Foam compositions, related articles and processes comprising silicone MQ resins

Abstract

The foam composition includes a vehicle having voids inside and a silicone MQ resin. The vehicle includes at least one of a silicone-free organic polymer or an organic monomer. The foam composition contains 50 weight percent or less of water. Also described are articles containing the foam composition, as well as processes for making the foam composition and the articles.

Description

Background Art

[0001] [Cross - Reference to Related Applications] This application claims the priority of U.S. Provisional Patent Application No. 63 / 348,396, filed on June 2, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] [Background Art] In a foam, the bubbles are separated from each other by thin liquid films. Typically, a surfactant functions by reducing the surface tension of a liquid so that bubbles introduced below the surface of the liquid can be maintained in the liquid. The surfactant can also adsorb at the interface between the bubble and the liquid film and stabilize the foam by providing a barrier against bubble coalescence. Typically, it is more difficult to form a foam in an organic liquid than to form an aqueous foam. Some fluorinated surfactants are known to produce stable foams in organic liquids. However, recently, there has been a trend in the industry away from using fluorinated surfactants.

[0003] Certain silicone surfactants have been reported to be useful for foaming organic liquids in U.S. Patent No. 4,415,615 (Esmay et al.). On the other hand, silicone MQ resins have been reported to be defoamers in U.S. Patent No. 6,207,722 (Juen et al.) and in the pamphlet "Your Technology - Siltech Chemistry" published by Siltech Corporation, Toronto, Canada in August 2016.

[0004] Inorganic particles are included in many foam compositions for various reasons. Some of these particles function as nucleating agents. Other particles act as fillers that change the physical properties of the composition, for example, changing the rheology of the composition. Still other particles, such as hydrophobic fumed silica, have been found to function as defoaming agents. Fumed silica, also known as pyrogenic silica, consists of primary particles that are irreversibly bonded to each other in the form of aggregates having an average size of 200 nm to 300 nm. U.S. Patent No. 6,586,483 (Kolb et al.) reports a foam composition comprising surface-modified nanoparticles having a particle size of about 100 nanometers or less. U.S. Patent No. 7,141,612 (Baran, Jr. et al.) reports a foam composition comprising surface-modified organic molecules such as fullerenes, dendrimers, organic polymer microspheres, and combinations thereof.

SUMMARY OF THE INVENTION

[0005] The inventors herein report that a composition comprising a silicone MQ resin has the ability to form a persistent foam in an organic liquid. Surprisingly, a composition comprising a silicone MQ resin has the ability to form a persistent foam despite reports that the silicone MQ resin is a defoaming agent. Poly(alkylene oxide) modified polydimethylsiloxane and alkoxylated alcohol have been reported to be useful as surfactants, but in some embodiments, a composition comprising a silicone MQ resin and poly(alkylene oxide) modified polydimethylsiloxane or alkoxylated alcohol surprisingly has the ability to form a persistent foam more than a composition comprising either poly(alkylene oxide) modified polydimethylsiloxane or alkoxylated alcohol alone.

[0006] In one aspect, the present disclosure provides a foam composition comprising a vehicle having internal voids and a silicone MQ resin. The vehicle comprises at least one of a silicone-free organic polymer or an organic monomer. The foam composition comprises 50 weight percent or less water.

[0007] In another aspect, the present disclosure provides an adhesive tape (e.g., a pressure-sensitive adhesive tape) comprising the above-described foam composition.

[0008] In another aspect, the present disclosure provides an article comprising the above-described foam composition. The article can be, for example, a gasket or an automotive body molding.

[0009] In another aspect, the present disclosure provides a process for producing the above-described foam composition, the process comprising introducing a blowing agent into a composition comprising a vehicle and a silicone MQ resin to form voids in the composition.

[0010] In another aspect, the present disclosure provides a process for making a tape, the process comprising foaming an adhesive composition comprising a vehicle comprising at least one of a silicone MQ resin and a silicone-free organic polymer or organic monomer, and subsequently applying the composition to a substrate.

[0011] As used herein, In this application, terms such as "a," "an," and "the" are not intended to refer only to a single entity, but include general classifications, and specific examples thereof may be used for illustration. The terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of" and "comprises at least one of" followed by a listing refer to any one of the items in the listing, and any combination of two or more of the items in the listing. All numerical ranges include their endpoints and non-integer values between the endpoints, unless otherwise stated (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0012] The term "acrylic" refers to polymers, oligomers, and monomers of both acrylic and methacrylic.

[0013] The term “(meth)acrylate” with respect to a monomer, oligomer or polymer means a vinyl-functional alkyl ester formed as a reaction product of an alcohol with acrylic acid or methacrylic acid. “(Meth)acrylate” includes methacrylate and acrylate, individually and collectively.

[0014] Unless otherwise specified, the terms “alkyl group” and the prefix “alk-” encompass both straight-chain and branched-chain groups having up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6 or 5 carbons).

[0015] “Alkylene” is the polyvalent (e.g., divalent or trivalent) form of the “alkyl” group as defined above.

[0016] “Arylalkylene” refers to an “alkylene” moiety to which an aryl group is attached.

[0017] As used herein, “aryl” and “arylene” include, for example, carbocyclic aromatic rings or ring systems optionally containing at least one heteroatom (e.g., O, S or N) within a ring optionally substituted with up to five substituents, including one or more alkyl groups (e.g., methyl or ethyl) having up to 4 carbon atoms, an alkoxy group having up to 4 carbon atoms, a halo group (i.e., fluoro, chloro, bromo or iodo), a hydroxy group or a nitro group, and examples thereof include phenyl, naphthyl, biphenyl, fluorenyl, as well as furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl and thiazolyl.

[0018] The term "polymer" refers to a molecule having a structure that includes a plurality of repetitions of units derived, actually or conceptually, from one or more monomers. The term "monomer" refers to a molecule of low relative molecular weight that can combine with others to form a polymer. The term "polymer" includes homopolymers and copolymers, and also homopolymers or copolymers that can be formed in a miscible blend, for example, by coextrusion or reaction. The term "polymer" includes random polymers, block polymers, graft polymers, and star polymers. The term "copolymer" includes oligomers.

[0019] A "unit" of a polymer or oligomer is a segment of the polymer or oligomer derived from a single monomer.

[0020] The term "crosslinking" generally refers to the formation of a network polymer in which polymer chains are connected to each other by chemical covalent bonds through crosslinkable molecules or groups. Crosslinked polymers are generally characterized by insolubility, but can be swellable in the presence of a suitable solvent. The term "crosslinked" includes being partially crosslinked. Thermosetting polymers are crosslinked.

[0021] The term "persistent foam" refers to the presence of gas voids in the composition for at least 5 minutes after the composition has foamed.

[0022] The term "hydrocarbon" refers to a compound having only carbon atoms and hydrogen atoms. For a hydrocarbon alcohol or a hydrocarbon surfactant, the descriptor "hydrocarbon" excludes the hydroxyl group or hydrophilic group of the surfactant.

[0023] The term "ceramic" refers to glass, crystalline ceramics, glass ceramics, and combinations thereof.

[0024] The above summary of the present disclosure is not intended to describe each or all implementations of the disclosed embodiments. The following description illustrates exemplary embodiments in more detail. Accordingly, it should be understood that the drawings and the following description are for illustrative purposes only and should not be construed as unduly limiting the scope of the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION

[0025] The foam composition of the present disclosure and / or the foam composition useful in the process of the present disclosure contains a silicone MQ resin. The silicone MQ resin is a structural unit called an M unit represented by the formula (R)3SiO 1 / 2 and an organosilicon polymer made from a Q unit represented by the formula SiO 4 / 2 wherein Si is silicon, O is oxygen, and R is either hydrogen or an aliphatic or aromatic organic group. Accordingly, the silicone MQ resin contains a silicon atom bonded to one oxygen atom and a silicon atom bonded to four oxygen atoms. A representative structure of the silicone MQ resin is shown in Formula I below.

[0026]

CHEMICAL

[0027] The ratio of M units to Q units affects the properties of the silicone MQ resin. A silicone MQ resin having an M:Q ratio greater than 1 is typically liquid at room temperature. A silicone MQ resin having an M:Q ratio of 1 or less is typically solid at room temperature. As used herein, "room temperature" refers to 20°C to 25°C. In some embodiments, the silicone MQ resin has an M:Q ratio of at least 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, or 1.5:1. In some embodiments, the silicone MQ resin has an M:Q ratio of at least 0.8:1, 0.9:1, 1:1, 1.1:1, or 1.2:1. The maximum M:Q ratio is 4:1. For silicone MQ resins, the M:Q ratio is typically 3:1 or less, and in some embodiments, 2.9:1, 2.8:1, 2.7:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, or 2:1 or less. For the purposes of this disclosure, the M:Q ratio is determined by NMR spectroscopy using the method described in the Examples section below.

[0028] The silicone MQ resin is represented by the formula (R)3-Si-R 1 with one or more compounds represented by the formula (R 1 )4Si, where R is as defined above in any of its embodiments, and R 1is a hydrolyzable group. The term "hydrolyzable group" refers to a group that can react with water under atmospheric pressure conditions. The reaction with water can optionally be catalyzed by an acid or a base. Suitable hydrolyzable groups include halogen (e.g., iodine, bromo, chloro); alkoxy (e.g., -O-alkyl), aryloxy (e.g., -O-aryl), acyloxy (e.g., -O-C(O)-alkyl), amino (e.g., -NR A )(R B ), polyalkyleneoxy; and oxime (e.g., -O-N=C-(R A )(R B ), where in each formula, each R A or R B is independently hydrogen or alkyl). In some embodiments, each R 1 is independently halogen or alkoxy optionally substituted with halogen. In some embodiments, each R 1 is independently chloro or alkoxy having up to 12 (or up to 6 or 4) carbon atoms. In some embodiments, each R is independently methoxy or ethoxy. When compounds of the formula (R)3-Si-R 1 and (R 1 )4Si react, R 1 is converted to a hydrolyzed group such as -OH during hydrolysis. The Si-OH groups react with each other to form silicone-oxygen bonds. Hydrolysis and condensation can be carried out by conventional methods, for example, by heating compounds of the formula R-Si(R 1 )3 and optionally R 2 -Si(R 1 )3 in water in the presence of an acid or a base, optionally.

