.

[0075] In the foregoing description, certain terms have been used for the purpose of brevity, clarity, and understanding. No unnecessary limitations should be inferred from these terms beyond the requirements of the prior art, as they are used for descriptive purposes and are intended to be interpreted broadly.

[0076] Furthermore, the descriptions and illustrations of various embodiments of the present invention are exemplary, and the present invention is not limited to the exact details shown or described.

Claims

1. A composition, characterized in that, Include: Continuous hydrophilic adhesives; Dispersed phase hydrophobic adhesive; At least one surfactant; At least one plasticizer; said plasticizer is selected from fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof; The weight ratio of the hydrophilic adhesive to the plasticizer is between about 1:4 and about 4:

1.

2. The composition according to claim 1, characterized in that, The continuous phase hydrophobic adhesive is a pressure-sensitive adhesive.

3. The composition according to claim 1, characterized in that, The dispersed hydrophilic adhesive is a pressure-sensitive adhesive.

4. The composition according to claim 1, characterized in that, The dispersed phase hydrophobic adhesive comprises a polymer selected from the following components: polyisobutylene, polyacrylate, polymethacrylate, silicone, polybutadiene, styrene-butadiene copolymer, polyisoprene, and combinations thereof.

5. The composition according to claim 1, characterized in that, The dispersed phase also contains a solvent.

6. The composition according to claim 5, characterized in that, The solvent is water.

7. The composition according to claim 1, characterized in that, It also contains at least one light stabilizer.

8. The composition according to claim 1, characterized in that, It also contains at least one rheology modifier.

9. The composition according to claim 1, characterized in that, The continuous phase hydrophilic adhesive comprises at least one polymer or copolymer selected from: polyacrylic acid, polymethacrylic acid, copolymers comprising acrylic acid and at least one acrylic acid monomer, vinyl ether anhydride copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, polyethylene glycol copolymers, naturally occurring or naturally derived or synthetic water-soluble polymers and combinations thereof.

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

1.

11. The composition according to claim 1, characterized in that, The continuous phase hydrophilic adhesive contains a solvent.

12. The composition according to claim 11, characterized in that, The solvent is a polar solvent.

13. The composition according to claim 11, characterized in that, The solvent is water.

14. The composition according to claim 1, characterized in that, The surfactant is a nonionic surfactant.

15. The composition according to claim 14, characterized in that, The nonionic surfactant is selected from fatty alcohol ethoxylates, tristyrylphenol ethoxylates, alkyl ether sulfates, sulfosuccinates, polysorbates, glycerides, and combinations thereof.

16. The composition according to claim 1, characterized in that, The weight ratio of the dispersed hydrophobic adhesive to the continuous hydrophilic adhesive is between about 5:95 and about 95:

5.

17. The composition according to claim 16, characterized in that, The weight ratio between the dispersed hydrophobic adhesive and the continuous hydrophilic adhesive is between about 20:80 and about 80:

20.

18. The composition according to claim 1, characterized in that, The particle size of the dispersed hydrophobic adhesive is between about 0.1 micrometers and about 20 micrometers.

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