[0029] After hydrolysis and condensation, typically -OH groups are present in the silicone MQ resin. The -OH groups are further reacted with an end-capping agent to convert them to hydrolyzed groups, for example, converting -OH to OSi(R)3. Suitable end-capping agents include, for example, those having the formula R 1 -Si(R)3 and O[Si(R)3]2, where in the formula, R 1is as defined above in any of its embodiments. Suitable end-capping agents include those having the formula H-Si(R)3 that can react with hydroxyl groups in the presence of a transition metal catalyst (e.g., a palladium catalyst and a platinum catalyst). The silicone MQ resin contains a further group having the formula -Si(R)3 after end-capping, wherein R is, independently of the other R groups in the silicone MQ resin, as defined above in any of its embodiments. In some embodiments, the silicone MQ resin has a hydroxyl content in the range of 185 to 1840 milliequivalents per kilogram (meq / kg). In some embodiments, the silicone MQ resin has a hydroxyl content in the range of 500 to 1000 milliequivalents per kilogram (meq / kg). For the purposes of the present disclosure, the hydroxyl content is determined by NMR spectroscopy using the method described in the following examples to determine the MQ ratio.

[0030] Depending on the M:Q stoichiometry, synthetic preparation, and end-capping, the silicone MQ resin can adopt various polycyclic structures and can have various properties such as solubility in an organic vehicle. Although Formula I is shown as having a structured structure at least in the central part, it should be understood that the silicone MQ resin can have a more random structure. Thus, silicone MQ resins useful for practicing the present disclosure include three-dimensional and branched random copolymers.

[0031] Silicone MQ resins can be obtained from various commercial suppliers, for example, from Siltech, Corporation, Toronto, Ontario, Canada under the trade name "SILMER Q"; from Dow Chemical Company, Midland, Michigan under the trade name "DOWSIL"; from Wacker Chemie, Munich, Germany, from Momentive Performance Materials, Waterford, New York under the trade name "SILGRIP"; from BYK-Chemie, Wesel, Germany, and from Gelest, Inc., Morrisville, Pennsylvania. Silicone MQ resins have been reported to provide release properties, lubricity, tack, flexibility, and / or water repellency. Further, MQ resins have been explicitly reported as "defoamers" and "anti-foaming agents". Silicone MQ resins are generally not known as surfactants. In some embodiments, the silicone MQ resin does not include those represented by an alkyloxy group, for example, of the formula -(OR 2 ) n -OR 3 , where n, R 2 , and R 3 are as defined below in any of those embodiments.

[0032] In some embodiments, the silicone MQ resin is present in the foam composition in the range of 0.1 weight percent to 10 weight percent, based on the total weight of the foam composition. In some embodiments, the silicone MQ resin is present in the foam composition in the range of 0.1 weight percent to 5 weight percent, or in the range of 0.5 weight percent to 3 weight percent, based on the total weight of the foam composition. The silicone MQ resin may be present in the foam composition in an amount of at least 0.1, 0.2, 0.3, 0.4, or 0.5 weight percent and at most 10, 5, 4, or 3 weight percent, based on the total weight of the foam composition.

[0033] In some embodiments, the foam composition of the present disclosure or the foam composition made by the process of the present disclosure further comprises a nonionic surfactant. In some embodiments, the foam composition of the present disclosure or the foam composition made by the process of the present disclosure further comprises a poly(alkylene oxide) modified polydimethylsiloxane. Polydimethylsiloxane is an organosilicon polymer composed of structural units called D units represented by the formula (R)2SiO 2 / 2 and is an organic silicon polymer composed of structural units called D units represented by the formula, where Si is silicon, O is oxygen, and R is a methyl group. In some embodiments, the poly(alkylene oxide) modified polydimethylsiloxane is not fluorinated. In some embodiments, the poly(alkylene oxide) modified polydimethylsiloxane is not halogenated. Polydimethylsiloxane contains a repeating divalent unit represented by Formula II:

[0034]

Chemical formula

[0035]

Chemical formula

[0036] In some embodiments, the poly(alkylene oxide) modified polydimethylsiloxane useful in the foam compositions of the present disclosure can be represented by Formula IV:

[0037]

Chemical formula

[0038] The number of repeating units and the molecular weight of the polysiloxane can be determined, for example, by nuclear magnetic resonance (NMR) spectroscopy using techniques known to those skilled in the art. Molecular weights, particularly for high molecular weight materials such as number average molecular weight and weight average molecular weight, can also be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using techniques known to those skilled in the art. For the purposes of the present disclosure, the number average molecular weight of the poly(alkylene oxide) modified polydimethylsiloxane is determined by NMR spectroscopy using the method described in the following examples.

[0039] In some embodiments, the foam composition of the present disclosure or the foam composition produced by the process of the present disclosure further comprises an alkoxylated alcohol. In some embodiments, the alcohol has a linear or branched hydrocarbon chain having 10 to 20 carbon atoms. Suitable alkoxylated alcohols include those represented by the formula R 10 -(OR 2 ) n wherein R 2 and n are as described above in any of those embodiments, and R 10 is a linear or branched alkyl or alkenyl chain having 10 to 20 carbon atoms. The alkoxylated alcohol is a random or block form of polyoxyethylene (POE) and polyoxypropylene (POP) units (i.e., wherein OR 2is independently -OCH2CH2-, -OCH(CH3)CH2-, or -OCH2CH(CH3)-, and n is 1 to 100, 3 to 50, or 5 to 20). At least one of them may be included. Suitable examples include POE(4 - 11) lauryl ether, POE(10 - 20) cetyl ether, POE(4 - 20) oleyl ether, POP(5) lauryl ether, POP(7) cetyl ether, POP(10) oleyl ether, and POE(3)POP(5) lauryl ether. The numerical values in parentheses for POE and POP indicate the number of units of oxyethylene units and oxypropylene units. In some embodiments, the alkoxylated alcohol is an alcohol ethoxylate. Suitable alkoxylated alcohols include, for example, a 5 - mole ethoxylate of a linear primary C12 - C14 alcohol available as a surfactant with the trade name "SURFONIC L24 - 5" from Huntsman Corporation, The Woodlands, Tex., and an alcohol ethoxylate available as the trade name "ECOSURF EH - 6" from Dow Chemical Company. In some embodiments, the alkoxylated (e.g., ethoxylated, propoxylated, or a combination thereof) alcohol is an alkoxylated branched - chain alcohol, and in some embodiments, it is an alkoxylated geranylgeraniol. C 10 Examples of geranylgeraniol are represented by the formula:

[0040] [Chemical formula] Suitable alkoxylated geranylgeraniols include those available under the trade name "LUTENSOL XP" from BASF Corporation, Florham Park, New Jersey.

[0041] In some embodiments, at least one of the silicone MQ resin and the poly(alkylene oxide) modified polydimethylsiloxane or alkoxylated alcohol is present in the foam composition in a combined amount of from 0.1 weight percent to 10 weight percent, based on the total weight of the foam composition. In some embodiments, at least one of the silicone MQ resin and the poly(alkylene oxide) modified polydimethylsiloxane or alkoxylated alcohol is present in the foam composition in the range of from 0.1 weight percent to 5 weight percent, or in a combined amount of from 0.5 weight percent to 3 weight percent, based on the total weight of the foam composition. At least one of the silicone MQ resin and the poly(alkylene oxide) modified polydimethylsiloxane or alkoxylated alcohol may be present in the foam composition in a combined amount of at least 0.1, 0.2, 0.3, 0.4, or 0.5 weight percent and at most 10, 5, 4, or 3 weight percent, based on the total weight of the foam composition. In some embodiments, the foam composition does not contain a fluorinated surfactant.

[0042] The foam composition of the present disclosure and / or the foam composition useful in the process of the present disclosure includes a vehicle having voids therein. The vehicle includes at least one of a silicone-free organic polymer or an organic monomer. In some embodiments, the vehicle includes an organic polymer and an organic monomer used to make the organic polymer. The voids may be present on the surface of the composition, dispersed throughout the composition, or a combination thereof. In some applications, the voids are uniformly dispersed throughout the composition. The voids generally contain at least one gas and thus may be referred to as gas voids or bubbles. In some embodiments, the foam composition includes a cellular structure in which the voids are in the form of closed cells. In some embodiments, the foam composition is an open-cell foam.

[0043] The vehicle of the foam composition of the present disclosure or the vehicle of the foam composition made by one of the processes of the present disclosure can include various components and can be in the form of a solid, a liquid, or a combination thereof. The vehicle can be selected based on the desired properties of the foam composition (e.g., tackiness, rigidity, hardness, density, volume, transparency, flexibility, conformity, resilience, creep, strength, modulus of elasticity, elongation, chemical resistance, temperature resistance, environmental resistance, and compressibility). In some embodiments, upon foaming, the vehicle is a liquid and can be, for example, a solution, an emulsion, a suspension, a dispersion, a syrup, or a melt. In some embodiments, the vehicle includes an organic liquid. Useful examples of organic liquids include acids, alcohols, ketones, aldehydes, amines, ethers, hydrocarbons, halocarbons, monomers, oligomers, and polymers.

[0044] In some embodiments, the vehicle includes water. In some embodiments, the vehicle is water-free. The foam composition includes 50, 40, 30, 20, 10, 5, or 1 weight percent or less of water.

[0045] Examples of useful organic vehicles include organic polymers. Suitable organic polymers for the vehicle include nitrile rubber (e.g., acrylonitrile-butadiene), polyisoprene rubber, polychloroprene rubber, polybutadiene rubber, butyl rubber, ethylene-propylene-diene monomer rubber (EPDM), Santoprene® polypropylene-EPDM elastomer, ethylene-propylene rubber, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-styrene rubber, styrene-isoprene-styrene rubber, styrene-ethylene-butylene-styrene rubber, styrene-ethylene-propylene-styrene rubber, polyisobutylene rubber, ethylene vinyl acetate rubber, polymethacrylate rubber, polyacrylate rubber (e.g., a copolymer of isooctyl acrylate and acrylic acid or any of those further detailed below), polyester, polyether ester, polyvinyl ether, polyurethane, and natural and synthetic rubber resins including thermosetting rubbers and thermoplastic rubbers and elastomers such as blends and copolymers thereof. Useful copolymers include linear, radial, star-shaped and tapered block copolymers and combinations thereof.

[0046] Other elastomers suitable for the vehicle include fluoroelastomers (e.g., polytetrafluoroethylene, polyvinylidene fluoride, hexafluoropropylene, and fluorinated ethylene-propylene copolymer), fluorosilicone and chloroelastomers (e.g., chlorinated polyethylene), and combinations thereof.

[0047] As further examples of organic polymers suitable for vehicles, there may be mentioned thermoplastic resins such as polyacrylonitrile, acrylonitrile-butadiene-styrene, styrene-acrylonitrile, cellulose, chlorinated polyether, ethylene vinyl acetate, fluorocarbons (such as polychlorotrifluoroethylene, polytetrafluoroethylene, fluorinated ethylene-propylene, and polyvinylidene fluoride), polyamides (such as polycaprolactam, polyhexamethylene adipamide, polyhexamethylene sebacamide, polyundecanamide, polylaurylamide, and polyacrylamide), polyimides (such as polyetherimide), polycarbonates, polyolefins (such as polyethylene, polypropylene, polybutene, and poly-4-methylpentene), polyalkylene terephthalates (such as polyethylene terephthalate), polyalkylene oxides (such as polyphenylene oxide), polystyrene, polyurethanes, polyisocyanurates, vinyl polymers (such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyvinylidene chloride), and combinations thereof.

[0048] Further examples of organic polymers suitable for the vehicle include thermosetting resins such as polyesters and polyurethanes, and their hybrids and copolymers including acylated urethanes and acylated polyesters, amino resins (e.g., aminoplast resins, alkylated urea-formaldehyde resins, melamine-formaldehyde resins), acrylate resins (e.g., polyacrylates and polymethacrylates, vinyl acrylates, acrylated epoxies, acrylated polyurethanes, acrylated polyesters, acrylated acryl, acrylated polyethers, and acrylated oils), alkyd resins such as urethane alkyd resins, polyester resins, reactive urethane resins, phenolic resins (e.g., resol resins, novolak resins, and phenol-formaldehyde resins), phenol / latex resins, epoxy resins (e.g., bisphenol epoxy resins, aliphatic and cycloaliphatic epoxy resins, epoxy / urethane resins, and epoxy / acrylate resins), isocyanate resins, isocyanurate resins, reactive vinyl resins, and mixtures thereof.

[0049] In some embodiments, the vehicle comprises at least one of isocyanate, polyurethane, or polyurea. A wide variety of isocyanates and polyols and polyurethanes made therefrom can be used in the foam compositions of the present disclosure. In some embodiments, the foam composition is a polyurethane foam, and the process for making the foam composition is a process for making a polyurethane foam.

[0050] In some embodiments, the vehicle comprises an organic polymer other than silicone or a silicone-containing polymer. In some embodiments, the vehicle comprises an organic polymer other than acrylated silicone, silicone-containing polyurethane, or epoxy / silicone resin.

[0051] In some embodiments, the vehicle includes an adhesive composition such as a pressure-sensitive adhesive composition, a hot-melt adhesive composition, a thermosetting adhesive composition, and a thermoplastic adhesive composition. The vehicle can include any pressure-sensitive adhesive composition that can be coated, hot-melt coated, radiation curable (e.g., by electron beam, actinic rays such as visible and UV, and heat), and combinations thereof. Suitable pressure-sensitive adhesive (PSA) compositions for the vehicle include tackifying rubber adhesives (e.g., natural rubber, olefin, polyisoprene, polybutadiene, polyurethane, styrene-isoprene-styrene and styrene-butadiene-styrene block copolymers and other elastomers), and tackifying and non-tackifying acrylic adhesive compositions. In some embodiments, the PSA composition does not contain silicone rubber and / or does not include silicone rubber.

[0052] In some embodiments, the vehicle includes at least one of an acrylic polymer (e.g., acrylic PSA) or a precursor thereof (e.g., a first and optionally a second acrylic monomer). In some embodiments, the vehicle includes a copolymer of an alkyl ester of acrylic acid as a first monomer and optionally a small amount of a second monomer. Useful acrylic esters include acrylic or methacrylic esters of monohydric alcohols having 1 to 20 carbon atoms. Suitable acrylic or methacrylic esters of monohydric alcohols include those represented by formula V: CH2=C(R 5 )COOR 6 (V) [wherein, R 5 is hydrogen or a methyl group, and R 6is an alkyl group having 4 to 20, 4 to 18, 4 to 16, 4 to 12, 6 to 12 or 8 to 12 carbon atoms, and may be linear, branched, cyclic or polycyclic. Examples of suitable monomers represented by Formula V include n-butyl acrylate, s-butyl acrylate, t-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, n-dodecyl acrylate, isomyristyl acrylate, n-tridecyl acrylate, n-tetradecyl acrylate, lauryl acrylate, stearyl acrylate, isostearyl acrylate, isobornyl acrylate, 2-methylbutyl acrylate, 4-methyl-2-pentyl acrylate, octadecyl acrylate, 2-propylheptyl acrylate, methacrylates of the aforementioned acrylates, and combinations thereof. Further examples of suitable monomers for the vehicle include at least two or at least three mixtures of structural isomers of secondary alkyl (meth)acrylates of Formula (VI):

[0053] [Chemical formula] [wherein, R 7 and R 8 are each independently a C1-C 30 saturated linear alkyl group, and the total number of carbon atoms in R 7 and R 8 is 7 to 31, and R 5 is hydrogen or a methyl group]. R 7 and R 8The total number of carbon atoms in some embodiments can be 7 to 27, 7 to 25, 7 to 21, 7 to 17, 7 to 11, or 7. Methods for making and using such monomers and monomer mixtures are described in U.S. Patent No. 9,102,774 (Clapper et al.).

[0054] The second monomer unit can be more polar than the first monomer unit. Examples of suitable second monomers useful for preparing acrylic PSAs include acrylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid), acrylamides (e.g., acrylamide, methacrylamide, N-ethylacrylamide, N-hydroxyethylacrylamide, N-octylacrylamide, N-t-butylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-ethyl-N-dihydroxyethylacrylamide, and the methacrylamides of the aforementioned acrylamides), hydroxyl or amino-substituted acrylates (e.g., 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, 10-hydroxydecyl acrylate, 12-hydroxylauryl acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate, dimethylaminoethyl acrylate, t-butylaminoethyl acrylate, aminoethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, and the methacrylates of the aforementioned acrylates), N-vinylpyrrolidone, N-vinylcaprolactam, alpha-olefins, vinyl ethers, vinyl esters (vinyl acetate, vinyl benzoate, vinyl 4-tert-butylbenzoate, vinyl cinnamate, vinyl decanoate, vinyl neodecanoate, vinyl neononanoate, vinyl pivalate, vinyl propionate, vinyl stearate, and vinyl valerate), allyl ethers, styrenic monomers (e.g., 4-tert-butoxystyrene, 4-(tert-butyl)styrene, 4-chloromethylstyrene, chloromethylstyrene, 3-chlorostyrene, 2(diethylamino)ethylstyrene, 2-methylstyrene, 4-methylstyrene, 4-nitrostyrene, and 4-vinylbenzoic acid), maleates, and combinations thereof.In some embodiments, the acrylic polymer comprises at least one second monomer unit of acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, N-substituted acrylamide, N,N-disubstituted acrylamide, hydroxyalkyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, maleic anhydride or itaconic acid. Other useful monomers that may be present in the acrylate-based adhesive composition include ethylenically unsaturated monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and combinations thereof.

[0055] Crosslinked acrylic PSA can be prepared, for example, by including one or more polyfunctional crosslinkable monomers in the formulation. Suitable polyfunctional monomers include diacrylate esters of diols such as ethylene glycol diacrylate, diethylene glycol diacrylate, propanediol diacrylate, butanediol diacrylate, butane-1,3-diyl diacrylate, pentanediol diacrylate, hexanediol diacrylate (including 1,6-hexanediol diacrylate), heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate, and dimethacrylates of any of the aforementioned diacrylates. Further suitable polyfunctional monomers include polyacrylate esters of polyols such as glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, dipentaerythritol pentaacrylate, methacrylates of any of the aforementioned acrylates, and combinations thereof. Further suitable polyfunctional crosslinkable monomers include polyfunctional acrylate oligomers containing two or more acrylate groups. The polyfunctional acrylate oligomer may be a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, a polyether acrylate, a polyacrylic acrylate, a methacrylate of any of the aforementioned acrylates, or a combination thereof. Crosslinking can also be achieved without a crosslinking agent by using high energy radiation such as gamma rays or electron beam radiation.

[0056] Typically, an alkyl ester of acrylic acid (e.g., the first monomer is used in an amount of 75 weight percent to 100 weight percent based on the total weight of the monomers for making the acrylic polymer, and the second monomer above is used in an amount of 0 weight percent to 25 weight percent based on the total weight of the monomers for making the acrylic polymer. In some embodiments, the first monomer is used in an amount of at least 80, 85, 90, 92, 95, 97, 98 weight percent, or 99 weight percent based on the total weight of the monomers, and the second monomer is used in an amount of at most 20, 15, 10, 8, 5, 3, 2 weight percent, or 1 weight percent based on the total weight of the monomers. These percentages also reflect the percentages of the various monomer units in the acrylic polymer. When present, the polyfunctional crosslinkable monomer can be used in an amount of 0.002 parts to 2 parts per 100 parts of the monofunctional monomer, e.g., about 0.01 part to about 0.5 part or about 0.05 part to 0.15 part per 100 parts of the monofunctional monomer.

[0057] The vehicle can include any of these monomers, a polymer made from any of these monomers, or a combination thereof.

[0058] When the vehicle includes a monomer, the polymerization of the monomer can be achieved by various conventional free radical polymerization methods (e.g., solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization), which can be initiated chemically, thermally, and / or by radiation. The polymerization can be initiated by actinic rays (e.g., visible light or ultraviolet light), electron beam rays, and combinations thereof.

[0059] The vehicle can also include free radical initiators such as thermal initiators and photoinitiators. Certain photoinitiators, when used, can also be consumed during the reaction with light and may not need to be present in the foam composition of the present disclosure. In some embodiments, the foam composition further includes a photoinitiator or a fragment thereof. Any suitable photoinitiator may be useful in a foam composition comprising at least one acrylic monomer, such as the first and second acrylic monomers as described above in any of those embodiments. Suitable photoinitiators include type I or type II photoinitiators. Suitable photoinitiators can also include acetophenone, benzyl ketal, alkylaminoacetophenone, benzoylphosphine oxide, benzoin ether, benzophenone, and benzoyl formate ester. In some embodiments, the free radical photoinitiator is a type I (cleavage type) photoinitiator. Cleavage type photoinitiators include acetophenone, alpha-aminoalkylphenone, benzoin ether, benzoyloxime, acyl (e.g., benzoyl) phosphine oxide, acyl (e.g., benzoyl) phosphinate, and mixtures thereof.

[0060] Examples of useful benzoin ethers include benzoin methyl ether and benzoin butyl ether. Examples of suitable acetophenone compounds include 4 - diethylaminoacetophenone, 1 - hydroxycyclohexyl phenyl ketone, 2 - benzyl - 2 - dimethylamino - 4'-morpholinobutyrophenone, 2 - hydroxy - 2 - methyl - 1 - phenylpropan - 1 - one, and 2,2 - dimethoxy - 1,2 - diphenylethane - 1 - one. Examples of suitable acylphosphine oxides, acylphosphinates, and acylphosphonates include bis(2,6 - dimethoxybenzoyl)-2,4,4 - trimethylpentylphosphine oxide, phenylbis(2,4,6 - trimethylbenzoyl)phosphine oxide, ethylphenyl(2,4,6 - trimethylbenzoyl)phosphinate, (2,4,6 - trimethylbenzoyl)diphenylphosphine oxide, dimethylpivaloylphosphonate and poly(oxy - 1,2 - ethanediyl), α,α’,α”-1,2,3 - propanetriyltris[ω - [[phenyl(2,4,6 - trimethylbenzoyl)phosphinyl]oxy]. Many photoinitiators are available, for example, under the trade name "IRGACURE" from BASF (Vandalia, Ill.), and under the trade names "OMNIRAD" and "ESACURE" from IGM Resins (Waalwijk, Netherlands). Two or more of any of these photoinitiators may be used in combination in any desired combination. The photoinitiator can be selected, for example, based on the desired curing wavelength and compatibility with the composition.

[0061] Examples of suitable thermal initiators include (e.g., benzoyl peroxide, dibenzoyl peroxide, dilauryl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide), hydroperoxides (e.g., butyl hydroperoxide and cumene hydroperoxide), dicyclohexyl peroxydicarbonate, t-butyl perbenzoate, and azo compounds such as 2,2,-azo-bis(isobutyronitrile) (AIBN), and combinations thereof. Examples of commercially available thermal initiators include initiators available under the trade name “VAZO” from The Chemours Company (Wilmington, DE), such as “VAZO 64” (2,2’-azobis(isobutyronitrile)), “VAZO 52”, “VAZO 65” and “VAZO 68”, and initiators available under the trade name “CELOGEN” from CelChem LLC, Naples, FL. Peroxides are available from various suppliers.

[0062] The initiator is used in an amount effective to promote the polymerization of the monomers present in the vehicle, and that amount varies depending on polymerization process factors such as, for example, the type of initiator, the molecular weight of the initiator, the intended use of the resulting adhesive composition, and temperature. The photoinitiator can be used in any amount effective to promote the polymerization of the monomers (e.g., from 0.1 part to about 5 parts, 0.2 part to about 2 parts, or about 0.1 part to about 1 part per 100 parts of monofunctional monomer used to make an acrylic polymer).

[0063] In some embodiments, the vehicle includes a photoinitiator that can be regarded as a photo-crosslinking agent. Examples of suitable photo-crosslinking agents include ethylenically unsaturated compounds that have the ability to abstract hydrogen in the excited state (e.g., acrylated benzophenone, such as those described in U.S. Patent No. 4,737,559 (Kellen et al.)), p-acryloxybenzophenone available from Sartomer Company, Exton, PA, p-N-(methacryloyl-4-oxapentamethylene)-carbamoyloxybenzophenone, monomers such as N-(benzoyl-p-phenylene)-N'-(methacryloxy-methylene)-carbodiimide as described in U.S. Patent No. 5,073,611 (Rehmer et al.), and p-acryloxy-benzophenone) and paraacryloxyethoxybenzophenone; monofunctional benzophenones (e.g., benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4-methylbenzophenone, 4-(2-hydroxyethylthio)-benzophenone and 4-(4-tolylthio)-benzophenone); polyfunctional benzophenones (e.g., carboxymethoxy-benzophenone and the diester of polytetramethylene glycol 250); anthraquinone photo-crosslinking agents (e.g., anthraquinone, 2-methylanthraquinone, 2-t-butylanthraquinone, 2-ethylanthraquinone, 2-phenylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 1,2-dimethylanthraquinone, 1-methoxy-2-methylanthraquinone, 2-acetylanthraquinone and 2,6-di-t-butylanthraquinone);Thioxanthone photo-crosslinking agents (for example, thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl 7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 1-ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)-thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)-thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide, 6-ethoxycarbonyl-2-methoxythioxanthone; and 6-ethoxycarbonyl-2-methylthioxanthone); halomethyl-1,3,5-triazines (for example, 2,4-bis(trichloromethyl)-6-(4-methoxy)phenyl)-s-triazine; 2,4-bis(trichloromethyl)-6-(3,4-dimethoxy)phenyl)-s-triazine; 2,4-bis(trichloromethyl)-6-(3,4,5-trimethoxy)phenyl)-s-triazine; 2,4-bis(trichloromethyl)-6-(2,4-dimethoxy)phenyl)-s-triazine; 2,4-bis(trichloromethyl)-6-(3-methoxy)phenyl)-s-triazine described in U.S. Patent No. 4,330,590 (Vesley);Also included are 2,4-bis(trichloromethyl)-6-naphthylenyl-s-triazine and 2,4-bis(trichloromethyl)-6-(4-methoxy)naphthylenyl-s-triazine as described in U.S. Patent No. 4,329,384 (Vesley). The photo-crosslinking agent may be present in the acrylic polymer in any useful amount. For example, in a vehicle containing at least one acrylic monomer, such as the vehicle containing the first and second acrylic monomers in any of those embodiments, an amount of from 0.001 part to 10 parts, 0.001 part to 5 parts, 0.001 part to 2 parts, 0.001 part to 1 part, 0.001 part to 0.5 part, or 0.001 part to 0.1 part per 100 parts of the monofunctional monomer may be useful.;

[0064] The polymerizable vehicle may also contain a chain transfer agent. The chain transfer agent can be selected to be soluble in the monomer mixture to be polymerized. Examples of suitable chain transfer agents include triethylsilane and mercaptan.

[0065] In some embodiments of the foam composition of the present disclosure and / or the foam composition produced by the method of the present disclosure, the vehicle is derived from a composition comprising at least one acrylic monomer, such as the first and second acrylic monomers described above in any of those embodiments, and a polymer prepared from partial polymerization of at least one acrylic monomer. The vehicle may be a solution of the polymer in at least one monomer, for example, it may be polymerized by about 3 percent to 15 percent. In some embodiments, the vehicle comprises at least 75 weight percent, 80 weight percent, 85 weight percent, 90 weight percent or 95 weight percent of monomer based on the total weight of the vehicle. In some embodiments, the vehicle is exposed to ultraviolet irradiation to provide a solution of the polymer in at least one acrylic monomer. A solution of the polymer in at least one acrylic monomer can also be prepared by partial free radical polymerization using a thermal initiator or other free radical source.

[0066] A useful solventless polymerization method is disclosed in U.S. Patent No. 4,379,201 (Heilmann et al.). First, a mixture of a first and a second monomer is exposed to UV irradiation in an inert environment for a time sufficient to form a coatable base syrup, together with a portion of a photoinitiator, and subsequently polymerized by adding a crosslinking agent and the remaining photoinitiator. The crosslinking can be, for example, with any of the above-mentioned polyfunctional crosslinkable monomers in any of the above amounts. This final syrup containing the crosslinking agent (e.g., having a Brookfield viscosity of about 500 centipoise (cps) to about 10,000 cps at 23°C, about 100 cps to about 6,000 cps at 23°C, or about 5,000 cps to about 7,500 cps at 23°C, measured at 60 revolutions per minute using a No. 4 LTV spindle) can be coated onto a substrate. After coating the syrup onto the substrate, further polymerization and crosslinking can be carried out in an inert environment (e.g., nitrogen, carbon dioxide, helium, and argon, which does not contain oxygen). A sufficiently inert atmosphere can be obtained by covering the layer of the photoactive syrup with a polymer film that is permeable to UV irradiation or electron beam irradiation, such as a silicone-treated PET film.

[0067] Any suitable light source such as a fluorescent UV bulb, mercury lamp (e.g., low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp), xenon lamp, metal halide lamp, electrodeless lamp, incandescent lamp, LED, and laser can be used. In the case of a broadband light source (e.g., fluorescent UV bulb, mercury lamp, or incandescent lamp), a filter may be useful to narrow the wavelength range within or outside the wavelengths absorbed by the UV absorber and / or to modify the intensity of the light source.

[0068] The vehicle and / or foam composition can also include other components, such as curing agents, curing accelerators, catalysts, tackifiers, plasticizers, dyes, flame retardants, adhesion promoters (such as coupling agents like silane coupling agents), pigments, impact resistance improvers, flow regulators, foaming agents, fillers (such as talc, zinc oxide, and fused silica), glass and polymer microspheres and fine particles, conductive particles, heat conductive particles, fibers, antistatic agents, hindered phenols, amines, and antioxidants such as sulfur and phosphorus hydroperoxide decomposers, UV absorbers, stabilizers (such as hindered amine light stabilizers and heat stabilizers), and viscosity regulators such as fumed silica.

[0069] The foam composition of the present disclosure and / or the foam composition produced by the method of the present disclosure may include hollow microspheres (e.g., hollow ceramic (e.g., glass) microspheres, or hollow polymer microspheres, such as elastomeric particles, e.g., those available under the trade name "EXPANCEL" from Akzo Nobel (Amsterdam, The Netherlands). Examples of hollow ceramic microspheres include alumina / silica microspheres ("FILLITE", Pluess-Stauffer International) having a particle size in the range of 5 microns to 300 microns and a specific gravity of 0.7, aluminum silicate microspheres ("Z-LIGHT") having a specific gravity of about 0.45 to about 0.7, calcium carbonate-coated polyvinylidene copolymer microspheres ("DUALITE 6001AE", Pierce & Stevens Corp.) having a specific gravity of 0.13, and glass bubbles commercially available from 3M Company (Saint Paul, Minnesota) as "3M GLASS BUBBLES", grades K1, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S38XHS, S42HS, S42XHS, S60, S60HS, iM30K, iM16K, XLD3000, XLD6000, and G-65, and any of the HGS series of "3M GLASS BUBBLES". A foam containing hollow microspheres is called a syntactic foam. The foam adhesive may also include a hydrocarbon elastomer as described in U.S. Patent No. 5,024,880 (Vesley et al.).

[0070] In some embodiments, the vehicle comprising the adhesive composition comprises tackifiers useful for improving the tack of the surface of the PSA. In some embodiments, the foam composition does not comprise a tackifier. Useful tackifiers can have a number average molecular weight of up to 10,000 grams / mole, a softening point of at least 70° C. as determined using a ring and ball apparatus, and a glass transition temperature of at least −30° C. as measured by differential scanning calorimetry. Useful tackifiers are typically amorphous. In some embodiments, the tackifier is miscible with the PSA polymer, such that no macroscopic phase separation occurs in the PSA. In some embodiments, there is also no microscopic phase separation in the PSA. In some embodiments, the tackifier comprises at least one of rosin, rosin ester, esters of hydrogenated rosin, polyterpenes (e.g., those based on α-pinene, β-pinene or limonene), aliphatic hydrocarbon resins (e.g., those based on cis- or trans-piperylene, isoprene, 2-methyl-but-2-ene, cyclopentadiene, dicyclopentadiene or combinations thereof), aromatic resins (e.g., those based on styrene, α-methylstyrene, methyl indene, indene, coumarone or combinations thereof), or mixed aliphatic-aromatic hydrocarbon resins. Any of these tackifying resins may be (e.g., partially or fully) hydrogenated.Examples of suitable tackifiers include those obtained from “FLORAL” such as “FORAL 85E” (glycerol ester of highly hydrogenated refined gum rosin), commercially available from Eastman, Middelburg, NL; “FORAL 3085” (glycerol ester of highly hydrogenated refined wood rosin), commercially available from Pinova, Brunswick, GA; “ESCOREZ” such as “ESCOREZ 2520” and “ESCOREZ 5615” (aliphatic / aromatic hydrocarbon resins), commercially available from ExxonMobil Corp., Houston, TX; “ARKON” such as the fully hydrogenated hydrocarbon resin “ARKON P125”, commercially available from Arakawa Chemical Inc., Chicago, Illinois; and “REGALITE” such as “REGALITE 7100” (partially hydrogenated hydrocarbon resin), commercially available from Eastman, Kingsport, Tennessee.

[0071] In some embodiments, the vehicle comprises a tackifier in an amount of at least about 1 weight percent and up to about 50 weight percent, based on the total weight of the vehicle. In some embodiments, the tackifier is present in an amount ranging from 1 weight percent to 25 weight percent, 2 weight percent to 20 weight percent, 2 weight percent to 15 weight percent, 1 weight percent to 10 weight percent, or 3 weight percent to 10 weight percent, based on the total weight of the vehicle.

[0072] For example, in order to reduce the vitrification of the adhesive composition, a plasticizer may be added. Suitable plasticizers include various polyalkylene oxides (e.g., polyethylene oxide or propylene oxide), adipic acid esters, formic acid esters, phosphoric acid esters, benzoic acid esters, phthalic acid esters, polyisobutylene, polyolefins, and sulfonamides, naphthenic oils, plasticizing aids such as materials described as plasticizers in Dictionary of Rubber, K.F. Heinisch, pp. 359, John Wiley & Sons, New York (1974), oils, elastomer oligomers, and waxes. When using a plasticizer, the amount of the plasticizer used varies depending on the properties of the plasticizer and the compatibility with the vehicle.

[0073] In some embodiments, the foam composition of the present disclosure and / or the foam composition made by the process of the present disclosure are substantially solvent-free. Common organic solvents include aliphatic and cycloaliphatic hydrocarbons (e.g., hexane, heptane, and cyclohexane), hydrocarbon solvents (e.g., benzene, toluene, xylene, and d-limonene); acyclic and cyclic ketones (e.g., acetone, methyl ethyl ketone, and methyl isobutyl ketone, pentanone, hexanone, cyclopentanone, and cyclohexanone); ethers (e.g., diethyl ether, glyme, diglyme, diisopropyl ether, and tetrahydrofuran), esters (e.g., ethyl acetate and butyl acetate), sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone), halogenated solvents (e.g., methyl chloroform, 1,1,2-trichloro-1,2,2-trifluoroethane, trichloroethylene, and trifluorotoluene), and alcohol solvents (e.g., propanol such as methanol, ethanol, or isopropanol). The foam composition may be substantially free of any of these solvents. The term "substantially free" means that the foam composition may contain up to 0.5, 0.1, 0.05 weight percent, or up to 0.01 weight percent of any of these solvents, or may contain none of these solvents. These percentages are based on the total weight of the foam composition.

[0074] In some embodiments, the vehicle includes a silane coupling agent. Examples of useful silane couplings include organosilanes such as alkylchlorosilanes, alkoxysilanes (e.g., methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, phenyltriethoxysilane, polytriethoxysilane, vinyltrimethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, vinyltri(t-butoxy)silane, vinyltris(isobutoxy)silane, vinyltris(isopropenoxy)silane, and vinyltris(2-methoxyethoxy)silane); N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethylcarbamate; N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethylcarbamate; silane-functional (meth)acrylates (e.g., 3-(methacryloyloxy)propyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(acryloyloxypropyl)methyldimethoxysilane, 3-(methacryloyloxy)propyldimethylethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, 3-(methacryloyloxy)propyldimethylethoxysilane, and 3-(methacryloyloxy)propenyltrimethoxysilane);Epoxysilanes, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethoxydimethoxysilane, and 3-glycidoxypropyltriethoxysilane; and aminosilanes, such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. The silane coupling agent can be used in an amount of about 0.05 wt% or more or about 0.1 wt% or more and about 2 wt% or less or about 1 wt% or less based on the total weight of the vehicle.;

[0075] In some embodiments, the foam composition of the present disclosure and / or the foam composition made by the process of the present disclosure further comprises a blowing agent. Useful blowing agents include physical blowing agents and chemical blowing agents, any of which may be inorganic or organic. Useful chemical blowing mechanisms include in-situ gas generation by chemical reaction; decomposition of the components of the composition, e.g., decomposition of components that release gas upon thermal decomposition; evaporation of the components of the composition, e.g., evaporation of a liquid gas; volatilization of gas in the composition due to a decrease in pressure of the composition or volatilization of gas in the composition due to heating of the composition; and combinations thereof.

[0076] Examples of chemical blowing agents include water and azo-based, carbonate-based, and hydrazide-based molecules including, for example, 4,4'-oxybis(benzenesulfonyl)hydrazide, 4,4'-oxybenzenesulfonyl semicarbazide, azodicarbonamide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate, azodiisobutyronitrile, benzenesulfonhydrazide, trihydrazinotriazine, metal salts of azodicarboxylic acid, oxalic acid hydrazide, hydrazocarboxylate, diphenyloxide-4,4'-disulfohydrazide, tetrazole compounds, sodium bicarbonate, ammonium bicarbonate, preparations of carbonate compounds and polycarbonates, mixtures of citric acid and sodium bicarbonate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, N,N'-dinitrosopentamethylenetetramine, and combinations thereof. Water is a blowing agent useful for making polyurethane foams. Water reacts with isocyanate to ultimately form carbon dioxide, which foams the polyurethane.

[0077] Suitable inorganic physical blowing agents include, for example, nitrogen, argon, oxygen, water, air, helium, sulfur hexafluoride, and combinations thereof.

[0078] Useful organic physical blowing agents include carbon dioxide, aliphatic hydrocarbons, aliphatic alcohols, fully and partially halogenated aliphatic hydrocarbons such as methylene chloride, and combinations thereof. Examples of suitable aliphatic hydrocarbon blowing agents include members of the alkane series of hydrocarbons such as, for example, methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, and blends thereof. Useful aliphatic alcohols include, for example, methanol, ethanol, n-propanol, and isopropanol, and combinations thereof. Suitable fully and partially halogenated aliphatic hydrocarbons include, for example, fluorocarbons, chlorocarbons, and chlorofluorocarbons, and combinations thereof.

[0079] Examples of suitable halogenated (in some embodiments, fluorinated) blowing agents include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,3,3-pentafluoropropane, pentafluoroethane (HFC-125), difluoromethane (HFC-32), perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane, methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124), trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichloro-trifluoroethane (CFC-113), dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane, and combinations thereof. In some embodiments, the blowing agent is not halogenated. In some embodiments, the blowing agent is not fluorinated.

[0080] The blowing agents can be used as single components, as mixtures and combinations thereof, and as mixtures with other co-blowing agents. The blowing agents can be added to the composition in an amount sufficient to achieve the desired foam density.

[0081] In some embodiments, the foam compositions of the present disclosure and / or foam compositions made by the processes of the present disclosure further comprise a nucleating agent. The nucleating agent can be any conventional nucleating agent. The amount of nucleating agent added can be selected according to the desired cell size, the selected blowing agent, and the density of the vehicle. Examples of inorganic nucleating agents in particulate form include clay, talc, silica, and diatomaceous earth.

[0082] The organic nucleating agent can decompose or react at a given temperature. An example of an organic nucleating agent is a combination of an alkali metal salt of a polycarboxylic acid and a carbonate or bicarbonate. Examples of useful alkali metal salts of polycarboxylic acids include the monosodium salt of 2,3-dihydroxy-butanedioic acid (i.e., sodium hydrogen tartrate), the monopotassium salt of butanedioic acid (i.e., potassium hydrogen succinate), the trisodium and tripotassium salts of 2-hydroxy-1,2,3-propanetricarboxylic acid (i.e., sodium citrate and potassium citrate, respectively), and the disodium salt of ethanedioic acid (i.e., sodium oxalate), and polycarboxylic acids such as 2-hydroxy-1,2,3-propanetricarboxylic acid, and combinations thereof. Examples of carbonates and bicarbonates include sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, calcium carbonate, and combinations thereof. One contemplated combination is a combination of a mono-alkali metal salt of a polycarboxylic acid (e.g., sodium citrate or sodium tartrate) and a carbonate or bicarbonate. It is contemplated that mixtures of different nucleating agents can be added to the vehicle. Other useful nucleating agents include the stoichiometric mixture of citric acid and sodium bicarbonate.

[0083] In some embodiments, the foam composition of the present disclosure has a foam half-life of at least 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 45 minutes, or 60 minutes at 22°C. In this application, the foam half-life is determined by placing approximately 30 grams of a 1 weight percent solution of silicone MQ resin alone or in combination with a surfactant in a vehicle into a 4-ounce glass jar, and bubbling nitrogen through the mixture for 5 minutes at 22°C while stirring the mixture with a magnetic stir bar set to a low setting using the apparatus described in the Example Syrup Bubbling Test. Stop bubbling and stop the magnetic stir bar. Measure the height of the foam with a ruler. Measure the time required for half of the liquid to drain from the foam (i.e., to provide half of the initial volume of the liquid) to provide the foam half-life.

[0084] As shown by the comparison of Examples 1-13 and Comparative Examples CE1-CE12 in the following examples, silicone MQ resin, which has been reported to be an antifoaming agent or foam inhibitor, is a surprisingly good foam stabilizer in a vehicle of acrylic monomers. In fact, silicone MQ resin has been shown to be a better foam stabilizer than various surfactants that have been expected to be more suitable for stabilizing foams. As shown by the comparison of Examples 11 and 12 and Comparative Examples 13 and 14 in the following examples, silicone MQ resin, which has been reported to be an antifoaming agent or foam inhibitor, is not detrimental to the foaming ability of certain silicone and hydrocarbon surfactants in a vehicle of acrylic monomers. In fact, silicone MQ resin has been shown to enhance the foaming ability of the surfactant in Example 12.

[0085] The present disclosure provides a process for making the foam composition of the present disclosure in any of its embodiments. The process includes introducing a blowing agent into a composition comprising a vehicle and a silicone MQ resin to form voids in the composition. The blowing agent may be any of the chemical or physical blowing agents described above. The composition can be foamed according to various foaming methods such as those described in, for example, U.S. Patent Nos. 5,024,880 (Vesley et al.), 4,895,745 (Vesley et al.), and 4,748,061 (Vesley et al.).

[0086] The composition may be prepared by forming gas voids in the composition using various mechanisms such as mechanical mechanisms, chemical mechanisms, and combinations thereof. Useful mechanical foaming mechanisms include agitating the composition (e.g., shaking, stirring, and / or whipping the composition), injecting gas into the composition, e.g., inserting a nozzle beneath the surface of the composition and blowing gas into the composition, and combinations thereof. In some embodiments, introducing the blowing agent includes at least one of agitating the composition or injecting gas into the composition. In some embodiments, the blowing agent includes at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon, or nitrous oxide.

[0087] The foam compositions of the present disclosure and / or foam compositions made by the processes of the present disclosure are suitable for use in a variety of applications. Representative examples of foam applications include adhesives, flotation, applications in the automotive industry such as automotive body moldings, applications related to automotive glazing such as gaskets and seals, applications in the construction industry such as structural components (e.g., sized lumber, molded trim, posts, beams, and molded structural members), etc., cementitious materials and gypsum materials such as lightweight ceramics, landfill covers, odor barriers, dust covers, fire extinguishing and fireproof foams, liquid containment booms (e.g., booms for containing oil spills), and fillers for gaps and voids present in oil wells and tunnels and in soil. Other foam applications include packaging, commercial cleaning products such as cleaners for vertical cleaning applications, inks, deinking compositions, surface coatings such as foam coatings for paper and fabric treatment, etc.

[0088] The foam composition can also be formulated for use in applications such as medical applications including bandages and wound dressings, and household and industrial applications including cups, plates, earplugs, cushions, pillows, thermal insulators, e.g., dampers for suppressing sound and absorbing vibrations (e.g., buffering vibrations of machine covers), and combinations thereof, and baffles.

[0089] In another embodiment, the foam composition is formulated to be useful, for example, as a gasket or seal for sealing areas from dust, moisture, organic vapors, and combinations thereof. Examples of sealing applications include sealing gaps between components within a computer printer, sealing of electronic devices, and sealing of skylight assemblies.

[0090] The foam composition can be formulated to provide a foam that is flexible and conformable, fills gaps, and bonds to irregular surfaces. The foam can also be formulated to provide a seal, cushion vibrations, dampen vibrations, resist shock, withstand a wide temperature range, or provide good thermal insulation, or a combination of these properties, and to provide a bond line.

[0091] The foam composition can be in the form of a tape, such as a pressure-sensitive adhesive tape. Useful foam tape structures include a foam composition disposed on a substrate, such as a backing or release liner, and optionally wound in the form of a roll. In some embodiments, the foam tape structure includes an adhesive composition disposed on the surface of the foam tape, which forms a tape having an adhesive layer on one side of the foam tape, i.e., a single-coated adhesive foam tape. In another embodiment, the foam composition may be in the form of a tape having adhesive layers on two major surfaces of the foam tape, which is known as a double-coated foam tape.

[0092] The present disclosure provides a process for making an adhesive tape, the process including applying a foam composition to a substrate. The application of the foam composition to the substrate can be carried out after foaming using any of the methods described above, i.e., after forming voids therein. The foam composition can be applied to the substrate using various methods (e.g., dipping, spraying, brushing, roll coating, bar coating). In some embodiments, the composition can be coated onto a liner using a notch bar for gap setting that provides a desired thickness, and another liner may be added to maintain a gap of the desired thickness. Any of the foam compositions described above in any of those embodiments can be applied to the substrate, but in some embodiments, the vehicle includes monomers and optionally polymers, and the process further includes polymerizing the monomers. In some embodiments, the process further includes crosslinking the foam composition. When polymerization or crosslinking using a UV light source such as any of the above is used, an optional useful amount of UV irradiation such as from about 1,000 mJ / cm 2 to about 10,000 mJ / cm 2 can be used, 1,000 mJ / cm 2 to about 5,000 mJ / cm 2 can be used, or from about 1,000 mJ / cm 2 to about 3,000 mJ / cm 2 can be used.

[0093] Adhesive foams have various useful applications such as, for example, joining two substrates together, attachment applications using articles such as hooks, hangers, and holders, joining applications such as adhesively joining two or more containers, e.g., boxes, together for later separation, attaching articles to surfaces such as walls, floors, ceilings, and counters, and replacing mechanical fasteners, mastics, or liquid adhesives. When joining rough or irregular surfaces, the properties and formulation of the foam tape can be selected to provide a foam tape that evenly distributes stress across the joined area. Other adhesive foam applications include, for example, structural adhesives and in-situ foam adhesives.

[0094] In other embodiments, the foam composition includes other components such as scrims, films, tissues, and combinations thereof, which are dispersed in the foam or arranged in a layered structure with the foam composition, for example, in the form of alternating layers, interpenetrating layers, and combinations thereof. Other useful foam structures include multilayer foam structures that include layers of foam, where these layers differ in at least one property such as density and composition, for example.

[0095] The foam composition can also be subjected to post - processes such as die - cutting, cross - linking, and sterilization, for example.

[0096] Some embodiments of the present disclosure In a first embodiment, the present disclosure provides a foam composition comprising a vehicle having internal voids, the vehicle comprising at least one of a silicone - free organic polymer or an organic monomer, and a silicone MQ resin, wherein the foam composition comprises 50 weight percent or less water. In a second embodiment, the present disclosure provides the foam composition according to the first embodiment, wherein the foam composition comprises 40, 30, 20, 10, 5, 4, 3, 2, or 1 weight percent or less water. In a third embodiment, the present disclosure provides the foam composition according to the first or second embodiment, wherein the silicone MQ resin has an M:Q ratio of at least 0.8:1, 0.9:1, 1:1, 1.1:1, or 1.2:1. In a fourth embodiment, the present disclosure provides the foam composition according to any one of the first to third embodiments, wherein the silicone MQ resin has an M:Q ratio of 2.5:1 or 2:1 or less. In a fifth embodiment, the present disclosure provides that the silicone MQ resin comprises one or more compounds represented by the formula (R)3 - Si - R 1 and one or more compounds represented by the formula (R 1) Prepared by reaction with one or more compounds represented by 4Si, wherein each R is independently hydrogen, alkyl, aryl, alkylene, at least one of which is interrupted or terminated by arylene or heterocyclylene, and alkyl and alkylene are each interrupted or terminated by arylene or heterocyclylene at least one of which, unsubstituted or substituted with halogen, optionally interrupted by at least one chain-linked -O-, -NR’-, -S-, -Si-, or combinations thereof, and aryl, arylene, and heterocyclylene are unsubstituted or substituted with at least one alkyl, alkoxy, halogen, or combinations thereof, each R 1 is independently a hydrolyzable group, and provides the foam composition according to any one of the first to fourth embodiments. R may be other than hydrogen. R is an alkyloxy group, for example, of the formula -(OR 2 ) n -OR 3 group, wherein n, R 2 , and R 3is free of a base as defined below in any of those embodiments. In a sixth embodiment, the present disclosure provides a foam composition according to any one of the first to fifth embodiments, wherein the silicone MQ resin contains an alkyl group or a methyl group. In a seventh embodiment, the present disclosure provides a foam composition according to any one of the first to sixth embodiments, wherein the silicone MQ resin has a hydroxyl content in the range of 185 to 1840 milliequivalents per kilogram (185 to 1840 milliequivalents per kilogram). In an eighth embodiment, the present disclosure provides a foam composition according to any one of the first to seventh embodiments, wherein the MQ resin is present in the foam composition in an amount of 0.1 weight percent to 10 weight percent, 0.1 weight percent to 5 weight percent, or 0.5 weight percent to 5 weight percent based on the total weight of the foam composition. In a ninth embodiment, the present disclosure provides a foam composition according to any one of the first to eighth embodiments, further comprising a poly(alkylene oxide) modified polydimethylsiloxane. In a tenth embodiment, the present disclosure provides that the poly(alkylene oxide) modified polydimethylsiloxane has a repeating divalent unit represented by formula II:

[0097] [Chemical Formula] and a terminal unit represented by the formula -Q-(OR 2 ) n -OR 3 or formula III:

[0098] [Chemical Formula] comprising at least one of the divalent units represented by, wherein each Q is independently alkylene, arylene, or aryl, at least one of which is interrupted or terminated by aryl, each of which is optionally interrupted or terminated by at least one of ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, or thiourea, and each OR 2 is independently -OCH2CH2-, -OCH(CH3)CH2-, -OCH2CH2CH2-, -OCH2CH(CH3)-, -OCH2CH2CH2CH2-, -OCH(CH2CH3)CH2-, -OCH2CH(CH2CH3)-, and -OC(CH3)2CH2-, each n is independently a value from 5 to 300, and each R 3is hydrogen, alkyl, acyl, aryl, or arylalkylenyl, and aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or a combination thereof, and provides the foam composition according to the ninth embodiment. In the eleventh embodiment, the present disclosure provides the foam composition according to the ninth or tenth embodiment, wherein the poly(alkylene oxide) modified polydimethylsiloxane has a number average molecular weight of 50,000 grams / mole or less, 40,000 grams / mole or less, 30,000 grams / mole or less, 20,000 grams / mole or less, or 10,000 grams / mole or less. In the twelfth embodiment, the present disclosure provides the foam composition according to any one of the ninth to eleventh embodiments, wherein the poly(alkylene oxide) modified polydimethylsiloxane contains an ethyleneoxy group, a proyleneoxy group, or a combination thereof. In the thirteenth embodiment, the present disclosure provides the foam composition according to any one of the first to twelfth embodiments, further comprising an alkoxylated alcohol. In the fourteenth embodiment, the present disclosure provides the foam composition according to the thirteenth embodiment, wherein the alkoxylated alcohol is an alkoxylated hydrocarbon alcohol. In the fifteenth embodiment, the present disclosure provides the foam composition according to the thirteenth or fourteenth embodiment, wherein the alkoxylated alcohol is an ethoxylated hydrocarbon alcohol. In the sixteenth embodiment, the present disclosure provides the foam composition according to any one of the ninth to fifteenth embodiments, wherein at least one of the silicone MQ resin and the poly(alkylene oxide) modified polydimethylsiloxane alkoxylated alcohol is present in the foam composition in a combined amount of 0.1 weight percent to 10 weight percent, 0.1 weight percent to 5 weight percent, or 0.5 weight percent to 5 weight percent based on the total weight of the foam composition.

[0099] In the 17th embodiment, the present disclosure provides the foam composition according to any one of the 1st to 16th embodiments, wherein the vehicle contains at least one of a thermoplastic polymer, a thermosetting polymer, or an elastomer. In the 18th embodiment, the present disclosure provides the foam composition according to any one of the 1st to 17th embodiments, wherein the vehicle contains at least one of a polyester, a polyurethane, an amino resin, an alkyd resin, a phenol resin, an epoxy resin, an isocyanate resin, an isocyanurate resin, or an acrylic polymer. In the 19th embodiment, the present disclosure provides the foam composition according to any one of the 1st to 18th embodiments, wherein the vehicle contains a crosslinked polymer. In the 20th embodiment, the present disclosure provides the foam composition according to any one of the 1st to 19th embodiments, wherein the vehicle contains at least one of an acrylate polymer or an acrylic polymer. In the 21st embodiment, the present disclosure provides the foam composition according to any one of the 1st to 19th embodiments, wherein the vehicle is a mixture of at least two or at least three of isooctyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, butyl acrylate, acrylic acid, or a structural isomer of a secondary alkyl (meth)acrylate of the following formula (VI):

[0100] [Chemical formula] [wherein, R 7 and R 8 are each independently a C1-C 30 saturated straight-chain alkyl group, and the total number of carbon atoms in R 7 and R 8 is 7 to 31, and R 5Provided is the foam composition according to any one of the first to nineteenth embodiments, which contains at least one of a polymer that is a hydrogen or methyl group or contains any unit thereof. In the twenty-second embodiment, the present disclosure provides the foam composition according to any one of the first to twenty-first embodiments, wherein the vehicle contains acrylic acid and at least one of isooctyl acrylate or 2-ethylhexyl acrylate. In the twenty-third embodiment, the present disclosure provides the foam composition according to any one of the first to twenty-second embodiments, wherein the vehicle contains a polyolefin. In the twenty-fourth embodiment, the present disclosure provides the foam composition according to any one of the first to twenty-third embodiments, wherein the vehicle contains at least one of a novolak resin, a resol resin, or a polyurea resin. In the twenty-fifth embodiment, the present disclosure provides the foam composition according to any one of the first to twenty-fourth embodiments, wherein the vehicle contains at least one of an isocyanate, a polyurethane, or a polyurea. In the twenty-sixth embodiment, the present disclosure provides the foam composition according to any one of the first to twenty-fifth embodiments, wherein the vehicle contains at least one of an alcohol, an aldehyde, a ketone, an ester, an ether, an amine, an amide, or a hydrocarbon.

[0101] In the 27th embodiment, the present disclosure provides a foam composition according to any one of the 1st to 26th embodiments, wherein the vehicle has a gap inside. In the 28th embodiment, the present disclosure provides a foam composition according to the 27th embodiment, wherein the gap contains at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon, or nitrous oxide. In the 29th embodiment, the present disclosure provides a foam composition according to any one of the 1st to 28th embodiments, further comprising a blowing agent. In the 30th embodiment, the present disclosure provides a foam composition according to the 29th embodiment, wherein the blowing agent contains at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon, or nitrous oxide. In the 31st embodiment, the present disclosure provides a foam composition according to any one of the 1st to 30th embodiments, having a foam half-life of at least 10 minutes at 22°C. In the 32nd embodiment, the present disclosure provides a foam composition according to any one of the 1st to 31st embodiments, further comprising at least one of fumed silica, hollow ceramic microspheres, or hollow polymer microspheres. In the 33rd embodiment, the present disclosure provides a foam composition according to any one of the 1st to 32nd embodiments, wherein the foam composition does not contain a fluorinated surfactant.

[0102] In the 34th embodiment, the present disclosure provides a foam composition according to any one of the 1st to 33rd embodiments, wherein the vehicle contains an adhesive composition. In the 35th embodiment, the present disclosure provides a foam composition according to the 34th embodiment, wherein the vehicle contains a pressure-sensitive adhesive composition. In the 36th embodiment, the present disclosure provides a foam composition according to the 34th embodiment, wherein the vehicle contains a hot-melt adhesive composition. In the 37th embodiment, the present disclosure provides an adhesive tape containing the foam composition according to any one of the 34th to 36th embodiments. In the 38th embodiment, the present disclosure provides an article containing the foam composition according to any one of the 1st to 36th embodiments.

[0103] In the 39th embodiment, the present disclosure provides a process for producing the adhesive tape described in the 37th embodiment, the process including applying a foam composition to a substrate. In the 40th embodiment, the present disclosure provides the process described in the 39th embodiment, wherein the vehicle includes an organic monomer and optionally a silicone-free organic substance, and the process further includes polymerizing the organic monomer. In the 41st embodiment, the present disclosure provides the process described in the 39th or 40th embodiment, the process further including crosslinking the foam composition. In the 42nd embodiment, the present disclosure provides a process for producing the foam composition according to any one of the 1st to 36th embodiments, the process including introducing a foaming agent into a composition including a vehicle and a silicone MQ resin to form voids in the composition. In the 43rd embodiment, the present disclosure provides the process described in the 42nd embodiment, wherein introducing the foaming agent includes at least one of stirring the composition or injecting gas into the composition. In the 44th embodiment, the present disclosure provides the process described in the 43rd embodiment, wherein the foaming agent includes at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon, or nitrous oxide.

[0104] The following specific but non-limiting examples will serve to illustrate the present disclosure.

Examples

[0105] Unless otherwise specified, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight. In this section, the following abbreviations are used: g = gram, cm = centimeter, Ga = gauge, LPM = liter / minute, mM = millimole, mm = millimeter, mL = milliliter, and NMR = nuclear magnetic resonance. The materials used in the examples and their suppliers are shown in Table 1 below.

[0106]

Table 1

[0107] Determination of M:Q ratio A sample of approximately 150 mg was placed into a PTFE NMR tube and dissolved with 2 mL of 0.1 mM Cr(OAcAc)3 in CDCl3. S1 29 NMR data was collected on a 600 MHz JEOL NMR spectrometer equipped with a 10 mm JEOL silicon-free probe. The M:Q ratio was determined by integrating the M region of the Si NMR spectrum from 17 - 5 ppm. 29 The Q region of the Si NMR spectrum, -90 to -115 ppm, was also integrated. The M:Q ratio is the corresponding integration ratio. The data is shown in Table 4 below. 29

[0108] Molecular Weight Measurement of Poly(alkylene oxide) Modified Polydimethylsiloxane A sample of approximately 150 mg of the resin was placed into a PTFE NMR tube and dissolved with 2 mL of 0.1 mM Cr(OAcAc)3 in CDCl3. S1 29 NMR data was collected on a 600 MHz JEOL NMR spectrometer equipped with a 10 mm JEOL silicon-free probe and the number average molecular weight was determined. The organosilicon "EFKA SL3257" was determined to have a number average molecular weight of 2135 grams / mole.

[0109] Preparation of Triethylsilyl Group-Capped Silicone MQ Resin (TES-Capped MQ Resin) Silicone MQ resin "SQO-299" (10.0 g) was dissolved in heptane (10.0 g), and subsequently triethylsilane (2.0 g) was added in a 100 mL round-bottom flask. Then, Pd / C (0.1 g) (5.0 wt% Pd loading) was added to the above mixture at room temperature. The addition of Pd / C resulted in a rapid evolution of hydrogen gas indicating the substitution of silanol by the triethylsilyl group. The reaction mixture was stirred for 24 hours. The reaction mixture was passed through a 0.5 micron glass filter to separate the Pd / C from the reaction mixture. Finally, unreacted triethylsilane was removed using a vacuum to obtain the triethylsilyl-capped MQ resin.

[0110] ​Examples 1 to 13 (EX1 to EX13) and Comparative Examples (CE1 to CE12) for the Foamed Column Screening Test 0.20 g of silicone MQ resin (shown in Table 4 below) was weighed into a tall glass sample vial and added to EX1 to EX10 and EX13. For CE1 to CE12, 0.20 g of surfactant shown in Table 4 below was added to the sample vial. For EX11 to EX12, a 50:50 mixture of 0.2 g of silicone MQ resin and the surfactant shown in Table 4 below was added to the sample vial. Subsequently, 10.0 g of an acrylic monomer mixture (90 parts by weight of 2-EHA: 10 parts by weight of AA) was added to the sample vial. The sample vial was capped and evaluated using the foamed column screening test described below. The data is shown in Table 4 below.

[0111] Foamed Column Screening Test (Manual Stirring) The prepared samples of the acrylic monomer mixture containing Examples 1 to 13 and Comparative Examples CE1 to CE12 were thoroughly combined by shaking the sample vial vigorously for 15 seconds and allowing the contents to settle. Next, the sample vial was placed on a horizontal plane. Using a ruler, the height of the foam was visually measured. A photograph was taken and the data was immediately recorded to record the height of the foam column. The time required for half of the liquid to be drained from the foam (i.e., to provide half of the initial volume of the liquid) was measured and the foam half-life was reported. The overall evaluation is further described in Table 2 below.

[0112]

Table 2

[0113] Examples 1A to 13A (EX1A to EX13A) and Comparative Examples (CE1A to CE12A) for the Syrup Bubbling Test A coatable viscosity syrup polymer was prepared by charging 90 parts of 2-EHA, 10 parts of AA, and 0.04 parts per 100 parts of monomer of “OMNIRAD 651” into a 1 quart jar and stirring until the photoinitiator was dissolved to obtain a homogeneous mixture. The mixture was degassed by introducing nitrogen gas through a tube inserted through the opening in the lid of the jar and bubbled vigorously for at least 5 minutes. While stirring, the mixture was exposed to UV-A light until a pre-adhesive syrup having a viscosity deemed suitable for coating was formed. After UV exposure, air was introduced into the jar. The light source was an LED array having a peak emission wavelength of 365 nm.

[0114] 30.0 g of syrup was weighed into a 4 ounce glass jar equipped with a magnetic stir bar. Then, 0.30 g of silicone MQ resin (shown in Table 4 below) was added to the glass jars of EX1A to EX10A and EX13A. For CE1A to CE12A, 0.30 g of surfactant shown in Table 4 below was added to the glass jar. For EX11A and EX12A, 0.30 g of a 50:50 mixture of silicone MQ resin and surfactant shown in Table 4 below was added to the glass jar. Then, the samples were capped. The samples were stirred on a magnetic stir plate for 5 minutes and then subjected to the syrup bubbling test described below. The data is shown in Table 4 below.

[0115] Syrup Bubbling Test A bubbling device was installed. The house nitrogen line was connected to a Cole-Palmer 5 LPM flow meter. The flow meter was connected to a tube equipped with a long 18Ga needle. The lid of the prepared sample glass jar was replaced with a lid equipped with a glass adapter, which is a hollow tube attached through the hole of the lid of a standard jar. A septum was inserted into the glass adapter together with a 16Ga needle (for ventilation). Then, the long 18Ga needle was inserted into the septum. Then, nitrogen was released, the flow rate was adjusted to 4 LPM, and it was confirmed that the ventilation needle was functioning. Then, a magnetic stir bar was stirred on a magnetic stir plate at the "low" setting. Then, the long needle was pushed into the bottom of the jar. The device was bubbled for 5 minutes. Then, the needle was removed and the magnetic stir bar was stopped. Then, the closed glass jar lid was reapplied and the glass jar was left standing at the surface height.

[0116] Using a ruler, the height of the foam was visually measured. A photo was taken and the data was immediately recorded to record the height and persistence of the foam column. The time required for half of the liquid to be drained from the foam (i.e., providing half of the initial volume of the liquid) was measured and the foam half-life was reported. The overall evaluation is shown in Table 3 below.

[0117]

Table 3

[0118] It should be understood that various modifications and changes to the present disclosure can be made by those skilled in the art without departing from the scope and spirit of the present disclosure, and that the present invention should not be overly limited to the exemplary embodiments described herein.

[0119]

Table 4

Claims

1. A foam composition, A vehicle having internal voids, comprising at least one of a silicone-free organic polymer or an organic monomer, and Silicone MQ resin, A foam composition comprising the above, wherein the foam composition contains 50% by weight or less of water.

2. The foam composition according to claim 1, wherein the silicone MQ resin has an M:Q ratio of at least 0.8:

1.

3. The foam composition according to claim 1, wherein the MQ resin contains methyl groups and has a hydroxyl content in the range of 185 to 1840 milliequivalents per kilogram.

4. The foam composition according to claim 1, wherein the silicone MQ resin is present in the foam composition at a level of 0.1 to 10 weight percent based on the total weight of the foam composition.

5. The foam composition according to claim 1, further comprising a poly(alkylene oxide)-modified polydimethylsiloxane having a number average molecular weight of 50,000 grams / mol or less, wherein the alkylene oxide comprises an ethylene oxy group, a propylene oxy group, or a combination thereof.

6. The foaming composition according to claim 1, further comprising an ethoxylated alcohol.

7. The foam composition according to claim 1, having a foam half-life of at least 10 minutes at 22°C.

8. The foam composition according to claim 1, further comprising at least one of fumed silica, hollow ceramic microspheres, or hollow polymer microspheres.

9. The foam composition according to claim 1, wherein the vehicle comprises a silicone-free organic polymer, and the silicone-free organic polymer comprises at least one of polyester, polyurethane, polyurea, amino resin, alkyd resin, phenolic resin, epoxy resin, isocyanate resin, isocyanurate resin, or acrylic polymer.

10. The foam composition according to claim 1, wherein the vehicle comprises the silicone-free organic polymer, and the silicone-free organic polymer is crosslinked.

11. The foam composition according to claim 1, wherein the vehicle comprises at least one of acrylate or acrylic polymer.

12. The aforementioned vehicle, Isooctyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, butyl acrylate, acrylic acid, and a mixture of at least two or at least three structural isomers of the following secondary alkyl (meth)acrylates: 【Chemistry 1】 Or, Isooctyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, butyl acrylate, acrylic acid, or a mixture of at least two or at least three structural isomers of secondary alkyl (meth)acrylates of the following formulas: 【Chemistry 2】 polymer containing units [In the formula, R ７ and R ８ Each of them is independent of C １ ~C ３０ It is a saturated linear alkyl group, R ７ and R ８ The total number of carbon atoms in R is 7 to 31. ５ [This is either a hydrogen or methyl group.] The foam composition according to claim 1, comprising at least one of the following.

13. The foam composition according to any one of claims 1 to 12, wherein the vehicle comprises an adhesive composition.

14. An adhesive tape comprising the foam composition described in claim 13.

15. A process for producing a foam composition according to any one of claims 1 to 12, comprising introducing a foaming agent into a composition comprising the vehicle and the silicone MQ resin to form voids in the composition.

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